JP3395514B2 - Dielectric porcelain composition - Google Patents
Dielectric porcelain compositionInfo
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- JP3395514B2 JP3395514B2 JP10235996A JP10235996A JP3395514B2 JP 3395514 B2 JP3395514 B2 JP 3395514B2 JP 10235996 A JP10235996 A JP 10235996A JP 10235996 A JP10235996 A JP 10235996A JP 3395514 B2 JP3395514 B2 JP 3395514B2
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は電子機器用磁器コン
デンサ及びマイクロ波領域において誘電体共振器として
利用される誘電体磁器組成物に関するものである。TECHNICAL FIELD The present invention relates to a ceramic capacitor for electronic equipment and a dielectric ceramic composition used as a dielectric resonator in the microwave region.
【０００２】[0002]
【従来の技術】以下に従来の誘電体磁器組成物について
説明する。誘電体磁器組成物として下記のような系が知
られている。2. Description of the Related Art A conventional dielectric ceramic composition will be described below. The following systems are known as dielectric porcelain compositions.
【０００３】ＢａＯ・ＴｉＯ2・Ｎｄ2Ｏ3系
ＢａＯ・ＴｉＯ2・Ｓｍ2Ｏ3系
Ｂｉ2Ｏ3・ＣａＯ・Ｎｂ2Ｏ5・ＣｕＯ系
例えば０．０９ＢａＯ・０．５６ＴｉＯ2・０．３５Ｎ
ｄＯ3/2の組成比からなる誘電体磁器組成物を使用し、
誘電体磁器円板を作製し、電気特性、および結晶粒径お
よび誘電体磁器密度を測定すると、誘電率：６７、静電
容量温度係数：Ｎ４０ｐｐｍ／℃、Ｑ：３０００、絶縁
抵抗：８．０×１０12Ω、絶縁破壊強度：１２ｋｖ／mm
および結晶粒径：１〜５μｍ、および誘電体磁器密度：
５．６ｇ／cm3の値が得られた。[0003] BaO · TiO 2 · Nd 2 O 3 system BaO · TiO 2 · Sm 2 O 3 system Bi 2 O 3 · CaO · Nb 2 O 5 · CuO system e.g. 0.09BaO · 0.56TiO 2 · 0.35N
Using a dielectric porcelain composition having a composition ratio of dO 3/2 ,
Dielectric porcelain discs were produced, and electrical characteristics, crystal grain size and dielectric porcelain density were measured. Dielectric constant: 67, temperature coefficient of capacitance: N 40 ppm / ° C., Q: 3000, insulation resistance: 8.0 × 10 12 Ω, dielectric breakdown strength: 12 kv / mm
And crystal grain size: 1 to 5 μm, and dielectric ceramic density:
A value of 5.6 g / cm 3 was obtained.
【０００４】[0004]
【発明が解決しようとする課題】上記構成の誘電体磁器
は結晶粒径が大きく、素体密度が小さかった。そしてこ
の誘電体磁器の表面に電極を形成するためにＣｕメッキ
を行おうとすると、酸溶液中でエッチング処理する際、
磁器の内部まで酸エッチングされて磁器の機械的強度と
磁器の表面に形成されるＣｕ電極の接着強度の低下を招
き、誘電体デバイスの信頼性に悪影響を及ぼすという問
題点を有していた。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The dielectric ceramic having the above-mentioned structure has a large crystal grain size and a small element density. Then, when Cu plating is performed to form an electrode on the surface of this dielectric ceramic, when etching treatment is performed in an acid solution,
There is a problem in that the mechanical strength of the porcelain and the adhesive strength of the Cu electrode formed on the surface of the porcelain are reduced due to acid etching to the inside of the porcelain, which adversely affects the reliability of the dielectric device.
【０００５】そこで本発明は結晶粒径が均一微細で、誘
電体磁器密度の大きい誘電体磁器組成物を提供すること
を目的とするものである。Therefore, an object of the present invention is to provide a dielectric ceramic composition having a uniform and fine crystal grain size and a high dielectric ceramic density.
【０００６】[0006]
【課題を解決するための手段】この目的を達成するため
に本発明の誘電体磁器組成物は、一般式ｘ［（ＢａＯ）
1-m（ＳｒＯ）m］・ｙ［（ＴｉＯ2）1-n（ＺｒＯ2）n］
・ｚＲ2Ｏ3で表され、この一般式中Ｒは、Ｌａ，Ｐｒ，
Ｎｄ，Ｓｍから選ばれる一種以上の希土類元素であり、
ｍ，ｎの値が、０．０１≦ｍ≦０．５０、０．００１≦
ｎ≦０．２５０なる範囲にあり、ｘ，ｙおよびｚはモル
比を表し、ｘ＋ｙ＋ｚ＝１であり、ｘ，ｙ，ｚの値が
（表２）に示すａ，ｂ，ｃ，ｄ，ｅで囲まれるモル比の
範囲にある組成１００ｍｏｌ％に対してＰｂＯを１０ｍ
ｏｌ％以下（ただし、０ｍｏｌ％を除く）の範囲で含有
する主成分組成物１００重量部に対して、副成分として
ニオブ酸化物をＮｂ2Ｏ5に換算して０．３〜５．０重量
部含有させたものである。To achieve this object, the dielectric ceramic composition of the present invention has the general formula x [(BaO)]
1-m (SrO) m ] y [(TiO 2 ) 1-n (ZrO 2 ) n ]
Represented by zR 2 O 3 , R in this general formula is La, Pr,
One or more rare earth elements selected from Nd and Sm,
The values of m and n are 0.01 ≦ m ≦ 0.50, 0.001 ≦
In the range of n ≦ 0.250, x, y and z represent a molar ratio, x + y + z = 1, and the values of x, y and z are a, b, c, d and e shown in (Table 2). 10 mol of PbO with respect to 100 mol% of composition within the range of the molar ratio surrounded by
0.3 to 5.0 parts by weight of niobium oxide as an accessory component converted to Nb 2 O 5 with respect to 100 parts by weight of the main component composition contained in the range of ol% or less (excluding 0 mol%). This is partly included.
【０００７】[0007]
【表２】 [Table 2]
【０００８】この構成によると、一般式中のＲをＬａ，
Ｐｒ，Ｎｄ，Ｓｍから選ぶことにより、Ｌａ，Ｐｒ，Ｎ
ｄ，Ｓｍの順で静電容量温度係数をプラス方向に任意に
移行することができる。また主成分に対してニオブ酸化
物を含有させることにより、焼結性が向上し、磁器の緻
密化とともに結晶粒子が均一微細化されるので、絶縁抵
抗、絶縁破壊強度を大きくできるとともに共振器のＱの
低下を防ぐことができる。According to this structure, R in the general formula is La,
By selecting from Pr, Nd, Sm, La, Pr, N
The temperature coefficient of capacitance can be arbitrarily shifted in the positive direction in the order of d and Sm. In addition, by containing niobium oxide in the main component, the sinterability is improved, and the porcelain becomes denser and the crystal grains are made uniform and fine, so that the insulation resistance and the dielectric breakdown strength can be increased and the resonator It is possible to prevent the Q from decreasing.
【０００９】また磁器の密度が大きいので、この誘電体
磁器組成物を用いて例えば積層セラミックコンデンサな
どの積層型電子部品を形成し、実装する際通常マンハッ
タン現象と呼ばれるようなチップ立ちを防ぐことができ
る。Further, since the density of porcelain is high, when this dielectric ceramic composition is used to form and mount a multilayer electronic component such as a multilayer ceramic capacitor, it is possible to prevent chip standing, which is usually called the Manhattan phenomenon. it can.
【００１０】さらに本発明の誘電体磁器組成物を用いて
誘電体共振器を作製する場合無電解Ｃｕメッキにより電
極を形成したとしても誘電体共振器素体と電極との接着
強度が高いので、高信頼性の誘電体共振器を得ることが
できる。Furthermore, when a dielectric resonator is manufactured using the dielectric ceramic composition of the present invention, the adhesive strength between the dielectric resonator element body and the electrode is high even if the electrode is formed by electroless Cu plating. A highly reliable dielectric resonator can be obtained.
【００１１】[0011]
【発明の実施の形態】本発明の請求項１に記載の発明は
一般式としてｘ［（ＢａＯ）1-m（ＳｒＯ）m］・ｙ
［（ＴｉＯ2）1-n（ＺｒＯ2）n］・ｚＲ2Ｏ3で表され、
この一般式中Ｒは、Ｌａ，Ｐｒ，Ｎｄ，Ｓｍから選ばれ
る一種以上の希土類元素であり、ｍ，ｎの値が０．０１
≦ｍ≦０．５０、０．００１≦ｎ≦０．２５０なる範囲
にあり、ｘ，ｙおよびｚはモル比を表し、ｘ＋ｙ＋ｚ＝
１で、ｘ，ｙ，ｚの値が（表２）に示すａ，ｂ，ｃ，
ｄ，ｅで囲まれるモル比の範囲にある組成１００ｍｏｌ
％に対して、ＰｂＯを１０ｍｏｌ％以下（ただし、０ｍ
ｏｌ％を除く）の範囲で含有する主成分組成物１００重
量部に対して、副成分として、少なくともニオブ酸化物
をＮｂ2Ｏ5に換算して０．３〜５．０重量部含有してな
ることを特徴とする誘電体磁器組成物であり、結晶粒子
が均一微細化された、磁器密度、絶縁抵抗、絶縁破壊強
度が大きく、共振器のＱの低下を防ぐことができるもの
である。BEST MODE FOR CARRYING OUT THE INVENTION The invention described in claim 1 of the present invention has a general formula of x [(BaO) 1-m (SrO) m ] .y.
[(TiO 2 ) 1-n (ZrO 2 ) n ] .zR 2 O 3 ,
In this general formula, R is one or more rare earth elements selected from La, Pr, Nd, and Sm, and the values of m and n are 0.01.
≦ m ≦ 0.50, 0.001 ≦ n ≦ 0.250, x, y and z represent molar ratios, and x + y + z =
1, the values of x, y, z are a, b, c, shown in (Table 2).
Composition 100 mol in the range of molar ratio surrounded by d and e
%, PbO is 10 mol% or less (however, 0 m
(excluding ol%), at least 0.3 to 5.0 parts by weight of niobium oxide converted into Nb 2 O 5 as a sub-component is contained with respect to 100 parts by weight of the main component composition. It is a dielectric porcelain composition characterized in that the crystal grains are uniformly miniaturized, the porcelain density, the insulation resistance and the dielectric breakdown strength are large, and the Q of the resonator can be prevented from lowering.
【００１２】[0012]
【００１３】請求項２に記載の発明は、一般式としてｘ
［（ＢａＯ）1-m（ＳｒＯ）m］・ｙ［（ＴｉＯ2）
1-n（ＺｒＯ2）n］・ｚＲ2Ｏ3で表され、この一般式中
ＲはＬａ，Ｐｒ，Ｎｄ，Ｓｍから選ばれる一種以上の希
土類元素であり、ｍ，ｎの値が、０．０１≦ｍ≦０．５
０、０．００１≦ｎ≦０．２５０なる範囲にあり、ｘ，
ｙおよびｚはモル比を表し、ｘ＋ｙ＋ｚ＝１でｘ，ｙ，
ｚの値が（表２）に示すａ，ｂ，ｃ，ｄ，ｅで囲まれる
モル比の範囲にある組成１００ｍｏｌ％に対して、Ｂｉ
2Ｏ3を５ｍｏｌ％以下（ただし０ｍｏｌ％を除く）及び
ＰｂＯを１０ｍｏｌ％以下（ただし０ｍｏｌ％を除く）
の範囲で含有する主成分組成物１００重量部に対して、
副成分として、少なくともニオブ酸化物をＮｂ2Ｏ5に換
算して０．３〜５．０重量部含有してなることを特徴と
する誘電体磁器組成物であり、結晶粒子が均一微細化さ
れた、磁器密度、絶縁抵抗、絶縁破壊強度が大きく、共
振器のＱの低下を防ぐことができるものである。The invention described in claim 2 has the general formula x
[(BaO) 1-m (SrO) m ] ・ y [(TiO 2 )
1-n (ZrO 2 ) n ] · zR 2 O 3 , wherein R is one or more rare earth elements selected from La, Pr, Nd, and Sm, and m and n have values of 0. .01 ≦ m ≦ 0.5
0, 0.001 ≦ n ≦ 0.250, x,
y and z represent molar ratios, and x + y + z = 1, x, y,
For a composition of 100 mol% in which the value of z is in the range of molar ratios surrounded by a, b, c, d, and e shown in (Table 2), Bi
2 O 3 5 mol% or less (excluding 0 mol%) and PbO 10 mol% or less (excluding 0 mol%)
To 100 parts by weight of the main component composition contained in the range of
A dielectric porcelain composition characterized by containing 0.3 to 5.0 parts by weight of at least niobium oxide converted into Nb 2 O 5 as an accessory component, wherein crystal grains are uniformly refined. Further, the porcelain density, insulation resistance, and dielectric breakdown strength are large, and it is possible to prevent the Q of the resonator from decreasing.
【００１４】請求項３に記載の発明は、請求項１及び２
の内いずれか一つに記載の誘電体磁器組成物１００重量
部に対して、副成分としてＧｅ，Ｐｂ，Ｆ，Ｂｉ，Ｓ
ｂ，Ｂ，Ｎｂ，Ｐ，Ｚｎ，Ｓｉ，Ａｌ，Ｍｏ，Ｗ，Ｌ
ｉ，Ｎａ，Ｋ，Ｃａ，Ｂａ，Ｍｇ，Ｔｉ，Ｚｒ，Ｓｎ，
Ｉｎ，Ｇｄ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｄ
ｙ，Ｙｂ，Ｙ，Ｆｅ，Ｃｒ，Ｍｎ，Ｃｏ，Ｎｉ，Ｃｕ，
Ａｇ及びＡｕから選ばれる少なくとも二種以上を含有す
る低融点物質またはガラス成分を２０重量部（ただし０
重量部を除く）以下の範囲で添加させて成ることを特徴
とする誘電体磁器組成物であり、９００〜１１００℃の
低温で焼結できるものである。The invention described in claim 3 is the same as claims 1 and 2.
To 100 parts by weight of the dielectric ceramic composition described in any one of the above, Ge, Pb, F, Bi and S as auxiliary components.
b, B, Nb, P, Zn, Si, Al, Mo, W, L
i, Na, K, Ca, Ba, Mg, Ti, Zr, Sn,
In, Gd, La, Ce, Pr, Nd, Sm, Eu, D
y, Yb, Y, Fe, Cr, Mn, Co, Ni, Cu,
20 parts by weight of a low melting point substance or glass component containing at least two kinds selected from Ag and Au (however, 0
(Excluding parts by weight) A dielectric ceramic composition characterized by being added in the following range, which can be sintered at a low temperature of 900 to 1100 ° C.
【００１５】請求項４に記載の発明は、ニオブ酸化物に
代えて、タンタル酸化物をＴａ2Ｏ5に換算して０．１〜
１０．０重量部含有したことを特徴とする請求項１，２
及び３のうちいずれか一つに記載の誘電体磁器組成物で
あり、絶縁抵抗、絶縁破壊強度及びＣｕ電極の接着強度
の大きいものである。According to a fourth aspect of the invention, in place of the niobium oxide, the tantalum oxide is converted into Ta 2 O 5 in an amount of 0.1 to 0.1.
The content of 10.0 parts by weight is included.
And the dielectric ceramic composition according to any one of 3 and 3 , which has high insulation resistance, dielectric breakdown strength, and Cu electrode adhesion strength.
【００１６】請求項５に記載の発明は、ニオブ酸化物に
代えて、バナジウム酸化物がＶ2Ｏ5に換算して０．００
５〜１．０００重量部含有させたことを特徴とする請求
項１，２及び３のうちいずれか一つに記載の誘電体磁器
組成物であり、絶縁抵抗、絶縁破壊強度及びＣｕ電極の
接着強度の大きいものである。According to a fifth aspect of the invention, vanadium oxide is used as 0.002 in terms of V 2 O 5 in place of niobium oxide.
The dielectric ceramic composition according to any one of claims 1, 2 and 3 , wherein the dielectric resistance, the dielectric breakdown strength and the adhesion of the Cu electrode are contained in an amount of 5 to 1.000 parts by weight. It has high strength.
【００１７】請求項６に記載の発明は、ニオブ酸化物に
代えて、Ｎｂ2Ｏ5，Ｔａ2Ｏ5，Ｖ2Ｏ5から選ばれる二種
以上を、Ｎｂ2Ｏ5が０．３〜５．０重量部、Ｔａ2Ｏ5が
０．１〜１０．０重量部、Ｖ2Ｏ5が０．００５〜１．０
重量部の範囲で含有してなることを特徴とする請求項
１，２及び３のうちいずれか一つに記載の誘電体磁器組
成物であり、誘電率、Ｑ、絶縁抵抗、絶縁破壊強度が大
きく、正静電容量温度係数の小さいものである。According to a sixth aspect of the invention, in place of the niobium oxide, two or more kinds selected from Nb 2 O 5 , Ta 2 O 5 and V 2 O 5 are added, and Nb 2 O 5 is 0.3 to 0.3. 5.0 parts by weight, Ta 2 O 5 is 0.1 to 10.0 parts by weight, V 2 O 5 is 0.005 to 1.0
The dielectric porcelain composition according to any one of claims 1, 2 and 3 , wherein the dielectric porcelain composition has a dielectric constant, a Q, an insulation resistance, and a dielectric breakdown strength. It is large and has a small positive electrostatic capacitance temperature coefficient.
【００１８】[0018]
【実施例】以下、本発明の一実施例について説明する。EXAMPLES An example of the present invention will be described below.
【００１９】（実施例１）出発原料には化学的に高純度
のＢａＮｂ2Ｏ6（所定のモル比のＢａＣＯ3とＮｂ2Ｏ5
とを１１００℃の温度で３時間仮焼し、その後平均粒径
０．５μｍに微粉砕した。），Ｌａ2Ｏ3，Ｐｒ6Ｏ11，
Ｎｄ2Ｏ3，Ｓｍ2Ｏ3，ＴｉＯ2，ＺｒＯ2，Ｂｉ2Ｏ3，Ｐ
ｂＯ，ＳｒＣＯ3およびＢａＣＯ3粉末を（表３）に示す
組成比になるように秤量し、めのうボールを備えたゴム
内張りのボールミルに純水とともに入れ、湿式混合後、
脱水乾燥した。Example 1 As a starting material, chemically high-purity BaNb 2 O 6 (BaCO 3 and Nb 2 O 5 in a predetermined molar ratio) was used.
And were calcined at a temperature of 1100 ° C. for 3 hours and then finely pulverized to an average particle size of 0.5 μm. ), La 2 O 3 , Pr 6 O 11 ,
Nd 2 O 3 , Sm 2 O 3 , TiO 2 , ZrO 2 , Bi 2 O 3 , P
The bO, SrCO 3 and BaCO 3 powders were weighed so that the composition ratios shown in (Table 3) were obtained, put into a rubber-lined ball mill equipped with agate balls together with pure water, and after wet mixing,
It was dehydrated and dried.
【００２０】[0020]
【表３】 [Table 3]
【００２１】この乾燥粉末を高アルミナ質のルツボに入
れ、空気中で１１００℃にて２時間仮焼した。この仮焼
粉末を、めのうボールを備えたゴム内張りのボールミル
に純水とともに入れ、湿式粉砕後、脱水乾燥した。次に
この粉砕粉末に、有機バインダーを加え、均質とした
後、３２メッシュのふるいを通して整粒し、金型と油圧
プレスを用いて成形圧力１ｔｏｎ／cm2で直径１５mm、
厚み０．４mmに成形した。次いで、成形円板をジルコニ
ア粉末を敷いたアルミナ質のサヤに入れ、空気中にて１
２５０〜１４５０℃の焼成温度で２時間焼成し、（表
３）の試料番号１〜１８に示す組成比の誘電体磁器を得
た。The dried powder was placed in a crucible of high alumina quality and calcined in air at 1100 ° C. for 2 hours. This calcined powder was put into a rubber-lined ball mill equipped with agate balls together with pure water, wet pulverized, and then dehydrated and dried. Next, an organic binder was added to this pulverized powder to make it homogenous, and the powder was sized through a 32 mesh sieve, and the diameter was 15 mm at a molding pressure of 1 ton / cm 2 using a die and a hydraulic press.
Molded to a thickness of 0.4 mm. Next, the molded disc is put into an alumina-based sheath coated with zirconia powder and placed in air for 1
Firing was performed at a firing temperature of 250 to 1450 ° C. for 2 hours to obtain dielectric porcelain having the composition ratio shown in sample numbers 1 to 18 of (Table 3).
【００２２】このようにして得られた誘電体磁器円板
は、厚みと直径と重量を測定し、重量を厚みと直径より
算出した体積で除算し、誘電体磁器密度とした。The thickness, diameter and weight of the dielectric ceramic disk thus obtained were measured, and the weight was divided by the volume calculated from the thickness and diameter to obtain the dielectric ceramic density.
【００２３】誘電率、Ｑ、静電容量温度係数測定用試料
は、誘電体磁器円板の両面全体に銀電極を焼き付け、絶
縁抵抗、絶縁破壊強度測定用試料は、誘電体磁器円板の
外周より内側に１mmの幅で銀電極の無い部分を設け、銀
電極を焼き付けた。そして、誘電率、Ｑ、静電容量温度
係数は、横河ヒューレット・パッカード（株）製デジタ
ルＬＣＲメータのモデル４２７５Ａを使用し、測定温度
２０℃、測定電圧１．０Ｖｒｍｓ、測定周波数１ＭHzで
の測定より求めた。なお、静電容量温度係数は、２０℃
と８５℃の静電容量を測定し、次式により求めた。Samples for measuring the dielectric constant, Q, and temperature coefficient of capacitance were printed with silver electrodes on both sides of the dielectric ceramic disk. Samples for measuring insulation resistance and dielectric breakdown strength were prepared on the outer circumference of the dielectric ceramic disk. A portion without a silver electrode having a width of 1 mm was provided inside and the silver electrode was baked. Then, the dielectric constant, Q, and temperature coefficient of capacitance are measured at a measurement temperature of 20 ° C., a measurement voltage of 1.0 Vrms, and a measurement frequency of 1 MHz using a model 4275A of a digital LCR meter manufactured by Yokogawa Hewlett-Packard Co. I asked more. The temperature coefficient of capacitance is 20 ° C.
And the electrostatic capacity at 85 ° C. were measured and determined by the following formula.
【００２４】 ＴＣ＝（Ｃ−Ｃｏ）／Ｃｏ×１／６５×１０6 ＴＣ：静電容量温度係数（ｐｐｍ／℃） Ｃｏ：２０℃での静電容量（ｐＦ） Ｃ ：８５℃での静電容量（ｐＦ） また、誘電率は次式より求めた。TC = (C-Co) / Co × 1/65 × 10 6 TC: Temperature coefficient of capacitance (ppm / ° C.) Co: Capacitance at 20 ° C. (pF) C: Static at 85 ° C. Capacitance (pF) Further, the dielectric constant was obtained from the following equation.
【００２５】Ｋ＝１４３．８×Ｃｏ×ｔ／Ｄ2
Ｋ ：誘電率
Ｃｏ：２０℃での静電容量（ｐＦ）
Ｄ ：誘電体磁器の直径（mm）
ｔ ：誘電体磁器の厚み（mm）
さらに、絶縁抵抗は、横河ヒューレット・パッカード
（株）製ＨＲメータのモデル４３２９Ａを使用し、測定
電圧５０Ｖ．Ｄ．Ｃ．、測定時間１分間による測定より
求めた。K = 143.8 × Co × t / D 2 K: Dielectric constant Co: Capacitance (pF) at 20 ° C. D: Diameter of dielectric ceramic (mm) t: Thickness of dielectric ceramic (mm ) Further, the insulation resistance was measured using Yokogawa Hewlett-Packard Co., Ltd. HR meter model 4329A at a measurement voltage of 50V. D. C. The measurement time was 1 minute.
【００２６】そして、絶縁破壊強度は、菊水電子工業
（株）製高電圧電源ＰＨＳ３５Ｋ−３形を使用し、試料
をシリコンオイル中に入れ、昇圧速度５０Ｖ／ｓｅｃに
より求めた絶縁破壊電圧を誘電体厚みで除算し、１mm当
りの絶縁破壊強度とした。Regarding the dielectric breakdown strength, a high voltage power source PHS35K-3 type manufactured by Kikusui Electronics Co., Ltd. was used, the sample was put in silicon oil, and the dielectric breakdown voltage was obtained by the step-up speed of 50 V / sec. It was divided by the thickness to obtain the dielectric breakdown strength per 1 mm.
【００２７】また、結晶粒径は、倍率４００での光学顕
微鏡観察より求めた。上記測定結果を試料番号１〜１８
別に（表４）に示す。The crystal grain size was determined by observing with an optical microscope at a magnification of 400. The above measurement results are sample numbers 1 to 18
The results are shown separately (Table 4).
【００２８】[0028]
【表４】 [Table 4]
【００２９】図１は本発明にかかる組成物の主成分の組
成範囲を示す三元図であり、主成分の組成範囲を限定し
た理由を図１を参照しながら説明する。すなわち、Ａ領
域では焼結が著しく困難であり誘電率、Ｑ値、絶縁抵抗
が低下する。また、Ｂ領域ではＱ値の低下と静電容量温
度係数がマイナス側に大きくなり実用的でなくなる。さ
らに、Ｃ領域では静電容量温度係数がマイナス側に大き
くなりすぎて実用的でなくなる。そして、Ｄ領域では静
電容量温度係数がプラス方向に移行するが誘電率が小さ
く実用的でなくなる。また、ＲをＬａ，Ｐｒ，Ｎｄ，Ｓ
ｍから選ぶことによりＬａ，Ｐｒ，Ｎｄ，Ｓｍの順で誘
電率を大きく下げることなく静電容量温度係数をプラス
方向に移行することが可能であり、Ｌａ，Ｐｒ，Ｎｄ，
Ｓｍの一種あるいは組合せにより静電容量温度係数の調
節が任意に可能である。ＳｒＯとＺｒＯ2の置換は、誘
電率を大きく低下させずに静電容量温度係数をプラス方
向に移行させ任意の調節を可能にし、Ｑ値、絶縁抵抗、
Ｃｕ電極接着強度を大きくする効果がある。しかし過剰
量の場合、誘電率、Ｑ値、Ｃｕ電極接着強度の低下を招
くので置換量は限定される。また、上記に限定される組
成範囲に対してＢｉ 2Ｏ3，ＰｂＯをそれぞれ、もしくは
同時に含有させた主成分に対して、更にＮｂ 2Ｏ5を添加
含有させることで、結晶粒子の均一微細化、緻密化が図
られ、絶縁抵抗、絶縁破壊強度及びＣｕ電極の接着強度
を大きくすることが可能である。さらに電極による導体
損失が小さくなり、共振器のＱの低下を防ぐことができ
る。Ｂｉ2Ｏ3，ＰｂＯの含有量が、全く無い場合、或い
は過剰量の場合、ポーラスな磁器になり、絶縁抵抗、絶
縁破壊強度及びＣｕ電極接着強度が著しく低下する。そ
して主成分に対し、必須成分である副成分Ｎｂ2Ｏ5を含
有することにより、絶縁抵抗、絶縁破壊強度及びＣｕ電
極接着強度を大きくする効果を有し、Ｎｂ2Ｏ5の含有量
が主成分１００重量部に対し、０．３重量部未満はそれ
ほど絶縁破壊強度及び電極接着強度が大きくなく、この
発明の範囲から除外した。一方、Ｎｂ2Ｏ5の含有量が主
成分に対し、５．０重量部を越えるとＱ、絶縁抵抗が小
さくなり、静電容量温度係数がマイナス側に大きくなり
実用的でなくなる。FIG. 1 is a set of main components of the composition according to the present invention.
It is a ternary diagram showing the composition range, and the composition range of the main component is limited.
The reason for this will be described with reference to FIG. That is, A territory
Is extremely difficult to sinter in the region, permittivity, Q value, insulation resistance
Is reduced. In the B region, the Q value decreases and the capacitance temperature rises.
The frequency coefficient increases to the negative side, making it impractical. It
Moreover, in the C region, the temperature coefficient of capacitance is large on the negative side.
It becomes too practical to be practical. And in the D area,
The temperature coefficient of capacitance shifts in the positive direction, but the dielectric constant is small
Becomes impractical. In addition, R is La, Pr, Nd, S
Invite La, Pr, Nd, Sm in this order by selecting from m
Capacitance temperature coefficient is increased without significantly reducing the electric rate
It is possible to move in the direction of La, Pr, Nd,
Adjustment of the temperature coefficient of capacitance by one or a combination of Sm
Clauses are optional. SrO and ZrO2Replacement is an invitation
How to add the temperature coefficient of capacitance without greatly reducing the electric conductivity
Direction, allowing arbitrary adjustment, Q value, insulation resistance,
This has the effect of increasing the Cu electrode adhesion strength. But excess
In the case of the amount, the dielectric constant, the Q value, and the Cu electrode adhesive strength may decrease.
Therefore, the substitution amount is limited. Also, the groups limited to the above
Bi for the range 2O3, PbO respectively, or
Nb is further added to the main component contained at the same time. 2OFiveAdd
By including it, it is possible to make the crystal grains uniform and fine.
Insulation resistance, dielectric breakdown strength and Cu electrode adhesion strength
Can be increased. Conductor with electrodes
The loss is small and it is possible to prevent the Q of the resonator from decreasing.
It Bi2O3, If there is no PbO content, or
Is an excessive amount, it becomes porous porcelain, insulation resistance,
The edge breaking strength and the Cu electrode adhesive strength are significantly reduced. So
Then, with respect to the main component, a subcomponent Nb that is an essential component2OFiveIncluding
By having an insulation resistance, a dielectric breakdown strength and a Cu electric
Nb has the effect of increasing the polar adhesion strength.2OFiveContent of
Is less than 0.3 parts by weight for 100 parts by weight of the main component
Dielectric breakdown strength and electrode adhesion strength are not as high as
Excluded from the scope of the invention. On the other hand, Nb2OFiveThe content of
If the amount exceeds 5.0 parts by weight, the component Q and insulation resistance are small.
And the temperature coefficient of capacitance increases to the negative side.
It becomes impractical.
【００３０】必須の副成分であるＮｂソースはＮｂ2Ｏ5
を出発原料としても良いが、あらかじめ合成したチタン
酸化物、あるいはＢａＮｂ2Ｏ6，ＲＮｂＴｉＯ6（Ｒ＝
Ｌａ，Ｐｒ，Ｎｄ，Ｓｍ），ＢｉＮｂＯ4，Ｐｂ3Ｎｂ4
Ｏ13など主成分中の１成分以上と合成させた前駆体を出
発原料とし、原料粉の平均粒径が０．８μｍ以下（粒度
分布の最大値が１．０μｍ以下）のＮｂソースを用いる
ことが望ましい。この理由は、出発原料がＮｂ2Ｏ5の時
に比較してセラミックス中に均一に分散、固溶化するた
め組成均質性が向上し、その結果として焼結反応が均一
に進行し、結晶粒子の異常粒成長が抑制されて微細組織
の均一、微細化が図られるからである。粒径１．０μｍ
以上のＮｂソース原料粉が混入している場合、組成均質
性の低下によって焼結時に異常粒成長を生じ、絶縁抵
抗、絶縁破壊強度、およびＣｕ電極接着強度の低下を招
く場合がある。The Nb source, which is an essential subcomponent, is Nb 2 O 5
Although the starting material may be a starting material, titanium oxide or BaNb 2 O 6 , RNbTiO 6 (R =
La, Pr, Nd, Sm), BiNbO 4 , Pb 3 Nb 4
Use a precursor synthesized with one or more of the main components such as O 13 as a starting material, and use an Nb source with a raw material powder having an average particle size of 0.8 μm or less (maximum particle size distribution of 1.0 μm or less). Is desirable. The reason for this is that compared to when the starting material is Nb 2 O 5 , it is more evenly dispersed and solid-solved in the ceramics, improving the composition homogeneity, and as a result, the sintering reaction proceeds uniformly and abnormal crystal grains occur. This is because grain growth is suppressed and the fine structure is made uniform and fine. Particle size 1.0 μm
When the above Nb source raw material powder is mixed, abnormal grain growth may occur at the time of sintering due to a decrease in composition homogeneity, resulting in a decrease in insulation resistance, dielectric breakdown strength, and Cu electrode adhesion strength.
【００３１】（実施例２）実施例１で用いた（表３）に
示す試料番号９を基本成分とし、１１００℃以下で液相
となる低融点物質またはガラス成分を平均粒径０．４〜
０．６μｍ（粒度分布の最大値が１．０μｍ以下）まで
微粉砕したものを添加し、適当な仮焼温度、焼成温度に
変更した以外は実施例１と同様に処理して（表５）に示
す試料番号１９〜３３に示す誘電体磁器を得、実施例１
と同様に処理して特性を測定し、その結果を試料番号１
９〜３３別に（表６）に示す。(Example 2) The sample No. 9 shown in (Table 3) used in Example 1 was used as a basic component, and a low melting point substance or a glass component which becomes a liquid phase at 1100 ° C or less had an average particle size of 0.4 to
Finely pulverized to 0.6 μm (maximum value of particle size distribution is 1.0 μm or less) was added, and treated in the same manner as in Example 1 except that the calcination temperature and the firing temperature were changed to appropriate values (Table 5). The dielectric ceramics shown in sample numbers 19 to 33 shown in FIG.
The characteristics are measured in the same manner as in 1. and the result is sample number 1.
It is shown in (Table 6) separately for 9 to 33.
【００３２】[0032]
【表５】 [Table 5]
【００３３】[0033]
【表６】 [Table 6]
【００３４】主成分の組成範囲と構成を限定した理由
は、実施例１と同様であるので説明は省略する。The reason for limiting the composition range and composition of the main component is the same as that of the first embodiment, and the description thereof will be omitted.
【００３５】主成分に対し、低融点物質またはガラス成
分を含有させることにより、主成分原料粉の周囲を１１
００℃以下の低温度で充分濡らして焼結を促進させると
同時に、主成分組成と反応するため焼成温度を低下させ
ることができる。低融点物質またはガラス成分の含有量
が、主成分１００重量部に対し、２０重量部を越えると
低誘電率、低Ｑおよび、機械的強度の弱い２次相が析出
したり、焼結を阻害する場合がある。このため、誘電率
が低下したりＱ値および電極の接着強度の低下を招き実
用的でなくなるため、本発明の範囲から除外した。By incorporating a low melting point substance or a glass component into the main component, 11
At a low temperature of 00 ° C. or lower, it is sufficiently wetted to promote sintering, and at the same time, it reacts with the main component composition, so that the firing temperature can be lowered. When the content of the low melting point substance or the glass component exceeds 20 parts by weight with respect to 100 parts by weight of the main component, a secondary phase having a low dielectric constant, a low Q and weak mechanical strength is precipitated, or sintering is inhibited. There is a case. For this reason, the dielectric constant is lowered and the Q value and the adhesive strength of the electrodes are lowered, which makes it impractical. Therefore, it was excluded from the scope of the present invention.
【００３６】また、低融点物質、ガラス成分の粒径は、
大きな粒径のものが混入している場合焼結時に粒界部に
偏析して、機械的強度やＣｕ電極の接着強度に悪影響を
与えることがある。したがって最大でも１．０μｍ以下
であることが望ましい。The particle diameters of the low melting point substance and the glass component are
When a material having a large particle size is mixed, it may segregate at the grain boundary portion during sintering, which may adversely affect the mechanical strength and the adhesive strength of the Cu electrode. Therefore, it is desirable that the maximum is 1.0 μm or less.
【００３７】なお、本実施例において試料番号１９〜２
２，２４〜２６，２８，３０〜３２で示した低融点物
質、ガラス成分以外でもＧｅ，Ｐｂ，Ｂｉ，Ｂ，Ｎｂ，
Ｐ，Ｚｎ，Ｓｉ，Ａｌ，Ｍｏ，Ｌｉ，Ｃａ，Ｂａ，Ｍ
ｇ，Ｔｉ，Ｚｒ，Ｓｎ，Ｉｎ，Ｇｄ，Ｌａ，Ｃｅ，Ｐ
ｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｄｙ，Ｙｂ，Ｙ，Ｆｅ，Ｃｒ，
Ｍｎ，Ｃｏ，Ｎｉ，Ｃｕ，Ａｇ及びＡｕから選ばれる少
なくとも二種以上から成る低融点物質またはガラス成分
を添加含有させることで、前記組成の特徴を有する９０
０〜１１００℃の低温で焼結できる誘電体磁器組成物を
得ることができる。従って高周波特性に優れた低融点の
Ａｇ，Ａｇ−Ｐｄ，Ａｕ等の高導電率電極と同時焼成で
きることとなり、高信頼性の積層型高周波誘電体フィル
タの実現及び積層磁器コンデンサの高周波特性を良好に
することができる。In this example, sample numbers 19 to 2
2, 24-26, 28, 30-32, other than the low melting point substances and glass components, Ge, Pb, Bi, B, Nb,
P, Zn, Si, Al, Mo, Li, Ca, Ba, M
g, Ti, Zr, Sn, In, Gd, La, Ce, P
r, Nd, Sm, Eu, Dy, Yb, Y, Fe, Cr,
By having a low melting point substance or glass component consisting of at least two or more selected from Mn, Co, Ni, Cu, Ag and Au added and contained, it is possible to obtain the characteristics of the composition 90
It is possible to obtain a dielectric ceramic composition that can be sintered at a low temperature of 0 to 1100 ° C. Therefore, it is possible to co-fire with high-conductivity electrodes such as low melting point Ag, Ag-Pd, Au, etc., which have excellent high-frequency characteristics, and realize a highly reliable laminated high-frequency dielectric filter and excellent high-frequency characteristics of laminated ceramic capacitors. can do.
【００３８】（実施例３）実施例１の高純度のＢａＮｂ
2Ｏ6に代えて、あらかじめ同様に合成した高純度のＢａ
Ｔａ2Ｏ6粉末を（表７）に示す組成比になるように秤量
し、以降の工程を実施例１と同様に処理して（表７）の
試料番号３４〜３８に示す組成比の誘電体磁器円板を
得、実施例１と同様に処理して特性を測定し、その結果
を試料番号３４〜３８別に（表８）に示す。Example 3 High-purity BaNb of Example 1
Instead of 2 O 6 , high-purity Ba that was synthesized in the same way in advance was used.
Ta 2 O 6 powder was weighed so as to have the composition ratio shown in (Table 7), and the subsequent steps were processed in the same manner as in Example 1 to obtain the dielectric composition having the composition ratio shown in Sample Nos. 34 to 38 of (Table 7). A body porcelain disk was obtained and treated in the same manner as in Example 1 to measure the characteristics, and the results are shown in Table 8 for each of sample numbers 34 to 38.
【００３９】[0039]
【表７】 [Table 7]
【００４０】[0040]
【表８】 [Table 8]
【００４１】主成分の組成範囲と構成を限定した理由
は、実施例１と同様であるので説明は省略する。The reason for limiting the composition range and composition of the main component is the same as in Example 1, and therefore the description thereof is omitted.
【００４２】主成分に対し副成分Ｔａ2Ｏ5を含有するこ
とにより、絶縁抵抗、絶縁破壊強度及びＣｕ電極接着強
度を大きくする効果を有し、Ｔａ2Ｏ5の含有量が主成分
１００重量部に対し、０．１重量部未満はそれほど絶縁
破壊強度とＣｕ電極接着強度が大きくなく、この発明の
範囲から除外した。一方、Ｔａ2Ｏ5の含有量が主成分に
対し、１０．０重量部を越えるとＱ、絶縁抵抗及びＣｕ
電極接着強度が小さくなり、静電容量温度係数がマイナ
ス側に大きくなり実用的でなくなる。また、実施例２と
同様に低融点物質またはガラス成分を含有させても同様
の効果が得られる。The inclusion of the sub-component Ta 2 O 5 with respect to the main component has the effect of increasing the insulation resistance, the dielectric breakdown strength and the Cu electrode adhesion strength, and the content of Ta 2 O 5 is 100 wt% of the main component. If the amount is less than 0.1 parts by weight, the dielectric breakdown strength and the Cu electrode adhesion strength are not so large, and therefore, were excluded from the scope of the present invention. On the other hand, when the content of Ta 2 O 5 exceeds 10.0 parts by weight with respect to the main component, Q, insulation resistance and Cu
The electrode adhesion strength decreases, and the capacitance temperature coefficient increases to the negative side, making it impractical. Further, similar effects to those in Example 2 can be obtained even if a low melting point substance or a glass component is contained.
【００４３】（実施例４）実施例１の高純度のＢａＮｂ
2Ｏ6に代えて、あらかじめ同様に合成した高純度のＢａ
Ｖ2Ｏ6粉末を（表９）に示す組成比になるように秤量
し、以降の工程を実施例１と同様に処理して（表９）の
試料番号３９〜４３に示す組成比の誘電体磁器円板を
得、実施例１と同様に処理して特性を測定した結果を試
料番号３９〜４３別に（表１０）に示す。Example 4 High-purity BaNb of Example 1
Instead of 2 O 6 , high-purity Ba that was synthesized in the same way in advance was used.
The V 2 O 6 powder was weighed so as to have the composition ratio shown in (Table 9), and the subsequent steps were treated in the same manner as in Example 1 to obtain the dielectric composition having the composition ratio shown in Sample Nos. 39 to 43 of (Table 9). A body porcelain disk was obtained, treated in the same manner as in Example 1, and the characteristics were measured. The results are shown in Table 10 for each of sample numbers 39 to 43.
【００４４】[0044]
【表９】 [Table 9]
【００４５】[0045]
【表１０】 [Table 10]
【００４６】主成分の組成範囲と構成を限定した理由
は、実施例１と同様であるので説明は省略する。The reason for limiting the composition range and composition of the main component is the same as that of the first embodiment, and the description thereof will be omitted.
【００４７】主成分に対し、副成分Ｖ2Ｏ5を含有するこ
とにより、絶縁抵抗、絶縁破壊強度及びＣｕ電極接着強
度を大きくする効果を有し、Ｖ2Ｏ5の含有量が主成分１
００重量部に対し、０．００５重量部未満はそれほど絶
縁破壊強度及びＣｕ電極接着強度が大きくなく、この発
明の範囲から除外した。一方、Ｖ2Ｏ5の含有量が主成分
に対し、１．０００重量部を越えるとＱ、絶縁抵抗、Ｃ
ｕ電極接着強度が小さくなり、実用的でなくなる。ま
た、実施例２と同様に低融点物質またはガラス成分を含
有させても同様の効果が得られる。By containing the subcomponent V 2 O 5 with respect to the main component, it has the effect of increasing the insulation resistance, the dielectric breakdown strength and the Cu electrode adhesion strength, and the content of V 2 O 5 is the main component 1.
When the amount is less than 0.005 parts by weight with respect to 00 parts by weight, the dielectric breakdown strength and the Cu electrode adhesive strength are not so large, and thus it was excluded from the scope of the present invention. On the other hand, when the content of V 2 O 5 exceeds 1.000 parts by weight with respect to the main component, Q, insulation resistance, C
The u-electrode adhesion strength is reduced, making it impractical. Further, similar effects to those in Example 2 can be obtained even if a low melting point substance or a glass component is contained.
【００４８】（実施例５）実施例１の高純度のＢａＮｂ
2Ｏ6に代えて、平均粒径０．５μｍに微粉砕した高純度
のＮｂ2Ｏ5，Ｔａ2Ｏ5およびＶ2Ｏ5粉末を（表１１）に
示す組成比になるように秤量し、以降の工程を実施例１
と同様に処理して（表１１）の試料番号４４〜４８に示
す組成比の誘電体磁器円板を得、実施例１と同様に処理
して特性を測定した結果を試料番号４４〜４８別に（表
１２）に示す。(Example 5) High-purity BaNb of Example 1
Instead of 2 O 6 , high-purity Nb 2 O 5 , Ta 2 O 5 and V 2 O 5 powder finely pulverized to an average particle size of 0.5 μm were weighed so that the composition ratio shown in (Table 11) was obtained. , The subsequent steps in Example 1
The dielectric porcelain disks having the composition ratios shown in Sample Nos. 44 to 48 of Table 11 are treated in the same manner as described in (1), and the characteristics are measured in the same manner as in Example 1, and the results are measured for each of Sample Nos. 44 to 48. It shows in (Table 12).
【００４９】[0049]
【表１１】 [Table 11]
【００５０】[0050]
【表１２】 [Table 12]
【００５１】主成分の組成範囲と構成を限定した理由
は、実施例１と同様であるので説明は省略する。The reason why the composition range and composition of the main component are limited is the same as that of the first embodiment, and the description thereof will be omitted.
【００５２】主成分に対し、副成分Ｎｂ2Ｏ5，Ｔａ
2Ｏ5，Ｖ2Ｏ5を含有することにより、絶縁抵抗、絶縁破
壊強度及びＣｕ電極接着強度を大きくする効果を有し、
Ｎｂ2Ｏ5，Ｔａ2Ｏ5，Ｖ2Ｏ5の含有量が主成分に対し、
特定量未満はそれほど絶縁破壊強度及びＣｕ電極接着強
度が大きくなく、この発明の範囲から除外した。一方、
Ｎｂ2Ｏ5，Ｔａ2Ｏ5，Ｖ2Ｏ5の含有量が主成分に対し、
特定量を越えるとＱ、絶縁抵抗が小さくなり、静電容量
温度係数がマイナス側に大きくなり実用的でなくなる。
また、Ｎｂ2Ｏ5，Ｔａ2Ｏ5，Ｖ2Ｏ5から選ばれる二種以
上を含有することにより、Ｎｂ2Ｏ5，Ｔａ2Ｏ5，Ｖ2Ｏ5
から選ばれる一種を含有するものに比べ、誘電率、Ｑ、
絶縁抵抗、絶縁破壊電圧が大きく、静電容量温度係数を
小さくすることができる。また、実施例２と同様に低融
点物質またはガラス成分を含有させても同様の効果が得
られる。With respect to the main component, subcomponents Nb 2 O 5 , Ta
By containing 2 O 5 and V 2 O 5 , it has an effect of increasing insulation resistance, dielectric breakdown strength and Cu electrode adhesive strength,
The content of Nb 2 O 5 , Ta 2 O 5 and V 2 O 5 is the main component,
When the amount is less than the specific amount, the dielectric breakdown strength and the Cu electrode adhesive strength are not so large, and thus it is excluded from the scope of the present invention. on the other hand,
The content of Nb 2 O 5 , Ta 2 O 5 and V 2 O 5 is the main component,
If it exceeds a specific amount, Q and insulation resistance will decrease, and the temperature coefficient of capacitance will increase to the negative side, making it impractical.
Further, Nb 2 O 5, Ta 2 O 5, V 2 O by containing two or more selected from 5, Nb 2 O 5, Ta 2 O 5, V 2 O 5
The dielectric constant, Q, and
The insulation resistance and breakdown voltage are large, and the temperature coefficient of capacitance can be reduced. Further, similar effects to those in Example 2 can be obtained even if a low melting point substance or a glass component is contained.
【００５３】なお、実施例における誘電体磁器の作製方
法では、ＢａＮｂ2Ｏ6，ＢａＴａ2Ｏ6，ＢａＶ2Ｏ6，Ｖ
2Ｏ5，Ｔａ2Ｏ5，Ｎｂ2Ｏ5，Ｌａ2Ｏ3，Ｐｒ6Ｏ11，Ｎ
ｄ2Ｏ3，Ｓｍ2Ｏ3，ＺｒＯ2，ＴｉＯ2，ＳｒＣＯ3およ
びＢａＣＯ3を使用したが、この方法に限定されるもの
ではなく、所望の組成比になるように、ＢａＴｉＯ3，
Ｂｉ2Ｔｉ3Ｏ9，Ｒ2Ｔｉ2Ｏ7（Ｒ＝Ｌａ，Ｐｒ，Ｎｄ，
Ｓｍ）などの化合物、あるいは炭酸塩、水酸化物など空
気中での加熱により、Ｖ2Ｏ5，Ｔａ2Ｏ5，Ｎｂ 2Ｏ5，Ｌ
ａ2Ｏ3，Ｐｒ6Ｏ11，Ｎｄ2Ｏ3，Ｓｍ2Ｏ3，ＴｉＯ2およ
びＢａＯとなる化合物を使用しても実施例と同程度の特
性を得ることができる。The method for manufacturing the dielectric ceramics in the examples
By law, BaNb2O6, BaTa2O6, BaV2O6, V
2OFive, Ta2OFive, Nb2OFive, La2O3, Pr6O11, N
d2O3, Sm2O3, ZrO2, TiO2, SrCO3And
And BaCO3Used, but limited to this method
Instead of BaTiO 3 to obtain the desired composition ratio.3，
Bi2Ti3O9, R2Ti2O7(R = La, Pr, Nd,
Sm) and other compounds, or carbonates, hydroxides, etc.
By heating in the air, V2OFive, Ta2OFive, Nb 2OFive, L
a2O3, Pr6O11, Nd2O3, Sm2O3, TiO2And
And a compound that becomes BaO is used, the same characteristics as those in the example are obtained.
You can get sex.
【００５４】また、主成分をあらかじめ仮焼し、副成分
を添加しても実施例と同程度の特性を得ることができ
る。Further, even if the main component is pre-calcined in advance and the sub-components are added, the same characteristics as those of the embodiment can be obtained.
【００５５】また、誘電体磁器用として一般に使用され
る工業用原料の二酸化チタン、例えばチタン工業（株）
製二酸化チタンＫＡ−１０Ｃ、古河鉱業（株）製二酸化
チタンＦＡ−５５Ｗには最大０．４５重量％のＮｂ2Ｏ5
が含まれるが、これらの二酸化チタンを使用して実施例
１の主成分の誘電体磁器を作製しても主成分１００重量
部に対して、Ｎｂ2Ｏ5の含有量は最大で０．２重量部で
あり、この発明の範囲外であるが、工業用原料の二酸化
チタン中のＮｂ2Ｏ5量を考慮し、不足分のＮｂ 2Ｏ5を含
有させることにより、実施例と同程度の特性を得ること
ができる。Further, it is generally used for dielectric ceramics.
Titanium dioxide as an industrial raw material, such as Titanium Industry Co., Ltd.
Titanium dioxide KA-10C manufactured by Furukawa Mining Co., Ltd.
Titanium FA-55W has a maximum Nb of 0.45% by weight.2OFive
Examples of using these titanium dioxides
100 weight of the main component even if the dielectric ceramic of the main component of 1 is made
Nb2OFiveContent of up to 0.2 parts by weight
Yes, it is outside the scope of the present invention.
Nb in titanium2OFiveInsufficient Nb considering the amount 2OFiveIncluding
To obtain the same characteristics as the embodiment.
You can
【００５６】また、上述の基本組成のほかに、Ｓｉ
Ｏ2，ＭｎＯ2，Ｆｅ2Ｏ3，ＺｎＯ，Ａｌ 2Ｏ3など一般に
フラックスと考えられている塩類、酸化物などを、特性
を損なわない範囲で加えることもできる。In addition to the above-mentioned basic composition, Si
O2, MnO2, Fe2O3, ZnO, Al 2O3Etc. in general
Characteristics of salts and oxides, which are considered to be flux,
Can be added as long as it does not impair.
【００５７】[0057]
【発明の効果】以上本発明の誘電体磁器組成物は、一般
式ｘ［（ＢａＯ）1-m（ＳｒＯ）m］・ｙ［（ＴｉＯ2）
1-n（ＺｒＯ2）n］・ｚＲ2Ｏ3で表され、この一般式中
Ｒは、Ｌａ，Ｐｒ，Ｎｄ，Ｓｍから選ばれる一種以上の
希土類元素であり、ｍ，ｎの値が、０．０１≦ｍ≦０．
５０、０．００１≦ｎ≦０．２５０なる範囲にあり、
ｘ，ｙおよびｚはモル比を表し、ｘ＋ｙ＋ｚ＝１であ
り、ｘ，ｙ，ｚの値が（表２）に示すａ，ｂ，ｃ，ｄ，
ｅで囲まれるモル比の範囲にある組成１００ｍｏｌ％に
対してＰｂＯを１０ｍｏｌ％以下（ただし、０ｍｏｌ％
を除く）の範囲で含有する主成分組成物１００重量部に
対して、副成分としてニオブ酸化物をＮｂ2Ｏ5に換算し
て０．３〜５．０重量部含有させたものであり、前記一
般式中のＲをＬａ，Ｐｒ，Ｎｄ，Ｓｍから選ぶことによ
り、Ｌａ，Ｐｒ，Ｎｄ，Ｓｍの順で静電容量温度係数を
プラス方向に任意に移行することができる。As described above, the dielectric ceramic composition of the present invention has the general formula x [(BaO) 1-m (SrO) m ] .y [(TiO 2 ).
1-n (ZrO 2 ) n ] · zR 2 O 3, where R is one or more rare earth elements selected from La, Pr, Nd, and Sm, and the values of m and n are 0.01 ≦ m ≦ 0.
50, 0.001 ≦ n ≦ 0.250,
x, y and z represent a molar ratio, x + y + z = 1, and the values of x, y and z are a, b, c, d, and shown in (Table 2).
10 mol% or less of PbO (provided that 0 mol% is contained with respect to a composition of 100 mol% in a molar ratio range surrounded by e)
In the range of 100 parts by weight of the main component composition contained in the range of 0.3 to 5.0 parts by weight of niobium oxide as a sub-component converted into Nb 2 O 5 . By selecting R in the general formula from La, Pr, Nd, and Sm, the temperature coefficient of capacitance can be arbitrarily shifted in the positive direction in the order of La, Pr, Nd, and Sm.
【００５８】また主成分に対してニオブ酸化物を含有さ
せることにより、焼結性が向上し、磁器の緻密化ととも
に結晶粒子が均一微細化されるので、絶縁抵抗、絶縁破
壊強度を大きくできるとともに共振器のＱの低下を防ぐ
ことができる。Further, by containing niobium oxide in the main component, the sinterability is improved, and the crystal grains are made finer with the densification of the porcelain, so that the insulation resistance and the dielectric breakdown strength can be increased. It is possible to prevent the Q of the resonator from decreasing.
【００５９】さらに誘電体磁器の密度が大きいので、こ
の誘電体磁器組成物を用いて例えば積層セラミックコン
デンサなどの積層型電子部品を形成し、実装する際通常
マンハッタン現象と呼ばれるようなチップ立ちを防ぐこ
とができる。Further, since the density of the dielectric porcelain is high, when this dielectric porcelain composition is used to form and mount a laminated electronic component such as a laminated ceramic capacitor, chip standing, which is usually called the Manhattan phenomenon, is prevented. be able to.
【００６０】また、本発明の誘電体磁器組成物を用いて
誘電体共振器を作製する場合無電解Ｃｕメッキにより電
極を形成したとしても誘電体共振器素体と電極との接着
強度が高いので、高信頼性の誘電体共振器を得ることが
できる。Further, when a dielectric resonator is manufactured using the dielectric ceramic composition of the present invention, the adhesive strength between the dielectric resonator element body and the electrode is high even if the electrode is formed by electroless Cu plating. Thus, a highly reliable dielectric resonator can be obtained.
【００６１】その上本発明の誘電体磁器組成物を用いた
コンデンサ、マイクロ波用誘電体共振器および積層型誘
電体フィルタは電気機器、通信機器の小型化および高信
頼性化に寄与するところが大であり工業的利用価値が大
きいものである。Moreover, the capacitor, the microwave dielectric resonator and the laminated dielectric filter using the dielectric ceramic composition of the present invention largely contribute to downsizing and high reliability of electric equipment and communication equipment. It has a great industrial utility value.
【図１】本発明の一実施例の誘電体磁器組成物の主成分
の組成範囲を説明する三元図FIG. 1 is a ternary diagram illustrating a composition range of main components of a dielectric ceramic composition according to an embodiment of the present invention.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平４−67513（ＪＰ，Ａ) 特開 平６−116022（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C04B 35/42 - 35/50 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-67513 (JP, A) JP-A-6-116022 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C04B 35/42-35/50 CA (STN) REGISTRY (STN)
Claims (6)
Ｏ）m］・ｙ［（ＴｉＯ2）1-n（ＺｒＯ2）n］・ｚＲ2Ｏ
3で表され、この一般式中Ｒは、Ｌａ，Ｐｒ，Ｎｄ，Ｓ
ｍから選ばれる一種以上の希土類元素であり、ｍ，ｎの
値が、０．０１≦ｍ≦０．５０、０．００１≦ｎ≦０．
２５０なる範囲にあり、ｘ，ｙおよびｚはモル比を表
し、ｘ＋ｙ＋ｚ＝１でｘ，ｙ，ｚの値が（表１）に示す
ａ，ｂ，ｃ，ｄ，ｅで囲まれるモル比の範囲にある組成
１００ｍｏｌ％に対してＰｂＯを１０ｍｏｌ％以下（た
だし、０ｍｏｌ％を除く）の範囲で含有する主成分組成
物１００重量部に対して、副成分として少なくともニオ
ブ酸化物をＮｂ2Ｏ5に換算して０．３〜５．０重量部含
有してなることを特徴とする誘電体磁器組成物。 【表１】 1. The general formula is x [(BaO) 1-m (Sr
O) m ] ・ y [(TiO 2 ) 1-n (ZrO 2 ) n ] ・ zR 2 O
In the general formula, R is La, Pr, Nd, S
It is one or more rare earth elements selected from m, and the values of m and n are 0.01 ≦ m ≦ 0.50, 0.001 ≦ n ≦ 0.
In the range of 250, x, y and z represent molar ratios, and x + y + z = 1 and the values of x, y and z are the molar ratios surrounded by a, b, c, d and e shown in (Table 1). With respect to 100 parts by weight of the main component composition containing PbO in an amount of 10 mol% or less (excluding 0 mol%) per 100 mol% of the composition in the range, at least niobium oxide as a sub-component is Nb 2 O. A dielectric ceramic composition containing 0.3 to 5.0 parts by weight in terms of 5 . [Table 1]
Ｏ）m］・ｙ［（ＴｉＯ2）1-n（ＺｒＯ2）n］・ｚＲ2Ｏ
3で表され、この一般式中Ｒは、Ｌａ，Ｐｒ，Ｎｄ，Ｓ
ｍから選ばれる一種以上の希土類元素であり、ｍ，ｎの
値が、０．０１≦ｍ≦０．５０、０．００１≦ｎ≦０．
２５０なる範囲にあり、ｘ，ｙおよびｚはモル比を表
し、ｘ＋ｙ＋ｚ＝１でｘ，ｙ，ｚの値が（表１）に示す
ａ，ｂ，ｃ，ｄ，ｅで囲まれるモル比の範囲にある組成
１００ｍｏｌ％に対してＢｉ2Ｏ3を５ｍｏｌ％以下（た
だし、０ｍｏｌ％を除く）及びＰｂＯを１０ｍｏｌ％以
下（ただし、０ｍｏｌ％を除く）の範囲で含有する主成
分組成物１００重量部に対して、副成分として少なくと
もニオブ酸化物をＮｂ2Ｏ5に換算して０．３〜５．０重
量部含有してなることを特徴とする誘電体磁器組成物。2. The general formula x [(BaO) 1-m (Sr
O) m ] ・ y [(TiO 2 ) 1-n (ZrO 2 ) n ] ・ zR 2 O
In the general formula, R is La, Pr, Nd, S
It is one or more rare earth elements selected from m, and the values of m and n are 0.01 ≦ m ≦ 0.50, 0.001 ≦ n ≦ 0.
In the range of 250, x, y and z represent molar ratios, and x + y + z = 1 and the values of x, y and z are the molar ratios surrounded by a, b, c, d and e shown in (Table 1). 100% by weight of the main component composition containing Bi 2 O 3 in an amount of 5 mol% or less (excluding 0 mol%) and PbO in an amount of 10 mol% or less (excluding 0 mol%) based on the composition of 100 mol% in the range. A dielectric ceramic composition containing at least 0.3 to 5.0 parts by weight of niobium oxide as Nb 2 O 5 as a subcomponent.
載の誘電体磁器組成物１００重量部に対して、副成分と
してＧｅ，Ｐｂ，Ｆ，Ｂｉ，Ｓｂ，Ｂ，Ｎｂ，Ｐ，Ｚ
ｎ，Ｓｉ，Ａｌ，Ｍｏ，Ｗ，Ｌｉ，Ｎａ，Ｋ，Ｃａ，Ｂ
ａ，Ｍｇ，Ｔｉ，Ｚｒ，Ｓｎ，Ｉｎ，Ｇｄ，Ｌａ，Ｃ
ｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｄｙ，Ｙｂ，Ｙ，Ｆｅ，
Ｃｒ，Ｍｎ，Ｃｏ，Ｎｉ，Ｃｕ，Ａｇ及びＡｕから選ば
れる少なくとも二種以上からなる低融点物質またはガラ
ス成分を２０重量部（ただし、０重量部を除く）以下の
範囲で添加させてなることを特徴とする誘電体磁器組成
物。3. Ge, Pb, F, Bi, Sb, B, Nb, P, as auxiliary components, relative to 100 parts by weight of the dielectric porcelain composition according to any one of claims 1 and 2 . Z
n, Si, Al, Mo, W, Li, Na, K, Ca, B
a, Mg, Ti, Zr, Sn, In, Gd, La, C
e, Pr, Nd, Sm, Eu, Dy, Yb, Y, Fe,
A low melting point substance or glass component consisting of at least two selected from Cr, Mn, Co, Ni, Cu, Ag and Au is added in an amount of 20 parts by weight (excluding 0 parts by weight) or less. A dielectric porcelain composition characterized by:
をＴａ2Ｏ5に換算して０．１〜１０．０重量部含有して
なることを特徴とする請求項１，２及び３のうちいずれ
か一つに記載の誘電体磁器組成物。4. Instead of niobium oxide, tantalum oxide according to claim 1, 2 and 3, characterized by containing 0.1-10.0 parts by weight in terms of Ta 2 O 5 The dielectric ceramic composition according to any one of the above.
物をＶ2Ｏ5に換算して０．００５〜１．０００重量部含
有してなることを特徴とする請求項１，２及び３のうち
いずれか一つに記載の誘電体磁器組成物。5. Instead of the niobium oxide, vanadium oxide according to claim 1, 2 and 3, characterized by containing from 0.005 to 1.000 parts by weight in terms of V 2 O 5 The dielectric ceramic composition according to any one of the above.
2Ｏ5，Ｖ2Ｏ5から選ばれる二種以上を、Ｎｂ2Ｏ5が０．
３〜５．０重量部、Ｔａ2Ｏ5が０．１〜１０．０重量
部、Ｖ2Ｏ5が０．００５〜１．０重量部の範囲で含有し
てなることを特徴とする請求項１，２及び３のうちいず
れか一つに記載の誘電体磁器組成物。6. Nb 2 O 5 , Ta instead of niobium oxide
Nb 2 O 5 has two or more kinds selected from V 2 O 5 and V 2 O 5 .
3 to 5.0 parts by weight, Ta 2 O 5 in an amount of 0.1 to 10.0 parts by weight, and V 2 O 5 in an amount of 0.005 to 1.0 parts by weight. Item 4. A dielectric ceramic composition according to any one of items 1, 2 and 3 .
Priority Applications (1)
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|---|---|---|---|
| JP10235996A JP3395514B2 (en) | 1995-04-25 | 1996-04-24 | Dielectric porcelain composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9915495 | 1995-04-25 | ||
| JP7-99154 | 1995-04-25 | ||
| JP10235996A JP3395514B2 (en) | 1995-04-25 | 1996-04-24 | Dielectric porcelain composition |
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| Publication Number | Publication Date |
|---|---|
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ID=26440292
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