JP2007076963A - Dielectric ceramic composition, and electronic component produced by using the same - Google Patents
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本発明は、誘電体磁器組成物に係り、特にマイクロ波領域で使用されるとともに、８７０℃以下の低温焼成が可能な誘電体磁器組成物及びそれを用いて作製される電子部品に関する。 The present invention relates to a dielectric ceramic composition, and more particularly to a dielectric ceramic composition that can be used in the microwave region and can be fired at a low temperature of 870 ° C. or lower, and an electronic component manufactured using the dielectric ceramic composition.
近年、携帯電話移動通信機器等の高周波機器は小型化、高機能化、低価格化、が望まれており、これらマイクロ波機器に使用される誘電体共振器、誘電体フィルター等も同様に小型、高機能、低価格の物が望まれている。 In recent years, high-frequency devices such as mobile phone mobile communication devices have been desired to be downsized, highly functional, and low-priced, and dielectric resonators, dielectric filters, etc. used in these microwave devices are similarly small. High-function, low-priced products are desired.
これら誘電体共振器等の材料として用いられる誘電体磁器組成物には、比誘電率（以下「Ｋ値」と言う）が９以下であること、マイクロ波領域でのＱ値が８０００以上と高いこと、Ａｇ内部電極を使用するために焼成温度は８７０℃以下であることが求められている。また、１ＭＨｚで＋２０℃を基準としたとき、１２５℃での温度範囲での静電容量の温度依存性（以下「ＴＣ」と言う）は１３０ｐｐｍ／℃以下であれば、更に望ましい。 These dielectric ceramic compositions used as materials for dielectric resonators and the like have a relative dielectric constant (hereinafter referred to as “K value”) of 9 or less and a high Q value of 8000 or more in the microwave region. In order to use an Ag internal electrode, the firing temperature is required to be 870 ° C. or lower. In addition, when + 20 ° C. is used as a reference at 1 MHz, it is more desirable that the temperature dependency of the capacitance in the temperature range at 125 ° C. (hereinafter referred to as “TC”) is 130 ppm / ° C. or less.
マイクロ波領域で使用可能なマイクロ波誘電体磁器組成物については、９００℃以下の低温焼成可能な誘電体磁器組成物として、Ｂａ−Ｃａ−Ｓｒ−Ｓｉ−Ｈｆ−Ａｌ−Ｔｉ系酸化物を主成分とする焼結体からなる誘電体磁器組成物が提案された（例えば特許文献１、特許文献２及び特許文献３を参照）。しかしかかる誘電体磁器組成物の製造過程で、少なくともＢａ、Ｃａ、Ｓｒ、Ｓｉを含む混合物を１７００℃に加熱し、熔融した混合物を水中に滴下して急冷し、ガラスを得る。このガラスを粉砕して微粉末とし、このガラス粉末に有機バインダーを加えて成形体を作製し、この成形体を焼成炉に入れ、成形体を９００℃で焼成する。 For microwave dielectric ceramic compositions that can be used in the microwave region, Ba-Ca-Sr-Si-Hf-Al-Ti-based oxides are mainly used as dielectric ceramic compositions that can be fired at a low temperature of 900 ° C. or lower. A dielectric ceramic composition composed of a sintered body as a component has been proposed (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3). However, in the process of manufacturing such a dielectric ceramic composition, a mixture containing at least Ba, Ca, Sr, and Si is heated to 1700 ° C., and the molten mixture is dropped into water and rapidly cooled to obtain glass. The glass is pulverized into a fine powder, and an organic binder is added to the glass powder to produce a molded body. The molded body is placed in a firing furnace, and the molded body is fired at 900 ° C.
このように１７００℃と言う高温でのガラス作成工程やガラスを含むため、得られる誘電体磁器組成物は、Ｑ値が３０００程度と低く、またＫ値も９以上と高い。 Thus, since the glass preparation process and glass at a high temperature of 1700 ° C. are included, the obtained dielectric ceramic composition has a low Q value of about 3000 and a high K value of 9 or more.
また、別に、Ｍｇ−Ａｌ−Ｓｉ系酸化物にＮｉ、Ｃｏを加えたマイクロ波誘電体磁器組成物がある（例えば特許文献４を参照）。これは焼成温度が１２００〜１５５０℃程度と非常に高い。他にもＭｇ−Ａｌ−Ｓｉ系酸化物にＹｂ、Ｉｎを加えたマイクロ波波誘電体磁器組成物があるが、これも焼成温度が１２００〜１５５０℃程度と非常に高い（例えば特許文献５を参照）。 In addition, there is a microwave dielectric ceramic composition in which Ni and Co are added to an Mg—Al—Si-based oxide (see, for example, Patent Document 4). This is a very high firing temperature of about 1200 to 1550 ° C. In addition, there is a microwave dielectric ceramic composition in which Yb and In are added to an Mg—Al—Si-based oxide, and this also has a very high firing temperature of about 1200 to 1550 ° C. (for example, see Patent Document 5). reference).
誘電体磁器組成物を製造するために低温で焼結できることは誘電体磁器の低価格化のために重要であり、焼結温度が高いと設備投資の大きい高温用炉が必要で、運転に要するエネルギーも大きく、環境負荷も大きい。 The ability to sinter at low temperatures to produce dielectric ceramic compositions is important for lowering the price of dielectric ceramics, and high sintering temperatures require high-temperature furnaces with high capital investment and require operation. The energy is large and the environmental burden is large.
誘電体磁器組成物を積層セラミックコンデンサとして使用する場合、内部電極として用いられているＰｄ、Ｐｔ、Ａｕ等の貴金属の代わりに安価なＡｇを用いることが積層セラミックコンデンサの低価格化のために有効である。Ａｇは前記Ｐｄ等の貴金属と比較して融点が低いため、誘電体磁器組成物を低温焼結ができないと内部電極にＡｇを使うのは難しい。Ａｇの融点は９６１．３℃であり、Ａｇが溶融、蒸発しないためには誘電体磁器組成物を９００℃以下で焼成するのが望ましく、８７０℃以下で焼成できれば、積層セラミックコンデンサは、製造プロセス上安定して生産することが可能だと言える。
本発明の目的は、マイクロ波領域で使用される誘電体磁器組成物として優れた電気的特性を満足し、誘電体磁器組成物の低温焼成を可能とし、内部電極として安価な銀を使用することできることにより大幅なコスト改善ができる誘電体磁器組成物及びそれを用いて作製される電子部品を提供するにある。 The object of the present invention is to satisfy excellent electrical characteristics as a dielectric ceramic composition used in the microwave region, enable low-temperature firing of the dielectric ceramic composition, and use inexpensive silver as an internal electrode. An object of the present invention is to provide a dielectric porcelain composition capable of greatly improving cost by being able to do so and an electronic component manufactured using the same.
本発明者等は、上述した課題を解決するために、ＺｎＯ、ＳｉＯ２、ＢａＯ、Ｂ２Ｏ３を含有する誘電体磁器組成物であって、ＺｎＯ、ＳｉＯ２及びＢａＯの合計質量並びにＢ２Ｏ３の質量を特定し、ＺｎＯ、ＳｉＯ２及びＢａＯが、ＺｎＯ、ＳｉＯ２及びＢａＯの三元図において、その合計質量に対する質量割合が特定の組成領域内にある場合に、マイクロ波領域で使用される誘電体磁器組成物として優れた電気的特性を満足し、誘電体磁器組成物の低温焼成を可能とし、内部電極として安価な銀を使用できることにより大幅なコスト改善ができる誘電体磁器組成物及びそれを用いて作製される電子部品を見出し、本発明を完成するに至った。 In order to solve the above-described problems, the present inventors are a dielectric ceramic composition containing ZnO, SiO 2 , BaO, B 2 O 3 , wherein the total mass of ZnO, SiO 2 and BaO and B 2 Specify the mass of O 3 and use ZnO, SiO 2 and BaO in the microwave region when the mass proportion of the total mass in the ternary diagram of ZnO, SiO 2 and BaO is in a specific composition region Dielectric porcelain composition that satisfies excellent electrical characteristics as a dielectric ceramic composition to be manufactured, enables low-temperature firing of the dielectric porcelain composition, and can significantly reduce costs by using inexpensive silver as an internal electrode And the electronic component produced using it was discovered, and it came to complete this invention.
かくして本発明によれば、以下の１〜６の発明が提供される。
１． ＺｎＯ、ＳｉＯ２、ＢａＯ、Ｂ２Ｏ３を含有する誘電体磁器組成物であって、ＺｎＯ、ＳｉＯ２及びＢａＯの、ＺｎＯと、ＳｉＯ２と、ＢａＯとの合計質量に対する質量割合が、図１に示すＺｎＯ、ＳｉＯ２及びＢａＯの三元図において、それぞれ５０％：３０％：２０％（点Ａ）、３０％：５０％：２０％（点Ｂ）、２０％：３０％：５０％（点Ｃ）、４５％：２０％：３５％（点Ｄ）の点Ａ−Ｂ−Ｃ−Ｄ−Ａを順に結ぶ直線によって囲まれる四辺形領域内にあり、ＺｎＯ、ＳｉＯ２、ＢａＯ及びＢ２Ｏ３の合計質量に対し、Ｂ２Ｏ３を１〜６質量％含有する誘電体磁器組成物。
２． 更に、Ａｌ２Ｏ３を、ＺｎＯ、ＳｉＯ２、ＢａＯ、Ｂ２Ｏ３、Ａｌ２Ｏ３の合計質量に対し、０〜１５質量％含有する、上記１記載の誘電体磁器組成物。
３． なお更に、ＭｇＯを、ＺｎＯ、ＳｉＯ２、ＢａＯ、Ｂ２Ｏ３、Ａｌ２Ｏ３及びＭｇＯの合計質量に対し、０〜３質量％含有する、上記２記載の誘電体磁器組成物。
４． Ｂ２Ｏ３１〜６質量部の一部〜全部が、Ｌｉ２Ｏ ０．４〜２．４質量部で置換される、上記１〜３のいずれか一項記載の誘電体磁器組成物。
５． 比誘電率が９以下であり、Ｑ値が８０００以上であり、１ＭＨｚで＋２０℃を基準としたとき、１２５℃での温度範囲での静電容量のＴＣが１３０ｐｐｍ／℃以下である、上記１〜４のいずれか一項記載の誘電体磁器組成物。
６． 上記１〜５のいずれか一項記載の誘電体磁器組成物によって形成される電子部品。
Thus, according to the present invention, the following inventions 1 to 6 are provided.
1. A dielectric ceramic composition containing ZnO, SiO 2 , BaO, B 2 O 3 , wherein the mass ratio of ZnO, SiO 2 and BaO to the total mass of ZnO, SiO 2 and BaO is as shown in FIG. In the ternary diagram of ZnO, SiO 2 and BaO shown in FIG. 5, 50%: 30%: 20% (point A), 30%: 50%: 20% (point B), 20%: 30%: 50% ( Point C), 45%: 20%: 35% (point D) in the quadrilateral region surrounded by a straight line connecting the points A-B-C-D-A, ZnO, SiO 2 , BaO and B 2 the total mass of the O 3 to, B 2 O 3 dielectric ceramic composition containing 1-6 wt%.
2. Furthermore, the Al 2 O 3, ZnO, SiO 2, BaO, the total mass of B 2 O 3, Al 2 O 3, containing 0 to 15 wt%, the dielectric ceramic composition of claim 1, wherein the.
3. Still further, the dielectric ceramic composition according to the above 2, wherein MgO is contained in an amount of 0 to 3% by mass with respect to the total mass of ZnO, SiO 2 , BaO, B 2 O 3 , Al 2 O 3 and MgO.
4). The dielectric ceramic composition according to any one of the above 1 to 3, wherein a part to all of 1 to 6 parts by mass of B 2 O 3 are substituted with 0.4 to 2.4 parts by mass of Li 2 O.
5. The dielectric constant is 9 or less, the Q value is 8000 or more, and the capacitance TC in the temperature range at 125 ° C. is 130 ppm / ° C. or less when the reference value is + 20 ° C. at 1 MHz. The dielectric ceramic composition as described in any one of -4.
6). The electronic component formed with the dielectric material ceramic composition as described in any one of said 1-5.
本発明の誘電体磁器組成物は、マイクロ波領域において、Ｋ値が９以下、Ｑ値が８０００以上と高く、８７０℃以下で焼結が可能であるという特性のものを提供できる。
８７０℃以下で焼結可能であるため炉等の設備投資を抑えられ、運転エネルギーも抑えることができ、内部電極にＡｇが１００％の物を使用することが可能であることから、安価に製造することができる。
In the microwave region, the dielectric ceramic composition of the present invention can provide a characteristic in which the K value is as high as 9 or less, the Q value is as high as 8000 or more, and sintering is possible at 870 ° C. or less.
Because it can be sintered at 870 ° C or less, it can reduce capital investment such as furnaces, can reduce operating energy, and can use 100% Ag for the internal electrode. can do.
本発明の誘電体磁器組成物は、ＺｎＯ、ＳｉＯ２、ＢａＯ、Ｂ２Ｏ３を含有する誘電体磁器組成物であって、ＺｎＯ、ＳｉＯ２及びＢａＯの、ＺｎＯと、ＳｉＯ２と、ＢａＯとの合計質量に対する質量割合が、図１に示すＺｎＯ、ＳｉＯ２及びＢａＯの三元図において、それぞれ５０％：３０％：２０％（点Ａ）、３０％：５０％：２０％（点Ｂ）、２０％：３０％：５０％（点Ｃ）、４５％：２０％：３５％（点Ｄ）の点Ａ−Ｂ−Ｃ−Ｄ−Ａを順に結ぶ直線によって囲まれる四辺形領域内にあり、ＺｎＯ、ＳｉＯ２、ＢａＯ及びＢ２Ｏ３の合計質量に対し、Ｂ２Ｏ３を１〜６質量％含有するものである。 The dielectric ceramic composition of the present invention is a dielectric ceramic composition containing ZnO, SiO 2 , BaO, B 2 O 3 , ZnO, SiO 2 and BaO, ZnO, SiO 2 , BaO and In the ternary diagram of ZnO, SiO 2 and BaO shown in FIG. 1, the mass ratio to the total mass is 50%: 30%: 20% (point A), 30%: 50%: 20% (point B), respectively. , 20%: 30%: 50% (point C), 45%: 20%: 35% (point D) in the quadrilateral region surrounded by the straight line connecting the points A-B-C-D-A , ZnO, SiO 2 , BaO and B 2 O 3 are contained in an amount of 1 to 6% by mass of B 2 O 3 .
本発明の誘電体磁器組成物は、ＺｎＯと、ＳｉＯ２と、ＢａＯとの焼成化合物（ＺＳＢ）が、図１に示すＺＳＢの三元図において、ＺＳＢの合計質量に対して、下記に示す質量％によって示す点Ａ−Ｂ−Ｃ−Ｄ−Ａを順に結ぶ直線によって囲まれる四辺形領域内にあることが必要である：
ＺＳＢが、ＺＳＢの三元図において、点Ａ−Ｂ−Ｃ−Ｄ−Ａを順に結ぶ直線によって囲まれる四辺形領域の範囲内では、誘電体磁器組成物は８７０℃以下で焼成して、誘電体磁器組成物のＫ値が９以下であり、Ｑ値が８０００以上であり、１ＭＨｚで＋２０℃を基準としたとき、１２５℃での温度範囲での静電容量のＴＣが１３０ｐｐｍ／℃以下である。 In the range of the quadrilateral region in which ZSB is surrounded by a straight line connecting points A-B-C-D-A in the ternary diagram of ZSB, the dielectric ceramic composition is fired at 870 ° C. or lower, and the dielectric The K value of the body porcelain composition is 9 or less, the Q value is 8000 or more, and the TC of the capacitance in the temperature range at 125 ° C. is 130 ppm / ° C. or less when the + 20 ° C. is 1 MHz at 1 MHz. is there.
ＺＳＢの質量割合が、図１に示すＺＳＢの三元図の点Ａ−Ｂ−Ｃ−Ｄ−Ａを順に結ぶ直線によって囲まれる四辺形領域内にあり、ＺＳＢ及びＢ２Ｏ３の合計質量に対し、Ｂ２Ｏ３を１質量％以上含有すると、誘電体磁器組成物は８７０℃以下で焼成して、誘電体磁器組成物のＫ値が９以下であり、Ｑ値が８０００以上であり、１ＭＨｚで＋２０℃を基準としたとき、１２５℃での温度範囲での静電容量のＴＣが１３０ｐｐｍ／℃以下である。 The mass proportion of ZSB is in a quadrilateral region surrounded by a straight line connecting the points A-B-C-D-A in the ternary diagram of ZSB shown in FIG. 1, and the total mass of ZSB and B 2 O 3 is On the other hand, when containing 1% by mass or more of B 2 O 3 , the dielectric ceramic composition is fired at 870 ° C. or less, the K value of the dielectric ceramic composition is 9 or less, and the Q value is 8000 or more, When the reference is + 20 ° C. at 1 MHz, the TC of the capacitance in the temperature range at 125 ° C. is 130 ppm / ° C. or less.
ＺＳＢの質量割合が、図１に示すＺＳＢの三元図の点Ａ−Ｂ−Ｃ−Ｄ−Ａを順に結ぶ直線によって囲まれる四辺形領域内にあり、ＺＳＢ及びＢ２Ｏ３の合計質量に対し、Ｂ２Ｏ３の含有が６質量％以下であると、誘電体磁器組成物のＫ値が９以下であり、Ｑ値が８０００以上であり、１ＭＨｚで＋２０℃を基準としたとき、１２５℃での温度範囲での静電容量のＴＣが１３０ｐｐｍ／℃以下である。 The mass proportion of ZSB is in a quadrilateral region surrounded by a straight line connecting the points A-B-C-D-A in the ternary diagram of ZSB shown in FIG. 1, and the total mass of ZSB and B 2 O 3 is On the other hand, when the content of B 2 O 3 is 6% by mass or less, the K value of the dielectric ceramic composition is 9 or less, the Q value is 8000 or more, and when the reference is + 20 ° C. at 1 MHz, 125 The TC of capacitance in the temperature range at ° C is 130 ppm / ° C or less.
本発明のＺＳＢ及びＢ２Ｏ３の誘電体磁器組成物に、Ａｌ２Ｏ３が、ＺＳＢ、Ｂ２Ｏ３、Ａｌ２Ｏ３の合計質量に対し、０〜１５質量％含有してよい。Ａｌ２Ｏ３の含有が１５質量％以下であると、誘電体磁器組成物は８７０℃以下で焼成して、誘電体磁器組成物のＫ値が９以下であり、Ｑ値が８０００以上であり、１ＭＨｚで＋２０℃を基準としたとき、１２５℃での温度範囲での静電容量のＴＣが１３０ｐｐｍ／℃以下である。 The dielectric ceramic composition of ZSB and B 2 O 3 of the present invention may contain 0 to 15% by mass of Al 2 O 3 with respect to the total mass of ZSB, B 2 O 3 and Al 2 O 3 . When the content of Al 2 O 3 is 15% by mass or less, the dielectric ceramic composition is fired at 870 ° C. or less, the K value of the dielectric ceramic composition is 9 or less, and the Q value is 8000 or more. When the reference is + 20 ° C. at 1 MHz, the TC of the capacitance in the temperature range at 125 ° C. is 130 ppm / ° C. or less.
Ａｌ２Ｏ３は、その含有量がＺＳＢ、Ｂ２Ｏ３、Ａｌ２Ｏ３の合計質量に対し、０〜１５質量％の範囲内で、増大するにつれて、１ＭＨｚで＋２０℃を基準としたとき、１２５℃での温度範囲での静電容量のＴＣが低下する傾向にある。 Al 2 O 3, the content is ZSB, the total mass of B 2 O 3, Al 2 O 3, in the range of 0 to 15 wt%, as increasing, when based on the + 20 ° C. at 1MHz , The TC of capacitance in the temperature range at 125 ° C. tends to decrease.
本発明のＺＳＢ及びＢ２Ｏ３の誘電体磁器組成物に、ＭｇＯが、ＺＳＢ、Ｂ２Ｏ３、Ａｌ２Ｏ３及びＭｇＯの合計質量に対し、０〜３質量％含有してよい。ＭｇＯの含有が３質量％以下であると、誘電体磁器組成物のＫ値が９以下であり、Ｑ値が８０００以上であり、１ＭＨｚで＋２０℃を基準としたとき、１２５℃での温度範囲での静電容量のＴＣが１３０ｐｐｍ／℃以下である。 MgO may be contained in the dielectric ceramic composition of ZSB and B 2 O 3 of the present invention in an amount of 0 to 3% by mass with respect to the total mass of ZSB, B 2 O 3 , Al 2 O 3 and MgO. When the content of MgO is 3% by mass or less, the dielectric ceramic composition has a K value of 9 or less, a Q value of 8000 or more, and a temperature range of 125 ° C. when + 20 ° C. is used as a reference at 1 MHz. The electrostatic capacity TC at 130 is 130 ppm / ° C. or less.
ＭｇＯは、その含有量がＺｎＯ、ＳｉＯ２、ＢａＯ、Ｂ２Ｏ３、Ａｌ２Ｏ３及びＭｇＯの合計質量に対し、０〜３質量％の範囲内で、増大するにつれて、一般的にＱ値及び１ＭＨｚで＋２０℃を基準としたとき、１２５℃での温度範囲での静電容量のＴＣが低下する傾向にある。 MgO, the content of ZnO, SiO 2, BaO, the total mass of B 2 O 3, Al 2 O 3 and MgO, in the range of 0-3 wt%, as increasing generally Q value When + 20 ° C. is used as a reference at 1 MHz, the TC of the capacitance in the temperature range at 125 ° C. tends to decrease.
Ｂ２Ｏ３は、１〜６質量％を一部〜全部Ｌｉ２Ｏ ０．４〜２．４質量％で置換してよい。Ｂ２Ｏ３とＬｉ２Ｏ（Ｌｉ２ＣＯ３に換算した質量を表す）との合計量は、１質量％以上であると、誘電体磁器組成物は、８７０℃以下で焼成が十分に行われ、Ｋ値が９以下であり、Ｑ値が８０００以上であり、１ＭＨｚで＋２０℃を基準としたとき、１２５℃での温度範囲での静電容量のＴＣが１３０ｐｐｍ／℃以下である。 B 2 O 3 is, may be substituted 1 to 6 wt% in some ~ total Li 2 O from .4 to 2.4 weight percent. When the total amount of B 2 O 3 and Li 2 O (representing mass converted to Li 2 CO 3 ) is 1% by mass or more, the dielectric ceramic composition is sufficiently fired at 870 ° C. or less. In other words, the K value is 9 or less, the Q value is 8000 or more, and the TC of the capacitance in the temperature range at 125 ° C. is 130 ppm / ° C. or less when + 20 ° C. is used as a reference at 1 MHz.
また、Ｂ２Ｏ３とＬｉ２Ｏ（Ｌｉ２ＣＯ３に換算した質量を表す）との合計量は、６質量％以下であると、誘電体磁器組成物は、Ｋ値が９以下であり、Ｑ値が８０００以上であり、１ＭＨｚで＋２０℃を基準としたとき、１２５℃での温度範囲での静電容量のＴＣが１３０ｐｐｍ／℃以下である。 When the total amount of B 2 O 3 and Li 2 O (representing the mass converted to Li 2 CO 3 ) is 6% by mass or less, the dielectric ceramic composition has a K value of 9 or less. The Q value is 8000 or more, and the TC of the capacitance in the temperature range at 125 ° C. is 130 ppm / ° C. or less when + 20 ° C. is the reference at 1 MHz.
ＳｉＯ２、ＺｎＯ、ＢａＯ、ＭｇＯ、Ｂ２Ｏ３、ＭｇＯ等の原料は、焼成により酸化物を生成する水酸化物、炭酸塩、硝酸塩等の金属塩を用いてもよい。本発明の誘電体磁器組成物中に、不可避不純物としてＡｌ、Ｃａ、Ｆｅ、Ｓｎ等が含まれることもある。 As raw materials such as SiO 2 , ZnO, BaO, MgO, B 2 O 3 , MgO, metal salts such as hydroxides, carbonates, and nitrates that generate oxides upon firing may be used. The dielectric ceramic composition of the present invention may contain Al, Ca, Fe, Sn, etc. as inevitable impurities.
上に説明した通りにして得た本発明の誘電体磁器組成物を単板型基板に用いる例について説明する。 An example in which the dielectric ceramic composition of the present invention obtained as described above is used for a single plate type substrate will be described.
ＺｎＯ、ＳｉＯ２、ＢａＣＯ３、Ｂ２Ｏ３及び／又はＬｉ２ＣＯ３、随意にＡｌ２Ｏ３、更にＭｇＯを出発原料とし表１に示す目的の組成になるように秤量し、これらを水等を媒体としてジルコニアビーズ等を粉砕媒体として用いて湿式混合した後に乾燥させて粉体を得る。得られた粉体に日信化学工業株式会社のアクリル系バインダーのようなバインダーを固形分で４％程度添加して造粒する。 ZnO, SiO 2 , BaCO 3 , B 2 O 3 and / or Li 2 CO 3 , optionally Al 2 O 3 , and MgO as starting materials are weighed to achieve the desired composition shown in Table 1, and these are water Using zirconia beads or the like as a grinding medium, etc. as a grinding medium, and then wet-mixing, and then drying to obtain a powder. To the obtained powder, a binder such as an acrylic binder from Nissin Chemical Industry Co., Ltd. is added in a solid content of about 4% and granulated.
このようにして調整された粒体を金型に充填し、成型機にて圧力を掛けて成型し、ディスク状サンプルを得る。 The particles adjusted in this way are filled into a mold and molded by applying pressure with a molding machine to obtain a disk-shaped sample.
こうして得られたサンプルを約８７０℃以下で空気中で焼成を行う。これら得られた焼成体磁器組成物にＡｇペーストを印刷し、約７００℃で焼付けして電極を形成して単板型基板を製造する。 The sample thus obtained is fired in air at about 870 ° C. or lower. An Ag paste is printed on the obtained fired ceramic composition and baked at about 700 ° C. to form an electrode to produce a single plate type substrate.
本発明の誘電体磁器組成物を単板型のコンデンサに用いる例を示す。
ＺｎＯ、ＳｉＯ２、ＢａＣＯ３、Ｂ２Ｏ３及び／又はＬｉ２ＣＯ３、随意にＡｌ２Ｏ３、更にＭｇＯを出発原料とし表１に示す目的の組成になるように秤量後し、水を媒体としジルコニアビーズを用いて１６時間湿式混合を行った後、乾燥して乾粉を得た。得られた粉体に日信化学工業株式会社のアクリルバインダー：ビニブランＳＢＡ−９２１５Ａを固形分で４％添加し造粒した。
An example in which the dielectric ceramic composition of the present invention is used for a single plate type capacitor will be described.
ZnO, SiO 2 , BaCO 3 , B 2 O 3 and / or Li 2 CO 3 , optionally Al 2 O 3 , and MgO as a starting material are weighed to achieve the target composition shown in Table 1, and water is added. Wet mixing was performed for 16 hours using zirconia beads as a medium, followed by drying to obtain a dry powder. The obtained powder was granulated by adding 4% of a solid content of acrylic binder: Vinyl Blanc SBA-9215A manufactured by Nissin Chemical Industry Co., Ltd.
このようにして調製した造粒粉を１２．０ｍｍφの金型に充填し、３０００ｋｇ／ｃｍ２の圧力で成型し、厚さ１２．０ｍｍのディスク状サンプルを得た。得られたサンプルを８７０℃で２時間大気焼成を行った。 The granulated powder thus prepared was filled in a 12.0 mmφ mold and molded at a pressure of 3000 kg / cm 2 to obtain a disc-shaped sample having a thickness of 12.0 mm. The obtained sample was subjected to air baking at 870 ° C. for 2 hours.
このように得られた誘電体磁器組成物にＡｇペーストを塗布し、７００℃で焼付けし電極を形成した。こうして得られたサンプルについて比誘電率、Ｑ値をマイクロ波領域（１ＧＨｚ）でＴＥＭ共振器法にて求めた。ただし、静電容量の温度変化率は１ＭＨｚで＋２０℃を基準とし＋１２５℃での静電容量のＴＣを求めた。 An Ag paste was applied to the dielectric ceramic composition thus obtained and baked at 700 ° C. to form an electrode. The specific permittivity and Q value of the sample thus obtained were determined in the microwave region (1 GHz) by the TEM resonator method. However, the temperature change rate of the capacitance was 1 MHz, and the TC of the capacitance at + 125 ° C. was obtained on the basis of + 20 ° C.
焼結の可否は以下のように求めた。
焼成後の試料を水中に入れロータリーポンプで１時間真空引きをして取り出し、試料表面に水がついていない状態で質量を測定し、これをＷ１とした。その後１５０℃で２時間乾燥し、自然放置し常温に戻った後に質量を測定しこれをＷ２とした。そして、次式により吸水率を求めた。
吸水率 Ｗａ＝｛（Ｗ１／ Ｗ２）‐１｝×１００ （％）
ここで、吸水率Ｗａ＜０。０２％を焼結とした。
The possibility of sintering was determined as follows.
Samples were removed after firing by a 1 hour vacuum on a rotary pump placed in water, to measure the mass in a state that does not have a water sample surface, which was used as W 1. Then dried for 2 hours at 0.99 ° C., which was used as a W 2 was measured mass after returning to the natural left at normal temperature. And the water absorption was calculated | required by following Formula.
Water absorption rate Wa = {(W 1 / W 2 ) −1} × 100 (%)
Here, the water absorption rate Wa <0.02% was set as sintering.
表１は得られた焼結体の単板コンデンサの特性を示した物であり、×印は本発明の範囲外の比較例である。また、表中Ｋは比誘電率を示し、組成の比率は質量比で表されている。 Table 1 shows the characteristics of the obtained single-plate capacitor of the sintered body, and the x marks are comparative examples outside the scope of the present invention. In the table, K represents a relative dielectric constant, and the composition ratio is represented by a mass ratio.
上記の表１において、組成番号１〜８はＺｎＯ−ＳｉＯ２−ＢａＯ （ＺＳＢ）、Ｂ２Ｏ３を質量比で９６：４の比率で一定にしておきＺＳＢの構成を１が点Ａ−Ｂ−Ｃ−Ｄ−Ａを順に結ぶ直線によって囲まれる四辺形領域内の点Ｓ（ＺｎＯ：ＳｉＯ２：ＢａＯ＝３５：３５：３０）、２〜５が本発明ＺＳＢの点Ａ−Ｂ−Ｃ−Ｄ−Ａを順に結ぶ直線によって囲まれる四辺形領域の端にあたる組成（点Ａ〜Ｄ）、６〜８が四辺形領域外にあたる組成（点Ｅ〜Ｇ）である。点Ａ−Ｂ−Ｃ−Ｄ−Ａを順に結ぶ直線によって囲まれる四辺形領域内である１〜５は８７０℃で焼結をしており、いずれも比誘電率が９以下でＱ値も８０００以上と大きく良い特性を示す。四辺形領域外である６〜８は焼結しているがＱ値が８０００未満と低くＴＣも＋１３０ｐｐｍ／℃以上と大きい。 In the above Table 1, composition numbers 1 to 8 are ZnO—SiO 2 —BaO 2 (ZSB), B 2 O 3 is kept constant at a mass ratio of 96: 4, and the ZSB configuration is 1 with point AB A point S (ZnO: SiO 2 : BaO = 35: 35: 30) in a quadrilateral region surrounded by a straight line connecting C-D-A in sequence, 2 to 5 are points A-B-C- A composition (points A to D) corresponding to the ends of the quadrangular region surrounded by a straight line connecting DA in sequence, and 6 to 8 are compositions (points EG) outside the quadrangular region. Points 1 to 5 in the quadrilateral region surrounded by straight lines connecting the points A-B-C-D-A are sintered at 870 ° C., all having a relative dielectric constant of 9 or less and a Q value of 8000. The above shows a large and good characteristic. Although 6-8 which are outside the quadrilateral region are sintered, the Q value is as low as less than 8000, and the TC is as large as +130 ppm / ° C. or more.
組成番号９〜１４はＳのＺＳＢ組成（ＺｎＯ：ＳｉＯ２：ＢａＯ＝３５：３５：３０）とし、Ｂ２Ｏ３とＺＳＢの合計質量に対して、Ｂ２Ｏ３を０〜８質量％の間で変えた。組成番号９のＢ２Ｏ３が０質量％では未焼結であり、Ｑ値も８０００未満と低く、ＴＣも＋１３０ｐｐｍ／℃以上と大きい。組成番号１０〜１３であるＢ２Ｏ３が１〜６質量％ではＱ値も８０００以上であり、Ｋも９以下であり、ＴＣも＋１３０ｐｐｍ／℃以下で良い特性を示す。しかし組成番号１４よりＢ２Ｏ３が８質量％になると焼結はするがＱ値が８０００未満、ＴＣも１３０ｐｐｍ／℃以上となる。これらのことよりＢ２Ｏ３は１〜６質量％が望ましい。 Composition numbers 9 to 14 are ZSB compositions of S (ZnO: SiO 2 : BaO = 35: 35: 30), and B 2 O 3 is 0 to 8% by mass with respect to the total mass of B 2 O 3 and ZSB. Changed between. When the composition number 9 B 2 O 3 is 0% by mass, it is unsintered, the Q value is as low as less than 8000, and the TC is as large as +130 ppm / ° C. or more. When B 2 O 3 having a composition number of 10 to 13 is 1 to 6% by mass, the Q value is 8000 or more, K is 9 or less, and TC is +130 ppm / ° C. or less. However, when B 2 O 3 is 8% by mass from the composition number 14, the sintering is performed, but the Q value is less than 8000, and the TC is also 130 ppm / ° C. or more. B 2 O 3 From these it is preferably 1-6 mass%.
組成番号１５〜２０はＳのＺＳＢ組成（ＺｎＯ：ＳｉＯ２：ＢａＯ＝３５：３５：３０）とし、質量比でＢ２Ｏ３を４質量％と固定しＡｌ２Ｏ３の組成量を変化させＺＳＢ、Ａｌ２Ｏ３、Ｂ２Ｏ３の合計が１００質量％となるようにＺＳＢを調整した。組成番号２０のＡｌ２Ｏ３が１８質量％の場合は、未焼成でＱ値が８０００未満、ＴＣも＋１３０ｐｐｍ／℃以上なのに対し組成番号１５〜１９であるＡｌ２Ｏ３が０〜１５質量％ではＱ値も８０００以上でありＫも９以下でＴＣも＋１３０ｐｐｍ／℃以下であり、よい電気的特性を示す。これらのことよりＡｌ２Ｏ３は０〜１５質量％が望ましい。 Composition numbers 15 to 20 are ZSB composition of S (ZnO: SiO 2 : BaO = 35: 35: 30), and B 2 O 3 is fixed at 4% by mass and the composition amount of Al 2 O 3 is changed. ZSB was adjusted so that the total of ZSB, Al 2 O 3 , and B 2 O 3 was 100% by mass. When Al 2 O 3 of composition number 20 is 18% by mass, the unfired Q value is less than 8000, and TC is +130 ppm / ° C. or higher, whereas Al 2 O 3 of composition number 15 to 19 is 0 to 15% by mass. In this case, the Q value is 8000 or more, K is 9 or less, TC is +130 ppm / ° C. or less, and good electrical characteristics are exhibited. Al 2 O 3 than that of those is preferably 0 to 15 mass%.
組成番号２１〜２７はＳのＺＳＢ組成（ＺｎＯ：ＳｉＯ２：ＢａＯ＝３５：３５：３０）とし、Ａｌ２Ｏ３を１０質量％、Ｂ２Ｏ３を４質量％と固定し、ＭｇＯの組成量を変化させ、ＺＳＢ、Ａｌ２Ｏ３、ＭｇＯ、Ｂ２Ｏ３の合計が１００質量％となるようにＺＳＢを調整した。組成番号２７のＭｇＯが５質量％の場合は、未焼成でＱ値が８０００未満、ＴＣも＋１３０ｐｐｍ／℃以上であるのに対し、組成番号２１〜２６であるＭｇＯが０〜３質量％ではＱ値も８０００以上であり、Ｋも９以下であり、ＴＣも＋１３０ｐｐｍ／℃以下であり、良好な電気的特性を示す。これらのことよりＭｇＯは０〜３質量％が望ましい。 Composition numbers 21 to 27 are ZSB compositions of S (ZnO: SiO 2 : BaO = 35: 35: 30), Al 2 O 3 is fixed at 10% by mass, B 2 O 3 is fixed at 4% by mass, and the composition of MgO The amount of ZSB was adjusted so that the total amount of ZSB, Al 2 O 3 , MgO, and B 2 O 3 was 100% by mass. When the MgO of the composition number 27 is 5% by mass, the unfired Q value is less than 8000, and the TC is +130 ppm / ° C. or more, whereas the MgO of the composition number 21 to 26 is 0 to 3% by mass. The value is 8000 or more, K is 9 or less, and TC is +130 ppm / ° C. or less, which shows good electrical characteristics. From these, MgO is preferably 0 to 3% by mass.
組成番号１０、１２、１３のＢ２Ｏ３をＬｉ２Ｏに置換した組成を組成番号２８、２９、３０とし、組成番号１３のＢ２Ｏ３の半分をＬｉ２Ｏに置換したものを組成番号３１とする。これらの特性はＢ２Ｏ３の組成であった特性とほぼ同じであり、Ｂ２Ｏ３を一部〜全部Ｌｉ２Ｏに置換しても良いことを示す。 Compositions obtained by substituting Li 2 O for B 2 O 3 with composition numbers 10, 12, and 13 are composition numbers 28, 29, and 30, and compositions obtained by substituting half of B 2 O 3 with composition number 13 for Li 2 O It is number 31. These characteristics are substantially the same as the composition is a characteristic of the B 2 O 3, indicating that the B 2 O 3 may be replaced with a part-whole Li 2 O and.
これらのことから、本発明においてはＺＳＢが８１〜９９質量％、Ａｌ２Ｏ３が０〜１５Ｖ質量％、ＭｇＯが０〜３質量％、Ｂ２Ｏ３１〜６質量％の範囲において電気的特性が良好である。また、ＺＳＢが８１〜９９。６質量％、Ａｌ２Ｏ３が０〜１５質量％、ＭｇＯが０〜３質量％、Ｌｉ２Ｏが０．４〜２．４質量％の範囲において電気的特性が良好である。すなわち比誘電率Ｋが９以下で、Ｑ値が８０００以上、ＴＣも＋１３０ｐｐｍ／℃以下と低く、また焼結温度も８７０℃と低く優れた誘電体磁器組成物が得られる。 For these reasons, ZSB is 81-99 mass% in the present invention, Al 2 O 3 is 0~15V mass%, MgO 0 to 3 wt%, electrical in B 2 O 3 1 to 6% by weight range Good characteristics. Further, the electrical characteristics are within the range of 81 to 99.6% by weight of ZSB, 0 to 15% by weight of Al 2 O 3 , 0 to 3% by weight of MgO, and 0.4 to 2.4% by weight of Li 2 O. Is good. That is, an excellent dielectric ceramic composition having a relative dielectric constant K of 9 or less, a Q value of 8000 or more, a low TC of +130 ppm / ° C. or less, and a low sintering temperature of 870 ° C. can be obtained.
本発明の誘電体磁器組成物は、マイクロ波領域において使用される種々の誘電体共振器用、誘電体フィルター、単板型又は積層セラミックコンデンサ等に用いることができる。 The dielectric ceramic composition of the present invention can be used for various dielectric resonators used in the microwave region, dielectric filters, single plate type or multilayer ceramic capacitors.
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