JP3624408B2 - Glass ceramic dielectric material - Google Patents

Description

【００２８】
表１のガラス試料は以下のように調製した。
【００２９】
まず原料として、純珪粉、酸化ランタン、酸化セリウム、酸化プラセオジウム、酸化ネオジウム、酸化チタン、炭酸バリウム、炭酸カルシウム、炭酸ストロンチウム、酸化亜鉛、酸化鉛、酸化ビスマス、酸化ジルコニウムを準備し、表中の各組成となるように原料を調合した後、白金坩堝に入れて１４００〜１５００℃で３〜６時間溶融してから、水冷ローラーによって薄板状に成形した。次いでこの成形体を粗砕した後、水を加えてボールミルにより湿式粉砕し、平均粒径が１．５〜３．０μｍの粉末とした。
【００３０】
こうして得られたガラス粉末は、１ＧＨｚの周波数で１５．９〜１８．６の比誘電率と１３〜２０×１０^−４の誘電損失を有していた。
【００３１】
また表２は、本実施例で使用するセラミックス粉末（試料ａ〜ｇ）を示すものである。
【００３２】
【表２】

【００３３】
表２中、試料ａのＡｌ_２ Ｏ_３ と試料ｂのＺｒＯ_２ は市販品を使用した。またそれ以外のセラミックス粉末は、原料として酸化ジルコニウム、純珪粉、酸化チタン、炭酸バリウム、酸化ネオジウムを準備し、表２のセラミックスとなるように各原料を調合した後、水を加えてボールミルにより２４時間湿式混合し、次いで乾燥させてから、表中の焼成条件で焼成し、この焼成物をボールミルで平均粒径が１．５〜３．０μｍになるまで粉砕することによって作製した。
【００３４】
こうして得られたセラミックス粉末は、１ＧＨｚの周波数で、９．０〜１００．０の比誘電率と、０．５〜８．０×１０^−４の誘電損失を有していた。
【００３５】
表３、４は、表１のガラス粉末と、表２のセラミックス粉末とを混合して作製したガラスセラミックス誘電体材料（試料Ｎｏ．１〜１６）を示すものである。
【００３６】
【表３】

【００３７】
【表４】

【００３８】
これらのガラスセラミック誘電体材料からなるグリーンシートを作製し、その複数枚を積層し焼結させる方法を以下に述べる。
【００３９】
まずガラス粉末とセラミック粉末を表中の割合で混合した後、所定量の結合剤、可塑剤及び溶剤を添加してスラリーを調製する。結合剤としては、例えばポリビニルブチラール樹脂、メタアクリル酸樹脂等、可塑剤としては、例えばフタル酸ジブチル等、溶剤としては、例えばトルエン、メチルエチルケトン等を使用することができる。
【００４０】
次いで上記のスラリーをポリエステルフィルム上にドクターブレード法によって塗布し、厚みが約０．２ｍｍのグリーンシートを作製する。その後、このグリーンシートを乾燥させ、所定寸法に切断してから、機械的加工を施してスルーホールを形成し、導体や電極となる低抵抗金属材料をスルーホール及びグリーンシート表面に印刷する。次いでこのようなグリーンシートの複数枚を積層し、熱圧着によって一体化する。
【００４１】
このようにして得た積層グリーンシートを、約３℃／分の速度で約５００℃まで昇温し、この温度で約３０分保持することによってグリーンシート中の有機物質を除去する。その後、約１０℃／分の速度で表中の焼成温度まで昇温し、その温度で表中の焼成時間保持して焼結させる。
【００４２】
表３、４から明らかなように、実施例の各試料は、９００℃の低温で焼成可能であり、得られた焼成体は１ＧＨｚの周波数で２０．４〜５８．７の比誘電率と１２〜２０×１０^−４の誘電損失を有していた。しかも曲げ強度が１８００ｋｇ／ｃｍ^２以上と高く、熱膨張係数が８１〜９０×１０^−７／℃であった。
【００４３】
なお、表中の比誘電率と誘電損失は、インピーダンスアナライザーを使用し、２５℃の温度での値を求めた。熱膨張係数は、石英押棒式のディラトメーターを使用して測定した。また軟化点は、周知のファイバー法によって測定した。さらに曲げ強度は、１０×４５×１ｍｍの大きさとなるように作製した焼成体を３点荷重測定法によって測定した。
【００４４】
また実施例では、本発明のガラスセラミックの製造方法として、グリーンシートの例を挙げたが、本発明はこれに限定されるものではなく、一般にセラミックの製造に用いられる各種の方法を適用することが可能である。
【００４５】
【発明の効果】
以上のように本発明のガラスセラミックス誘電体材料は、１０００℃以下の低温で焼成することが可能であり、電極や導体材料として銀や銅を使用することができる。またマイクロ波領域の周波数において高い比誘電率と低い誘電損失を有し、しかも耐熱性と機械的強度が高いため、マイクロ波用回路部品材料として好適である。[0001]
[Industrial application fields]
The present invention relates to a glass-ceramic dielectric material that has a high relative dielectric constant and a low dielectric loss, particularly at a frequency in the microwave region, specifically at a frequency of 0.1 GHz or higher, and is suitable as a circuit component material for microwaves. Is.
[0002]
[Prior art]
In the age of advanced information technology, information transmission tends to be faster and higher in frequency. In mobile communication devices such as automobile telephones and personal radio, new media devices such as satellite broadcasting, satellite communication, CATV, etc., there has been a strong push to make devices compact, and accordingly, dielectric resonators, etc. There is a strong demand for miniaturization of microwave circuit elements.
[0003]
The size of the microwave circuit element is based on the wavelength of the electromagnetic wave used. The wavelength λ of an electromagnetic wave propagating through a dielectric having a relative permittivity ε is λ ₀ when the wavelength in vacuum is
λ = λ ₀ / √ε
It becomes. The circuit element can be reduced in size in inverse proportion to the square root of ε. However, if the relative dielectric constant of the element is large, electromagnetic wave energy is concentrated in the element, and there is an advantage that leakage of electromagnetic waves is reduced.
[0004]
In recent years, various ceramics having a high relative dielectric constant at frequencies in the microwave region have been developed as circuit component materials due to the above circumstances.
[0005]
In addition, a material in which a resin is reinforced with glass fiber having a high relative dielectric constant at the above frequency has been developed and specifically disclosed in JP-A-4-322007 and JP-A-4-367537.
[0006]
[Problems to be solved by the invention]
As the above-mentioned ceramic material, for example, BaO—TiO ₂ ceramic, BaO—Ln ₂ O ₃ —TiO ₂ ceramic, composite perovskite ceramic, ZrO ₂ —TiO ₂ —SnO ₂ ceramic, and the like are known. These ceramic materials have high dielectric constant, low dielectric loss, and high strength. However, when these materials are formed into a sheet and laminated, and then fired to produce a multilayer high-frequency device or circuit board, it is necessary to fire at a temperature of 1200 ° C. or higher. Silver and copper cannot be used as a material, and it is necessary to use an expensive material with higher heat resistance, which has a disadvantage that the material cost is increased.
[0007]
In addition, the material in which the resin is reinforced with the glass fiber described above is superior in terms of cutting, drilling, and the like compared to ceramics, but when trying to obtain a relative dielectric constant of 10 or more at a frequency of 0.1 GHz or more. It is necessary to use a resin having a high relative dielectric constant such as polyvinylidene fluoride (ε = 13) or cyano resin (ε = 16 to 20) instead of the epoxy resin that has been widely used for circuit boards. . However, such a resin has a high dielectric loss (tan δ) at a high frequency (especially 100 MHz or more), and has poor performance as a circuit board material for microwaves. Moreover, a circuit board using such a resin also has a drawback that the heat resistance is basically low.
[0008]
An object of the present invention is to have a high dielectric constant and low dielectric loss at frequencies in the microwave region, and can be fired at a low temperature, so that silver or copper can be used as an electrode or a conductor material, and Another object of the present invention is to provide a glass-ceramic dielectric material that has high mechanical strength and good heat resistance and is suitable as a circuit component material for microwaves.
[0009]
[Means for Solving the Problems]
As a result of repeating various experiments, the present inventors have found that a crystalline glass powder mainly composed of SiO ₂ , Ln ₂ O ₃ , TiO ₂ , RO, ZnO, a ceramic powder having a high dielectric constant and a low dielectric loss, It is found that a glass-ceramic material that can achieve the above-mentioned object can be obtained by combining the above and is proposed as the present invention.
[0010]
That is, a glass ceramic dielectric material of the present invention, the glass powder 40-9 5% by weight percent, consists ceramic powder 60 to 5%, the glass powder is _{SiO 2 10~35%, Ln 2 O} 3 5~35 %, TiO ₂ 15-50%, RO 3-45%, ZnO 0.1-25%, PbO 0-30%, Bi ₂ O ₃ 0-30%, ZrO ₂ 0-25% To do.
[0011]
In the present invention, the reason for limiting the ratio of the glass powder and the ceramic powder as described above is that the glass powder is less than 40% (that is, the ceramic powder is more than 60%) and is difficult to be densified during firing. As a result, the dielectric strength of the sintered body is significantly reduced or a large number of pores are formed inside the fired body. On the other hand, the glass powder is more than 95% (i.e., the ceramic powder is less than 5%) and the glass component raised from the fired body surface, the adhesion strength between the conductor printed on the surface is reduced.
[0012]
The reasons for limiting the composition of the glass powder are as follows.
[0013]
SiO ₂ is a glass network former, and its content is 10 to 35%, preferably 15 to 30%. When SiO ₂ is less than 10%, the glass is out of the vitrification range and stable glass cannot be obtained, and when it exceeds 35%, the relative dielectric constant of the glass is lowered.
[0014]
Ln ₂ O ₃ (lanthanoid oxides such as La ₂ O ₃ , CeO ₂ , Pr ₆ O ₁₁ , and Nd ₂ O ₃ ) is a component that increases the relative dielectric constant and is a constituent component of the precipitated crystal, and its content is The total amount is 5 to 35%, preferably 10 to 30%. If the total amount of Ln ₂ O ₃ is less than 5%, the amount of precipitated crystals decreases, the relative permittivity decreases and the strength of the fired body decreases, and if it exceeds 35%, it tends to devitrify during glass molding.
[0015]
TiO ₂ is a component that increases the relative dielectric constant and is a constituent component of the precipitated crystal. The same becomes a glass network former and SiO _2, the content of 15 to 50%, preferably 20 to 45%. If the amount of TiO ₂ is less than 15%, the amount of precipitated crystals decreases, the relative permittivity decreases, and the strength of the fired body decreases. If it exceeds 50%, it tends to devitrify during glass forming.
[0016]
RO (alkaline earth metal oxides such as BaO, CaO, and SrO) is a component that increases the relative dielectric constant and is a constituent component of the precipitated crystal, and its content is 3 to 45% in total, preferably 5 to 35. %. When RO is less than 3%, the number of precipitated crystals decreases, the relative dielectric constant decreases, the strength of the fired body decreases, and the solubility deteriorates. When RO is more than 45%, devitrification tends to occur during glass forming.
[0017]
Each component of RO is preferably in the range of BaO 3 to 35%, CaO 0 to 15%, SrO 0 to 15%, particularly BaO 5 to 30%, CaO 0 to 10%, SrO 0 to 10%. It is desirable that
[0018]
ZnO is a component that increases the amount of precipitated crystals and improves solubility, and its content is 0.1 to 25%, preferably 1 to 20%. If the ZnO content is less than 0.1%, the amount of crystals deposited becomes insufficient and the solubility is lowered.
[0019]
PbO is a component that increases the dielectric constant and improves the solubility, and its content is 0 to 30%, preferably 0 to 25%. When PbO is more than 30%, the amount of precipitated crystals decreases and the strength of the sintered body decreases.
[0020]
Bi ₂ O ₃ is a component that increases the relative dielectric constant and improves the solubility in the same manner as PbO, and its content is 0 to 30%, preferably 0 to 25%. When Bi ₂ O ₃ is more than 30%, the amount of precipitated crystals decreases and the strength of the sintered body decreases.
[0021]
ZrO ₂ is a component that enhances the chemical durability of the glass, and its content is 0 to 25%, preferably 0 to 20%. If the amount of ZrO ₂ is more than 25%, the solubility becomes worse.
[0022]
As the ceramic powder used in the present invention, various materials can be used as long as they have a high dielectric constant and a low dielectric loss. In particular, it is preferable to use a ceramic material having a relative dielectric constant of 9 or more at 1 GHz and a dielectric loss of 20 × 10 ⁻⁴ or less.
[0023]
Preferred examples of such ceramic _{materials, Al 2 O 3, ZrO 2} , ZrSiO 4, ZrTiO 4, TiO 2, BaTi 4 O 9 and _Ba 2 _Ti 9 RO-TiO such _{O 20} and CaTiO ₃ and SrTiO _{3 2} type ceramic, Ln ₂ O ₃ —TiO ₂ type ceramic such as Nd ₄ Ti ₉ O ₂₄ and La ₄ Ti ₉ O ₂₄ , and RO-Ln ₂ O such as BaNd ₂ Ti ₅ O ₁₄ and SrPr ₂ Ti ₃ O ₁₀ One or a combination of two or more selected from the group of _3- TiO ₂ ceramics can be used.
[0024]
[Action]
The glass-ceramic dielectric material of the present invention is obtained by firing RO-TiO ₂ crystals such as Ba ₂ Ti ₉ O ₂₀ , CaTiO ₃ , SrTiO ₃ , La ₄ Ti ₉ O ₂₄ , Nd ₄ Ti ₉ from the glass by firing. Ln ₂ O ₃ —TiO ₂ based crystals such as O ₂₄ and RO—Ln ₂ O ₃ —TiO ₂ based crystals such as SrPr ₂ Ti ₃ O ₁₀ and BaNd ₂ Ti ₅ O ₁₄ are precipitated. Further, PbO and Bi ₂ O ₃ may be contained in the crystals of these systems. Since each of the above crystals has a high relative dielectric constant, a low dielectric loss, and a high mechanical strength, a fired body excellent in these characteristics can be obtained.
[0025]
【Example】
Hereinafter, the glass ceramic dielectric material of the present invention will be described based on examples.
[0026]
Table 1 shows the glass powders (samples A to F) used in this example.
[0027]
[Table 1]

[0028]
The glass samples in Table 1 were prepared as follows.
[0029]
First, pure silica powder, lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, titanium oxide, barium carbonate, calcium carbonate, strontium carbonate, zinc oxide, lead oxide, bismuth oxide, zirconium oxide are prepared. After preparing the raw materials so as to have each composition, it was put in a platinum crucible and melted at 1400 to 1500 ° C. for 3 to 6 hours, and then formed into a thin plate shape by a water-cooled roller. Next, this compact was roughly crushed, then water was added and wet pulverized by a ball mill to obtain a powder having an average particle size of 1.5 to 3.0 μm.
[0030]
The glass powder thus obtained had a dielectric constant of 15.9 to 18.6 and a dielectric loss of 13 to 20 × 10 ⁻⁴ at a frequency of 1 GHz.
[0031]
Table 2 shows ceramic powders (samples a to g) used in this example.
[0032]
[Table 2]

[0033]
In Table 2, commercially available products were used for Al ₂ O ₃ of sample a and ZrO ₂ of sample b. For other ceramic powders, zirconium oxide, pure silica powder, titanium oxide, barium carbonate, and neodymium oxide are prepared as raw materials. After preparing each raw material to become the ceramics shown in Table 2, water is added and ball milling is performed. The mixture was wet-mixed for 24 hours and then dried, then fired under the firing conditions in the table, and the fired product was pulverized with a ball mill until the average particle size became 1.5 to 3.0 μm.
[0034]
The ceramic powder thus obtained had a dielectric constant of 9.0 to 100.0 and a dielectric loss of 0.5 to 8.0 × 10 ⁻⁴ at a frequency of 1 GHz.
[0035]
Tables 3 and 4 show glass ceramic dielectric materials (sample Nos. 1 to 16) prepared by mixing the glass powder of Table 1 and the ceramic powder of Table 2.
[0036]
[Table 3]

[0037]
[Table 4]

[0038]
A method for producing a green sheet made of these glass ceramic dielectric materials and laminating and sintering the plurality of sheets will be described below.
[0039]
First, glass powder and ceramic powder are mixed at a ratio shown in the table, and then a predetermined amount of a binder, a plasticizer and a solvent are added to prepare a slurry. Examples of the binder include polyvinyl butyral resin and methacrylic acid resin, examples of the plasticizer include dibutyl phthalate, and examples of the solvent include toluene and methyl ethyl ketone.
[0040]
Next, the above slurry is applied onto a polyester film by a doctor blade method to produce a green sheet having a thickness of about 0.2 mm. Thereafter, the green sheet is dried and cut to a predetermined size, and then mechanical processing is performed to form a through hole, and a low-resistance metal material that becomes a conductor or an electrode is printed on the surface of the through hole and the green sheet. Next, a plurality of such green sheets are laminated and integrated by thermocompression bonding.
[0041]
The laminated green sheet thus obtained is heated to about 500 ° C. at a rate of about 3 ° C./min, and held at this temperature for about 30 minutes to remove organic substances in the green sheet. Thereafter, the temperature is raised to the firing temperature in the table at a rate of about 10 ° C./minute, and the sintering time in the table is maintained at that temperature for sintering.
[0042]
As is apparent from Tables 3 and 4, each sample of the example can be fired at a low temperature of 900 ° C., and the fired body obtained has a relative permittivity of 20.4 to 58.7 at a frequency of 1 GHz and 12 It had a dielectric loss of ˜20 × 10 ⁻⁴ . Moreover, the bending strength was as high as 1800 kg / cm ² or more, and the thermal expansion coefficient was 81 to 90 × 10 ⁻⁷ / ° C.
[0043]
In addition, the relative dielectric constant and dielectric loss in a table | surface calculated | required the value in the temperature of 25 degreeC using the impedance analyzer. The thermal expansion coefficient was measured using a quartz push rod type dilatometer. The softening point was measured by a well-known fiber method. Furthermore, the bending strength was measured by a three-point load measurement method for a fired body produced to have a size of 10 × 45 × 1 mm.
[0044]
In the examples, the example of the green sheet was given as the method for producing the glass ceramic of the present invention, but the present invention is not limited to this, and various methods generally used for the production of ceramics are applied. Is possible.
[0045]
【The invention's effect】
As described above, the glass ceramic dielectric material of the present invention can be fired at a low temperature of 1000 ° C. or lower, and silver or copper can be used as an electrode or a conductor material. Further, since it has a high relative dielectric constant and low dielectric loss at frequencies in the microwave region, and has high heat resistance and mechanical strength, it is suitable as a circuit component material for microwaves.

Claims (8)

It consists of 40 to 95% glass powder and 60 to 5% ceramic powder by weight percentage, and the glass powder is 10 to 35% SiO _{2, 5 to} 35% Ln ₂ O ₃ (lanthanoid oxide), 15 to 50 TiO _2. %, RO (alkaline earth metal oxide) 3 to 45%, ZnO 0.1 to 25%, PbO 0 to 30%, Bi ₂ O ₃ 0 to 30%, ZrO ₂ 0 to 25% Glass ceramic dielectric material. 2. The glass ceramic dielectric material according to claim 1, wherein the ceramic powder is made of a ceramic material having a relative dielectric constant of 9 or more and a dielectric loss of 20 × 10 ⁻⁴ or less at 1 GHz. A green sheet comprising the glass ceramic dielectric material according to claim 1. A glass ceramic fired body obtained by firing the glass ceramic dielectric material according to claim 1 . A glass ceramic fired body obtained by firing the green sheet of claim 3 . RO-TiO ₂ System crystal, Ln ₂ O _Three -TiO ₂ Crystals and / or RO-Ln ₂ O _Three -TiO ₂ The glass ceramic fired body according to claim 4 or 5, wherein a system crystal is precipitated. SiO in weight percentage ₂   10-35%, Ln ₂ O _Three (Lantanoid oxide) 5-35%, TiO ₂   15-50%, RO (alkaline earth metal oxide) 3-45%, ZnO 0.1-25%, PbO 0-30%, Bi ₂ O _Three   0-30%, ZrO ₂   A glass ceramic dielectric material was prepared by mixing 40 to 95% by weight of glass powder containing 0 to 25% and 60 to 5% by weight of ceramic powder, and then fired to produce RO-TiO. ₂ System crystal, Ln ₂ O _Three -TiO ₂ Crystals and / or RO-Ln ₂ O _Three -TiO ₂ A method for producing a fired glass ceramic body, characterized in that a system crystal is precipitated. The method for producing a fired glass ceramic body according to claim 7, wherein a green sheet is produced using a glass ceramic dielectric material and then fired.