【０００１】[0001]
【発明の属する技術分野】本発明は配線基板や回路部品
の作製に用いられ、１０００℃以下の低温で焼結できる
誘電体材料とその焼結体に関するものであり、特に携帯
電話、近距離無線通信、無線ＬＡＮ等の用途に用いられ
る高周波回路に十分対応できる低い比誘電率と誘電損失
を有する誘電体材料と、その焼結体に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dielectric material used for manufacturing wiring boards and circuit parts, which can be sintered at a low temperature of 1000.degree. C. or less, and a sintered body thereof. The present invention relates to a dielectric material having a low relative dielectric constant and a low dielectric loss that can sufficiently cope with a high-frequency circuit used for applications such as communication and wireless LAN, and a sintered body thereof.
【０００２】[0002]
【従来の技術】配線基板や回路部品として従来広く使用
されてきたアルミナセラミックは比誘電率が１０と高
く、信号処理の速度が遅いという欠点がある。また、導
体材料に高融点金属のタングステンを使用するため、導
体損失が高くなる。その欠点を補うために開発されたガ
ラスセラミックス誘電体材料は、ガラスとアルミナフィ
ラーの複合材料で比誘電率が６〜８とアルミナセラミッ
クスよりも低い。また、１０００℃以下の温度で焼成で
きるので、導体損失の低い銀、銅を内部導体として使用
できるという長所がある。2. Description of the Related Art Alumina ceramics, which have been widely used as wiring boards and circuit components, have a high relative dielectric constant of 10 and are disadvantageous in that signal processing is slow. In addition, since tungsten, which is a high melting point metal, is used as the conductor material, conductor loss increases. The glass-ceramic dielectric material developed to compensate for the disadvantage is a composite material of glass and alumina filler and has a relative dielectric constant of 6 to 8, which is lower than that of alumina ceramic. In addition, since firing can be performed at a temperature of 1000 ° C. or less, there is an advantage that silver or copper having low conductor loss can be used as the internal conductor.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、近年、
信号処理の周波数がさらに高くなってきており、誘電体
材料の誘電率をさらに下げたいという要求が高まってき
ている。However, in recent years,
As the frequency of signal processing becomes higher, there is an increasing demand to further lower the dielectric constant of dielectric materials.
【０００４】本発明の目的は１０００℃以下の温度で焼
成でき、しかも高周波回路部品として使用可能な低比誘
電率、低誘電損失を有する誘電体材料を提供することで
ある。また、アルミナセラミックスの熱膨張係数と大差
がなく、既存のオーバーコートガラスが使用できる誘電
体材料を提供することである。An object of the present invention is to provide a dielectric material which can be fired at a temperature of 1000 ° C. or less and has a low dielectric constant and a low dielectric loss which can be used as a high-frequency circuit component. Another object of the present invention is to provide a dielectric material which does not have a great difference from the thermal expansion coefficient of alumina ceramics and can use existing overcoat glass.
【０００５】[0005]
【課題を解決するための手段】本発明の高周波用低温焼
結誘電体材料は、質量百分率で、酸化物に換算してＳｉ
Ｏ2 ７０〜８５％、Ｂ2Ｏ3 １０〜２５％、Ｋ2Ｏ ０．
５〜５％、Ａｌ2Ｏ3０．０１〜１％からなるホウ珪酸ガ
ラス５０〜９０％とα−石英、α−クリストバライト、
β−トリジマイトの群から選ばれる１種以上のＳｉＯ2
フィラー１０〜５０％からなることを特徴とする。The low-temperature sintered dielectric material for high frequency waves according to the present invention is expressed in terms of mass percentage as Si oxide in terms of oxide.
O 2 70~85%, B 2 O 3 10~25%, K 2 O 0.
50-90% of borosilicate glass composed of 5-5% and 0.01-1% of Al2 O3 , α-quartz, α-cristobalite,
at least one SiO2 selected from the group of β-tridymite
It is characterized by comprising 10 to 50% of a filler.
【０００６】また本発明の焼結体は、質量百分率で、酸
化物に換算してＳｉＯ2 ７０〜８５％、Ｂ2Ｏ3 １０〜
２５％、Ｋ2Ｏ ０．５〜５％、Ａｌ2Ｏ3 ０．０１〜
１％からなるホウ珪酸ガラス５０〜９０％とα−石英、
α−クリストバライト、β−トリジマイトの群から選ば
れる１種以上のＳｉＯ2フィラー１０〜５０％からなる
原料粉末を焼結させてなることを特徴とする。Further, the sintered body of the present invention has a mass percentage of 70 to 85% of SiO2 and B2 O3 of 10 to 10% in terms of oxide.
25%, K 2 O 0.5~5% , Al 2 O 3 0.01~
1-% borosilicate glass 50-90% and α-quartz,
It is characterized by being obtained by sintering a raw material powder comprising 10 to 50% of at least one kind of SiO2 filler selected from the group consisting of α-cristobalite and β-tridymite.
【０００７】[0007]
【発明の実施の形態】本発明の高周波用低温焼結誘電体
材料は、１０００℃以下の温度で銀もしくは銅の導体材
料と同時焼成できる。またその焼結体は、比誘電率が３
〜４、誘電失が０．００３以下の特性を有する。BEST MODE FOR CARRYING OUT THE INVENTION The low-frequency sintered dielectric material for high frequency waves of the present invention can be co-fired with a silver or copper conductor material at a temperature of 1000 ° C. or less. The sintered body has a relative dielectric constant of 3
-4, has a property of dielectric loss of 0.003 or less.
【０００８】本発明の誘電体材料は、ホウ珪酸ガラスと
ＳｉＯ2フィラーからなるガラスセラミックス複合材料
である。The dielectric material of the present invention is a glass-ceramic composite material comprising borosilicate glass and SiO2 filler.
【０００９】ホウ珪酸ガラスの組成を上記のように限定
した理由を以下に述べる。The reason why the composition of the borosilicate glass is limited as described above will be described below.
【００１０】ＳｉＯ2はホウ珪酸ガラスの主成分であ
る。ＳｉＯ2が８５％より多いと焼結温度が１０００℃
以上となる。また、７０％より少ないと誘電率が４以下
とならない。ＳｉＯ2の好適な範囲は７８〜８３％であ
る。[0010] SiO2 is a main component of borosilicate glass. Sintering temperature of 1000 ° C when SiO2 is more than 85%
That is all. If it is less than 70%, the dielectric constant does not become 4 or less. A preferred range of SiO2 is 78 to 83%.
【００１１】Ｂ2Ｏ3はガラスの粘度を下げる成分であ
る。Ｂ2Ｏ3が２５％より多いと耐水性が劣化する。ま
た、１０％より少ないと焼結温度が１０００℃以上とな
る。Ｂ2Ｏ3の好適な範囲は１６〜２０％である。B2 O3 is a component that lowers the viscosity of glass. If B2 O3 is more than 25%, the water resistance deteriorates. If less than 10%, the sintering temperature will be 1000 ° C. or higher. A preferred range of B2 O3 is 16 to 20%.
【００１２】Ｋ2Ｏはガラスの溶融温度を下げるととも
に、銀を導体材料として選択した場合は、銀の拡散を抑
制する効果がある。Ｋ2Ｏが５％を超えると高周波の誘
電損失が高くなり、熱膨張係数も高くなる。また０．５
％より少ないと溶融温度を下げる効果がない。Ｋ2Ｏの
好適な範囲は１〜３％である。K2 O has the effect of lowering the melting temperature of glass and suppressing the diffusion of silver when silver is selected as the conductor material. If K2 O exceeds 5%, high-frequency dielectric loss increases, and the coefficient of thermal expansion also increases. 0.5
%, There is no effect of lowering the melting temperature. Suitable ranges of K2 O is 1-3%.
【００１３】Ａｌ2Ｏ3はガラスの化学的耐久性を向上さ
せるとともに、絶縁耐電圧を向上させる成分である。Ａ
ｌ2Ｏ3が０．０１％より少ないと、化学的耐久性が悪く
なり、粉砕やシート成型時の湿式プロセス中でアルカリ
（Ｋ2Ｏ）が溶出しやすくなる。また、そのため絶縁耐
電圧も低下し、基板や部品の小型化に伴って誘電体層が
薄肉化されるとショートし易くなる。Ａｌ2Ｏ3が１％よ
りも多いとガラスの溶融温度が高くなりすぎる。Ａｌ2
Ｏ3の好適な範囲は０．０１〜０．５％である。Al2 O3 is a component that improves the chemical durability of glass and also improves the dielectric strength voltage. A
When l2 O3 is less than 0.01%, chemical durability is deteriorated, and alkali (K2 O) is easily eluted in a wet process at the time of pulverization or sheet molding. In addition, the insulation withstand voltage also decreases, and if the dielectric layer is made thinner with the downsizing of the substrate or the component, short-circuiting easily occurs. If the content of Al2 O3 is more than 1%, the melting temperature of the glass becomes too high. Al2
Suitable range of O3 is 0.01 to 0.5%.
【００１４】また本発明の高周波用低温焼結誘電体材料
において使用するＳｉＯ2フィラーは、α−石英、α−
クリストバライト、β−トリジマイトの群から選ばれる
１種以上である。これらのフィラーを選択した理由は誘
電率、誘電損失が低いため、結果として複合材料の誘電
率、誘電損失を低くできるためである。The SiO2 filler used in the low-temperature sintered dielectric material for high frequency waves according to the present invention comprises α-quartz and α-quartz.
At least one selected from the group consisting of cristobalite and β-tridymite. The reason for selecting these fillers is that the dielectric constant and dielectric loss are low, and as a result, the dielectric constant and dielectric loss of the composite material can be reduced.
【００１５】本発明において、ガラスとフィラーの割合
は、ガラス５０〜９０質量％、好ましくは６０〜８０重
量％、フィラー１０〜５０重量％、好ましくは２０〜４
０質量％である。このように限定した理由は、フィラー
が５０％より多いと緻密化しなくなり、１０％よりも少
ないと曲げ強度が低くなり過ぎるとともに、低誘電損失
を達成し難くなるためである。In the present invention, the ratio of the glass to the filler is 50 to 90% by weight, preferably 60 to 80% by weight, and the filler is 10 to 50% by weight, preferably 20 to 4% by weight.
0% by mass. The reason for such limitation is that if the filler content is more than 50%, the filler is not densified, and if the filler content is less than 10%, the bending strength becomes too low, and it is difficult to achieve low dielectric loss.
【００１６】上記構成からなる本発明の材料は、例えば
グリーンシートの形態で使用することができる。The material of the present invention having the above structure can be used, for example, in the form of a green sheet.
【００１７】グリーンシートとして使用する場合、上記
組成を有するように調合されたガラスセラミックス原料
粉末の混合物からなる誘電体材料と共に、結合剤、可塑
剤及び溶剤を使用する。When used as a green sheet, a binder, a plasticizer and a solvent are used together with a dielectric material comprising a mixture of glass ceramic raw material powders prepared to have the above composition.
【００１８】誘電体材料のグリーンシート中の含有量
は、６０〜８０質量％程度が一般的である。The content of the dielectric material in the green sheet is generally about 60 to 80% by mass.
【００１９】結合剤は、乾燥後の膜強度を高め、また柔
軟性を付与する成分であり、その含有量は、５〜３０質
量％程度が一般的である。結合剤としてはポリビニルブ
チラール、ポリブチルメタアクリレート、ポリビニルブ
チラール、ポリメチルメタアクリレート、ポリエチルメ
タアクリレート、エチルセルロース等が使用可能であ
り、これらを単独あるいは混合して使用する。The binder is a component that increases the strength of the film after drying and imparts flexibility, and its content is generally about 5 to 30% by mass. As the binder, polyvinyl butyral, polybutyl methacrylate, polyvinyl butyral, polymethyl methacrylate, polyethyl methacrylate, ethyl cellulose and the like can be used, and these can be used alone or in combination.
【００２０】可塑剤は、乾燥速度をコントロールすると
共に、乾燥膜に柔軟性を与える成分であり、その含有量
は０．１〜１０質量％程度が一般的である。可塑剤とし
てはブチルベンジルフタレート、ジオクチルフタレー
ト、ジイソオクチルフタレート、ジカプリルフタレー
ト、ジブチルフタレート等が使用可能であり、これらを
単独あるいは混合して使用する。The plasticizer is a component that controls the drying speed and imparts flexibility to the dried film. The content of the plasticizer is generally about 0.1 to 10% by mass. As the plasticizer, butylbenzyl phthalate, dioctyl phthalate, diisooctyl phthalate, dicapryl phthalate, dibutyl phthalate, and the like can be used, and these can be used alone or as a mixture.
【００２１】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。As the solvent, for example, toluene, methyl ethyl ketone and the like can be used.
【００２２】グリーンシートを作製する一般的な方法と
しては、誘電体材料粉末、結合剤、可塑剤、及び溶剤か
らなるスラリーを、ドクターブレード法によってポリエ
チレンテレフタレート（ＰＥＴ）等のフィルムの上にシ
ート成形する。シート成形後、乾燥させることによって
溶媒や溶剤を除去し、グリーンシートとすることができ
る。As a general method for producing a green sheet, a slurry composed of a dielectric material powder, a binder, a plasticizer, and a solvent is formed into a sheet on a film such as polyethylene terephthalate (PET) by a doctor blade method. I do. After forming the sheet, the solvent and the solvent are removed by drying to obtain a green sheet.
【００２３】次に本発明の焼結体を説明する。Next, the sintered body of the present invention will be described.
【００２４】本発明の焼結体は、上記グリーンシート等
の形態で提供される誘電体材料を９００〜１０００℃の
温度で２０〜１２０分間焼成して焼結させたものであ
り、誘電率及び誘電損失が低いという特徴を有してい
る。The sintered body of the present invention is obtained by sintering the dielectric material provided in the form of the above green sheet or the like at a temperature of 900 to 1000 ° C. for 20 to 120 minutes to obtain a dielectric constant and a dielectric constant. It has the characteristic of low dielectric loss.
【００２５】本発明の焼結体は、種々の用途に適用可能
である。例えば多層基板の絶縁層用途の場合、乾燥させ
た上記グリーンシートを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。続いて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。さらに積層グリーンシ
ートを焼成することによって、ガラスセラミックスから
なる絶縁層（焼結体）を有する多層基板を得ることがで
きる。なお多層基板用途以外にも、半導体パッケージや
積層チップ部品等種々の電子部品の構成材として使用す
ることが可能である。The sintered body of the present invention is applicable to various uses. For example, in the case of an insulating layer application of a multilayer substrate, the dried green sheet is cut into a predetermined size, and then subjected to mechanical processing to form a through-hole. Print on the green sheet surface. Subsequently, a plurality of green sheets are laminated and integrated by thermocompression bonding. Further, by firing the laminated green sheet, a multilayer substrate having an insulating layer (sintered body) made of glass ceramic can be obtained. It can be used as a constituent material of various electronic components such as a semiconductor package and a laminated chip component in addition to the use of a multilayer substrate.
【００２６】[0026]
【実施例】以下、実施例に基づいて、本発明を詳述す
る。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail based on embodiments.
【００２７】[0027]
【表１】[Table 1]
【００２８】[0028]
【表２】[Table 2]
【００２９】まず表に示す組成となるようにガラス原料
を調合した後、白金坩堝に入れて１５００〜１６００℃
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ボールミルにより粗
砕した後、アルコールを加えて湿式粉砕し、平均粒径が
０．５〜３μｍのガラス粉末とした。さらに表に示した
セラミック粉末（平均粒径２μｍ）を添加し、混合して
試料を得た。First, a glass raw material was prepared so as to have a composition shown in the table, and then put in a platinum crucible at 1500 to 1600 ° C.
For 3 to 6 hours, and formed into a thin plate by a water-cooled roller. Next, the formed body was roughly crushed by a ball mill, and then wet-ground by adding alcohol to obtain a glass powder having an average particle diameter of 0.5 to 3 μm. Further, a ceramic powder (average particle size: 2 μm) shown in the table was added and mixed to obtain a sample.
【００３０】次に各試料に、結合剤としてポリビニルブ
チラールを１５質量％、可塑剤としてブチルベンジルフ
タレートを４質量％、及び溶剤としてトルエンを３０質
量％添加してスラリーを調製した。次いで上記のスラリ
ーを、ドクターブレード法によってグリーンシートに成
形し、乾燥させ、所定寸法に切断した後、複数枚を積層
し、熱圧着によって一体化した。さらに積層グリーンシ
ートを、焼成することによって焼結体を得た。Next, a slurry was prepared by adding 15% by mass of polyvinyl butyral as a binder, 4% by mass of butylbenzyl phthalate as a plasticizer, and 30% by mass of toluene as a solvent to each sample. Next, the slurry was formed into a green sheet by a doctor blade method, dried, cut into a predetermined size, and then a plurality of sheets were laminated and integrated by thermocompression bonding. Further, a sintered body was obtained by firing the laminated green sheet.
【００３１】焼成温度は、種々の温度で焼成した焼結体
にインクを塗布した後に拭き取り、インクが残らない
（＝緻密に焼結した）試料のうち最低の温度で焼成した
ものの焼成温度を記載した。また得られた焼結体につい
て、誘電率、誘電損失、熱膨張係数、アルカリ（Ｋ
2Ｏ）溶出量を評価した。結果を各表に示す。The firing temperature is the firing temperature of a sample fired at the lowest temperature among samples in which ink is applied to a sintered body fired at various temperatures and then wiped off and no ink remains (= densely sintered). did. Further, regarding the obtained sintered body, dielectric constant, dielectric loss, thermal expansion coefficient, alkali (K
It was evaluated2 O) elution. The results are shown in each table.
【００３２】表から明らかなように、実施例Ｎｏ．１〜
４の各試料は、１０００℃以下の温度で焼成可能であっ
た。また２．４ＧＨｚの周波数で誘電率が３．４〜３．
９、誘電損失が０．００１０〜０．００２９であった。As is clear from the table, the example No. 1 to
Each sample of No. 4 could be fired at a temperature of 1000 ° C. or less. The dielectric constant is 3.4 to 3.0 at a frequency of 2.4 GHz.
9. Dielectric loss was 0.0010 to 0.0029.
【００３３】一方、比較例であるＮｏ．５の試料は、Ｋ
2Ｏの含有量が多いため、誘電損失が０．００３５、膨
張係数が９．０ｐｐｍと大きくなった。Ｎｏ．６の試料
はフィラーとしてアルミナを使用したため、誘電率が
５．０と大きくなった。またＮｏ．７の試料は、ガラス
組成中にＡｌ2Ｏ3を含まないため、アルカリ溶出量が多
くなっていた。On the other hand, in Comparative Example No. Sample No. 5 is K
Due to the large content of2 O, the dielectric loss was increased to 0.0035 and the expansion coefficient was increased to 9.0 ppm. No. Sample No. 6 used alumina as a filler, and thus had a large dielectric constant of 5.0. No. Sample No. 7 contained a large amount of alkali elution because it did not contain Al2 O3 in the glass composition.
【００３４】なお誘電損失および誘電率の測定は原料粉
末を７×７×７０ｍｍの大きさにプレス成形したものを
９００〜１０００℃で焼成したものを試料とした。測定
周波数２.４ＧＨｚで空洞共振器摂動法により測定し
た。The dielectric loss and permittivity were measured by pressing a raw material powder to a size of 7 × 7 × 70 mm and firing it at 900 to 1000 ° C. as a sample. The measurement was performed by a cavity resonator perturbation method at a measurement frequency of 2.4 GHz.
【００３５】熱膨張係数は、熱機械分析装置にて測定し
た。The coefficient of thermal expansion was measured by a thermomechanical analyzer.
【００３６】アルカリ溶出量はガラス粉末を純水に分散
し、１２１℃で６０分間オートクレーブ処理したのち、
水分中のアルカリ量を原子吸光分析で評価した。The alkali elution amount was determined by dispersing the glass powder in pure water, and autoclaving at 121 ° C. for 60 minutes.
The amount of alkali in water was evaluated by atomic absorption analysis.
【００３７】[0037]
【発明の効果】本発明の高周波用低温焼結誘電体材料を
使用すれば、焼成温度が１０００℃以下であるため、銀
や銅の導体材料と同時焼成できる。しかも比誘電率が３
〜４、誘電損失が０．００３以下と低比誘電率、低誘電
損失の特性をもつガラスセラミックス焼結体となるた
め、高周波数帯域での信号処理を行う誘電体材料として
の機能を十分発揮し、多層配線基板や回路部品用途に好
適に使用できる。When the low-temperature sintered dielectric material for high frequency waves of the present invention is used, since the firing temperature is 1000 ° C. or less, it can be fired simultaneously with silver or copper conductor material. Moreover, the relative dielectric constant is 3
-4.Since it is a glass-ceramic sintered body with low relative dielectric constant and low dielectric loss as dielectric loss of 0.003 or less, it fully demonstrates its function as a dielectric material for signal processing in a high frequency band. However, it can be suitably used for multilayer wiring boards and circuit component applications.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000386288AJP4569000B2 (en) | 2000-12-20 | 2000-12-20 | Low-frequency sintered dielectric material for high frequency and its sintered body |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000386288AJP4569000B2 (en) | 2000-12-20 | 2000-12-20 | Low-frequency sintered dielectric material for high frequency and its sintered body |
| Publication Number | Publication Date |
|---|---|
| JP2002187768Atrue JP2002187768A (en) | 2002-07-05 |
| JP4569000B2 JP4569000B2 (en) | 2010-10-27 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000386288AExpired - LifetimeJP4569000B2 (en) | 2000-12-20 | 2000-12-20 | Low-frequency sintered dielectric material for high frequency and its sintered body |
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| JP (1) | JP4569000B2 (en) |
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| KR100621195B1 (en)* | 2004-02-06 | 2006-09-13 | 주식회사 아이엠텍 | Ceramic powder composition for LTC and its manufacturing method |
| KR101248913B1 (en) | 2011-03-29 | 2013-04-01 | 순천향대학교 산학협력단 | Synthesis of bio-active glass powders by the ultrasonic energy assisted hydrothermal method and their production method |
| WO2022191020A1 (en)* | 2021-03-12 | 2022-09-15 | 株式会社村田製作所 | Glass ceramic material, laminate, and electronic component |
| WO2022230475A1 (en)* | 2021-04-30 | 2022-11-03 | 日本電気硝子株式会社 | Glass ceramic dielectric material, sintered body, and circuit member for high-frequency use |
| US11760686B2 (en) | 2018-12-20 | 2023-09-19 | Murata Manufacturing Co., Ltd. | Glass ceramic material, laminate, and electronic component |
| CN117222607A (en)* | 2021-04-30 | 2023-12-12 | 日本电气硝子株式会社 | Glass ceramic dielectric material, sintered body, and circuit member for high frequency |
| US11903126B2 (en) | 2018-12-20 | 2024-02-13 | Murata Manufacturing Co., Ltd. | Laminate, electronic component, and laminate production method |
| US11924968B2 (en) | 2018-12-21 | 2024-03-05 | Murata Manufacturing Co., Ltd. | Layered body and electronic component |
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| CN107531577B (en) | 2015-05-15 | 2020-12-18 | 株式会社村田制作所 | Low-temperature-sintered ceramic material, ceramic sintered body, and ceramic electronic component |
| DE102018112069A1 (en)* | 2018-05-18 | 2019-11-21 | Schott Ag | Use of a flat glass in electronic components |
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| JPH0328171A (en)* | 1989-06-23 | 1991-02-06 | Nec Corp | Ceramic composition material |
| JPH03141153A (en)* | 1989-10-25 | 1991-06-17 | Nec Corp | Inorganic composition having low-temperature sintering property and low dielectric constant |
| JPH11302075A (en)* | 1998-04-17 | 1999-11-02 | Fuji Elelctrochem Co Ltd | Low temperature sintered dielectric porcelain composition |
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| KR100621195B1 (en)* | 2004-02-06 | 2006-09-13 | 주식회사 아이엠텍 | Ceramic powder composition for LTC and its manufacturing method |
| KR101248913B1 (en) | 2011-03-29 | 2013-04-01 | 순천향대학교 산학협력단 | Synthesis of bio-active glass powders by the ultrasonic energy assisted hydrothermal method and their production method |
| US11760686B2 (en) | 2018-12-20 | 2023-09-19 | Murata Manufacturing Co., Ltd. | Glass ceramic material, laminate, and electronic component |
| US11903126B2 (en) | 2018-12-20 | 2024-02-13 | Murata Manufacturing Co., Ltd. | Laminate, electronic component, and laminate production method |
| US11924968B2 (en) | 2018-12-21 | 2024-03-05 | Murata Manufacturing Co., Ltd. | Layered body and electronic component |
| WO2022191020A1 (en)* | 2021-03-12 | 2022-09-15 | 株式会社村田製作所 | Glass ceramic material, laminate, and electronic component |
| CN116981648A (en)* | 2021-03-12 | 2023-10-31 | 株式会社村田制作所 | Glass ceramic material, laminate, and electronic component |
| JP7597203B2 (en) | 2021-03-12 | 2024-12-10 | 株式会社村田製作所 | Glass ceramic material, laminate, and electronic component |
| WO2022230475A1 (en)* | 2021-04-30 | 2022-11-03 | 日本電気硝子株式会社 | Glass ceramic dielectric material, sintered body, and circuit member for high-frequency use |
| CN117222607A (en)* | 2021-04-30 | 2023-12-12 | 日本电气硝子株式会社 | Glass ceramic dielectric material, sintered body, and circuit member for high frequency |
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