JP2005041755A - Nonlead glass, glass ceramic composition, and electronic circuit board - Google Patents
Nonlead glass, glass ceramic composition, and electronic circuit board Download PDFInfo
- Publication number
- JP2005041755A JP2005041755A JP2003280061A JP2003280061A JP2005041755A JP 2005041755 A JP2005041755 A JP 2005041755A JP 2003280061 A JP2003280061 A JP 2003280061A JP 2003280061 A JP2003280061 A JP 2003280061A JP 2005041755 A JP2005041755 A JP 2005041755A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- electronic circuit
- circuit board
- less
- ceramic composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Glass Compositions (AREA)
Abstract
Description
本発明は、焼成して電子回路基板を作製するのに好適な無鉛ガラスおよびガラスセラミックス組成物、ならびに電子回路基板に関する。 The present invention relates to a lead-free glass and glass ceramic composition suitable for producing an electronic circuit board by firing, and an electronic circuit board.
従来、電子回路基板として用いられていた、アルミナ粉末を焼結して作製されるアルミナ基板は、アルミナ粉末の焼結温度が約１６００℃と高いために、アルミナ基板作製と同時に焼成する電極の材料としてはタングステン（融点：３４００℃）、モリブデン（融点：２６２０℃）等の高融点金属しか使用できず、比抵抗が小さいが融点が１６００℃以下である銀（融点：９６２℃）等の非・高融点金属を基板作製と同時に焼成する電極材料としては使用できない問題があった。 Conventionally, an alumina substrate that has been used as an electronic circuit substrate and is produced by sintering alumina powder has a high sintering temperature of about 1600 ° C., so that the electrode material is fired simultaneously with the alumina substrate production. For example, only high melting point metals such as tungsten (melting point: 3400 ° C.) and molybdenum (melting point: 2620 ° C.) can be used. There has been a problem that refractory metals cannot be used as electrode materials for firing at the same time as the production of the substrate.
また、樹脂製プリント配線基板（マザーボード）と組み合わせて使用される電子回路基板にはマザーボードとの膨張マッチングが求められる。膨張マッチングが不充分であると、ハンダ実装時や回路のオンオフ繰り返し等による基板温度変動に起因して問題が発生する。
このような問題を解決する電子回路基板用ガラスとして焼成時にクリストバライトを析出するガラスが提案されている（たとえば特許文献１参照。）。
Further, an expansion matching with a mother board is required for an electronic circuit board used in combination with a resin printed wiring board (mother board). Insufficient expansion matching causes problems due to substrate temperature fluctuations due to solder mounting, repeated circuit on / off, and the like.
As a glass for an electronic circuit board that solves such a problem, a glass in which cristobalite is deposited at the time of firing has been proposed (for example, see Patent Document 1).
前記クリストバライトを析出するガラスの粉末を焼成して得られた焼成体は線膨張係数が大きくマザーボードとの膨張マッチングが容易になるという点で優れているが、当該焼成体は２００〜２７０℃においてその膨張曲線に急激な変化（急激な伸び）が起こり、ハンダ実装時（典型的なハンダ固着温度は２５０℃またはそれ以下）等に問題が起こるおそれがある。
本発明は、線膨張係数が大きく、先に述べたような膨張曲線の急激な変化がない電子回路基板を非・高融点金属電極材料との同時焼成によって製造することが可能なガラスセラミックス組成物および無鉛ガラスの提供を目的とする。
The fired body obtained by firing the glass powder on which the cristobalite is deposited is excellent in that the linear expansion coefficient is large and the expansion matching with the mother board is easy, but the fired body is 200 to 270 ° C. An abrupt change (rapid elongation) occurs in the expansion curve, and a problem may occur when solder is mounted (typical solder fixing temperature is 250 ° C. or lower).
INDUSTRIAL APPLICABILITY The present invention is a glass ceramic composition capable of producing an electronic circuit board having a large linear expansion coefficient and no rapid change in the expansion curve as described above by co-firing with a non-refractory metal electrode material. And to provide lead-free glass.
本発明は、下記酸化物基準のモル％表示で、ＳｉＯ２ ４０〜７５％、Ｂ２Ｏ３ ０〜２０％、Ａｌ２Ｏ３ ３〜２０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ ０〜３０％、ＢａＯ １５〜３５％、から本質的になる無鉛ガラスを提供する。
また、質量百分率表示で、前記無鉛ガラスの粉末６５〜９０％、クリストバライト粉末１０〜３５％、から本質的になるガラスセラミックス組成物を提供する。
また、前記ガラスセラミックス組成物を焼成して得られる電子回路基板を提供する。
The present invention is expressed in terms of mol% based on the following oxides: SiO 2 40 to 75%, B 2 O 3 0 to 20%, Al 2 O 3 3 to 20%, MgO + CaO + SrO 0 to 30%, BaO 15 to 35%. Providing lead-free glass consisting essentially of
Moreover, the glass ceramic composition which consists essentially of the lead-free glass powder 65-90% and the cristobalite powder 10-35% by mass percentage display is provided.
Moreover, the electronic circuit board obtained by baking the said glass ceramic composition is provided.
本発明によれば、線膨張係数が大きく、先に述べたような膨張曲線の急激な変化がなく、かつ非・高融点金属電極材料との同時焼成によって製造が可能な電子回路基板、その製造に好適なガラスセラミックス組成物および無鉛ガラスが得られる。 According to the present invention, an electronic circuit board having a large linear expansion coefficient, no rapid change of the expansion curve as described above, and capable of being manufactured by simultaneous firing with a non-refractory metal electrode material, and its manufacture A glass ceramic composition and lead-free glass suitable for the above are obtained.
本発明の無鉛ガラス（以下、本発明のガラスという。）は通常、粉末化してガラス粉末とされ、典型的には電子回路基板の製造に用いられる。
本発明のガラスの軟化温度Ｔｓは９５０℃以下であることが好ましい。９５０℃超では本発明のガラスの粉末を９００℃で焼成して緻密な焼成体を得ることが困難になるおそれがある。より好ましくは９３０℃以下である。
The lead-free glass of the present invention (hereinafter referred to as the glass of the present invention) is usually pulverized into a glass powder, and is typically used for production of an electronic circuit board.
The softening temperature Ts of the glass of the present invention is preferably 950 ° C. or lower. If it exceeds 950 ° C., it may be difficult to obtain a dense fired product by firing the glass powder of the present invention at 900 ° C. More preferably, it is 930 degrees C or less.
本発明のガラスの３５ＧＨｚにおける比誘電率（εＧ）は８以下であることが好ましい。８超では電子回路基板製造に用いることができなくなるおそれがある。より好ましくは７．６以下である。
本発明のガラスの３５ＧＨｚにおける誘電損失（ｔａｎδＧ）は０．００５０以下であることが好ましい。０．００５０超では電子回路基板製造に用いることができなくなるおそれがある。より好ましくは０．００４０以下である。
本発明のガラスのεＧ、ｔａｎδＧはそれぞれ８以下、０．００５０以下であることが好ましい。
The relative dielectric constant (ε G ) at 35 GHz of the glass of the present invention is preferably 8 or less. If it exceeds 8, there is a possibility that it cannot be used for manufacturing an electronic circuit board. More preferably, it is 7.6 or less.
The dielectric loss (tan δ G ) at 35 GHz of the glass of the present invention is preferably 0.0050 or less. If it exceeds 0.0050, the electronic circuit board may not be usable. More preferably, it is 0.0040 or less.
It is preferable that ε G and tan δ G of the glass of the present invention are 8 or less and 0.0050 or less, respectively.
次に、本発明のガラスの組成について、モル％を単に％と記して以下に説明する。
ＳｉＯ２はネットワークフォーマであり、またεＧを低下させる成分であり、必須である。４０％未満ではガラスの安定性が損なわれ、失透しやすくなる。好ましくは５１％以上、より好ましくは５５％以上である。７５％超ではＴｓが高くなる。好ましくは６９％以下、より好ましくは６５％以下である。
Ｂ２Ｏ３は必須ではないが、εＧまたはｔａｎδＧを小さくする、Ｔｓを低下させる等のために２０％まで含有してもよい。２０％超では後述するグリーンシートの耐候性が低下する。好ましくは１０％以下、より好ましくは５％以下である。
Next, the composition of the glass of the present invention will be described below by simply describing mol% as%.
SiO 2 is a network former and a component that lowers ε G and is essential. If it is less than 40%, the stability of the glass is impaired and the glass tends to devitrify. Preferably it is 51% or more, More preferably, it is 55% or more. If it exceeds 75%, Ts becomes high. Preferably it is 69% or less, More preferably, it is 65% or less.
B 2 O 3 is not essential, but may be contained up to 20% in order to reduce ε G or tan δ G , lower Ts, and the like. If it exceeds 20%, the weather resistance of the green sheet described later is lowered. Preferably it is 10% or less, More preferably, it is 5% or less.
Ａｌ２Ｏ３はガラスを安定化させる成分であり、必須である。３％未満ではガラスが不安定になる。好ましくは５％以上である。２０％超ではＴｓが高くなる。好ましくは１３％以下、より好ましくは１０％以下である。
ＭｇＯ、ＣａＯおよびＳｒＯはいずれも必須ではないが、ガラスを安定化させる、ガラスの溶融温度を低下させる等のために合計で３０％まで含有してもよい。３０％超では、ガラスの安定性が損なわれ失透しやすくなる、または、本発明のガラスの粉末を本発明のガラスセラミックス組成物（以下、本発明の組成物という。）に用いたときその焼成体の膨張係数が小さくなるおそれがある。
ＢａＯはガラスの溶融温度を低下させる成分であり、必須である。１５％未満ではＴｓが高くなる。好ましくは２０％以上である。３５％超ではεＧまたはｔａｎδＧが大きくなる。好ましくは３２％以下である。
Al 2 O 3 is a component that stabilizes the glass and is essential. If it is less than 3%, the glass becomes unstable. Preferably it is 5% or more. If it exceeds 20%, Ts becomes high. Preferably it is 13% or less, More preferably, it is 10% or less.
MgO, CaO and SrO are not essential, but may be contained up to 30% in total for stabilizing the glass, lowering the melting temperature of the glass, and the like. If it exceeds 30%, the stability of the glass is impaired and devitrification tends to occur, or when the glass powder of the present invention is used in the glass ceramic composition of the present invention (hereinafter referred to as the composition of the present invention). There exists a possibility that the expansion coefficient of a sintered body may become small.
BaO is a component that lowers the melting temperature of the glass and is essential. If it is less than 15%, Ts becomes high. Preferably it is 20% or more. If it exceeds 35%, ε G or tan δ G becomes large. Preferably it is 32% or less.
本発明のガラスは本質的に上記成分からなるが、他の成分を本発明の目的を損なわない範囲で含有してもよい。そのような他の成分を含有する場合、その含有量の合計は１０％以下であることが好ましい。１０％超ではガラスが失透しやすくなるおそれがある。より好ましくは５％以下である。
前記他の成分として次のようなものが例示される。すなわち、ガラス溶融温度を低下させる、ガラスを安定化させる等のためにＴｉＯ２、ＺｒＯ２、ＣｅＯ２またはＳｎＯ２を含有してもよい。
なお、本発明のガラスはＺｎＯを含有しないことが好ましい。ＺｎＯを含有すると、本発明のガラスの粉末を本発明の組成物に用いたときその焼成体の膨張係数が小さくなるおそれがある。
また、本発明のガラスはＰｂＯを含有しない無鉛ガラスである。
The glass of the present invention consists essentially of the above components, but other components may be contained within a range not impairing the object of the present invention. When such other components are contained, the total content is preferably 10% or less. If it exceeds 10%, the glass tends to be devitrified. More preferably, it is 5% or less.
Examples of the other components are as follows. That is, TiO 2 , ZrO 2 , CeO 2 or SnO 2 may be contained in order to lower the glass melting temperature or stabilize the glass.
In addition, it is preferable that the glass of this invention does not contain ZnO. When ZnO is contained, when the glass powder of the present invention is used in the composition of the present invention, the expansion coefficient of the fired product may be reduced.
The glass of the present invention is a lead-free glass containing no PbO.
本発明のガラスは、ＳｉＯ２が５５〜６５％、Ｂ２Ｏ３が０〜１０％、Ａｌ２Ｏ３が５〜１０％、ＭｇＯ＋ＣａＯ＋ＳｒＯが０〜１５％、ＢａＯが２０〜３５％、であることが好ましい。 In the glass of the present invention, SiO 2 is 55 to 65%, B 2 O 3 is 0 to 10%, Al 2 O 3 is 5 to 10%, MgO + CaO + SrO is 0 to 15%, and BaO is 20 to 35%. It is preferable.
次に、本発明の組成物の組成について質量百分率表示を用いて説明する。
本発明のガラスの粉末は焼成体の緻密性を高める成分であり、必須である。好ましくは７３％以上である。９０％超ではクリストバライト粉末が少なくなる。好ましくは８７％以下である。
クリストバライト粉末は焼成体の膨張係数を大きくし、かつ前記２００〜２７０℃における膨張曲線の急激な変化が認められないような焼成体を得るための成分であり、必須である。好ましくは１３％以上である。３５％超では本発明のガラスの粉末が少なくなる。好ましくは２７％以下である。
Next, the composition of the composition of the present invention will be described using mass percentage display.
The glass powder of the present invention is a component that enhances the denseness of the fired body and is essential. Preferably, it is 73% or more. If it exceeds 90%, the cristobalite powder is reduced. Preferably it is 87% or less.
The cristobalite powder is a component for increasing the expansion coefficient of the fired body and for obtaining a fired body in which a rapid change in the expansion curve at 200 to 270 ° C. is not recognized, and is essential. Preferably it is 13% or more. If it exceeds 35%, the amount of the powder of the glass of the present invention decreases. Preferably it is 27% or less.
本発明の電子回路基板は本発明の組成物を焼成して得られる。焼成する温度は典型的には９００℃またはそれ以下である。
本発明の電子回路基板の５０〜２５０℃における平均線膨張係数（α）は１２０×１０−７／℃以上であることが好ましい。なお、αは典型的には２００×１０−７／℃以下である。
さらに、本発明の電子回路基板の３５ＧＨｚにおける比誘電率（ε）および誘電損失（ｔａｎδ）はそれぞれ８以下、０．００５０以下であることが好ましい。
The electronic circuit board of the present invention is obtained by firing the composition of the present invention. The firing temperature is typically 900 ° C. or lower.
It is preferable that the average linear expansion coefficient ((alpha)) in 50-250 degreeC of the electronic circuit board of this invention is 120 * 10 < -7 > / degreeC or more. Α is typically 200 × 10 −7 / ° C. or less.
Furthermore, the relative dielectric constant (ε) and dielectric loss (tan δ) at 35 GHz of the electronic circuit board of the present invention are preferably 8 or less and 0.0050 or less, respectively.
本発明の電子回路基板は通常、本発明の組成物をグリーンシート化して製造される。すなわち、本発明の組成物を樹脂と混合し、それに溶剤等を添加してスラリーとする。このスラリーをポリエチレンテレフタレート等のフィルム上にドクターブレード法等によって塗布し、シート状に成形する。その後乾燥して溶剤等を除去しグリーンシートとされる。このグリーンシートは焼成されて電子回路基板とされる。なお、前記樹脂として、ポリビニルブチラール、アクリル樹脂等が、前記溶剤として、フタル酸ジブチル、フタル酸ジオクチル、フタル酸ブチルベンジル等がそれぞれ例示される。 The electronic circuit board of the present invention is usually produced by forming the composition of the present invention into a green sheet. That is, the composition of the present invention is mixed with a resin, and a solvent or the like is added to form a slurry. This slurry is applied onto a film of polyethylene terephthalate or the like by a doctor blade method or the like, and formed into a sheet shape. Thereafter, it is dried to remove the solvent and the like to obtain a green sheet. This green sheet is fired to form an electronic circuit board. Examples of the resin include polyvinyl butyral and acrylic resin, and examples of the solvent include dibutyl phthalate, dioctyl phthalate, and butyl benzyl phthalate.
表のＳｉＯ２からＺｎＯまでの欄にモル％表示で示す組成となるように原料を調合、混合し、該混合された原料を白金ルツボに入れて１５００℃で１２０分間溶融し、薄板状のガラスに成型した後、アルミナ製ボールミルで粉砕してガラス粉末を得た。
得られたガラス粉末とクリストバライト粉末を質量比で４：１の割合で混合しガラスセラミックス組成物を得た。
例１〜４は実施例、例５〜７は比較例である。
The raw materials are prepared and mixed so that the composition shown in mol% is indicated in the columns from SiO 2 to ZnO in the table, and the mixed raw materials are put into a platinum crucible and melted at 1500 ° C. for 120 minutes to obtain a thin plate-like glass. And then pulverized with an alumina ball mill to obtain glass powder.
The obtained glass powder and cristobalite powder were mixed at a mass ratio of 4: 1 to obtain a glass ceramic composition.
Examples 1 to 4 are examples, and examples 5 to 7 are comparative examples.
ガラス粉末のＴｓ（単位：℃）、εＧ、ｔａｎδＧを、また、ガラスセラミック組成物を焼成して得られた焼成体のε、ｔａｎδ、α、２００〜２７０℃におけるその膨張曲線の急激な変化（急激な伸び）の有無、を以下のようにして測定・評価した。なお、「−」は測定しなかったことを示す。
Ｔｓ：示差熱分析により昇温速度１０℃／分で室温から１０００℃までの範囲で測定した。なお、アルミナ粉末を標準物質とした。
εＧ、ｔａｎδＧ：ガラス粉末４０ｇを６０ｍｍ×６０ｍｍの金型に入れて加圧成形したものを、９００℃で６０分間焼成した。得られた焼成体を５０ｍｍ×５０ｍｍ×０．２５ｍｍ厚に加工し、高周波測定装置を使用して、２０℃、３５ＧＨｚにおける比誘電率と誘電損失を測定した。
Ts (unit: ° C.), ε G , tan δ G of glass powder, and ε, tan δ, α of a fired body obtained by firing a glass ceramic composition, a rapid expansion of its expansion curve at 200 to 270 ° C. The presence or absence of change (rapid elongation) was measured and evaluated as follows. “-” Indicates that measurement was not performed.
Ts: measured by differential thermal analysis in the range from room temperature to 1000 ° C. at a heating rate of 10 ° C./min. Alumina powder was used as a standard substance.
ε G , tan δ G : 40 g of glass powder was put into a 60 mm × 60 mm mold and subjected to pressure molding, and baked at 900 ° C. for 60 minutes. The fired body thus obtained was processed into a thickness of 50 mm × 50 mm × 0.25 mm, and the relative dielectric constant and dielectric loss at 20 ° C. and 35 GHz were measured using a high-frequency measuring device.
ε、ｔａｎδ：ガラス粉末３２ｇとクリストバライト粉末８ｇを充分に混合して得られた混合物４０ｇを、εＧ、ｔａｎδＧの測定の場合と同様にして焼成した。得られた焼成体について、εＧ、ｔａｎδＧの測定の場合と同様にして２０℃、３５ＧＨｚにおける比誘電率と誘電損失を測定した。
α：ガラス粉末４ｇとクリストバライト粉末１ｇの混合物を５ｍｍ×５ｍｍ×５０ｍｍの金型に入れて加圧成型したものを９００℃で６０分間焼成した。得られた焼成体を直径５ｍｍ×高さ２０ｍｍの円柱状に加工し、６００℃までの膨張曲線を測定し、当該膨張曲線から５０℃〜２５０℃における平均線膨張係数を算出した。
急激な伸び：αの測定で得られた膨張曲線の２００〜２７０℃の領域において急激な変化が認められるか否かを調べた。
ε, tan δ: 40 g of a mixture obtained by thoroughly mixing 32 g of glass powder and 8 g of cristobalite powder was fired in the same manner as in the measurement of ε G and tan δ G. About the obtained sintered body, the relative dielectric constant and dielectric loss at 20 ° C. and 35 GHz were measured in the same manner as in the measurement of ε G and tan δ G.
α: A mixture of 4 g of glass powder and 1 g of cristobalite powder placed in a 5 mm × 5 mm × 50 mm mold and pressure molded was baked at 900 ° C. for 60 minutes. The obtained fired body was processed into a cylindrical shape having a diameter of 5 mm and a height of 20 mm, an expansion curve up to 600 ° C. was measured, and an average linear expansion coefficient at 50 ° C. to 250 ° C. was calculated from the expansion curve.
Rapid elongation: It was examined whether or not a rapid change was observed in the 200 to 270 ° C. region of the expansion curve obtained by the measurement of α.
Claims (6)
6. The electronic circuit board according to claim 5, wherein an average linear expansion coefficient at 50 to 250 ° C. is 120 × 10 −7 / ° C. or more, and a relative dielectric constant and dielectric loss at 35 GHz are 8 or less and 0.0050 or less, respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003280061A JP2005041755A (en) | 2003-07-25 | 2003-07-25 | Nonlead glass, glass ceramic composition, and electronic circuit board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003280061A JP2005041755A (en) | 2003-07-25 | 2003-07-25 | Nonlead glass, glass ceramic composition, and electronic circuit board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2005041755A true JP2005041755A (en) | 2005-02-17 |
Family
ID=34265998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003280061A Pending JP2005041755A (en) | 2003-07-25 | 2003-07-25 | Nonlead glass, glass ceramic composition, and electronic circuit board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2005041755A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007042291A (en) * | 2005-07-29 | 2007-02-15 | Tanaka Kikinzoku Kogyo Kk | Insulating paste |
| JPWO2018051987A1 (en) * | 2016-09-16 | 2019-06-27 | Ａｇｃ株式会社 | Glass substrate and laminated substrate |
-
2003
- 2003-07-25 JP JP2003280061A patent/JP2005041755A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007042291A (en) * | 2005-07-29 | 2007-02-15 | Tanaka Kikinzoku Kogyo Kk | Insulating paste |
| JPWO2018051987A1 (en) * | 2016-09-16 | 2019-06-27 | Ａｇｃ株式会社 | Glass substrate and laminated substrate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1974450A (en) | Lead free glass(es), thick film paste(s), tape composition(s) and low temperature cofired ceramic devices made therefrom | |
| KR20100121685A (en) | Lead-free low-melting-point glass composition having acid resistance | |
| CN1212996C (en) | Glass ceramic composition, glass ceramic sintered material and ceramic multilayer substrate | |
| JP5803453B2 (en) | Glass ceramic dielectric material and glass ceramic dielectric | |
| JPH11310458A (en) | Glass ceramic composition, its baking and glass ceramic composite material | |
| JP2004168597A (en) | Lead-free glass and composition for electronic circuit board | |
| JP2002220256A (en) | Lead-free glass, electronic circuit board composition, and the electronic circuit board | |
| JP2011084447A (en) | Non-lead glass and composite material | |
| JP2006124201A (en) | Nonlead glass, glass ceramic composition and dielectric | |
| JPH11335162A (en) | Composition for ceramic substrate and ceramic circuit part | |
| JP2006169047A (en) | Lead-free low melting point glass | |
| JP4229045B2 (en) | Electronic circuit board and lead-free glass for producing electronic circuit board | |
| JP2004339049A (en) | Lead-free glass for forming dielectric, glass ceramic composition for forming dielectric, dielectric and method of producing laminated dielectric | |
| JP2002338295A (en) | Alkali-free glass, composition for electronic circuit board and electronic circuit board | |
| JP2005041755A (en) | Nonlead glass, glass ceramic composition, and electronic circuit board | |
| JP2011079718A (en) | Bismuth-based non-lead glass and composite material | |
| JP2006256956A (en) | Glass ceramic sintered compact and circuit member for microwave | |
| JP6048665B2 (en) | Glass ceramic materials and glass ceramics | |
| JP2002220255A (en) | Lead-free glass, electronic circuit board composition, and the electronic circuit board | |
| JP2004244271A (en) | Lead-free glass, composition for electronic circuit board, and electronic circuit board | |
| JP4407199B2 (en) | Crystallized lead-free glass, glass ceramic composition, green sheet and electronic circuit board | |
| JP2003128431A (en) | Lead-free glass and glass ceramic composition | |
| WO2009119433A1 (en) | Lead-free glass and composition for lead-free glass ceramics | |
| JPH0517211A (en) | Substrate material and circuit substrate | |
| JP2641521B2 (en) | Wiring board |