JP2001158641A - Glass and glass ceramic composition - Google Patents
Glass and glass ceramic compositionInfo
- Publication number
- JP2001158641A JP2001158641A JP34188399A JP34188399A JP2001158641A JP 2001158641 A JP2001158641 A JP 2001158641A JP 34188399 A JP34188399 A JP 34188399A JP 34188399 A JP34188399 A JP 34188399A JP 2001158641 A JP2001158641 A JP 2001158641A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- ceramic composition
- pigment
- filler
- present
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0054—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
- C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2214/00—Nature of the non-vitreous component
- C03C2214/20—Glass-ceramics matrix
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はガラスおよびガラス
セラミックス組成物に関し、さらに詳しくは電子部品用
の絶縁材料、特に低比誘電率、高膨張発現性および高耐
熱性である絶縁材料に適するガラスおよびガラスセラミ
ックス組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass and glass-ceramic composition, and more particularly to an insulating material for electronic parts, particularly a glass suitable for an insulating material having a low dielectric constant, high expansion and high heat resistance. The present invention relates to a glass ceramic composition.
【０００２】[0002]
【従来の技術】従来、回路基板には安価な樹脂製回路基
板が広く使用されている。しかし、樹脂製回路基板に
は、強度が低い、耐熱性が低く長時間使用すると変形す
る、などの問題があった。したがって、高い信頼性が求
められる回路基板にはガラスセラミック製多層回路基板
が使用されることが多かった。近年、電子部品の高密度
実装化に伴い、樹脂製回路基板とガラスセラミックス多
層回路基板とをハンダ付けする複合化技術の検討が進め
られている。2. Description of the Related Art Conventionally, inexpensive resin circuit boards have been widely used as circuit boards. However, the resin circuit board has problems such as low strength, low heat resistance, and deformation when used for a long time. Therefore, a glass ceramic multilayer circuit board is often used for a circuit board requiring high reliability. 2. Description of the Related Art In recent years, with the increase in the mounting density of electronic components, studies have been made on a composite technique for soldering a resin circuit board and a glass ceramic multilayer circuit board.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、前記複合化
技術を可能とするガラスおよびガラスセラミックス組成
物の提供を目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a glass and glass-ceramic composition which enables the above-mentioned composite technique.
【０００４】[0004]
【課題を解決するための手段】本発明は、軟化点が７０
０℃以上であるガラスであって、該ガラスの粉末を焼成
して得られる焼成物の５０〜３５０℃における平均線膨
張係数が１２０×１０-7〜３５０×１０-7／℃であり、
該焼成物の室温での１ＭＨｚにおける比誘電率が７．５
以下であることを特徴とするガラスを提供する。According to the present invention, the softening point is 70%.
A glass having a temperature of 0 ° C. or higher, wherein a fired product obtained by firing a powder of the glass has an average linear expansion coefficient at 50 to 350 ° C. of 120 × 10 −7 to 350 × 10 −7 / ° C.,
The fired product has a relative dielectric constant at 1 MHz at room temperature of 7.5.
Provided is a glass characterized by the following.
【０００５】また、本発明は、フィラーおよび顔料の少
なくともいずれか一方と、上記ガラスの粉末とから実質
的になり、該フィラーおよび該顔料の含有量の合計が
０．１〜５０重量％であり、該ガラスの粉末の含有量が
５０〜９９．９重量％であることを特徴とするガラスセ
ラミックス組成物を提供する。Further, the present invention substantially comprises at least one of a filler and a pigment and the glass powder, and the total content of the filler and the pigment is 0.1 to 50% by weight. And a glass ceramic composition characterized in that the content of the glass powder is 50 to 99.9% by weight.
【０００６】本発明者は、前記複合化技術における問題
が、ガラスセラミックス製多層回路基板に使用されるガ
ラスセラミックス組成物にあり、また、該組成物の必須
成分であるガラス粉末にあることを見出し、本発明に至
った。The present inventor has found that the problem in the above-mentioned compounding technique lies in the glass-ceramic composition used for the glass-ceramic multilayer circuit board, and also in the glass powder which is an essential component of the composition. This has led to the present invention.
【０００７】[0007]
【発明の実施の形態】つぎに好ましい実施の形態を挙げ
て本発明をさらに具体的に説明する。本発明のガラス
は、通常粉末状にして使用される。本発明のガラス粉末
および本発明のガラスセラミックス組成物は、樹脂製回
路基板とハンダ付けして使用される多層回路基板に使用
される。すなわち、本発明のガラスの粉末またはガラス
セラミックス組成物をスラリー化した後、塗布および焼
成してグリーンシートとし、このグリーンシートを用い
て多層回路基板が作製される。この多層回路基板は、Ｉ
Ｃ、ＬＳＩなどを内蔵する。また、前記焼成は通常８０
０〜１，０００℃で行なわれる。Next, the present invention will be described more specifically with reference to preferred embodiments. The glass of the present invention is usually used in powder form. The glass powder of the present invention and the glass-ceramic composition of the present invention are used for a multilayer circuit board used by soldering to a resin circuit board. That is, after the glass powder or the glass ceramic composition of the present invention is slurried, it is applied and fired to form a green sheet, and a multilayer circuit board is manufactured using the green sheet. This multilayer circuit board has I
Built-in C, LSI, etc. The calcination is usually 80
Performed at 0-1,000 ° C.
【０００８】前記多層回路基板は、５０〜３５０℃にお
ける平均線膨張係数が１３０×１０-7〜３００×１０-7
／℃である樹脂製回路基板とハンダ付けされる。以下、
５０〜３５０℃における平均線膨張係数を単に膨張係数
という。The multilayer circuit board has an average coefficient of linear expansion at 50 to 350 ° C. of 130 × 10 -7 to 300 × 10 -7.
/ ° C soldered to a resin circuit board. Less than,
The average linear expansion coefficient at 50 to 350 ° C is simply referred to as an expansion coefficient.
【０００９】本発明のガラスセラミックス組成物は、本
発明のガラスの粉末の他に、フィラーおよび顔料の少な
くともいずれか一方を含有する。フィラーは膨張係数の
制御または高強度化のための成分であり、顔料は着色の
ための成分である。The glass-ceramic composition of the present invention contains at least one of a filler and a pigment in addition to the glass powder of the present invention. The filler is a component for controlling the expansion coefficient or increasing the strength, and the pigment is a component for coloring.
【００１０】本発明のガラスの軟化点は７００℃以上で
ある。７００℃未満では耐酸性などを低下させる成分、
たとえば、アルカリ金属酸化物の含有量が多くなり過ぎ
て化学的耐久性が低下し、多層回路基板の実装工程中の
メッキ工程において問題が発生するおそれがある。好ま
しくは７５０℃以上、より好ましくは７８０℃以上、特
に好ましくは８００℃以上である。また、該軟化点は１
０００℃以下であることが好ましい。より好ましくは９
５０℃以下、特に好ましくは９００℃以下である。[0010] The softening point of the glass of the present invention is 700 ° C or higher. If the temperature is lower than 700 ° C., a component that lowers acid resistance,
For example, the content of the alkali metal oxide becomes too large, and the chemical durability is reduced, which may cause a problem in a plating process during a mounting process of the multilayer circuit board. It is preferably at least 750 ° C, more preferably at least 780 ° C, particularly preferably at least 800 ° C. The softening point is 1
It is preferable that the temperature is not higher than 000 ° C. More preferably 9
It is 50 ° C. or lower, particularly preferably 900 ° C. or lower.
【００１１】本発明のガラスの粉末を焼成して得られる
焼成物の膨張係数は１２０×１０-7〜３５０×１０-7／
℃である。この範囲外では、前記焼成物を含有する多層
回路基板の膨張係数と樹脂製回路基板の膨張係数の差が
大きくなり過ぎ、ハンダ付け部が破損するおそれがあ
る。前記膨張係数は、好ましくは１５０×１０-7／℃以
上、より好ましくは２００×１０-7／℃以上、特に好ま
しくは２５０×１０-7／℃以上である。前記焼成は、通
常は８００〜１，０００℃で行なわれ、典型的には９０
０℃で行なわれる。また、前記焼成が行なわれる時間は
典型的には３０分間である。The expansion coefficient of the fired product obtained by firing the glass powder of the present invention is 120 × 10 -7 to 350 × 10 -7 /
° C. Outside this range, the difference between the expansion coefficient of the multilayer circuit board containing the fired product and the expansion coefficient of the resin circuit board becomes too large, and the soldered portion may be damaged. The expansion coefficient is preferably at least 150 × 10 −7 / ° C., more preferably at least 200 × 10 −7 / ° C., particularly preferably at least 250 × 10 −7 / ° C. The calcination is usually performed at 800 to 1,000 ° C, typically 90 ° C.
Performed at 0 ° C. Further, the time for the calcination is typically 30 minutes.
【００１２】前記焼成物には、α−石英、トリジマイト
およびクリストバライトからなる群から選ばれる１種以
上の結晶が析出していることが好ましい。これらの３種
の結晶のいずれもが析出していないと、該焼成物の膨張
係数が小さくなり過ぎるおそれがある。これら３種の結
晶のうち、α−石英が析出していることがより好まし
い。It is preferable that at least one crystal selected from the group consisting of α-quartz, tridymite and cristobalite is precipitated in the fired product. When none of these three types of crystals are precipitated, the coefficient of expansion of the fired product may be too small. More preferably, α-quartz is precipitated out of these three types of crystals.
【００１３】上記本発明のガラスの好ましい組成は、下
記酸化物基準の重量％表示で実質的に、 ＳｉＯ2 ６８〜８５、 Ｂ2Ｏ3 １３〜２３、 Ｎａ2Ｏ １．５〜５、 Ｌｉ2Ｏ＋Ｋ2Ｏ ０〜３、 Ａｌ2Ｏ3 ０〜１０、 ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ＋ＺｎＯ ０〜５、 ＳｎＯ2＋ＴｉＯ2＋ＺｒＯ2＋ＣｅＯ2 ０〜５、 からなる。The preferred composition of the glass of the present invention is substantially as follows: SiO 2 68 to 85, B 2 O 3 13 to 23, Na 2 O 1.5 to 5, Li 2 O + K 2 O 0-3, Al 2 O 3 0-10, MgO + CaO + SrO + BaO + ZnO 0-5, SnO 2 + TiO 2 + ZrO 2 + CeO 2 0-5.
【００１４】本発明のガラスセラミックス組成物は、フ
ィラーおよび顔料の少なくともいずれか一方と、上記の
本発明のガラスの粉末とから実質的になり、該フィラー
および該顔料の含有量の合計が０．１〜５０重量％であ
り、該ガラスの粉末の含有量が５０〜９９．９重量％で
あることを特徴とする。The glass-ceramic composition of the present invention substantially comprises at least one of a filler and a pigment and the above-mentioned glass powder of the present invention, and the total content of the filler and the pigment is 0.1%. 1 to 50% by weight, and the content of the glass powder is 50 to 99.9% by weight.
【００１５】本発明のガラスまたは本発明のガラスセラ
ミックス組成物の使用に際しては、約８００〜１，００
０℃の温度にて熱処理することによって本発明の目的が
達成される。従って本発明のガラスの粉末または本発明
のガラスセラミックス組成物は上記範囲の温度にて熱処
理されることが前提となってる。以下に本発明のガラス
の好ましい組成について説明する。以下の説明において
「％」は「重量％」を意味する。When using the glass of the present invention or the glass-ceramic composition of the present invention, about 800 to 1,000
The object of the present invention is achieved by performing a heat treatment at a temperature of 0 ° C. Therefore, it is premised that the glass powder of the present invention or the glass ceramic composition of the present invention is heat-treated at a temperature in the above range. Hereinafter, a preferred composition of the glass of the present invention will be described. In the following description, “%” means “% by weight”.
【００１６】ＳｉＯ2の含有量は６８〜８５％であり、
ガラスのネットワークフォーマーとして必須成分であ
る。ＳｉＯ2の含有量が６８％より少ないと、得られる
ガラスの化学的耐久性、特に耐熱性や耐水性が低下する
ので好ましくない。より好ましくは７０％以上である。
一方、ＳｉＯ2の含有量が８５％を超えると、得られる
ガラスがガラス溶融過程で失透化傾向を生じるととも
に、高粘性になり過ぎて好ましくない。より好ましくは
７８％以下である。The content of SiO 2 is 68-85%,
It is an essential component as a glass network former. If the content of SiO 2 is less than 68%, the chemical durability of the obtained glass, particularly heat resistance and water resistance, are undesirably reduced. It is more preferably at least 70%.
On the other hand, when the content of SiO 2 exceeds 85%, the obtained glass tends to be devitrified in the glass melting process and becomes too high in viscosity, which is not preferable. It is more preferably at most 78%.
【００１７】Ｂ2Ｏ3の含有量は１３〜２３％であり、フ
ラックス材として必須成分である。Ｂ2Ｏ3の含有量が１
３％より低いと、得られるガラスの熔解性が高粘性にな
り過ぎて好ましくない。より好ましくは１５％以上であ
る。一方、Ｂ2Ｏ3の含有量が２３％を超えると、得られ
るガラスの化学的耐久性、特に耐水性が低下して好まし
くない。より好ましくは２１％以下である。The content of B 2 O 3 is 13 to 23%, and is an essential component as a flux material. B 2 O 3 content of 1
If it is lower than 3%, the meltability of the obtained glass becomes too high, which is not preferable. It is more preferably at least 15%. On the other hand, if the content of B 2 O 3 exceeds 23%, the chemical durability of the obtained glass, particularly the water resistance, is undesirably reduced. It is more preferably at most 21%.
【００１８】Ｎａ2Ｏの含有量は１．５〜５％であり、
フラックス材ならびに得られるガラスを高膨張発現性結
晶化ガラスとするうえで必須成分である。Ｎａ2Ｏの含
有量が１．５％より少ないと、焼成物の膨張係数が小さ
くなり過ぎる。より好ましくは２％以上である。一方、
Ｎａ2Ｏの含有量が５％を超えると、化学的耐久性が低
下し好ましくない。より好ましくは４％以下である。The content of Na 2 O is 1.5 to 5%,
It is an essential component to make the flux material and the obtained glass a crystallized glass having high expansion. When the content of Na 2 O is less than 1.5%, the expansion coefficient of the fired product becomes too small. It is more preferably at least 2%. on the other hand,
If the content of Na 2 O exceeds 5%, the chemical durability decreases, which is not preferable. It is more preferably at most 4%.
【００１９】Ｌｉ2ＯおよびＫ2Ｏはいずれも必須ではな
いが、フラックス材として導入しても差し支えない。導
入する場合の含有量は３％以下である。Ｌｉ2Ｏおよび
Ｋ2Ｏの含有量の合計が３％を超えると、得られるガラ
スの化学的耐久性、特に耐水性が低下し好ましくない。
より好ましくは２．５％以下である。Both Li 2 O and K 2 O are not essential, but may be introduced as a flux material. When introduced, the content is 3% or less. If the total content of Li 2 O and K 2 O exceeds 3%, the chemical durability of the obtained glass, particularly water resistance, is undesirably reduced.
It is more preferably at most 2.5%.
【００２０】Ａｌ2Ｏ3は必須成分ではないが、得られる
ガラスの化学的耐久性、特に耐酸性、耐水性向上材とし
て導入しても差し支えない。導入する場合の含有量は１
０％以下である。より好ましくは５％以下である。Although Al 2 O 3 is not an essential component, it may be introduced as a material for improving the chemical durability of the obtained glass, particularly acid resistance and water resistance. The content when introducing is 1
0% or less. It is more preferably at most 5%.
【００２１】ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯおよびＺ
ｎＯは選択成分であり、いずれも必須ではないが、高温
粘性調整のために、これらの含有量の合計が５％以下の
範囲で導入しても差し支えない。より好ましくは３％以
下である。MgO, CaO, SrO, BaO and Z
nO is a selected component, and none of them is essential. However, for the purpose of adjusting the viscosity at high temperature, the total of these contents may be introduced in a range of 5% or less. It is more preferably at most 3%.
【００２２】ＳｎＯ2、ＴｉＯ2、ＺｒＯ2およびＣｅＯ2
はいずれも必須成分ではないが、これらの含有量の合計
が５％以下であれば導入しても差し支えない。より好ま
しくは２％以下である。SnO 2 , TiO 2 , ZrO 2 and CeO 2
Are not essential components, but may be introduced if the total of their contents is 5% or less. It is more preferably at most 2%.
【００２３】本発明のガラスは、実質的に上記成分から
なることが好ましいが、本発明の目的を損なわない範囲
で他の成分を合計で１０％まで含有してもよい。たとえ
ば、Ｆｅ2Ｏ3、ＭｎＯ2、Ｎｉ2Ｏ3、ＣｏＯ3などの着色
成分を合量で３％まで含有してもよい。また、ＺｎＯ、
Ｓｂ2Ｏ3を溶解性向上、脱泡性向上のために合計で５％
まで含有してもよい。なお、鉛、ビスマスおよびカドミ
ウムについては、不純物レベルの量を超えて含有するこ
とは好ましくない。The glass of the present invention is preferably substantially composed of the above components, but may contain other components up to a total of 10% as long as the object of the present invention is not impaired. For example, coloring components such as Fe 2 O 3 , MnO 2 , Ni 2 O 3 and CoO 3 may be contained up to 3% in total. Also, ZnO,
5% in total for improving Sb 2 O 3 solubility and defoaming
May be contained. It is not preferable to contain lead, bismuth and cadmium in excess of the impurity level.
【００２４】つぎに、本発明のガラスセラミックス組成
物の組成について説明する。以下の表記中「％」は重量
％である。本発明のガラスセラミックス組成物におい
て、前記本発明のガラスの粉末は必須成分であり、その
含有量は５０〜９９．９％である。ガラスの粉末が５０
％未満では、ガラスセラミックス組成物を焼成して得ら
れる焼成物が焼結不足となる。好ましくは６０％以上で
ある。Next, the composition of the glass ceramic composition of the present invention will be described. In the following description, "%" is% by weight. In the glass-ceramic composition of the present invention, the glass powder of the present invention is an essential component, and its content is 50 to 99.9%. 50 glass powder
%, The sintered product obtained by firing the glass ceramic composition is insufficiently sintered. It is preferably at least 60%.
【００２５】フィラーまたは顔料は、少なくともいずれ
か一方を含有し、また、両者を併用しても差し支えな
い。フィラーおよび顔料の含有量の合計は０．１％以上
５０％以下である。顔料の含有量は２０％以下であるこ
とが好ましい。フィラーおよび顔料の合計量が５０％を
超えると、ガラスセラミックス組成物の焼成物が焼結不
足となる。両者の合計量は好ましくは４０％以下であ
る。The filler or the pigment contains at least one of them, and both may be used in combination. The total content of the filler and the pigment is 0.1% or more and 50% or less. The content of the pigment is preferably 20% or less. If the total amount of the filler and the pigment exceeds 50%, the fired product of the glass ceramic composition will be insufficiently sintered. The total amount of both is preferably 40% or less.
【００２６】フィラーは、ガラスセラミックス組成物の
焼成物の膨張係数の制御あるいは高強度化の目的で５０
％以下の範囲で含有することができる。好ましくは３０
％以下である。使用するフィラーとしては、たとえば、
α−アルミナ、α−石英、コージェライト、安定化ジル
コニア、マグネシア、フォルステライト、蛍石、ステア
タイト、ジルコン、β−ユークリプタイトなどが挙げら
れる。The filler is used for controlling the expansion coefficient of the fired product of the glass ceramic composition or for increasing the strength.
% Or less. Preferably 30
% Or less. As filler to be used, for example,
α-alumina, α-quartz, cordierite, stabilized zirconia, magnesia, forsterite, fluorite, steatite, zircon, β-eucryptite and the like.
【００２７】顔料は着色成分であり、２０％以下の範囲
で含有することができる。顔料の含有量が２０％を超え
ると、ガラスセラミックス組成物の焼成物が焼結不足と
なるおそれがあり好ましくない。より好ましくは１５％
以下である。顔料としては、色相が黒、緑、青、紫また
はそれらの混合色系である耐熱性着色顔料であって、
鉛、ビスマスおよびカドミウムのいずれも含まないも
の、たとえば、Ｃｕ−Ｃｒ−Ｍｎ系酸化物（黒色顔
料）、Ｃｏ−Ｖ−Ｆｅ系酸化物（紫色顔料）、Ｃｒ系酸
化物（緑色顔料）、Ｃｏ系酸化物（青色顔料）などの耐
熱性顔料が好ましい。The pigment is a coloring component and can be contained in a range of 20% or less. If the pigment content exceeds 20%, the fired product of the glass ceramic composition may be insufficiently sintered, which is not preferable. More preferably 15%
It is as follows. As the pigment, the hue is black, green, blue, purple or a heat-resistant coloring pigment of a mixed color system thereof,
Those not containing any of lead, bismuth and cadmium, for example, Cu-Cr-Mn-based oxide (black pigment), Co-V-Fe-based oxide (purple pigment), Cr-based oxide (green pigment), Co A heat-resistant pigment such as a system oxide (blue pigment) is preferable.
【００２８】本発明のガラスセラミックス組成物は実質
的に上記成分からなるが、本発明の目的を損なわない範
囲で他の成分、たとえば、本発明のガラスの粉末ではな
いガラス粉末などを１０％まで含有してもよい。本発明
のガラスセラミックス組成物の焼成物の膨張係数は、１
００×１０-7〜３５０×１０-7／℃であることが好まし
い。より好ましくは１２０×１０-7〜３００×１０-7／
℃である。膨張係数が１００×１０-7／℃より小さい
と、樹脂製回路基板の膨張係数（典型的には１３０×１
０-7〜１５０×１０-7／℃）との差が大きくなり過ぎ、
前記焼成物を含有する多層回路基板と樹脂製回路基板の
ハンダ付け部が破損するおそれがある。一方、３５０×
１０-7／℃より大きいと、やはり樹脂製回路基板の膨張
係数との差が大きくなり過ぎ、前記ハンダ付け部が破損
するおそれがある。The glass-ceramic composition of the present invention is substantially composed of the above-mentioned components. However, other components such as glass powder which is not the powder of the present invention may be added in an amount of up to 10% within a range not to impair the object of the present invention. May be contained. The coefficient of expansion of the fired product of the glass ceramic composition of the present invention is 1
It is preferably from 00 × 10 −7 to 350 × 10 −7 / ° C. More preferably, 120 × 10 −7 to 300 × 10 −7 /
° C. If the expansion coefficient is smaller than 100 × 10 −7 / ° C., the expansion coefficient of the resin circuit board (typically 130 × 1
0 −7 to 150 × 10 −7 / ° C.)
There is a possibility that the soldered portion between the multilayer circuit board containing the fired product and the resin circuit board may be damaged. On the other hand, 350x
If it is higher than 10 -7 / ° C, the difference from the expansion coefficient of the resin circuit board is too large, and the soldered portion may be damaged.
【００２９】つぎに本発明のガラスセラミックス組成物
の使用方法、および用途などを説明する。本発明のガラ
スセラミックス組成物は、エチルセルロースなどの樹脂
（バインダー）成分とα−テルピネオールなどの溶剤と
を含むビヒクルと混練して、ペースト化してスクリーン
印刷などに使用することができる。この際に使用するガ
ラスセラミックス組成物は、好ましくは中心粒径が０．
５〜１０μｍ、より好ましくは０．７〜３．５μｍの範
囲の粉体状である。また、本発明のガラスセラミックス
組成物をスラリー化、塗布および焼結してグリーンシー
トとして、このグリーンシートを用いて多層回路基板を
作成することができる。なお、前記本発明のガラスの粉
末も上記と同じように使用される。Next, the method of using the glass-ceramic composition of the present invention, its application, and the like will be described. The glass-ceramic composition of the present invention can be kneaded with a vehicle containing a resin (binder) component such as ethyl cellulose and a solvent such as α-terpineol, formed into a paste, and used for screen printing or the like. The glass-ceramic composition used at this time preferably has a center particle size of 0.1.
The powder is in the range of 5 to 10 μm, more preferably 0.7 to 3.5 μm. Further, the glass-ceramic composition of the present invention is slurried, applied and sintered to form a green sheet, and a multilayer circuit board can be prepared using this green sheet. The glass powder of the present invention is used in the same manner as described above.
【００３０】本発明のガラスおよび本発明のガラスセラ
ミックス組成物は、電子部品用絶縁ペースト、電子部品
用材料のバインダーガラス、封着用材料などに好適であ
る。前記電子部品用絶縁ペーストとしては、たとえば、
ＨＩＣ用オーバーコート、クロスオーバー、多層配線用
絶縁層材料などが挙げられる。The glass of the present invention and the glass-ceramic composition of the present invention are suitable for insulating paste for electronic parts, binder glass for materials for electronic parts, sealing materials and the like. Examples of the electronic component insulating paste include:
Examples include an overcoat for HIC, a crossover, and an insulating layer material for multilayer wiring.
【００３１】[0031]
【実施例】つぎに実施例および比較例を挙げて本発明を
さらに具体的に説明する。ガラスについては、目標組成
となるように各原料を調合し、これを坩堝などの容器に
入れ、１，４００〜１，６００℃で３〜５時間熔解して
ガラスとした。ついで、これを水砕またはフレーク状と
し、さらに粉砕装置により平均粒径が０．５〜１０μｍ
前後となるように粉砕した。ついで得られた粉末状のガ
ラスに、必要に応じてフィラーおよび／または顔料を表
１に示す配合比となるように混合し、実施例２〜８及び
比較例Ａ〜Ｂのガラスセラミックス組成物を作製した。
なお、実施例１はガラス粉末である。The present invention will be described more specifically with reference to examples and comparative examples. With respect to glass, each raw material was prepared so as to have a target composition, placed in a container such as a crucible, and melted at 1,400 to 1,600 ° C. for 3 to 5 hours to obtain glass. Then, this was granulated or flaked, and the average particle size was 0.5 to 10 μm by a pulverizer.
It was pulverized so that it would be back and forth. Then, a filler and / or a pigment are mixed into the obtained powdery glass as necessary so as to have a compounding ratio shown in Table 1, and the glass-ceramic compositions of Examples 2 to 8 and Comparative Examples AB are obtained. Produced.
Example 1 is a glass powder.
【００３２】上記ガラス粉末およびガラスセラミックス
組成物の特性ならびに信頼性評価についてはつぎの通り
実施した。 ａ）ガラス転移点（℃）、およびｂ）ガラス軟化点
（℃） 示差熱分析（ＤＴＡ）により１０℃／ｍｉｎ．の速度で
昇温した。結果を下記表１に示す。なお、得られたＤＴ
Ａパターンの代表的解析例は図１に示す通りである。The properties and reliability of the above glass powder and glass ceramic composition were evaluated as follows. a) glass transition point (° C.), and b) glass softening point (° C.) 10 ° C./min. by differential thermal analysis (DTA). The temperature was raised at the rate of The results are shown in Table 1 below. Note that the obtained DT
A typical analysis example of the pattern A is as shown in FIG.
【００３３】ｃ）析出結晶の有無 粉末サンプルを９００℃で３０分間焼成して得られた焼
成物について、Ｘ線回析を行い、結晶析出を同定した。
α−石英結晶の析出の有無を下記表１に示す。C) Presence or absence of precipitated crystals The fired product obtained by firing the powder sample at 900 ° C. for 30 minutes was subjected to X-ray diffraction to identify crystal precipitates.
The presence or absence of the precipitation of α-quartz crystals is shown in Table 1 below.
【００３４】ｄ）膨張係数（１０-7／℃） 粉末サンプルを、ドライプレスして８５０〜１，０００
℃（各２０分間保持）にて焼成し、研磨加工して測定用
サンプルを得た。ついで、そのサンプルを熱膨張計にて
測定し、５０〜３５０℃における平均線膨張係数を算出
した。結果を下記表１に示す。D) Expansion coefficient (10 −7 / ° C.) The powder sample is dry-pressed to 850 to 1,000.
C. (retained for 20 minutes each) and polished to obtain a sample for measurement. Next, the sample was measured with a thermal dilatometer, and the average linear expansion coefficient at 50 to 350 ° C. was calculated. The results are shown in Table 1 below.
【００３５】ｅ）焼結性 ８５０℃および９００℃の温度にて焼成して焼成物を作
製し、それを赤インク中に５分間浸漬し、その後流水に
て１分間赤インクを除去した。焼結性の良否の判断は、
赤インクの浸透が全くないものを良（○）とし、赤イン
クが焼成物表面に残留するものは否（×）とした。結果
を下記表１に示す。E) Sinterability A fired product was prepared by firing at temperatures of 850 ° C. and 900 ° C., immersed in red ink for 5 minutes, and then removed with running water for 1 minute. To determine the quality of sintering,
A sample with no permeation of red ink was evaluated as good (○), and a sample with red ink remaining on the surface of the fired product was evaluated as poor (x). The results are shown in Table 1 below.
【００３６】ｆ）比誘電率 ９００℃で焼成して得られた焼成物の１ＭＨｚにおける
比誘電率を室温で測定した。結果を下記表１に示す。F) Relative Dielectric Constant The relative dielectric constant at 1 MHz of the fired product obtained by firing at 900 ° C. was measured at room temperature. The results are shown in Table 1 below.
【００３７】[0037]
【表１】 [Table 1]
【００３８】註）上記表１における記号は下記の意味で
ある。 Ｆ１：α−アルミナ Ｆ２：α−石英 Ｆ３：コージェライト Ｆ４：安定化ジルコニア Ｆ５：蛍石 Ｆ６：マグネシア Ｆ７：フォルステライト Ｐ１：黒色顔料（Ｃｕ−Ｃｒ−Ｍｎ系酸化物） Ｐ２：紫色顔料（Ｃｏ−Ｖ−Ｆｅ系酸化物） Ｐ３：緑色顔料（Ｃｒ系酸化物） Ｐ４：青（Ｃｏ系酸化物） ％：重量％Note: The symbols in Table 1 have the following meanings. F1: α-alumina F2: α-quartz F3: cordierite F4: stabilized zirconia F5: fluorite F6: magnesia F7: forsterite P1: black pigment (Cu—Cr—Mn-based oxide) P2: purple pigment (Co -V-Fe-based oxide) P3: Green pigment (Cr-based oxide) P4: Blue (Co-based oxide)%:% by weight
【００３９】[0039]
【発明の効果】以上説明したように、本発明のガラスお
よびガラスセラミックス組成物は、低比誘電率、高膨張
発現性、高耐熱性であって、絶縁材料に適するガラスお
よびガラスセラミックス組成物である。特に、電子部品
用、パッケージ用材料または構造材料として有効であ
る。As described above, the glass and glass-ceramic composition of the present invention is a glass and glass-ceramic composition which has a low relative dielectric constant, a high expansion property and a high heat resistance and is suitable for an insulating material. is there. In particular, it is effective as a material for electronic parts, a package, or a structural material.
【図１】 本発明のガラスセラミックス組成物の結晶化
特性を示すＤＴＡパターンの代表的解析例を示す図。FIG. 1 is a diagram showing a typical analysis example of a DTA pattern showing the crystallization characteristics of the glass ceramic composition of the present invention.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G062 AA11 AA15 BB01 BB05 CC04 CC08 DA06 DA07 DB01 DB02 DB03 DC04 DD01 DE01 DE02 DE03 DF01 EA01 EA02 EA03 EB03 EC01 EC02 EC03 ED01 ED02 ED03 EE01 EE02 EE03 EF01 EF02 EF03 EG01 EG02 EG03 FA01 FA10 FB01 FB02 FB03 FC01 FC02 FC03 FD01 FE01 FE02 FE03 FF01 FG01 FH01 FJ01 FK01 FL01 FL02 FL03 GA01 GA10 GB01 GC01 GD01 GE01 HH01 HH03 HH05 HH07 HH09 HH11 HH13 HH15 HH17 HH20 JJ01 JJ03 JJ05 JJ07 JJ10 KK01 KK03 KK05 KK07 KK10 MM28 NN29 NN31 PP01 PP02 PP03 PP06 PP09 QQ01 QQ02 QQ03 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G062 AA11 AA15 BB01 BB05 CC04 CC08 DA06 DA07 DB01 DB02 DB03 DC04 DD01 DE01 DE02 DE03 DF01 EA01 EA02 EA03 EB03 EC01 EC02 EC03 ED01 ED02 ED03 EE01 EE02 EF03 EF01 EF03 FA10 FB01 FB02 FB03 FC01 FC02 FC03 FD01 FE01 FE02 FE03 FF01 FG01 FH01 FJ01 FK01 FL01 FL02 FL03 GA01 GA10 GB01 GC01 GD01 GE01 HH01 HH03 HH05 HH07 HH09 HH11 HH13 HH15 HH17 KK01 JJ01 KK01 JJ01 KK01 JJ01 KK01 JJ01 PP03 PP06 PP09 QQ01 QQ02 QQ03
Claims (7)
て、該ガラスの粉末を焼成して得られる焼成物の５０〜
３５０℃における平均線膨張係数が１２０×１０-7〜３
５０×１０-7／℃であり、該焼成物の室温での１ＭＨｚ
における比誘電率が７．５以下であることを特徴とする
ガラス。1. A glass having a softening point of 700 ° C. or higher, which is obtained by firing a powder of the glass.
Average linear expansion coefficient at 350 ° C. is 120 × 10 −7 to 3
50 × 10 −7 / ° C., 1 MHz at room temperature of the fired product
Wherein the relative dielectric constant of the glass is 7.5 or less.
よびクリストバライトからなる群から選ばれる１種以上
の結晶が析出していることを特徴とする請求項１に記載
のガラス。2. The glass according to claim 1, wherein at least one crystal selected from the group consisting of α-quartz, tridymite and cristobalite is precipitated in the fired product.
一方と、請求項１、２または３に記載のガラスの粉末と
から実質的になり、該フィラーおよび該顔料の含有量の
合計が０．１〜５０重量％であり、上記ガラスの粉末の
含有量が５０〜９９．９重量％であることを特徴とする
ガラスセラミックス組成物。4. A glass material substantially comprising at least one of a filler and a pigment and the glass powder according to claim 1, wherein the total content of the filler and the pigment is 0.1 to 0.1. A glass-ceramic composition, which is 50% by weight and the content of the glass powder is 50 to 99.9% by weight.
ージェライト、安定化ジルコニア、マグネシア、フォル
ステライト、蛍石、ステアタイト、ジルコンおよびβ−
ユークリプタイトからなる群から選択された少なくとも
１種である請求項４に記載のガラスセラミックス組成
物。5. The filler as claimed in claim 1, wherein the filler is α-alumina, α-quartz, cordierite, stabilized zirconia, magnesia, forsterite, fluorite, steatite, zircon and β-alumina.
The glass-ceramic composition according to claim 4, which is at least one selected from the group consisting of eucryptite.
らの混合色系である耐熱性着色顔料であり、かつ、鉛、
ビスマスおよびカドミウムのいずれも含まない請求項４
または５に記載のガラスセラミックス組成物。6. The pigment is a heat-resistant coloring pigment having a hue of black, green, blue, purple or a mixed color thereof, and is a lead,
5. The composition according to claim 4, wherein the composition contains neither bismuth nor cadmium.
Or the glass-ceramic composition according to 5.
ミックス組成物であって、該ガラスセラミックス組成物
を焼成して得られる焼成物の５０〜３５０℃における平
均線膨張係数が１００×１０-7〜３５０×１０-7／℃で
あることを特徴とするガラスセラミックス組成物。7. The glass-ceramic composition according to claim 4, 5 or 6, wherein the fired product obtained by firing the glass-ceramic composition has an average coefficient of linear expansion at 50 to 350 ° C. of 100 × 10. A glass ceramic composition having a temperature of -7 to 350 x 10-7 / C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34188399A JP4066582B2 (en) | 1999-12-01 | 1999-12-01 | Glass and glass ceramic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34188399A JP4066582B2 (en) | 1999-12-01 | 1999-12-01 | Glass and glass ceramic composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001158641A true JP2001158641A (en) | 2001-06-12 |
| JP4066582B2 JP4066582B2 (en) | 2008-03-26 |
Family
ID=18349489
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34188399A Expired - Fee Related JP4066582B2 (en) | 1999-12-01 | 1999-12-01 | Glass and glass ceramic composition |
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| Country | Link |
|---|---|
| JP (1) | JP4066582B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013099994A1 (en) * | 2011-12-27 | 2013-07-04 | 旭硝子株式会社 | Surface glass for capacitive touch sensors |
| JP2019112246A (en) * | 2017-12-22 | 2019-07-11 | 日本電気硝子株式会社 | Glass fiber and method for producing the same |
| CN112707638A (en) * | 2021-01-12 | 2021-04-27 | 成都光明光电股份有限公司 | Glass composition |
| CN112777931A (en) * | 2021-01-12 | 2021-05-11 | 成都光明光电股份有限公司 | Low dielectric constant glass |
| WO2022054694A1 (en) * | 2020-09-08 | 2022-03-17 | 日本電気硝子株式会社 | Glass, and method for measuring dielectric properties using same |
| WO2023106269A1 (en) * | 2021-12-10 | 2023-06-15 | Ａｇｃ株式会社 | Glass ceramic composition |
-
1999
- 1999-12-01 JP JP34188399A patent/JP4066582B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013099994A1 (en) * | 2011-12-27 | 2013-07-04 | 旭硝子株式会社 | Surface glass for capacitive touch sensors |
| JPWO2013099994A1 (en) * | 2011-12-27 | 2015-05-11 | 旭硝子株式会社 | Surface glass for capacitive touch sensors |
| JP2019112246A (en) * | 2017-12-22 | 2019-07-11 | 日本電気硝子株式会社 | Glass fiber and method for producing the same |
| WO2022054694A1 (en) * | 2020-09-08 | 2022-03-17 | 日本電気硝子株式会社 | Glass, and method for measuring dielectric properties using same |
| CN112707638A (en) * | 2021-01-12 | 2021-04-27 | 成都光明光电股份有限公司 | Glass composition |
| CN112777931A (en) * | 2021-01-12 | 2021-05-11 | 成都光明光电股份有限公司 | Low dielectric constant glass |
| CN112777931B (en) * | 2021-01-12 | 2022-04-15 | 成都光明光电股份有限公司 | Low dielectric constant glass |
| WO2023106269A1 (en) * | 2021-12-10 | 2023-06-15 | Ａｇｃ株式会社 | Glass ceramic composition |
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| Publication number | Publication date |
|---|---|
| JP4066582B2 (en) | 2008-03-26 |
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