JP3887032B2 - Ceramic green sheet - Google Patents
Ceramic green sheet Download PDFInfo
- Publication number
- JP3887032B2 JP3887032B2 JP32838995A JP32838995A JP3887032B2 JP 3887032 B2 JP3887032 B2 JP 3887032B2 JP 32838995 A JP32838995 A JP 32838995A JP 32838995 A JP32838995 A JP 32838995A JP 3887032 B2 JP3887032 B2 JP 3887032B2
- Authority
- JP
- Japan
- Prior art keywords
- green sheet
- binder
- acrylic resin
- low
- ceramic green
- 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.)
- Expired - Lifetime
Links
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Description
【０００１】
本発明は、低温焼成のガラスセラミック基板の製造に使用される低温焼成用セラミックグリーンシートに関する。特に、Ａｇ、Ｃｕ、Ａｕなどの低融点金属を配線材料とする低温焼成のガラスセラミック配線基板または窒化アルミニウム配線基板の製造に好適に使用される低温焼成用セラミックグリーンシートに関する。
【０００２】
【従来の技術】
従来、ＬＳＩなどの半導体素子を実装する基板として、アルミナ系セラミックを絶縁材料とする配線基板が使用されてきた。しかし、アルミナ系セラミック材料の焼成温度が高く、同時焼成が可能な配線材料としては高融点金属であるＷ、Ｍｏ等が使われるため、導通抵抗が１０〜２０ｍΩ／□（ｍΩ／ｍｍ2）と高くなる問題を有していた。そこで、Ａｇ、Ｃｕ、Ａｕなどの低抵抗な配線材料と、それらと同時焼成可能な低温焼成絶縁材料としてガラスあるいはガラスセラミックとを用いる配線基板が使用されるようになってきた。また、半導体素子からの熱放散性を上げるために基板材料の高熱伝導化も要求されており、最近ではアルミナよりも熱伝導率の高い窒化アルミニウムセラミックを用いる配線基板の使用も行われている。
【０００３】
ところで、このような配線基板、特に多層の配線を有する配線基板の場合、セラミックの粉末とバインダ−を含むセラミックグリ−ンシ−トを成形し、該セラミックグリ−ンシ−トに必要に応じてビアホ−ルを形成した後にメタライズぺ−ストで配線印刷を施し、積層、脱バインダ−、焼成することで製造が行われている。ここで、セラミックグリ−ンシ−トに求められる特性としては、脱バインダ−性すなわちバインダ−の熱分解性が良く、生加工時の取り扱い性に優れることが要求される。取り扱い性とは具体的には、適度な機械的強度（シ−ト強度）、適度な柔軟性、メタライズぺ−ストとの接着性等が挙げられる。特に、近年は高密度配線化が求められ、それにともなってビア径の微細化、ビア間の狭ピッチ化の要求が著しく、セラミックグリ−ンシ−トもその要求に応じる必要がある。
【０００４】
上記セラミックグリ−ンシ−ト成形用のバインダ−として、従来ＰＶＢ（ポリビニルブチラ−ル）が広く用いられてきた。しかし、ＰＶＢはＷ、Ｍｏ等の配線材料を用いるアルミナ基板用のバインダ−としては、満足できるものであったが、熱分解温度が比較的高いため、配線材料がＣｕなどの酸化され易い材料の場合や、セラミックが窒化アルミニウムなどの酸化され易い材料の場合、あるいはガラスセラミックなどの焼成温度が低い場合には、グリ−ンシ−トのバインダ−としては不適である。そこでこのような場合、比較的低温度で熱分解するアクリル系バインダ−が注目されている。例えば、特開平２−３５７９０号では平均分子量２．０×１０5以上のメタクリル酸メチルポリマ−からなるバインダ−が上記目的のセラミックグリ−ンシ−トのバインダ−として有効であると提案されている。しかし、バインダ−が単にメタクリル酸メチルポリマ−であることだけでは脱バインダ−性、シ−ト強度に優れるものの、グリ−ンシ−トの生加工性、特に狭ピッチの微細ビアホ−ル形成の要求を十分満足できないものと判断して、鋭意検討を行い、本発明に至ったのである。
【０００５】
【発明が解決しようとする課題】
すなわち、本発明は特にＡｇ、Ｃｕ、Ａｕなどの低融点金属を配線材料とする低温焼成のガラスセラミック配線基板、または窒化アルミニウムなどの酸化され易い材料からなる非酸化物セラミック配線基板の製造に使用されるセラミックグリ−ンシ−トに関して、脱バインダ−性に優れ、生加工時の取り扱い性、具体的には適度なシ−ト強度、適度な柔軟性、特に狭ピッチの微細なビアホ−ルの形成性に優れるセラミックグリ−ンシ−トを提供することを課題としてなされたものである。
【０００６】
上記課題を解決するための請求項１の発明は、セラミック原料粉末とバインダ−とを含む低温焼成用セラミックグリーンシ−トにおいて、上記セラミック原料粉末が、ホウケイ酸系ガラスとアルミナ粉末との混合物であり、上記バインダ−が平均分子量２．０×１０５以上、酸価２．４以上７．２以下、ガラス転移温度（Ｔｇ）５０℃以上９０℃以下のアクリル樹脂であることを特徴とする低温焼成用セラミックグリーンシ−トを要旨とする。
【０００７】
請求項２の発明は、上記バインダーがメタクリル酸エチル系のアクリル樹脂である請求項1に記載の低温焼成用セラミックグリーンシートを要旨とする。
【０００８】
請求項３の発明は、上記アクリル樹脂が、メタクリル酸エチルの単独重合体、又は、メタクリル酸エチルと、メタクリル酸メチル及びメタクリル酸ブチルの一方とからなる共重合体である請求項２に記載の低温焼成用セラミックグリーンシートを要旨とする。
【０００９】
請求項４の発明は、上記アクリル樹脂がメタクリル酸エチルの単独重合体である請求項２に記載の低温焼成用セラミックグリーンシートを要旨とする。
【００１０】
請求項５の発明は、上記バインダーが平均分子量２．６×１０ ５ 以上、酸価４．８以上７．２以下、ガラス転移温度（Ｔｇ）６５℃以上９０℃以下のアクリル樹脂である請求項２、３又は４に記載の低温焼成用セラミックグリーンシ−トを要旨とする。
【００１１】
請求項６の発明は、更に、可塑剤として、ジオクチルフタレ−ト（ＤＯＰ）及び／又はジブチルフタレ−ト（ＤＢＰ）を含む請求項２ないし５のいずれかの１項に記載の低温焼成用セラミックグリーンシートを要旨とする。
請求項７の発明は、上記アクリル樹脂がメタクリル酸エチルの単独重合体、又はメタクリル酸エチルと、メタクリル酸メチル及びメタクリル酸ブチルの一方とからなる共重合体であり、該アクリル樹脂は平均分子量２．６×１０５以上、酸価４．８以上７．２以下、ガラス転移温度（Ｔｇ）６５℃以上９０℃以下であり、更に、可塑剤として、ジオクチルフタレ−ト（ＤＯＰ）及び／又はジブチルフタレ−ト（ＤＢＰ）を含む請求項１に記載の低温焼成用セラミックグリーンシートを要旨とする。
請求項８の発明は、上記アクリル樹脂がメタクリル酸エチルの単独重合体、又はメタクリル酸エチルとメタクリル酸メチルとからなる共重合体であり、該アクリル樹脂は平均分子量２．６×１０５以上、酸価４．８以上７．２以下、ガラス転移温度（Ｔｇ）８０℃以上９０℃以下であり、更に、可塑剤として、ジオクチルフタレ−ト（ＤＯＰ）及び／又はジブチルフタレ−ト（ＤＢＰ）を含む請求項１に記載の低温焼成用セラミックグリーンシートを要旨とする。
請求項９の発明は、上記アクリル樹脂がメタクリル酸エチルの単独重合体であり、該アクリル樹脂は平均分子量２．６×１０５以上、酸価４．８以上７．２以下、ガラス転移温度（Ｔｇ）８０℃以上９０℃以下であり、更に、可塑剤として、ジオクチルフタレ−ト（ＤＯＰ）及び／又はジブチルフタレ−ト（ＤＢＰ）を含む請求項１に記載のセラミックグリーンシートを要旨とする。
【００１２】
ここでバインダ−の平均分子量は公知の分析法、例えばゲル浸透クロマトグラフ法（ＧＰＣ法）などを用いて測定される。またバインダ−の平均分子量が２．０×１０5以上とするのは、２．０×１０5未満では十分なシ−ト強度を得られないためである。一方、バインダ−の平均分子量を大きくし過ぎると、例えば５．０×１０5以上とすると、溶剤への溶解性が低下し、また脱バインダ−性の低下が問題となり好ましくない。バインダ−の酸価とは、アクリル系バインダ−の単位重量に含まれるＣＯＯＨ基（カルボキシル基）の量を表すもので、簡易に測定できるためバインダ−１ｇを中和するのに必要なＫＯＨのｍｇ数で表現される値を言う。この酸価が２．４以上であるのは、２．４未満であるとセラミック粉末の分散状態が悪く、成形したグリ−ンシ−トのシ−ト強度が低くなるためである。また酸価が７．２以下であるのは、これより酸価が大きいとバインダ−の熱分解性が悪くなり、焼成したセラミック中に多くの残留炭素を含み、焼成後の色ムラの原因となったり、セラミック自体の電気絶縁性が悪化するためである。
【００１３】
バインダ−のガラス転移点（Ｔｇ）は、ＪＩＳ Ｋ−７１７２に準じて測定される。またバインダ−のガラス転移点（Ｔｇ）が５０℃以上９０℃以下とするのは以下の理由による。ガラス転移点が５０℃未満であると、得られるグリ−ンシ−トのシ−ト強度が低く、また生加工時にグリ−ンシ−トが伸縮し、寸法精度に支障を来すため好ましくない。またガラス転移点が９０℃より高いと、グリ−ンシ−トの可塑性が低くなり生加工性に劣るため好ましくない。すなわちグリ−ンシ−トにパンチングによりビアホ−ルの穴開け加工をすると、バリ、クラックを生じてしまう。なお、グリ−ンシ−トの可塑性は可塑剤の更なる添加により若干解消されるものの、脱バインダ−性が悪くなるため好ましくない。
【００１４】
メタクリル酸エチル系のアクリル樹脂とは、メタクリル酸エチルモノマ−を主な出発原料とし、その官能基が上記酸価となるようにＣＯＯＨ基で置換され、さらに上記平均分子量となるように重合したものを本発明では言う。
【００１５】
またグリ−ンシ−トを成形する前に、セラミック粉末とバインダ−と溶剤等とからなるスラリ−を作製するが、そこで用いる溶剤としてエタノ−ル、ブタノ−ルなどのアルコ−ル系の溶剤、トルエン、キシレンなどの芳香族系の溶剤、ＭＥＫ（メチルエチルケトン）などのケトン系の溶剤が使用できる。これらは、それぞれの単成分または複合成分の混合系で使用でき、それは適宜要求される粘性、揮発性、添加される分散剤、可塑剤等との相性により決定される。なお可塑剤としてジオクチルフタレ−ト（ＤＯＰ）および、またはジブチルフタレ−ト（ＤＢＰ）等を使用することができる。
【００１６】
【発明の実施の形態】
以下に本発明の実施の形態を、本発明の範囲内の例を実施例として、また本発明の範囲外の例を比較例として記載する。
【００１７】
【実施例】
実施例１
セラミック原料粉末としてＳｉＯ2、Ａｌ2Ｏ3、Ｂ2Ｏ3を主成分組成とするホウケイ酸系ガラス粉末とアルミナ粉末とを用意した。ガラス粉末はＳｉＯ2、Ａｌ2Ｏ3、Ｂ2Ｏ3等の粉末を混合し、溶融後、急冷してカレット状とし、さらに粉砕、分級を行い、５０％粒子径（Ｄ50）＝５μmとなるようにして作製した。一方、アルミナ粉末として、市販の低ソ−ダのα−アルミナ粉でＤ50＝３μmであるものを用意した。
【００１８】
バインダ−としては、平均分子量２．６×１０5、酸価４．８、ガラス転移温度（Ｔｇ）８０℃であるメタクリル酸エチル系のアクリル樹脂を用意した。なお上記平均分子量は、東ソ−製ＧＰＣ分取装置を使用し、カラムはTSKgelIG3000、2000、2000H8の３本を使用し、次の条件で求めた。温度４０℃、流速５ｍｌ／分、溶離液クロロホルム、検出器ＲＩ−８０１。
【００１９】
次にアルミナ製のポットに、上記のホウケイ酸系ガラス粉末とアルミナ粉末とを重量比で５：５、総量で１Ｋｇとなるように秤量して入れた。さらに溶剤としてＭＥＫを２００ｇ、前記のアクリル樹脂を１００ｇ、可塑剤としてＤＯＰを５０ｇ、分散剤５ｇを上記ポットへ入れ１０時間混合した。こうしてグリ−ンシ−ト成形用のスラリ−を得た。このスラリ−を用いて、ドクタ−ブレ−ド法でシ−ト厚み０．４ｍｍのグリ−ンシ−トを得た。
【００２０】
グリ−ンシ−トのシ−ト強度および伸び率の測定は、平行部分の幅：４ｍｍ、つかみ具間距離：２０ｍｍ、引っ張速度１０ｍｍ／分とし、その他の条件はＪＩＳ Ｋ−７１１３に準拠して行った。シ−ト強度は平均（ｎ＝１０）で３８ｋｇ／ｃｍ2であり十分なものであった。またシ−トの伸び率（引張破壊伸）は２０％であった。これらを表１に示す。
【００２１】
【表１】
次にグリ−ンシ−トの脱バインダ−性を以下のように試験した。作製したグリ−ンシ−トを５層、すなわち２ｍｍ厚となるように積層し、さらに５０ｍｍ角に切断し生成形体とした。そして、大気中２５０℃、１０時間の熱処理で脱バインダ−を行った。脱バインダ−後の成形体の残留炭素量を分析したところ２．５重量％であった。さらに大気中５００℃、５時間の熱処理を行ったところ残留炭素量は０．０７重量％に低下していた。次に大気中２５０℃、１０時間の熱処理を行った成形体を、大気中９５０℃、３時間の熱処理で焼成を行った。こうして得られたガラスセラミック基板は、クラック等のない満足できるものであった。
【００２３】
また、グリ−ンシ−トとＡｇ系の配線材料とを用いた配線基板を以下のように作製した。まずグリ−ンシ−トに、パンチングにより０．１２ｍｍφのビアホ−ルを０．２０ｍｍ間隔で形成したところ、ビアホ−ル間にクラックは発生しなかった。次にビアホ−ルにＡｇ系のビア用ぺ−ストを充填してビア配線部を形成した。次にグリ−ンシ−ト表面に、Ａｇ系の配線ぺ−ストを使用して配線パタ−ンを印刷し形成した。配線ぺ−ストの溶剤にはタ−ピネオ−ルを用いたが、印刷、乾燥後のグリ−ンシ−トの縮みは０．１％未満で良好であった。次に、配線等を形成した複数のグリ−ンシ−トを積層し、５０℃の条件で熱圧着し積層体を得た。得られた積層体は変形がなく良好であった。さらに積層体を大気中２５０℃、１０時間の熱処理で脱バインダ−を行い、次いで大気中９５０℃、３時間の熱処理で焼成を行った。こうしてＡｇ系の配線を有する多層配線基板を得た。得られた多層配線基板は導通抵抗は低く満足できるものであり、また電気的にオ−プン、ショ−トの無い良好なものであった。
【００２４】
実施例２
バインダ−として、平均分子量２．６×１０5、酸価２．４、ガラス転移温度（Ｔｇ）８０℃であるメタクリル酸エチル系のアクリル樹脂を用意した。その他については実施例１と同様にしてグリ−ンシ−トを作製した。得られたグリ−ンシ−トのシ−ト強度は２１Ｋｇ／ｃｍ2、シ−ト伸び率は１９％であり、実施例１の酸価が４．８のバインダ−に比べシ−ト強度がやや劣るものであった。しかし、実施例１と同様に脱バインダ−性や、生加工性は良好なものであった。また焼成して得られたガラスセラミック基板は、クラック等のない満足できるものであった。さらに、実施例１と同様にＡｇ系の配線を有する多層配線基板を作製したが、良好なものが得られた。
【００２５】
実施例３
バインダ−として、平均分子量２．６×１０5、酸価７．２、ガラス転移温度（Ｔｇ）８０℃であるメタクリル酸エチル系のアクリル樹脂を用意した。その他については実施例１と同様にしてグリ−ンシ−トを作製した。得られたグリ−ンシ−トのシ−ト強度は５０Ｋｇ／ｃｍ2、シ−ト伸び率は２１％であり、実施例１の酸価が４．８のバインダ−に比べシ−ト強度が大きいものであった。実施例１と同様に脱バインダ−試験を行ったところ、大気中２５０℃、１０時間の熱処理での成形体の残留炭素量は３．０重量％であり、さらに続けて大気中５００℃、５時間の熱処理後の残留炭素量は０．０８重量％と実施例１に比べて若干高いものであった。しかし焼成して得られたガラスセラミック基板は、変色、クラック等のない満足できるものであった。また、実施例１と同様にＡｇ系の配線を有する多層配線基板を作製したが、良好なものが得られた。
【００２６】
実施例４
バインダ−として、平均分子量２．０×１０5、酸価４．８、ガラス転移温度（Ｔｇ）８０℃であるメタクリル酸エチル系のアクリル樹脂を用意した。その他については実施例１と同様にしてグリ−ンシ−トを作製した。得られたグリ−ンシ−トのシ−ト強度は２３Ｋｇ／ｃｍ2、シ−ト伸び率は２０％であり、実施例１の平均分子量が２．６×１０5のバインダ−に比べシ−ト強度が小さいものであった。しかし生加工性は特に問題のないものであった。また、脱バインダ−性も実施例１と同程度の良好なものであった。得られたガラスセラミック基板は、クラック等のない満足できるものであった。さらに、実施例１と同様にＡｇ系の配線を有する多層配線基板を作製したが、良好なものが得られた。
【００２７】
実施例５
バインダ−として、平均分子量３．０×１０5 、酸価４．８、ガラス転移温度（Ｔｇ）８０℃であるメタクリル酸エチル系のアクリル樹脂を用意した。その他については実施例１と同様にしてグリ−ンシ−トを作製した。得られたグリ−ンシ−トのシ−ト強度は４２Ｋｇ／ｃｍ2、シ−ト伸び率は２０％であり、実施例１の平均分子量が２．６×１０5のバインダ−に比べシ−ト強度が大きいものであった。また、生加工性、脱バインダ−性も実施例１と同程度の良好なものであった。得られたガラスセラミック基板は、クラック等のない満足できるものであった。さらに、実施例１と同様にＡｇ系の配線を有する多層配線基板を作製したが、良好なものが得られた。
【００２８】
実施例６
バインダ−として、平均分子量２．６×１０5 酸価４．８、ガラス転移温度（Ｔｇ）９０℃であるメタクリル酸エチルモノマ−とメタクリル酸メチルモノマ−が５：５の割合で重合された共重合体からなるアクリル樹脂を用意した。その他については実施例１と同様にしてグリ−ンシ−トを作製した。得られたグリ−ンシ−トのシ−ト強度は４５Ｋｇ／ｃｍ2と高いものであり、シ−ト伸び率は１９％であった。生加工性に関しては、グリ−ンシ−トにパンチングにより０．１２ｍｍφのビアホ−ルを０．２０ｍｍ間隔で形成したところ、ビアホ−ル壁面にバリが発生するものがあったが、簡単に取り除くことができる程度であった。その他の生加工性に関しては特に問題とはならなかった。脱バインダ−性に関しては実施例１と同程度に良好であった。焼成したガラスセラミック基板は、クラック等のない満足できるものであった。さらに実施例１と同様にＡｇ系の配線を有する多層配線基板を作製したが、良好なものが得られた。
【００２９】
実施例７
バインダ−として、平均分子量２．６×１０5、 酸価４．８、ガラス転移温度（Ｔｇ）５０℃であるメタクリル酸ブチル系のアクリル樹脂を用意した。その他については実施例１と同様にしてグリ−ンシ−トを作製した。得られたグリ−ンシ−トのシ−ト強度は２４Ｋｇ／ｃｍ2、シ−ト伸び率は２２％であった。これも実施例１と同様に生加工性、脱バインダ−性に問題がなく、良好な多層配線基板を得ることができた。
【００３０】
実施例８
バインダ−として、平均分子量２．６×１０5 、酸価４．８、ガラス転移温度（Ｔｇ）６５℃であるメタクリル酸エチルモノマ−とメタクリル酸ブチルモノマ−が５：５の割合で重合された共重合体からなるアクリル樹脂を用意した。その他については実施例１と同様にしてグリ−ンシ−トを作製した。得られたグリ−ンシ−トのシ−ト強度は２８Ｋｇ／ｃｍ2、シ−ト伸び率は２０％であり満足できるものであった。これも実施例１と同様に生加工性、脱バインダ−性に問題がなく、良好な多層配線基板を得ることができた。
【００３１】
参考例１
セラミック粉末として窒化アルミニウム粉末を９５重量部と、その焼結助剤として酸化イットリウム（Ｙ2Ｏ3）粉末を５重量部とし、その他については実施例１と同様にしてグリ−ンシ−トを作製した。得られたグリ−ンシ−トのシ−ト強度は３２Ｋｇ／ｃｍ2、シ−ト伸び率は２０％であり満足できるものであった。また生加工性に関しても実施例１と同様に優れたものであった。
【００３２】
次にグリ−ンシ−トの脱バインダ−性を実施例１と同様に試験した。大気中２５０℃、１０時間の熱処理で脱バインダ−を行ったところ、残留炭素量は２．３重量％であった。さらに大気中５００℃、５時間の熱処理を行ったところ残留炭素量は０．０７重量％に低下していた。その際、窒化アルミニウム粉末の酸化の有無についてＸ線回折法により確認したところ、酸化により生成すると考えられるＡｌ2Ｏ3のピ−クは確認されず、窒化アルミニウム粉末は酸化されずに脱バインダ−が可能であることが確認された。次で大気中５００℃、５時間の熱処理を行った成形体を、窒素雰囲気中１７５０℃、５時間の熱処理で焼成を行った。こうして得られた窒化アルミニウム基板は、クラック、変色等のない満足できるものであった。
【００３３】
参考例２
バインダ−として実施例７と同じ平均分子量２．６×１０5、酸価４．８、ガラス転移温度（Ｔｇ）５０℃であるメタクリル酸ブチル系のアクリル樹脂を用意した。その他については参考例１と同様にしてグリ−ンシ−トを作製した。得られたグリ−ンシ−トのシ−ト強度は２３Ｋｇ／ｃｍ2、シ−ト伸び率は２１％であり満足できるものであった。また生加工性、脱バインダ−性に関しても参考例１と同様に優れたものであった。また、得られた基板も満足できるものであった。
【００３４】
比較例１
バインダ−として、平均分子量２．６×１０5、酸価０、ガラス転移温度（Ｔｇ）８０℃であるメタクリル酸エチル系のアクリル樹脂を用意した。その他については実施例１と同様にしてスラリ−を得た。得られたスラリ−はセラミック粉末の分散性が低く、ゲル化が確認された。次に実施例１と同様にしてグリ−ンシ−トを作製した。得られたグリ−ンシ−トのシ−ト強度は１０Ｋｇ／ｃｍ2と低く不十分なものであった。このように酸価が低いと、シ−ト成形性の良いスラリ−が得られず、グリ−ンシ−トを成形してもシ−ト強度が低いことがわかる。
【００３５】
比較例２
バインダ−として、平均分子量２．６×１０5、酸価９．６、ガラス転移温度（Ｔｇ）８０℃であるメタクリル酸エチル系のアクリル樹脂を用意した。その他については実施例１と同様にしてグリ−ンシ−トを作製した。得られたグリ−ンシ−トのシ−ト強度は６４Ｋｇ／ｃｍ2、シ−ト伸び率は２２％であり、実施例１の酸価が４．８のバインダ−に比べシ−ト強度が大きいものであった。しかし、実施例１と同様に脱バインダ−試験を行ったところ、大気中２５０℃、１０時間の熱処理での成形体の残留炭素量は３．５重量％であり、さらに続けて大気中５００℃、５時間の熱処理後の残留炭素量は０．１２重量％と実施例１に比べて高いものであった。また焼成して得られたガラスセラミック基板は、灰色の着色のあるものであった。また実施例１と同様にＡｇ系の配線を有する多層配線基板を作製したが、Ａｇ系の配線部の周囲にＡｇ系の配線材料の拡散による黄色の変色も確認された。このように、酸価が大きいと、シ−ト強度が向上するものの、脱バインダ−性及び配線層に問題を生じることがわかる。
【００３６】
比較例３
バインダ−として、平均分子量１．８×１０5、酸価４．８、ガラス転移温度（Ｔｇ）８０℃であるメタクリル酸エチル系のアクリル樹脂を用意した。その他については実施例１と同様にしてグリ−ンシ−トを作製した。得られたグリ−ンシ−トのシ−ト強度は１０Ｋｇ／ｃｍ2と低く不十分なものであった。このようにアクリル樹脂の平均分子量が２．０×１０5未満であると、シ−ト強度が低いことがわかる。
【００３７】
比較例４
バインダ−として、平均分子量２．６×１０5、酸価４．８、ガラス転移温度（Ｔｇ）１００℃であるメタクリル酸メチル系のアクリル樹脂を用意した。その他については実施例１と同様にしてグリ−ンシ−トを作製した。得られたグリ−ンシ−トのシ−ト強度は５５Ｋｇ／ｃｍ2と高いものであり、シ−ト伸び率は１７％であった。しかし、グリ−ンシ−トに、パンチングにより０．１２ｍｍφのビアホ−ルを０．２０ｍｍ間隔で形成したところ、ビアホ−ル間にクラックが発生した。
【００３８】
【発明の効果】
セラミック原料粉末とバインダ−とを含む低温焼成用セラミックグリーンシ−トにおいて、上記セラミック原料粉末が、ホウケイ酸系ガラスとアルミナ粉末との混合物であり、上記バインダ−が平均分子量２．０×１０５以上、酸価２．４以上７．２以下、ガラス転移温度（Ｔｇ）５０℃以上９０℃以下のアクリル樹脂を用いることにより、脱バインダ−性に優れ、また生加工時の取り扱い性、特に狭ピッチの微細ビアホ−ルの形成性に優れるものとすることができる。[0001]
The present invention relates to a low-temperature fired ceramic green sheet used for producing a low-temperature fired glass ceramic substrate. In particular, the present invention relates to a low-temperature fired ceramic green sheet suitably used for manufacturing a low-temperature fired glass ceramic wiring board or an aluminum nitride wiring board using a low melting point metal such as Ag, Cu, or Au as a wiring material.
[0002]
[Prior art]
Conventionally, as a substrate for mounting a semiconductor element such as an LSI, a wiring substrate using an alumina-based ceramic as an insulating material has been used. However, since the firing temperature of the alumina-based ceramic material is high, and a wiring material that can be fired simultaneously is W, Mo or the like having a high melting point, the conduction resistance is 10 to 20 mΩ / □ (mΩ / mm 2 ). Had a problem to become high. Therefore, a wiring board using a low-resistance wiring material such as Ag, Cu, or Au and glass or glass ceramic as a low-temperature fired insulating material that can be fired simultaneously with them has been used. In addition, in order to increase the heat dissipation from the semiconductor element, it is also required to increase the thermal conductivity of the substrate material, and recently, a wiring substrate using an aluminum nitride ceramic having a higher thermal conductivity than alumina is also used.
[0003]
By the way, in the case of such a wiring board, in particular, a wiring board having multilayer wiring, a ceramic green sheet containing ceramic powder and a binder is formed, and via-holes are formed on the ceramic green sheet as necessary. Manufacturing is performed by forming wiring, printing with a metallized paste, and laminating, debinding, and firing. Here, as a characteristic required for the ceramic green sheet, it is required that the binder removal property, that is, the thermal decomposition property of the binder is good and the handling property at the time of raw processing is excellent. Specific examples of handleability include moderate mechanical strength (sheet strength), moderate flexibility, adhesion to metallized paste, and the like. In particular, in recent years, high-density wiring has been demanded, and accordingly, there has been a great demand for finer via diameters and narrower pitches between vias, and ceramic green sheets need to meet these demands.
[0004]
Conventionally, PVB (polyvinyl butyral) has been widely used as a binder for forming the ceramic green sheet. However, although PVB was satisfactory as a binder for an alumina substrate using a wiring material such as W or Mo, the thermal decomposition temperature is relatively high, so that the wiring material is an easily oxidized material such as Cu. If the ceramic is an easily oxidized material such as aluminum nitride, or if the firing temperature is low such as glass ceramic, it is not suitable as a binder for the green sheet. Therefore, in such a case, an acrylic binder that thermally decomposes at a relatively low temperature has attracted attention. For example, JP-A-2-35790 proposes that a binder made of a methyl methacrylate polymer having an average molecular weight of 2.0 × 10 5 or more is effective as a binder for the above-mentioned ceramic green sheet. However, although the binder is simply a methyl methacrylate polymer, it has excellent binder removal properties and sheet strength. However, there is a demand for green sheet bioprocessability, especially the formation of fine via holes with a narrow pitch. Judging that it was not sufficiently satisfactory, the present inventors conducted intensive studies and reached the present invention.
[0005]
[Problems to be solved by the invention]
That is, the present invention is particularly used for the production of a low-temperature fired glass ceramic wiring board using a low melting point metal such as Ag, Cu, or Au, or a non-oxide ceramic wiring board made of an easily oxidized material such as aluminum nitride. With regard to the ceramic green sheet to be used, it has excellent binder removal property, handling property during raw processing, specifically moderate sheet strength, moderate flexibility, especially fine via holes with narrow pitch An object of the present invention is to provide a ceramic green sheet having excellent formability.
[0006]
The invention of claim 1 for solving the above-mentioned problems is that the ceramic raw material powder is a mixture of a borosilicate glass and an alumina powder in a ceramic green sheet for low-temperature firing containing a ceramic raw material powder and a binder. There, the binder - low temperature, wherein the average molecular weight 2.0 × 10 5 or more, an acid value less than 2.4 7.2 or less, a glass transition temperature (Tg) 50 ° C. or higher 90 ° C. or less of the acrylic resin The gist is a ceramic green sheet for firing .
[0007]
A second aspect of the present invention, the binder is summarized as the low-temperature fired ceramic green sheet according to claim 1 is an acrylic resin of ethyl methacrylate system.
[0008]
The invention according to claim 3 is the acrylic resin according to claim 2, wherein the acrylic resin is a homopolymer of ethyl methacrylate or a copolymer composed of ethyl methacrylate and one of methyl methacrylate and butyl methacrylate . The gist is a ceramic green sheet for low-temperature firing .
[0009]
The gist of the invention of claim 4 is the ceramic green sheet for low-temperature firing according to claim 2 , wherein the acrylic resin is a homopolymer of ethyl methacrylate .
[0010]
In the invention of claim 5, the binder is an acrylic resin having an average molecular weight of 2.6 × 10 5 or more, an acid value of 4.8 to 7.2, and a glass transition temperature (Tg) of 65 ° C. or more and 90 ° C. or less. The gist of the ceramic green sheet for low-temperature firing described in 2, 3, or 4 .
[0011]
The invention according to claim 6 further includes a ceramic for low-temperature firing according to any one of claims 2 to 5, further comprising dioctyl phthalate (DOP) and / or dibutyl phthalate (DBP) as a plasticizer. The gist is the green sheet.
The invention according to claim 7 is that the acrylic resin is a homopolymer of ethyl methacrylate or a copolymer comprising ethyl methacrylate and one of methyl methacrylate and butyl methacrylate, and the acrylic resin has an average molecular weight of 2 0.6 × 10 5 or more, acid value 4.8 or more and 7.2 or less, glass transition temperature (Tg) 65 ° C. or more and 90 ° C. or less, and further, as a plasticizer, dioctyl phthalate (DOP) and / or The gist of the ceramic green sheet for low-temperature firing according to claim 1 containing dibutyl phthalate (DBP).
The invention according to claim 8 is that the acrylic resin is a homopolymer of ethyl methacrylate or a copolymer composed of ethyl methacrylate and methyl methacrylate, and the acrylic resin has an average molecular weight of 2.6 × 10 5 or more, It has an acid value of 4.8 or more and 7.2 or less, a glass transition temperature (Tg) of 80 ° C. or more and 90 ° C. or less, and dioctyl phthalate (DOP) and / or dibutyl phthalate (DBP) as a plasticizer. The gist of the ceramic green sheet for low-temperature firing according to claim 1 is included.
In the invention of claim 9, the acrylic resin is a homopolymer of ethyl methacrylate, and the acrylic resin has an average molecular weight of 2.6 × 10 5 or more, an acid value of 4.8 to 7.2, and a glass transition temperature ( Tg) It is 80 degreeC or more and 90 degrees C or less, and also makes a summary the ceramic green sheet of Claim 1 which contains dioctyl phthalate (DOP) and / or dibutyl phthalate (DBP) as a plasticizer.
[0012]
Here, the average molecular weight of the binder is measured using a known analysis method such as gel permeation chromatography (GPC method). The average molecular weight of the binder is 2.0 × 10 5 or more because a sufficient sheet strength cannot be obtained if the binder is less than 2.0 × 10 5 . On the other hand, if the average molecular weight of the binder is excessively increased, for example, if it is 5.0 × 10 5 or more, the solubility in a solvent is lowered, and the reduction of the binder removal property is not preferable. The acid value of the binder represents the amount of COOH group (carboxyl group) contained in the unit weight of the acrylic binder, and since it can be easily measured, mg of KOH required to neutralize the binder-1 g A value expressed as a number. This acid value is 2.4 or more because if it is less than 2.4, the dispersed state of the ceramic powder is poor and the sheet strength of the molded green sheet is lowered. Also, the acid value is 7.2 or less because if the acid value is higher than this, the thermal decomposability of the binder deteriorates, and the fired ceramic contains a large amount of residual carbon, which causes color unevenness after firing. This is because the electrical insulation of the ceramic itself deteriorates.
[0013]
The glass transition point (Tg) of the binder is measured according to JIS K-7172. The glass transition point (Tg) of the binder is 50 ° C. or more and 90 ° C. or less for the following reason. When the glass transition point is less than 50 ° C., the sheet strength of the obtained green sheet is low, and the green sheet expands and contracts during raw processing, which is not preferable. On the other hand, if the glass transition point is higher than 90 ° C., the plasticity of the green sheet is lowered and the raw processability is inferior. That is, if a hole is drilled in the green sheet by punching, burrs and cracks are generated. Although the plasticity of the green sheet is slightly eliminated by further addition of a plasticizer, it is not preferable because the binder removal property is deteriorated.
[0014]
The ethyl methacrylate acrylic resin is obtained by using ethyl methacrylate monomer as a main starting material, substituted with a COOH group so that the functional group has the above acid value, and further polymerized to have the above average molecular weight. In the present invention it says.
[0015]
Before forming a green sheet, a slurry composed of ceramic powder, a binder, a solvent and the like is prepared. As a solvent used there, an alcohol solvent such as ethanol or butanol, Aromatic solvents such as toluene and xylene, and ketone solvents such as MEK (methyl ethyl ketone) can be used. These can be used in a mixed system of each single component or composite component, and it is determined by the compatibility with the required viscosity, volatility, added dispersant, plasticizer and the like. Dioctyl phthalate (DOP) and / or dibutyl phthalate (DBP) can be used as the plasticizer.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described as examples within the scope of the present invention, and examples outside the scope of the present invention as comparative examples.
[0017]
【Example】
Example 1
As ceramic raw material powder, borosilicate glass powder and alumina powder having SiO 2 , Al 2 O 3 and B 2 O 3 as main component compositions were prepared. Glass powder is a mixture of SiO 2 , Al 2 O 3 , B 2 O 3, etc., melted, rapidly cooled to cullet, further pulverized and classified, and 50% particle size (D 50 ) = 5 μm It was made as follows. On the other hand, as the alumina powder, a commercially available low-soda α-alumina powder having D 50 = 3 μm was prepared.
[0018]
As the binder, an ethyl methacrylate acrylic resin having an average molecular weight of 2.6 × 10 5 , an acid value of 4.8, and a glass transition temperature (Tg) of 80 ° C. was prepared. The average molecular weight was determined using the Tosoh GPC preparatory apparatus and three columns TSKgelIG3000, 2000, and 2000H8 under the following conditions. Temperature 40 ° C., flow rate 5 ml / min, eluent chloroform, detector RI-801.
[0019]
Next, the borosilicate glass powder and the alumina powder were weighed into an alumina pot so that the weight ratio was 5: 5 and the total amount was 1 kg. Further, 200 g of MEK as a solvent, 100 g of the acrylic resin, 50 g of DOP as a plasticizer, and 5 g of a dispersant were placed in the pot and mixed for 10 hours. Thus, a slurry for forming a green sheet was obtained. Using this slurry, a green sheet having a sheet thickness of 0.4 mm was obtained by the doctor blade method.
[0020]
The measurement of the sheet strength and elongation of the green sheet is as follows: the width of the parallel part is 4 mm, the distance between the gripping tools is 20 mm, the pulling speed is 10 mm / min, and other conditions conform to JIS K-7113. went. The sheet strength was 38 kg / cm 2 on average (n = 10), which was sufficient. The sheet elongation (tensile elongation at break) was 20%. These are shown in Table 1.
[0021]
[Table 1]
Next, the binder removal property of the green sheet was tested as follows. The produced green sheets were laminated so as to have a thickness of 5 mm, that is, 2 mm thick, and further cut into 50 mm squares to form a formed shape. The binder was removed by heat treatment at 250 ° C. for 10 hours in the atmosphere. When the amount of residual carbon in the molded body after debinding was analyzed, it was 2.5% by weight. Furthermore, when a heat treatment was performed at 500 ° C. for 5 hours in the atmosphere, the amount of residual carbon was reduced to 0.07% by weight. Next, the molded body that had been heat-treated at 250 ° C. for 10 hours in the atmosphere was fired by heat treatment at 950 ° C. for 3 hours in the air. The glass ceramic substrate thus obtained was satisfactory without cracks.
[0023]
A wiring board using a green sheet and an Ag-based wiring material was produced as follows. First, when 0.12 mmφ via holes were formed on the green sheet by punching at intervals of 0.20 mm, no cracks were generated between the via holes. Next, a via wiring portion was formed by filling the via hole with an Ag-based via paste. Next, a wiring pattern was printed and formed on the surface of the green sheet using an Ag-based wiring paste. As the solvent for the wiring paste, terpineol was used, but the shrinkage of the green sheet after printing and drying was good at less than 0.1%. Next, a plurality of green sheets on which wirings and the like were formed were laminated and thermocompression bonded at 50 ° C. to obtain a laminated body. The obtained laminate was good without deformation. Further, the laminate was subjected to binder removal by heat treatment at 250 ° C. for 10 hours in the atmosphere, and then baked by heat treatment at 950 ° C. for 3 hours in the air. Thus, a multilayer wiring board having Ag-based wiring was obtained. The obtained multilayer wiring board was satisfactory because of its low conduction resistance and no electrical open or short.
[0024]
Example 2
As a binder, an ethyl methacrylate acrylic resin having an average molecular weight of 2.6 × 10 5 , an acid value of 2.4, and a glass transition temperature (Tg) of 80 ° C. was prepared. The green sheet was prepared in the same manner as in Example 1 for the others. The obtained green sheet has a sheet strength of 21 kg / cm 2 , a sheet elongation of 19%, and the sheet strength is higher than that of the binder having an acid value of 4.8 in Example 1. Somewhat inferior. However, as in Example 1, the binder removal property and the raw workability were good. Further, the glass ceramic substrate obtained by firing was satisfactory without cracks. Furthermore, a multilayer wiring board having an Ag-based wiring was produced in the same manner as in Example 1, but a good one was obtained.
[0025]
Example 3
An ethyl methacrylate acrylic resin having an average molecular weight of 2.6 × 10 5 , an acid value of 7.2, and a glass transition temperature (Tg) of 80 ° C. was prepared as a binder. The green sheet was prepared in the same manner as in Example 1 for the others. The obtained green sheet has a sheet strength of 50 kg / cm 2 and a sheet elongation of 21%, and the sheet strength is higher than that of the binder having an acid value of 4.8 in Example 1. It was a big one. When the binder removal test was carried out in the same manner as in Example 1, the residual carbon content of the molded body after heat treatment at 250 ° C. in the atmosphere for 10 hours was 3.0% by weight, followed by 500 ° C. in the atmosphere at 5 ° C. The amount of residual carbon after the heat treatment over time was 0.08% by weight, which was slightly higher than that in Example 1. However, the glass ceramic substrate obtained by firing was satisfactory without discoloration or cracks. In addition, a multilayer wiring board having an Ag-based wiring was produced in the same manner as in Example 1, but a good one was obtained.
[0026]
Example 4
As a binder, an ethyl methacrylate acrylic resin having an average molecular weight of 2.0 × 10 5 , an acid value of 4.8, and a glass transition temperature (Tg) of 80 ° C. was prepared. The green sheet was prepared in the same manner as in Example 1 for the others. The obtained green sheet has a sheet strength of 23 Kg / cm 2 and a sheet elongation of 20%, which is higher than that of the binder of Example 1 having an average molecular weight of 2.6 × 10 5. The strength was low. However, the raw processability was not particularly problematic. Further, the binder removal property was as good as that of Example 1. The obtained glass ceramic substrate was satisfactory without cracks. Furthermore, a multilayer wiring board having an Ag-based wiring was produced in the same manner as in Example 1, but a good one was obtained.
[0027]
Example 5
An ethyl methacrylate acrylic resin having an average molecular weight of 3.0 × 10 5 , an acid value of 4.8, and a glass transition temperature (Tg) of 80 ° C. was prepared as a binder. The green sheet was prepared in the same manner as in Example 1 for the others. The obtained green sheet has a sheet strength of 42 Kg / cm 2 and a sheet elongation of 20%, which is higher than that of the binder of Example 1 having an average molecular weight of 2.6 × 10 5. The strength was high. In addition, the raw workability and binder removal properties were as good as those in Example 1. The obtained glass ceramic substrate was satisfactory without cracks. Furthermore, a multilayer wiring board having an Ag-based wiring was produced in the same manner as in Example 1, but a good one was obtained.
[0028]
Example 6
As a binder, a copolymer obtained by polymerizing ethyl methacrylate monomer and methyl methacrylate monomer having an average molecular weight of 2.6 × 10 5 acid value of 4.8 and a glass transition temperature (Tg) of 90 ° C. in a ratio of 5: 5. An acrylic resin made of The green sheet was prepared in the same manner as in Example 1 for the others. The sheet strength of the obtained green sheet was as high as 45 kg / cm 2 and the sheet elongation was 19%. Regarding the raw workability, when 0.12mmφ via holes were formed at 0.20mm intervals on the green sheet by punching, there were burrs on the via hole wall surface, but they should be removed easily. It was only possible. Other raw processability was not particularly problematic. The binder removal property was as good as in Example 1. The fired glass ceramic substrate was satisfactory without cracks. Further, a multilayer wiring board having an Ag-based wiring was produced in the same manner as in Example 1, but a good one was obtained.
[0029]
Example 7
A butyl methacrylate acrylic resin having an average molecular weight of 2.6 × 10 5 , an acid value of 4.8, and a glass transition temperature (Tg) of 50 ° C. was prepared as a binder. The green sheet was prepared in the same manner as in Example 1 for the others. The obtained green sheet had a sheet strength of 24 kg / cm 2 and a sheet elongation of 22%. Similarly to Example 1, there was no problem in raw workability and binder removal property, and a good multilayer wiring board could be obtained.
[0030]
Example 8
Copolymerization in which ethyl methacrylate monomer and butyl methacrylate monomer having an average molecular weight of 2.6 × 10 5 , an acid value of 4.8, and a glass transition temperature (Tg) of 65 ° C. were polymerized in a ratio of 5: 5. A combined acrylic resin was prepared. The green sheet was prepared in the same manner as in Example 1 for the others. The obtained green sheet was satisfactory, with a sheet strength of 28 kg / cm 2 and a sheet elongation of 20%. Similarly to Example 1, there was no problem in raw workability and binder removal property, and a good multilayer wiring board could be obtained.
[0031]
Reference example 1
95 parts by weight of aluminum nitride powder as the ceramic powder and 5 parts by weight of yttrium oxide (Y 2 O 3 ) powder as the sintering aid were used, and the green sheet was prepared in the same manner as in Example 1. did. The obtained green sheet was satisfactory, with a sheet strength of 32 Kg / cm 2 and a sheet elongation of 20%. The raw processability was also excellent as in Example 1.
[0032]
Next, the binder removal property of the green sheet was tested in the same manner as in Example 1. When the binder was removed by heat treatment at 250 ° C. for 10 hours in the atmosphere, the residual carbon content was 2.3% by weight. Furthermore, when a heat treatment was performed at 500 ° C. for 5 hours in the atmosphere, the amount of residual carbon was reduced to 0.07% by weight. At that time, the presence / absence of oxidation of the aluminum nitride powder was confirmed by X-ray diffraction. As a result, Al 2 O 3 peaks considered to be generated by oxidation were not confirmed, and the aluminum nitride powder was not oxidized and removed from the binder. Is confirmed to be possible. Next, the molded body that had been heat-treated at 500 ° C. for 5 hours in the atmosphere was fired by heat treatment at 1750 ° C. for 5 hours in a nitrogen atmosphere. The aluminum nitride substrate thus obtained was satisfactory without cracks or discoloration.
[0033]
Reference example 2
A butyl methacrylate acrylic resin having an average molecular weight of 2.6 × 10 5 as in Example 7, an acid value of 4.8, and a glass transition temperature (Tg) of 50 ° C. was prepared as a binder. Other than that, a green sheet was prepared in the same manner as in Reference Example 1 . The obtained green sheet was satisfactory, with a sheet strength of 23 kg / cm 2 and a sheet elongation of 21%. Further, the raw workability and binder removal property were also excellent as in Reference Example 1 . Moreover, the obtained substrate was satisfactory.
[0034]
Comparative Example 1
An ethyl methacrylate acrylic resin having an average molecular weight of 2.6 × 10 5 , an acid value of 0, and a glass transition temperature (Tg) of 80 ° C. was prepared as a binder. Other than that, a slurry was obtained in the same manner as in Example 1. The obtained slurry had low dispersibility of the ceramic powder, and gelation was confirmed. Next, a green sheet was prepared in the same manner as in Example 1. The sheet strength of the obtained green sheet was as low as 10 kg / cm 2 and was insufficient. Thus, it can be seen that when the acid value is low, a slurry with good sheet formability cannot be obtained, and even if the green sheet is molded, the sheet strength is low.
[0035]
Comparative Example 2
As a binder, an ethyl methacrylate acrylic resin having an average molecular weight of 2.6 × 10 5 , an acid value of 9.6, and a glass transition temperature (Tg) of 80 ° C. was prepared. The green sheet was prepared in the same manner as in Example 1 for the others. The obtained green sheet has a sheet strength of 64 kg / cm 2 , a sheet elongation of 22%, and the sheet strength is higher than that of the binder having an acid value of 4.8 in Example 1. It was a big one. However, when the binder removal test was performed in the same manner as in Example 1, the residual carbon content of the molded body after heat treatment at 250 ° C. for 10 hours in the atmosphere was 3.5% by weight, followed by 500 ° C. in the atmosphere. The amount of residual carbon after the heat treatment for 5 hours was 0.12% by weight, which was higher than that in Example 1. Moreover, the glass-ceramic board | substrate obtained by baking was a thing with gray coloring. In addition, a multilayer wiring board having an Ag-based wiring was produced in the same manner as in Example 1, but yellow discoloration due to diffusion of the Ag-based wiring material was also confirmed around the Ag-based wiring portion. Thus, it can be seen that when the acid value is large, the sheet strength is improved, but problems occur in the binder removal property and the wiring layer.
[0036]
Comparative Example 3
As a binder, an ethyl methacrylate acrylic resin having an average molecular weight of 1.8 × 10 5 , an acid value of 4.8, and a glass transition temperature (Tg) of 80 ° C. was prepared. The green sheet was prepared in the same manner as in Example 1 for the others. The sheet strength of the obtained green sheet was as low as 10 kg / cm 2 and was insufficient. Thus, it can be seen that the sheet strength is low when the average molecular weight of the acrylic resin is less than 2.0 × 10 5 .
[0037]
Comparative Example 4
A methyl methacrylate acrylic resin having an average molecular weight of 2.6 × 10 5 , an acid value of 4.8, and a glass transition temperature (Tg) of 100 ° C. was prepared as a binder. The green sheet was prepared in the same manner as in Example 1 for the others. The sheet strength of the obtained green sheet was as high as 55 kg / cm 2 and the sheet elongation was 17%. However, when 0.12 mmφ via holes were formed on the green sheet by punching at intervals of 0.20 mm, cracks were generated between the via holes.
[0038]
【The invention's effect】
In a ceramic green sheet for low-temperature firing including a ceramic raw material powder and a binder, the ceramic raw material powder is a mixture of borosilicate glass and alumina powder, and the binder has an average molecular weight of 2.0 × 10 5. As described above, by using an acrylic resin having an acid value of 2.4 or more and 7.2 or less and a glass transition temperature (Tg) of 50 ° C. or more and 90 ° C. or less, the binder removal property is excellent and the handling property during raw processing is particularly narrow. It is possible to make the pitch fine via holes excellent in formability.
Claims (9)
上記セラミック原料粉末が、ホウケイ酸系ガラスとアルミナ粉末との混合物であり、
上記バインダ−が平均分子量２．０×１０５以上、酸価２．４以上７．２以下、ガラス転移温度（Ｔｇ）５０℃以上９０℃以下のアクリル樹脂であることを特徴とする低温焼成用セラミックグリーンシ−ト。In a ceramic green sheet for low-temperature firing containing ceramic raw material powder and a binder,
The ceramic raw material powder is a mixture of borosilicate glass and alumina powder,
The binder is an acrylic resin having an average molecular weight of 2.0 × 10 5 or more, an acid value of 2.4 to 7.2, and a glass transition temperature (Tg) of 50 ° C. to 90 ° C. Ceramic green sheet.
該アクリル樹脂は平均分子量２．６×１０５以上、酸価４．８以上７．２以下、ガラス転移温度（Ｔｇ）６５℃以上９０℃以下であり、
更に、可塑剤として、ジオクチルフタレ−ト（ＤＯＰ）及び／又はジブチルフタレ−ト（ＤＢＰ）を含む請求項１に記載の低温焼成用セラミックグリーンシート。The acrylic resin is a homopolymer of ethyl methacrylate, or a copolymer consisting of ethyl methacrylate and one of methyl methacrylate and butyl methacrylate,
The acrylic resin has an average molecular weight of 2.6 × 10 5 or more, an acid value of 4.8 to 7.2, a glass transition temperature (Tg) of 65 ° C. or more and 90 ° C. or less,
The ceramic green sheet for low-temperature firing according to claim 1, further comprising dioctyl phthalate (DOP) and / or dibutyl phthalate (DBP) as a plasticizer.
該アクリル樹脂は平均分子量２．６×１０５以上、酸価４．８以上７．２以下、ガラス転移温度（Ｔｇ）８０℃以上９０℃以下であり、
更に、可塑剤として、ジオクチルフタレ−ト（ＤＯＰ）及び／又はジブチルフタレ−ト（ＤＢＰ）を含む請求項１に記載の低温焼成用セラミックグリーンシート。The acrylic resin is a homopolymer of ethyl methacrylate, or a copolymer composed of ethyl methacrylate and methyl methacrylate,
The acrylic resin has an average molecular weight 2.6 × 10 5 or more, an acid value 4.8 or 7.2 or less, glass transition temperature (Tg) at 80 ° C. or higher 90 ° C. or less,
The ceramic green sheet for low-temperature firing according to claim 1, further comprising dioctyl phthalate (DOP) and / or dibutyl phthalate (DBP) as a plasticizer.
該アクリル樹脂は平均分子量２．６×１０５以上、酸価４．８以上７．２以下、ガラス転移温度（Ｔｇ）８０℃以上９０℃以下であり、
更に、可塑剤として、ジオクチルフタレ−ト（ＤＯＰ）及び／又はジブチルフタレ−ト（ＤＢＰ）を含む請求項１に記載のセラミックグリーンシート。The acrylic resin is a homopolymer of ethyl methacrylate,
The acrylic resin has an average molecular weight 2.6 × 10 5 or more, an acid value 4.8 or 7.2 or less, glass transition temperature (Tg) at 80 ° C. or higher 90 ° C. or less,
The ceramic green sheet according to claim 1, further comprising dioctyl phthalate (DOP) and / or dibutyl phthalate (DBP) as a plasticizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32838995A JP3887032B2 (en) | 1995-11-21 | 1995-11-21 | Ceramic green sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32838995A JP3887032B2 (en) | 1995-11-21 | 1995-11-21 | Ceramic green sheet |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006265736A Division JP4037440B2 (en) | 2006-09-28 | 2006-09-28 | Manufacturing method of glass ceramic multilayer wiring board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09142941A JPH09142941A (en) | 1997-06-03 |
| JP3887032B2 true JP3887032B2 (en) | 2007-02-28 |
Family
ID=18209713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32838995A Expired - Lifetime JP3887032B2 (en) | 1995-11-21 | 1995-11-21 | Ceramic green sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3887032B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3771099B2 (en) | 1999-01-27 | 2006-04-26 | 松下電器産業株式会社 | Green sheet and manufacturing method thereof, manufacturing method of multilayer wiring board, manufacturing method of double-sided wiring board |
| JP4792167B2 (en) * | 2000-04-27 | 2011-10-12 | 京セラ株式会社 | Porcelain, manufacturing method thereof, and high-frequency wiring board |
| TW200615323A (en) | 2004-06-21 | 2006-05-16 | Sekisui Chemical Co Ltd | Binder resin composition, paste, and green sheet |
| JP4692116B2 (en) * | 2005-07-13 | 2011-06-01 | Ｔｄｋ株式会社 | CERAMIC COATING AND METHOD FOR PRODUCING LAMINATED ELECTRONIC COMPONENT |
| JP6631345B2 (en) * | 2016-03-17 | 2020-01-15 | 藤倉化成株式会社 | Resin composition for forming ceramic green sheet and material for forming ceramic green sheet |
-
1995
- 1995-11-21 JP JP32838995A patent/JP3887032B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09142941A (en) | 1997-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0423752A2 (en) | Dielectric compositions | |
| JPS6028296A (en) | Ceramic multilayer printed circuit board | |
| JPS6230638A (en) | Manufacture of glass-ceramic composite substrate | |
| JPS6245720B2 (en) | ||
| JPH0649594B2 (en) | Crystallizable low dielectric constant low dielectric loss composition | |
| EP0132740A2 (en) | Method of forming a dielectric substrate | |
| JP2007184247A (en) | Thick film conductor composition for multilayer electronic circuits and devices and processing technology thereof | |
| JP3887032B2 (en) | Ceramic green sheet | |
| JP4037440B2 (en) | Manufacturing method of glass ceramic multilayer wiring board | |
| JP4420136B2 (en) | Manufacturing method of ceramic molded body | |
| JP3019138B2 (en) | Silver-based conductive paste and multilayer ceramic circuit board using the same | |
| JPH08161931A (en) | Conductive paste, and conductive body and multilayer ceramic board using it | |
| CN100432020C (en) | Green sheet coating material, green sheet, method for producing green sheet, and method for producing electronic device | |
| JP3216260B2 (en) | Low temperature fired ceramic multilayer substrate and method of manufacturing the same | |
| JP2010126381A (en) | Green sheet | |
| EP0605421A1 (en) | Low dielectric constant substrate and method of making | |
| JP3518841B2 (en) | Substrate and method of manufacturing the same | |
| JP4731790B2 (en) | Manufacturing method of small chip for semiconductor mounting substrate | |
| EP0312824B1 (en) | Ceramic structure with copper based conductors and method for forming such a structure | |
| JPH02141458A (en) | Low-temperature calcined ceramic multilayered base plate and production thereof | |
| JP3607712B2 (en) | Green sheet for aluminum nitride ceramic substrate | |
| JP4449344B2 (en) | Oxide porcelain composition and ceramic multilayer substrate | |
| JP3426820B2 (en) | Copper metallized composition and method for producing glass ceramic wiring board using the same | |
| JP3488793B2 (en) | Manufacturing method of green sheet for ceramic substrate | |
| JPH11157945A (en) | Manufacturing method of ceramic electronic component and green sheet for dummy used therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20050419 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050426 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050623 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20050623 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050726 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050831 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060801 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060928 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20061102 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20061124 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091201 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091201 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101201 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101201 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111201 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111201 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121201 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121201 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131201 Year of fee payment: 7 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |