JP4425386B2 - Low melting point glass and sealing composition - Google Patents
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- JP4425386B2 JP4425386B2 JP28535799A JP28535799A JP4425386B2 JP 4425386 B2 JP4425386 B2 JP 4425386B2 JP 28535799 A JP28535799 A JP 28535799A JP 28535799 A JP28535799 A JP 28535799A JP 4425386 B2 JP4425386 B2 JP 4425386B2
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- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
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- 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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
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Description
【０００１】
【発明の属する技術分野】
本発明は、各種電子部品やガラス部品等の封着、接着、被覆等に使用する封着材に好適であり、特にディスプレイパネル等の封着に好適な、鉛およびフッ素を含有しない、非晶質の低融点ガラスおよびこの低融点ガラスを含有する封着用組成物に関するものである。
【０００２】
【従来の技術】
電子部品やガラス部品等を封着、接着または被覆するためのガラス質の封着材には、封着等の後の気密性を維持するため、良好な化学的耐久性が求められるとともに、封着、接着または被覆等の作業を行う際、ガラス質の封着材が充分に軟化し流動する温度、すなわち封着温度まで加熱しなければならないため、たとえば、電子部品等を気密封着する場合、電子部品の回路や基板等に熱によるダメージを与えないように、封着材の封着温度は、より低温であることが望まれている。さらに、強固な接着力を持たせるためには、封着材と封着、接着または被覆される部品等を構成する材料との接着強度が強く、かつ、封着材とそれらの材料の熱膨張係数（α）ができるだけ近似していることが必要となる。
【０００３】
ところで、ガラスの熱膨張係数を小さくするということは、ガラスの原子レベルの結合を強くすることであり、結合が強くなれば、ガラスの封着温度が上がってしまい、前記の封着材の封着温度を低下させることと相反することとなる。
したがって、ガラス質の封着材により、各種電子部品等に使用される基板やディスプレイパネル等の熱膨張係数が小さい材料を低温で、封着、接着または被覆するのは困難とされてきた。
この困難を克服し、上記要求を満たすため、種々の低融点ガラス、すなわち融点が低く封着温度が低いガラス、あるいは、ガラス転移点（Ｔｇ）が低いガラスであれば封着温度が低いことから、低いガラス転移点を有するガラスが封着材として開発されてきた。特に、従来、ＰｂＯ−Ｂ2Ｏ3系の低融点ガラスを用いた封着材は、デイスプレイパネルの封着や、ブラウン管のパネルとファンネルとの封着に広く一般に使用されてきた。しかし、鉛は環境等に対し好ましくない影響を与える成分であるため、ＰｂＯ成分を含有するガラスの製造や廃棄物処理には、排水の水質検査や廃棄物の分別処理等が必要とされ、環境対策のために高いコストを要するので、鉛を含有しない封着材が望まれている。
【０００４】
鉛を含有しない低融点ガラスとして、特開昭５２−１５５１１号公報には、Ｐ2Ｏ5−ＺｎＯ−Ｎａ2Ｏ系のガラスが開示されているが、このガラスは、封着温度が４５０℃以上と高いうえ、化学的耐久性も充分とは言い難い。特開平９−２７８４８３号公報には、ビスマス系低融点ガラスが開示されているが、このガラスもガラス転移点（Ｔｇ）が３７０℃以上、封着温度が４３０℃以上と高いという問題がある。また、特開昭６１−１５１０４２号公報には、Ｐ2Ｏ5−ＲＯ−Ｒ2Ｏ−Ｆ2系の低融点ガラスが開示されている。このガラスは比較的低い封着温度を有しているものの、フッ素を含有しているため、プラズマディスプレイパネル等の電子部品の封着に使用した場合、揮発したフッ素やフッ化物が電極を痛めることがあり、製品の信頼性を考慮した場合好ましくない。
【０００５】
【発明が解決しようとする課題】
本発明は、前記従来技術の有する欠点を総合的に解決する目的でなされたものであり、低いガラス転移点（Ｔｇ）を有し、各種電子部品やガラス部品等の材料を低温で封着、接着および被覆することが可能であり、鉛およびフッ素を含有しない非晶質の低融点ガラス、ならびにこの低融点ガラスを含有し、低い封着温度を有し、熱膨張係数（α）を一段と小さい値に調整可能であり、各種電子部品の基板やディスプレイパネルのように熱膨張係数が比較的小さい材料を低温で封着、接着および被覆することが可能な封着用組成物を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明者は、前記目的を解決するために鋭意試験研究を重ねた結果、Ｐ2Ｏ5−ＳｎＯ系ガラスに、ＲＯ成分（ＲＯは、ＭｇＯ、ＣａＯ、ＳｒＯおよびＢａＯの１種または２種以上）を導入することにより、化学的耐久性を向上させ、さらに、Ｌｉ2ＯおよびＬｉ2Ｏ以外の１種または２種以上のＲ2Ｏ（アルカリ金属酸化物）成分を含有させることにより、化学的耐久性を損なわずに、良好な流動性を示し、強固な接着強度を有する低融点ガラスが得られることを見出し、また、上記低融点ガラスの粉末に、低熱膨張耐火性フィラーを添加することにより、封着温度の上昇を最小限に抑えて良好な流動性を維持しつつ、一段と小さい熱膨張係数（α）を有し、かつ、より強固な接着強度および機械的強度を有する封着用組成物が得られることを見出し、本発明をなすに至った。
【０００７】
すなわち、本発明にかかる請求項１に記載の発明は、酸化物基準のモル％で表して、Ｐ２Ｏ５ ４５％を超え６０％まで、
ＳｎＯ ２０〜２８．５％、
ＭｇＯ ０〜１０％、
ＣａＯ ０〜１０％、
ＳｒＯ ０〜１０％、
ＢａＯ ０〜１０％、
ただし、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの合計量０．５〜１０％、
Ｌｉ２Ｏ １０．５〜２５％、
Ｎａ２Ｏ ０〜１０％、
Ｋ２Ｏ ０〜１０％、
Ｒｂ２Ｏ ０〜１０％、
Ｃｓ２Ｏ ０〜１０％、
ただし、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２ＯおよびＣｓ２Ｏの１種または２種以上を含有し、
Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｒｂ２Ｏ＋Ｃｓ２Ｏの合計量 １５％を超え３０％まで、
ＳｉＯ２ ０〜 ５％、
Ｂ２Ｏ３ ０〜 ５％、
Ａｌ２Ｏ３ ０〜 ５％、
ＺｎＯ ０〜３．５％の組成からなることを特徴とする低融点ガラスである。
【０００８】
請求項２に記載の発明は、請求項１に記載の低融点ガラスにおいて、ガラス転移点（Ｔｇ）が２２０〜３００℃の範囲にあることを特徴とする。
【０００９】
本発明にかかる請求項３に記載の発明は、請求項１または２に記載の低融点ガラスを含有し、鉛およびフッ素を含有しないことを特徴とする封着用組成物である。
【００１０】
請求項４に記載の発明は、請求項３に記載の封着用組成物において、酸化物基準のモル％で表して、Ｐ２Ｏ５ ４５％を超え６０％まで、
ＳｎＯ ２０〜２８．５％、
ＭｇＯ ０〜１０％、
ＣａＯ ０〜１０％、
ＳｒＯ ０〜１０％、
ＢａＯ ０〜１０％、
ただし、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの合計量０．５〜１０％、
Ｌｉ２Ｏ １０．５〜２５％、
Ｎａ２Ｏ ０〜１０％、
Ｋ２Ｏ ０〜１０％、
Ｒｂ２Ｏ ０〜１０％、
Ｃｓ２Ｏ ０〜１０％、
ただし、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２ＯおよびＣｓ２Ｏの１種または２種以上を含有し、
Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｒｂ２Ｏ＋Ｃｓ２Ｏの合計量 １５％を超え３０％まで、
ＳｉＯ２ ０〜 ５％、
Ｂ２Ｏ３ ０〜 ５％、
Ａｌ２Ｏ３ ０〜 ５％、
ＺｎＯ ０〜３．５％の組成からなる低融点ガラスの粉末５０〜９０体積％と、鉛およびフッ素を含有しない低熱膨張耐火性フィラー１０〜５０体積％とからなることを特徴とする。
【００１１】
請求項５に記載の発明は、請求項４に記載の封着用組成物において、低熱膨張耐火性フィラーが、β−ユークリプタイト、β−スポジュメン、コージェライト、ムライト、石英、アルミナ、ジルコン、アルミノケイ酸リチウム系ガラスセラミックスおよびウィレマイト系セラミックスより選ばれる１種または２種以上であることを特徴とする。
【００１２】
【発明の実施の形態】
以下、本発明の実施の形態について説明する。
まず、本発明にかかる非晶質の低融点ガラスの組成を前記のように限定した理由を説明する。
Ｐ2Ｏ5成分は、ガラスを形成し、かつ、低融点で安定な非晶質ガラスを得るために、必要不可欠な成分であるが、その量が４５％以下であると、ガラスが高粘性となり封着温度が上昇し、さらに、ガラスの結晶化傾向が大きくなり封着時のガラスの流動性が悪くなる。また、その量が６０％を超えるとガラスの化学的耐久性の劣化が著しくなり実用性が乏しくなる。
【００１３】
ＳｎＯ成分は、Ｐ２Ｏ５成分とともに低融点で安定な非晶質ガラスを得るため、本発明の低融点ガラスに欠くことのできない成分であるが、その量が２０％未満であると、ガラスの熱膨張係数が大きくなりすぎるとともに化学的耐久性が劣化し、２８．５％を超えるとガラス転移点が上昇し、低温での封着に適さなくなる。
【００１４】
ＭｇＯ、ＣａＯ、ＳｒＯおよびＢａＯ成分は、いずれも、ガラスの粘性をあまり高めずに化学的耐久性を向上させる効果があるが、これら４成分の１種または２種以上の合計量が０．５％未満では、上記効果が得られず、また、合計量が１０％を超えると、ガラスの粘性が増大して低温での封着に適さなくなる。
【００１５】
Ｒ2Ｏ（アルカリ金属酸化物）成分は、ガラスの溶融性を高め、粘性を下げて、より低温での封着を可能にするとともに、接着強度を高める効果を有するため、本発明の低融点ガラスに欠くことのできない成分であり、さらに、２種以上のＲ2Ｏ成分を共存させることによって、上記効果はより顕著になり、かつ、ガラスの化学的耐久性をより良好に維持できるが、Ｒ2Ｏの合計量が、１５％以下ではこれらの効果が充分に得られず、また、合計量が３０％を超えると、ガラスの化学的耐久性が劣化し、熱膨張係数が大きくなりすぎる。
Ｒ2Ｏ成分のうちＬｉ2Ｏ成分は、上記効果に加えて、ガラスの化学的耐久性を損なわず、かつ、熱膨張係数をあまり大きくすることなく、ガラスを低融点にする効果が大きく、これらの効果を得るために１０．５％以上必要であるが、その量が２５％を超えると、ガラスの失透傾向が大きくなる。
【００１６】
上述した２種以上のＲ2Ｏ成分を共存させることによる効果を得るためには、Ｌｉ2Ｏ成分以外のＲ2Ｏ成分、すなわち、Ｎａ2Ｏ、Ｋ2Ｏ、Ｒｂ2ＯおよびＣｓ2Ｏ成分の１種または２種以上を含有させる必要があるが、Ｎａ2Ｏ、Ｋ2Ｏ、Ｒｂ2ＯおよびＣｓ2Ｏ成分の量が、それぞれ、１０％を超えると、ガラスの化学的耐久性が悪化し、熱膨張係数が大きくなりすぎる。
【００１７】
ＳｉＯ2およびＢ2Ｏ3成分は、いずれも、ガラスの熱膨張係数を低め、化学的耐久性を向上させるため任意に添加し得るが、それらの量がそれぞれ、５％を超えると、ガラスの粘性が高まり、低温での封着に適さなくなる。
【００１８】
ＺｎＯ成分は、熱膨張係数を低め、ガラスを安定にする効果があり、任意に添加し得るが、その量が３．５％を超えると、ガラスの粘性が高まり、低温での封着に適さなくなる。
【００１９】
以上の組成からなる非晶質の低融点ガラスは、化学的に安定であり、ガラス転移点（Ｔｇ）が２２０〜３００℃と低く、封着時に良好な流動性を示し、低温での封着が可能である。
また、ガラスであることから、当然のことながら、使用時の形態は特に制限がなく、板状、棒状等のバルク状または粉末状等、その用途に応じて種々の形状に成形、加工して使用することができ、電子部品やガラス部品等を低温で封着、接着および被覆する封着用組成物に好適に使用できる。
【００２０】
本発明の封着用組成物は、上記低融点ガラスを含有し、鉛およびフッ素を含有しないものである。本発明の低融点ガラスは、前述のように低いガラス転移点を有し、封着時に良好な流動性を示すことから、本発明の封着用組成物は、上記低融点ガラスのみからなるものであってもよい。
【００２１】
また、本発明の封着用組成物としては、上記低融点ガラスの粉末５０〜９０体積％と、鉛およびフッ素を含有しない低熱膨張耐火性フィラー１０〜５０体積％とからなるように、両者を混合したものでもよい。
上記低融点ガラスは、例えば、ディスプレイパネル用ガラス等と比べると、その熱膨張係数が大きいが、低熱膨張耐火性フィラーを混合することにより、低い封着温度を維持しつつ、熱膨張係数が一段と小さくなり、ディスプレイパネル用ガラス等と近似または同等の熱膨張係数を有する封着用組成物となる。さらに、低熱膨張耐火性フィラーを混合することにより、接着強度および機械的強度をより高める効果も得られる。
【００２２】
ここで使用する鉛およびフッ素を含有しない低熱膨張耐火性フィラーとしては、β−ユークリプタイト、β−スポジュメン、コージェライト、ムライト、石英、アルミナ、ジルコン、アルミノケイ酸リチウム系ガラスセラミックスおよびウィレマイト系セラミックスから選ばれる１種または２種以上が好ましい。
【００２３】
上記低熱膨張耐火性フィラーは、封着用組成物の熱膨張係数の調整および接着強度の向上等の目的で添加されるが、その量が１０体積％未満では、上記効果が充分でなく、また、５０体積％を超えると、封着等の作業時に封着用組成物が十分に流動しなくなり、充分な接着強度や、気密性を保てなくなる。特に優れた接着強度や、気密性を得るためには、低熱膨張耐火性フィラーの量を２０〜４０体積％とし、低融点ガラスの粉末の量を６０〜８０体積％とすることが好ましい。
【００２４】
低融点ガラスの粉末と低熱膨張耐火性フィラーとからなる封着用組成物は、秤量、調合したガラス原料を坩堝等の容器に入れて溶融し、溶融ガラスを、薄板状に成形して急冷したり、または、ローラーにより急冷してフレーク状にしたりした後、ボールミル等を用いて粉砕し、篩を通過させる等の方法により必要な粒度に分級して得られた粉末状の低融点ガラスと、必要に応じて篩等にかけた粉末状、粒状等の低熱膨張耐火性フィラーとを、所定の割合で混合して得られる。
【００２５】
【実施例】
以下、本発明にかかる低融点ガラスおよび封着用組成物の実施例を説明する。表１は、本発明の低融点ガラスの実施例（Ｎｏ．１〜Ｎｏ．３）の組成と、これらのガラスの熱膨張係数（α）およびガラス転移点（Ｔｇ）を示したものである。
【００２６】
表１において、熱膨張係数（α）は、上記各実施例で得られたガラスから作製した棒状試料（長さ５０ｍｍ×直径４ｍｍ）について、押棒式熱膨張測定装置を用いて、３０〜１８０℃の温度範囲における熱膨張係数（α）を測定した結果であり、ガラス転移点（Ｔｇ）は、示差熱分析計（ＤＴＡ）を用いて測定した結果である。
【００２７】
【表１】
【００２８】
なお、本発明の低融点ガラスは、酸化物、水酸化物等の通常のガラス原料を所定の組成割合で秤量、混合した後、白金坩堝または石英坩堝等を用いて、ガラスの溶融性の難易度に応じて、約７００℃〜１１００℃で、３０分〜２時間加熱して溶融し、攪拌、均質化した後、薄板状に成形することにより容易に得ることができ、前記実施例（Ｎｏ．１〜Ｎｏ．３）のガラスは、表１に示した組成割合となるように、原料を秤量、混合し、石英坩堝中で、９００℃で、１時間加熱して溶融し、攪拌、均質化した後、薄板状に成形して得た。
【００２９】
表２は、表１に示した実施例（Ｎｏ．１〜Ｎｏ．３）の低融点ガラスの粉末と、低熱膨張耐火性フィラーとを混合して得られた本発明の実施例（Ｎｏ．７〜Ｎｏ．９）の封着用組成物の組成と、これらの封着用組成物の熱膨張係数（α）および封着温度を示したものである。上記実施例（Ｎｏ．７〜Ｎｏ．９）の封着用組成物は、表１に示した実施例（Ｎｏ．１〜Ｎｏ．３）の低融点ガラスを、前記条件で溶融し、薄板状に成形し、急冷した後、ボールミルで粉砕し、３５０メッシュの篩を通過させて得た平均粒径５μｍの低融点ガラスの粉末と、２５０メッシュの篩を通過させた低熱膨張耐火性フィラーとを、表２中の体積割合となるように混合して得た。なお、実施例Ｎｏ．８およびＮｏ．９では、アルミノケイ酸リチウム系ガラスセラミックスとして株式会社オハラ製のクリアセラムＺ（株式会社オハラ商品名）を用いた。
【００３０】
表２において、熱膨張係数（α）は、上記各実施例の混合粉末を焼結し、加工して作製した棒状試料（長さ５０ｍｍ×直径４ｍｍ）について、押棒式熱膨張測定装置を用いて、３０〜１８０℃の温度範囲における熱膨張係数（α）を測定した結果であり、封着温度は、上記各実施例の混合粉末を焼結し、加工して作製した円板状の試料（高さ５ｍｍ×直径２０ｍｍ）を加熱して１０℃毎に昇温していき、直径が２３ｍｍ以上となった時の温度である。
【００３１】
【表２】
表２に示すとおり、本発明の実施例（Ｎｏ．７〜Ｎｏ．９）の封着用組成物は、３０〜１８０℃の温度範囲において、７９〜８６×１０−７／℃の範囲の熱膨張係数（α）を有しており、表１に示した低融点ガラスと比べて、一段と小さく、ディスプレイパネル用ガラスの熱膨張係数（約８０×１０−７／℃）に近似または同等の熱膨張係数を有している。また、封着温度も、４２０℃と低く、実施例（Ｎｏ．７〜Ｎｏ．９）の封着用組成物は、小さい熱膨張係数と、低い封着温度を有する。したがって、ディスプレイパネルのように小さい熱膨張係数を有し、かつ、低温で封着することが望ましい電子部品等の封着等に用いるのに好適である。
【００３３】
【発明の効果】
以上、説明したように本発明にかかる低融点ガラスは、特定組成範囲のＰ2Ｏ5−ＳｎＯ−ＲＯ−Ｒ2Ｏ系のガラスであるから、低いガラス転移点（Ｔｇ）を有し、電子部品等を低温で、封着、接着および被覆することができ、化学的に安定で接着強度および化学的耐久性が優れている。
また、フッ素成分を含有しないことから、電子部品等の封着等に使用しても、その品質に悪影響を及ぼすことがないため、電子部品等の信頼性を高めることができる。さらに、鉛を含有しないため環境対策等にコストを要しない利点がある。
また、本発明にかかる低融点ガラスの粉末と、低熱膨張耐火性フィラーとからなる封着用組成物は、上記効果に加えて、低い封着温度を維持しつつ、熱膨張係数（α）を一段と小さい値に調整することができるため、ディスプレイパネルのように小さい熱膨張係数を有する材料を４２０℃以下の低温で、電子部品の回路や基板等に熱によるダメージを与えることなく、封着、接着および被覆することが可能であり、さらに、接着強度および機械的強度をより高める効果も奏する。[0001]
BACKGROUND OF THE INVENTION
The present invention is suitable for sealing materials used for sealing, bonding, coating, etc. of various electronic parts and glass parts, and particularly suitable for sealing display panels, etc., and does not contain lead and fluorine, and is amorphous. High melting point glass and a sealing composition containing the low melting point glass.
[0002]
[Prior art]
A glassy sealing material for sealing, adhering or coating electronic parts, glass parts, etc. is required to have good chemical durability in order to maintain airtightness after sealing, etc. When performing operations such as attaching, bonding or coating, the glassy sealing material must be heated to the temperature at which the glassy sealing material sufficiently softens and flows, ie, the sealing temperature. The sealing temperature of the sealing material is desired to be lower so as not to damage the circuit of the electronic component, the substrate, etc. due to heat. Furthermore, in order to have a strong adhesive force, the adhesive material has a strong adhesive strength between the material constituting the part to be sealed, bonded or coated, and the thermal expansion of the sealing material and those materials. It is necessary that the coefficient (α) is as close as possible.
[0003]
By the way, reducing the thermal expansion coefficient of glass means strengthening the bonding at the atomic level of the glass. If the bonding becomes strong, the sealing temperature of the glass rises, and the sealing of the sealing material described above is increased. This is contrary to lowering the deposition temperature.
Therefore, it has been difficult to seal, bond or coat materials having a low coefficient of thermal expansion such as substrates and display panels used in various electronic components at low temperatures by vitreous sealing materials.
In order to overcome this difficulty and satisfy the above requirements, various low-melting glasses, that is, glasses having a low melting point and a low sealing temperature, or glasses having a low glass transition point (Tg) have a low sealing temperature. Glass having a low glass transition point has been developed as a sealing material. In particular, a sealing material using a PbO—B 2 O 3 low melting point glass has been widely used for sealing a display panel and a CRT panel and a funnel. However, since lead is a component that has an unfavorable impact on the environment, the manufacture of glass containing PbO components and waste treatment require water quality inspection of wastewater, waste separation treatment, etc. Since a high cost is required for the countermeasure, a sealing material containing no lead is desired.
[0004]
As a low melting point glass not containing lead, Japanese Patent Application Laid-Open No. 52-15511 discloses a P 2 O 5 —ZnO—Na 2 O-based glass. This glass has a sealing temperature of 450 ° C. In addition to the above, it is difficult to say that chemical durability is sufficient. Japanese Patent Laid-Open No. 9-278483 discloses a bismuth-based low-melting glass, but this glass also has a problem that the glass transition point (Tg) is 370 ° C. or higher and the sealing temperature is 430 ° C. or higher. JP-A-61-151042 discloses a P 2 O 5 —RO—R 2 O—F 2 low melting point glass. Although this glass has a relatively low sealing temperature, it contains fluorine, so when used to seal electronic components such as plasma display panels, volatilized fluorine and fluoride can damage the electrode. This is not preferable when considering the reliability of the product.
[0005]
[Problems to be solved by the invention]
The present invention was made for the purpose of comprehensively solving the disadvantages of the prior art, has a low glass transition point (Tg), and seals various electronic parts and glass parts at a low temperature. Amorphous low-melting glass that does not contain lead and fluorine, and contains this low-melting glass, has a low sealing temperature, and has a lower coefficient of thermal expansion (α). It is an object to provide a sealing composition that can be adjusted to a value and can seal, bond and coat a material having a relatively low coefficient of thermal expansion such as a substrate or display panel of various electronic components at a low temperature. And
[0006]
[Means for Solving the Problems]
As a result of intensive studies and studies to solve the above-mentioned object, the inventor of the present invention has added an RO component (RO is one or more of MgO, CaO, SrO and BaO) to P 2 O 5 —SnO glass. ) To improve chemical durability, and further to contain one or more R 2 O (alkali metal oxide) components other than Li 2 O and Li 2 O. Found that low melting point glass having good fluidity and strong adhesive strength can be obtained without impairing the mechanical durability, and adding a low thermal expansion refractory filler to the above low melting point glass powder Therefore, the sealing composition has a lower coefficient of thermal expansion (α) and a stronger adhesive strength and mechanical strength while maintaining a good fluidity while minimizing an increase in the sealing temperature. To get things Heading, the present invention has been accomplished.
[0007]
That is, the invention according to claim 1 according to the present invention is expressed in mol% of oxide basis and exceeds 45% of P 2 O 5 to 60%.
SnO 20~ 28.5%,
MgO 0-10%,
CaO 0-10%,
SrO 0-10%,
BaO 0-10%,
However, the total amount of MgO + CaO + SrO + BaO 0.5-10%,
Li 2 O 10.5-25%,
Na 2 O 0-10%,
K 2 O 0~10%,
Rb 2 O 0~10%,
Cs 2 O 0~10%,
However, it contains one or more of Na 2 O, K 2 O, Rb 2 O and Cs 2 O,
Total amount of Li 2 O + Na 2 O + K 2 O + Rb 2 O + Cs 2 O exceeding 15% to 30%,
SiO 2 0~ 5%,
B 2 O 3 0-5%,
Al 2 O 3 0-5%,
It is a low melting glass characterized by comprising a composition of ZnO 0 to 3.5 %.
[0008]
The invention described in claim 2 is the low-melting glass according to claim 1, wherein the glass transition point (Tg) is in the range of 220 to 300 ° C.
[0009]
Invention of Claim 3 concerning this invention is the sealing composition characterized by containing the low melting glass of Claim 1 or 2, and not containing lead and a fluorine.
[0010]
The invention according to claim 4 is the sealing composition according to claim 3, expressed in terms of mol% based on oxide, exceeding 45% of P 2 O 5 and up to 60%.
SnO 20~ 28.5%,
MgO 0-10%,
CaO 0-10%,
SrO 0-10%,
BaO 0-10%,
However, the total amount of MgO + CaO + SrO + BaO 0.5-10%,
Li 2 O 10.5-25%,
Na 2 O 0-10%,
K 2 O 0~10%,
Rb 2 O 0~10%,
Cs 2 O 0~10%,
However, it contains one or more of Na 2 O, K 2 O, Rb 2 O and Cs 2 O,
Total amount of Li 2 O + Na 2 O + K 2 O + Rb 2 O + Cs 2 O exceeding 15% to 30%,
SiO 2 0~ 5%,
B 2 O 3 0-5%,
Al 2 O 3 0-5%,
It is characterized by comprising 50 to 90% by volume of a low melting glass powder composed of ZnO 0 to 3.5 % and 10 to 50% by volume of a low thermal expansion refractory filler containing no lead and fluorine.
[0011]
The invention according to claim 5 is the sealing composition according to claim 4, wherein the low thermal expansion refractory filler is β-eucryptite, β-spodumene, cordierite, mullite, quartz, alumina, zircon, aluminosilicate. One type or two or more types selected from lithium acid glass ceramics and willemite ceramics.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below.
First, the reason why the composition of the amorphous low-melting glass according to the present invention is limited as described above will be described.
The P 2 O 5 component is an indispensable component for forming a glass and obtaining a stable amorphous glass having a low melting point. If the amount is 45% or less, the glass is highly viscous. As a result, the sealing temperature rises, the crystallization tendency of the glass increases, and the fluidity of the glass during sealing deteriorates. On the other hand, if the amount exceeds 60%, the chemical durability of the glass is significantly deteriorated and the practicality becomes poor.
[0013]
The SnO component is an indispensable component in the low melting point glass of the present invention in order to obtain a low melting point and stable amorphous glass together with the P 2 O 5 component, but if the amount is less than 20%, the glass When the thermal expansion coefficient is too large, the chemical durability deteriorates, and if it exceeds 28.5 %, the glass transition point rises and it becomes unsuitable for sealing at a low temperature.
[0014]
The MgO, CaO, SrO and BaO components all have the effect of improving the chemical durability without significantly increasing the viscosity of the glass, but the total amount of one or more of these four components is 0.5. If it is less than%, the above effect cannot be obtained, and if the total amount exceeds 10%, the viscosity of the glass increases and it becomes unsuitable for sealing at low temperatures.
[0015]
The R 2 O (alkali metal oxide) component increases the meltability of the glass, lowers the viscosity, enables sealing at a lower temperature, and has the effect of increasing the adhesive strength. It is an indispensable component of glass, and further, by coexisting two or more R 2 O components, the above effect becomes more remarkable, and the chemical durability of the glass can be maintained better. If the total amount of R 2 O is 15% or less, these effects cannot be sufficiently obtained, and if the total amount exceeds 30%, the chemical durability of the glass deteriorates and the thermal expansion coefficient becomes too large. .
Li 2 O component of the R 2 O component in addition to the above effects, without impairing the chemical durability of the glass, and, without too large a thermal expansion coefficient, a large effect of the glass low melting point, In order to obtain these effects, 10.5% or more is necessary, but if the amount exceeds 25%, the tendency of devitrification of the glass increases.
[0016]
In order to obtain the effect of the coexistence of two or more of R 2 O component described above, R 2 O component other than Li 2 O component, i.e., Na 2 O, K 2 O , Rb 2 O and Cs 2 O It is necessary to contain one or more components, but if the amount of Na 2 O, K 2 O, Rb 2 O and Cs 2 O components exceeds 10%, the chemical durability of the glass Deteriorates and the thermal expansion coefficient becomes too large.
[0017]
Both SiO 2 and B 2 O 3 components can be optionally added to lower the coefficient of thermal expansion of the glass and improve its chemical durability, but when their amount exceeds 5% respectively, Viscosity increases, making it unsuitable for sealing at low temperatures.
[0018]
The ZnO component has the effect of lowering the coefficient of thermal expansion and stabilizing the glass, and can be optionally added. However, when the amount exceeds 3.5 %, the viscosity of the glass increases and it is suitable for sealing at a low temperature. Disappear.
[0019]
An amorphous low-melting glass having the above composition is chemically stable, has a low glass transition point (Tg) of 220 to 300 ° C., exhibits good fluidity at the time of sealing, and is sealed at a low temperature. Is possible.
In addition, since it is glass, naturally, the form at the time of use is not particularly limited, and it is molded and processed into various shapes according to its use, such as a plate shape, a bulk shape such as a rod shape, or a powder shape. It can be used suitably for a sealing composition for sealing, adhering and coating electronic parts, glass parts and the like at low temperatures.
[0020]
The sealing composition of this invention contains the said low melting glass, and does not contain lead and a fluorine. Since the low melting glass of the present invention has a low glass transition point as described above and exhibits good fluidity at the time of sealing, the sealing composition of the present invention consists of only the above low melting glass. There may be.
[0021]
Moreover, as a sealing composition of this invention, both are mixed so that it may consist of 50-90 volume% of said low melting glass powder, and 10-50 volume% of low thermal expansion refractory fillers which do not contain lead and fluorine. You may have done.
The low-melting glass has a larger thermal expansion coefficient than, for example, display panel glass, etc., but by mixing a low thermal expansion refractory filler, the thermal expansion coefficient is further increased while maintaining a low sealing temperature. It becomes small and it becomes the sealing composition which has a thermal expansion coefficient approximate or equivalent to the glass for display panels. Furthermore, the effect of further increasing the adhesive strength and mechanical strength can be obtained by mixing the low thermal expansion refractory filler.
[0022]
The low thermal expansion refractory filler containing no lead and fluorine used here is from β-eucryptite, β-spodumene, cordierite, mullite, quartz, alumina, zircon, lithium aluminosilicate glass ceramics and willemite ceramics. One or two or more selected are preferable.
[0023]
The low thermal expansion refractory filler is added for the purpose of adjusting the thermal expansion coefficient of the sealing composition and improving the adhesive strength. However, if the amount is less than 10% by volume, the above effect is not sufficient. If it exceeds 50% by volume, the sealing composition will not sufficiently flow during the operation such as sealing, and sufficient adhesive strength and airtightness cannot be maintained. In order to obtain particularly excellent adhesive strength and airtightness, it is preferable that the amount of the low thermal expansion refractory filler is 20 to 40% by volume and the amount of the low melting point glass powder is 60 to 80% by volume.
[0024]
A sealing composition composed of a low melting glass powder and a low thermal expansion refractory filler is weighed and melted by putting the prepared glass raw material in a container such as a crucible, and the molten glass is molded into a thin plate and rapidly cooled. Or powdered low-melting glass obtained by rapidly cooling with a roller to form flakes, pulverizing with a ball mill, etc., and passing through a sieve, etc. And a low thermal expansion refractory filler such as powder or granules applied to a sieve or the like according to the above, and mixed at a predetermined ratio.
[0025]
【Example】
Examples of the low-melting glass and sealing composition according to the present invention will be described below. Table 1 shows the compositions of Examples (No. 1 to No. 3 ) of the low melting point glass of the present invention, the thermal expansion coefficient (α) and the glass transition point (Tg) of these glasses.
[0026]
In Table 1, the coefficient of thermal expansion (α) is 30 to 180 ° C. using a push rod type thermal expansion measuring device for a rod-like sample (length 50 mm × diameter 4 mm) produced from the glass obtained in each of the above examples. The glass transition point (Tg) is the result of measurement using a differential thermal analyzer (DTA).
[0027]
[Table 1]
[0028]
The low melting point glass of the present invention is obtained by weighing and mixing ordinary glass materials such as oxides and hydroxides at a predetermined composition ratio, and then using a platinum crucible or a quartz crucible, etc. Depending on the degree, it can be obtained easily by heating at about 700 ° C. to 1100 ° C. for 30 minutes to 2 hours to melt, stirring and homogenizing, and then forming into a thin plate shape. .1 to No. 3 ), the raw materials were weighed and mixed so as to have the composition ratio shown in Table 1, and melted by heating at 900 ° C. for 1 hour in a quartz crucible. Then, it was obtained by forming into a thin plate shape.
[0029]
Table 2 shows an example of the present invention (No. 7) obtained by mixing the low melting glass powder of the example (No. 1 to No. 3 ) shown in Table 1 and the low thermal expansion refractory filler. ～No. 9 and the composition of the sealing composition of) shows the thermal expansion coefficient (alpha) and sealing temperatures of these sealing compositions. Above examples (No.7~No. 9) sealing composition of the low melting point glass of the embodiment shown in Table 1 (No.1~No. 3), it melted at the conditions, a thin plate After forming, quenching, and pulverizing with a ball mill and passing through a 350 mesh sieve, a low melting glass powder having an average particle size of 5 μm, and a low thermal expansion refractory filler passing through a 250 mesh sieve, It was obtained by mixing so that the volume ratio in Table 2 was obtained. In addition, Example No. 8 and no. No. 9 used Clear Serum Z (trade name of OHARA Inc.) manufactured by OHARA INC. As lithium aluminosilicate glass ceramics.
[0030]
In Table 2, the coefficient of thermal expansion (α) is measured using a push rod type thermal expansion measuring device for a rod-shaped sample (length 50 mm × diameter 4 mm) produced by sintering and processing the mixed powder of each of the above examples. The thermal expansion coefficient (α) in the temperature range of 30 to 180 ° C. is measured, and the sealing temperature is a disk-shaped sample (sintered and processed by mixing the mixed powders of the above examples). This is the temperature at which the diameter is increased to 23 mm or more by increasing the temperature every 10 ° C. by heating (height 5 mm × diameter 20 mm).
[0031]
[Table 2]
As shown in Table 2, the sealing compositions of Examples (No. 7 to No. 9 ) of the present invention have a thermal expansion in the range of 79 to 86 × 10 −7 / ° C. in the temperature range of 30 to 180 ° C. It has a coefficient (α), is much smaller than the low melting point glass shown in Table 1, and has a thermal expansion coefficient close to or equivalent to the thermal expansion coefficient (about 80 × 10 −7 / ° C.) of display panel glass. Has a coefficient. Moreover, sealing temperature is also low as 420 degreeC, and the sealing composition of an Example (No. 7- No. 9 ) has a small thermal expansion coefficient and low sealing temperature. Therefore, it is suitable for use in sealing electronic parts or the like that have a small thermal expansion coefficient and are desirably sealed at a low temperature, such as a display panel.
[0033]
【The invention's effect】
As described above, since the low melting point glass according to the present invention is a P 2 O 5 —SnO—RO—R 2 O glass having a specific composition range, it has a low glass transition point (Tg) and is an electron. Parts, etc. can be sealed, adhered and coated at low temperatures, and are chemically stable and have excellent adhesive strength and chemical durability.
Moreover, since it does not contain a fluorine component, even if it is used for sealing electronic parts or the like, it does not adversely affect the quality of the electronic parts, so that the reliability of electronic parts and the like can be improved. Furthermore, since lead is not contained, there is an advantage that no cost is required for environmental measures.
In addition to the above effects, the sealing composition comprising the low melting glass powder according to the present invention and the low thermal expansion refractory filler further increases the thermal expansion coefficient (α) while maintaining a low sealing temperature. Because it can be adjusted to a small value, sealing and bonding of materials with a small coefficient of thermal expansion, such as display panels, at temperatures as low as 420 ° C and below, without causing heat damage to electronic component circuits and substrates In addition, it is possible to coat, and further, the adhesive strength and mechanical strength are further increased.
Claims (5)
ＳｎＯ ２０〜２８．５％、
ＭｇＯ ０〜１０％、
ＣａＯ ０〜１０％、
ＳｒＯ ０〜１０％、
ＢａＯ ０〜１０％、
ただし、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの合計量０．５〜１０％、
Ｌｉ２Ｏ １０．５〜２５％、
Ｎａ２Ｏ ０〜１０％、
Ｋ２Ｏ ０〜１０％、
Ｒｂ２Ｏ ０〜１０％、
Ｃｓ２Ｏ ０〜１０％、
ただし、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２ＯおよびＣｓ２Ｏの１種または２種以上を含有し、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｒｂ２Ｏ＋Ｃｓ２Ｏの合計量 １５％を超え３０％まで、
ＳｉＯ２ ０〜 ５％、
Ｂ２Ｏ３ ０〜 ５％、
Ａｌ２Ｏ３ ０〜 ５％、
ＺｎＯ ０〜３．５％の組成からなることを特徴とする低融点ガラス。Expressed in mol% on oxide basis, over 45% P 2 O 5 up to 60%,
SnO 20~ 28.5%,
MgO 0-10%,
CaO 0-10%,
SrO 0-10%,
BaO 0-10%,
However, the total amount of MgO + CaO + SrO + BaO 0.5-10%,
Li 2 O 10.5-25%,
Na 2 O 0-10%,
K 2 O 0~10%,
Rb 2 O 0~10%,
Cs 2 O 0~10%,
However, it contains one or more of Na 2 O, K 2 O, Rb 2 O and Cs 2 O, and the total amount of Li 2 O + Na 2 O + K 2 O + Rb 2 O + Cs 2 O exceeds 15% to 30%,
SiO 2 0~ 5%,
B 2 O 3 0-5%,
Al 2 O 3 0-5%,
A low-melting-point glass comprising a composition of ZnO 0 to 3.5 %.
ＳｎＯ ２０〜２８．５％、
ＭｇＯ ０〜１０％、
ＣａＯ ０〜１０％、
ＳｒＯ ０〜１０％、
ＢａＯ ０〜１０％、
ただし、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの合計量０．５〜１０％、
Ｌｉ２Ｏ １０．５〜２５％、
Ｎａ２Ｏ ０〜１０％、
Ｋ２Ｏ ０〜１０％、
Ｒｂ２Ｏ ０〜１０％、
Ｃｓ２Ｏ ０〜１０％、
ただし、Ｎａ２Ｏ、Ｋ２Ｏ、Ｒｂ２ＯおよびＣｓ２Ｏの１種または２種以上を含有し、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ＋Ｒｂ２Ｏ＋Ｃｓ２Ｏの合計量 １５％を超え３０％まで、
ＳｉＯ２ ０〜 ５％、
Ｂ２Ｏ３ ０〜 ５％、
Ａｌ２Ｏ３ ０〜 ５％、
ＺｎＯ ０〜３．５％の組成からなる低融点ガラスの粉末５０〜９０体積％と、鉛およびフッ素を含有しない低熱膨張耐火性フィラー１０〜５０体積％とからなることを特徴とする請求項３に記載の封着用組成物。Expressed in terms of mole percent on the oxide basis, up to 60% greater than the P 2 O 5 45%,
SnO 20~ 28.5%,
MgO 0-10%,
CaO 0-10%,
SrO 0-10%,
BaO 0-10%,
However, the total amount of MgO + CaO + SrO + BaO 0.5-10%,
Li 2 O 10.5-25%,
Na 2 O 0-10%,
K 2 O 0~10%,
Rb 2 O 0~10%,
Cs 2 O 0~10%,
However, it contains one or more of Na 2 O, K 2 O, Rb 2 O and Cs 2 O, and the total amount of Li 2 O + Na 2 O + K 2 O + Rb 2 O + Cs 2 O exceeds 15% to 30%,
SiO 2 0~ 5%,
B 2 O 3 0-5%,
Al 2 O 3 0-5%,
4. A low-melting-point glass powder having a composition of ZnO 0 to 3.5 % and 50 to 90% by volume, and low thermal expansion refractory filler containing no lead and fluorine, and 10 to 50% by volume. The sealing composition as described in 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28535799A JP4425386B2 (en) | 1999-10-06 | 1999-10-06 | Low melting point glass and sealing composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28535799A JP4425386B2 (en) | 1999-10-06 | 1999-10-06 | Low melting point glass and sealing composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001106549A JP2001106549A (en) | 2001-04-17 |
| JP4425386B2 true JP4425386B2 (en) | 2010-03-03 |
Family
ID=17690522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28535799A Expired - Fee Related JP4425386B2 (en) | 1999-10-06 | 1999-10-06 | Low melting point glass and sealing composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4425386B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924015A (en) * | 2016-06-24 | 2016-09-07 | 常州聚和新材料股份有限公司 | Glass material with low melting point and silver paste prepared from same |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3748533B2 (en) * | 2001-11-15 | 2006-02-22 | 旭テクノグラス株式会社 | Low melting glass and method for producing the same |
| GB0227843D0 (en) * | 2002-11-29 | 2003-01-08 | Johnson Matthey Plc | Glass composition |
| JPWO2006064733A1 (en) * | 2004-12-16 | 2008-06-12 | 松下電器産業株式会社 | Plasma display panel, manufacturing method thereof and sealing member |
| CN108423998B (en) * | 2018-05-31 | 2021-10-08 | 北京北旭电子材料有限公司 | Glass powder composition, glass sealing material, preparation method of glass sealing material and battery |
| JP6885433B2 (en) * | 2019-08-30 | 2021-06-16 | 昭和電工マテリアルズ株式会社 | Lead-free low melting point glass composition, low melting point glass composite material and low melting point glass paste containing the same, and sealing structures, electrical and electronic parts and painted parts using these. |
-
1999
- 1999-10-06 JP JP28535799A patent/JP4425386B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924015A (en) * | 2016-06-24 | 2016-09-07 | 常州聚和新材料股份有限公司 | Glass material with low melting point and silver paste prepared from same |
| CN105924015B (en) * | 2016-06-24 | 2019-02-19 | 常州聚和新材料股份有限公司 | A kind of frit of low melting point and silver paste prepared therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001106549A (en) | 2001-04-17 |
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