JP4839539B2 - Lead-free glass, glass frit, glass paste, electronic circuit components and electronic circuits - Google Patents
Lead-free glass, glass frit, glass paste, electronic circuit components and electronic circuits Download PDFInfo
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- JP4839539B2 JP4839539B2 JP2001222935A JP2001222935A JP4839539B2 JP 4839539 B2 JP4839539 B2 JP 4839539B2 JP 2001222935 A JP2001222935 A JP 2001222935A JP 2001222935 A JP2001222935 A JP 2001222935A JP 4839539 B2 JP4839539 B2 JP 4839539B2
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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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/06—Frit compositions, i.e. in a powdered or comminuted form containing halogen
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- 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
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
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- 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
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
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- 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
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
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- 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
- C03C3/14—Silica-free oxide glass compositions containing boron
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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
- C03C3/14—Silica-free oxide glass compositions containing boron
- C03C3/145—Silica-free oxide glass compositions containing boron containing aluminium or beryllium
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- 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
- C03C3/14—Silica-free oxide glass compositions containing boron
- C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
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- 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
- C03C3/14—Silica-free oxide glass compositions containing boron
- C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
- C03C3/155—Silica-free oxide glass compositions containing boron containing rare earths containing zirconium, titanium, tantalum or niobium
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- 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
- C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
-
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- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/16—Compositions for glass with special properties for dielectric glass
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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
- C03C4/00—Compositions for glass with special properties
- C03C4/20—Compositions for glass with special properties for chemical resistant glass
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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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
-
- 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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
- 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
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
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Description
【０００１】
【発明の属する技術分野】
本発明は、導体ペースト、抵抗ペースト等の電子回路部品用ペーストの結合材、電子回路のオーバーコート、等に好適な無鉛ガラス、ガラスフリットおよびガラスペーストに関する。
【０００２】
【従来の技術】
従来より、電子回路部品用ペーストの結合材、電子回路のオーバーコート用ペースト等には、鉛を含有するガラス粉末が広く使用されている。
【０００３】
【発明が解決しようとする課題】
近年、電子回路部品、電子回路、前記結合材、前記ペースト等に対して無鉛化が求められている。
本発明は、上記課題を解決できる無鉛ガラス、ガラスフリット、ガラスペースト、電子回路部品および電子回路の提供を目的とする。
【０００４】
本発明は、下記成分基準の質量百分率表示で、本質的に、
Ｂｉ２Ｏ３ ５６〜７５％、
Ｂ２Ｏ３ １９〜３０％、
ＳｎＯ２＋ＣｅＯ２ ０．２〜５％、
ＺｎＯ ０〜１５％、
ＳｉＯ２ ０〜２％、
Ａｌ２Ｏ３ ０〜１０％、
ＴｉＯ２ ０〜１０％、
ＺｒＯ２ ０〜５％、
Ｌｉ２Ｏ ０〜８％、
Ｎａ２Ｏ ０〜８％、
Ｋ２Ｏ ０〜８％、
ＭｇＯ ０〜１０％、
ＣａＯ ０〜１０％、
ＳｒＯ ０〜１０％、
ＢａＯ ０〜１０％、
ＣｕＯ ０〜５％、
Ｖ２Ｏ５ ０〜５％、
Ｆ ０〜５％、
からなる無鉛ガラスを提供する。
【０００５】
また、質量百分率表示で本質的に、前記無鉛ガラスの粉末６５〜１００％、無機顔料０〜３５％、セラミックフィラー０〜３５％からなるガラスフリットを提供する。
また、バインダ、溶剤および前記ガラスフリットを含有するガラスペーストを提供する。
また、前記無鉛ガラスを含有する電子回路素子を有する電子回路部品を提供する。
また、前記ガラスペーストを焼成して得られる電気絶縁層を有する電子回路を提供する。
【０００６】
【発明の実施の形態】
本発明の無鉛ガラス（以下本発明のガラスという。）は通常、粉砕され、質量平均粒径が典型的には１〜６μｍであるガラス粉末として使用される。
前記ガラス粉末は、導体ペースト、抵抗ペースト等の電子回路部品用ペーストの結合材として好適である。
【０００７】
また、前記ガラス粉末を、ＨＩＣ等の電子回路のオーバーコート用ペーストとして用いる場合、前記ガラス粉末はエチルセルロース等のバインダおよびα−テルピネオール等の有機溶剤と混練してガラスペーストとされる。
【０００８】
本発明のガラスの５０〜３５０℃における平均線膨張係数αは７０×１０−７〜９７×１０−７／℃であることが好ましい。また、本発明のガラスの軟化点ＴＳは４５０〜６００℃であることが好ましい。
【０００９】
次に、本発明のガラスの組成について、質量百分率表示を用いて以下に説明する。
Ｂｉ２Ｏ３は軟化点を低下させる成分であり必須である。５６％未満では軟化点が高くなりすぎる。好ましくは５８％以上である。８８％超では溶解時に失透するおそれがある。好ましくは８６％以下である。
【００１０】
Ｂ２Ｏ３は軟化点を低下させる、またはガラスを安定化させる成分であり、必須である。５％未満では軟化点が高くなりすぎる、または溶解時に失透するおそれがある。好ましくは７％以上である。３０％超では耐水性が低下する。好ましくは２８％以下である。
【００１１】
ＳｎＯ２およびＣｅＯ２ の少なくともいずれか一方は必須であり、ガラスを安定化させるために合計で５％までの範囲で含有してもよい。５％超では軟化点が高くなりすぎる。好ましくは合計で２％以下である。また、それらの含有量の合計は０．２％以上である。
【００１２】
ＺｎＯは必須ではないが軟化点を低下させるために２０％まで含有してもよい。２０％超では耐水性または耐酸性が低下する。好ましくは１５％以下である。
ＳｉＯ２は必須ではないが化学的耐久性を向上させるために１５％まで含有してもよい。１５％超では軟化点が高くなりすぎる。好ましくは１０％以下である。
【００１３】
Ａｌ２Ｏ３は必須ではないが化学的耐久性を向上させるために１０％まで含有してもよい。１０％超では軟化点が高くなりすぎる。好ましくは３％以下である。
ＴｉＯ２は必須ではないが化学的耐久性を向上させるために１０％まで含有してもよい。１０％超では軟化点が高くなりすぎる。好ましくは３％以下である。
ＺｒＯ２は必須ではないが化学的耐久性を向上させるために５％まで含有してもよい。５％超では軟化点が高くなりすぎる。好ましくは３％以下である。
【００１４】
Ｌｉ２Ｏ、Ｎａ２ＯおよびＫ２Ｏはいずれも必須ではないが、軟化点を低下させるためにそれぞれ８％まで含有してもよい。８％超ではαが大きくなりすぎる。好ましくはそれぞれ５％以下である。本発明のガラスを電子回路のオーバーコート用ペースト等の電気絶縁性が求められる用途に使用する場合、これらアルカリ金属酸化物は含有しないことが好ましい。
【００１５】
ＭｇＯ、ＣａＯ、ＳｒＯおよびＢａＯはいずれも必須ではないが、αを調整するためにそれぞれ１０％まで含有してもよい。１０％超では軟化点が高くなりすぎる。好ましくはそれぞれ５％以下である。
【００１６】
ＣｕＯおよびＶ２Ｏ５はいずれも必須ではないが、軟化点を低下させるために、または化学的耐久性を向上させるためにそれぞれ５％まで含有してもよい。５％超では溶解時に失透するおそれがある。好ましくはそれぞれ３％以下である。
Ｆは必須ではないが軟化点を低下させるために５％まで含有してもよい。５％超ではガラス溶解時に失透するおそれがある。好ましくは１％以下である。
【００１７】
本発明のガラスは本質的に上記成分からなるが、他の成分を本発明の目的を損なわない範囲で含有してもよい。該他の成分の含有量の合計は、好ましくは１０％以下、より好ましくは５％以下である。
なお、本発明のガラスは鉛を含有しない。また、カドミウムも含有しないことが好ましい。
【００１８】
次に、本発明のガラスフリットについて説明する。
本発明のガラスフリットを焼成して得られる焼成体の５０〜３５０℃における平均線膨張係数α’は５０×１０−７〜８７×１０−７／℃であることが好ましい。より好ましくはα’は８１×１０−７／℃以下である。なお、前記焼成する温度は典型的には５００〜６００℃である。
【００１９】
本発明のガラスフリットの軟化点ＴＳ’は４５０〜６００℃であることが好ましい。
本発明のガラスフリットは、ＴＳ’が４５０〜６００℃であり、かつ、α’が５０×１０−７〜８７×１０−７／℃であることがより好ましい。
【００２０】
次に、本発明のガラスフリットの組成について質量百分率表示を用いて説明する。
本発明のガラスの粉末は必須である。６５％未満では焼結性が低下する。好ましくは７０％以上である。
【００２１】
無機顔料は必須ではないが、焼成体を着色するために３５％まで含有してもよい。３５％超では焼結性が低下する。好ましくは３０％以下である。
無機顔料は所望の色に応じて適宜選択されるが、たとえば黒色無機顔料としては、鉄マンガン複酸化物、銅クロムマンガン複酸化物、コバルトクロム複酸化物、コバルト酸化物、クロム酸化物等を主成分とするものが例示される。
【００２２】
セラミックフィラーは必須ではないが、前記α’を低下させるために、または焼成体の強度を向上させるために３５％まで含有してもよい。３５％超では焼結性が低下する。好ましくは３０％以下である。
【００２３】
セラミックフィラーは、融点またはガラス転移点が７００℃以上である酸化物、ホウ化物、ケイ化物等の無機物の粉末であり、α−アルミナ、α−石英、ジルコン、コーディエライト、β−ユークリプタイト、フォルステライト、ムライト、ステアタイト、ホウ酸アルミニウムおよび石英ガラスからなる群から選ばれる１種以上の酸化物の粉末であることが好ましい。
【００２４】
本発明のガラスフリットは本質的に上記成分からなるが、他の成分を本発明の目的を損なわない範囲で含有してもよい。該他の成分の含有量の合計は好ましくは１０％以下、より好ましくは５％以下である。
【００２５】
本発明のガラスペーストは本発明のガラスフリットをバインダおよび溶剤と混練して作製される。バインダとしては、エチルセルロース、アクリル樹脂、スチレン樹脂、フェノール樹脂、ブチラール樹脂等が、溶剤としては、α−テルピネオール、ブチルカルビトールアセテート、フタル酸エステル等がそれぞれ例示される。なお、本発明の目的を損なわない範囲でバインダまたは溶剤以外の成分を含有してもよい。
【００２６】
本発明の電子回路部品は、本発明のガラスの粉末を結合材として含有する導体ペースト、抵抗ペースト等のペーストを塗布、焼成して得られる導体素子、抵抗素子等の電子回路素子を有し、当該電子回路素子は本発明のガラスを含有する。
【００２７】
本発明の電子回路は、本発明のガラスペーストを焼成して得られる電気絶縁層を有する電子回路であって、該電子回路としてＨＩＣが、前記電気絶縁層の用途としてＨＩＣのオーバーコートがそれぞれ例示される。
【００２８】
【実施例】
表１のＢｉ２Ｏ３からＦまでの欄に質量百分率表示で示すガラス組成となるように原料を調合、混合し、白金ルツボまたはセラミックス製ルツボを用いて１０００〜１３００℃で０．５〜２時間溶解して溶融ガラスとした。ガラスＡ〜Ｇは実施例である。比較例であるガラスＨ、Ｉはいずれも溶解時に失透した。
次に、前記溶融ガラスを急冷してフレーク状ガラスとし、これをボールミルで粉砕して、質量平均粒径が１〜６μｍのガラス粉末を得た。
【００２９】
ガラスＡ〜Ｇのα、ガラス転移点ＴＧ（単位：℃）、軟化点ＴＳ（単位：℃）、結晶化ピーク温度ＴＣ（単位：℃）を次のようにして測定した。結果を表１に示す。
α：ガラス粉末をドライプレス後６００℃に１５分間保持する焼成によって得られた焼成体について、５０〜３５０℃における平均線膨張係数を測定した。なお、ガラスＢについては測定しなかった。
ＴＧ、ＴＳ、ＴＣ：ガラス粉末について昇温速度１０℃／分の条件で示差熱分析により測定した。
【００３０】
次に、表２のガラス粉末から無機顔料までの欄に質量百分率表示で示す組成となるように調合、混合してガラスフリット１〜７を得た。
ガラス粉末としては、同表のガラスの欄に示すガラスの粉末を使用した。
【００３１】
セラミックフィラーとしては、ガラスフリット２、７については石英ガラス粉末を、ガラスフリット３についてはコーディエライト粉末を、ガラスフリット４についてはジルコン粉末を、ガラスフリット５についてはホウ酸アルミニウム粉末を、ガラスフリット６についてはα−アルミナ粉末をそれぞれ使用した。
無機顔料としては、ガラスフリット２、５、６については銅クロムマンガン複酸化物顔料を、ガラスフリット３についてはコバルト酸化物顔料を、ガラスフリット４、７についてはクロム酸化物顔料をそれぞれ使用した。
【００３２】
ガラスフリット１〜７を６００℃で１５分間焼成し、得られた焼成体のα’を測定した。また、ガラス転移点ＴＧ’（単位：℃）、軟化点ＴＳ’（単位：℃）、結晶化ピーク温度ＴＣ’（単位：℃）を昇温速度１０℃／分の条件で示差熱分析により測定した。結果を表２に示す。
【００３３】
【表１】
【表２】
【発明の効果】
本発明によれば、電子回路部品用ペーストの無鉛結合材、および電子回路のオーバーコート用無鉛ペーストが得られる。また、無鉛電子回路部品および無鉛電子回路素子を得ることが可能になる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a lead-free glass, a glass frit, and a glass paste suitable for a binder for electronic circuit component paste such as a conductor paste and a resistance paste, an overcoat for an electronic circuit, and the like.
[0002]
[Prior art]
Conventionally, lead-containing glass powder has been widely used in electronic circuit component paste binders, electronic circuit overcoat pastes, and the like.
[0003]
[Problems to be solved by the invention]
In recent years, there has been a demand for lead-free electronic circuit components, electronic circuits, the binder, the paste, and the like.
An object of the present invention is to provide a lead-free glass, a glass frit, a glass paste, an electronic circuit component, and an electronic circuit that can solve the above-described problems.
[0004]
The present invention is essentially a mass percentage display based on the following components:
Bi 2 O 3 56~ 75%,
B 2 O 3 19 ~30%,
SnO 2 + CeO 2 0 . 2-5%,
ZnO 0~ 15%,
SiO 2 0~ 2%,
Al 2 O 3 0-10%,
TiO 2 0-10%,
ZrO 2 0-5%,
Li 2 O 0-8%,
Na 2 O 0-8%,
K 2 O 0-8%,
MgO 0-10%,
CaO 0-10%,
SrO 0-10%,
BaO 0-10%,
CuO 0-5%,
V 2 O 5 0~5%,
F 0-5%,
A lead-free glass is provided.
[0005]
Moreover, the glass frit which consists essentially of the said lead-free glass powder 65-100%, inorganic pigment 0-35%, and ceramic filler 0-35% by the mass percentage display is provided.
Moreover, the glass paste containing a binder, a solvent, and the said glass frit is provided.
Moreover, the electronic circuit component which has an electronic circuit element containing the said lead-free glass is provided.
Moreover, the electronic circuit which has an electrical-insulation layer obtained by baking the said glass paste is provided.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The lead-free glass of the present invention (hereinafter referred to as the glass of the present invention) is usually pulverized and used as a glass powder having a mass average particle diameter of typically 1 to 6 μm.
The glass powder is suitable as a binder for electronic circuit component pastes such as conductor pastes and resistance pastes.
[0007]
When the glass powder is used as an overcoat paste for electronic circuits such as HIC, the glass powder is kneaded with a binder such as ethyl cellulose and an organic solvent such as α-terpineol to obtain a glass paste.
[0008]
The average linear expansion coefficient α of the glass of the present invention at 50 to 350 ° C. is preferably 70 × 10 −7 to 97 × 10 −7 / ° C. Further, the softening point T S of the glass of the present invention is preferably 450 to 600 ° C..
[0009]
Next, the composition of the glass of the present invention will be described below using mass percentage display.
Bi 2 O 3 is a component that lowers the softening point and is essential. If it is less than 56%, the softening point becomes too high. Preferably it is 58% or more. If it exceeds 88%, devitrification may occur during dissolution. Preferably it is 86% or less.
[0010]
B 2 O 3 is a component that lowers the softening point or stabilizes the glass and is essential. If it is less than 5%, the softening point may be too high, or devitrification may occur during dissolution. Preferably it is 7% or more. If it exceeds 30%, the water resistance decreases. Preferably it is 28% or less.
[0011]
At least one of SnO 2 and CeO 2 are essential, but may be incorporated in a range of up to 5% in total in order to stabilize the glass. If it exceeds 5%, the softening point becomes too high. Preferably, it is 2% or less in total. Further, the sum of their contents is Ru der 0.2% or more.
[0012]
ZnO is not essential, but may be contained up to 20% in order to lower the softening point. If it exceeds 20%, the water resistance or acid resistance will decrease. Preferably it is 15% or less.
SiO 2 is not essential, but may be contained up to 15% in order to improve chemical durability. If it exceeds 15%, the softening point becomes too high. Preferably it is 10% or less.
[0013]
Al 2 O 3 is not essential, but may be contained up to 10% in order to improve chemical durability. If it exceeds 10%, the softening point becomes too high. Preferably it is 3% or less.
TiO 2 is not essential, but may be contained up to 10% in order to improve chemical durability. If it exceeds 10%, the softening point becomes too high. Preferably it is 3% or less.
ZrO 2 is not essential, but may be contained up to 5% in order to improve chemical durability. If it exceeds 5%, the softening point becomes too high. Preferably it is 3% or less.
[0014]
Li 2 O, Na 2 O and K 2 O are not essential, but may be incorporated up to 8% in order to lower the softening point. If it exceeds 8%, α is too large. Preferably each is 5% or less. When the glass of the present invention is used for applications requiring electrical insulation properties such as an overcoat paste for electronic circuits, it is preferable not to contain these alkali metal oxides.
[0015]
MgO, CaO, SrO and BaO are not essential, but may be contained up to 10% in order to adjust α. If it exceeds 10%, the softening point becomes too high. Preferably each is 5% or less.
[0016]
Both CuO and V 2 O 5 are not essential, but may be incorporated up to 5% in order to lower the softening point or improve the chemical durability. If it exceeds 5%, devitrification may occur during dissolution. Preferably each is 3% or less.
F is not essential, but may be contained up to 5% in order to lower the softening point. If it exceeds 5%, devitrification may occur when the glass is melted. Preferably it is 1% or less.
[0017]
The glass of the present invention consists essentially of the above components, but other components may be contained within a range not impairing the object of the present invention. The total content of the other components is preferably 10% or less, more preferably 5% or less.
The glass of the present invention does not contain lead. Moreover, it is preferable not to contain cadmium.
[0018]
Next, the glass frit of the present invention will be described.
The average linear expansion coefficient α ′ at 50 to 350 ° C. of the fired product obtained by firing the glass frit of the present invention is preferably 50 × 10 −7 to 87 × 10 −7 / ° C. More preferably, α ′ is 81 × 10 −7 / ° C. or less. The firing temperature is typically 500 to 600 ° C.
[0019]
The glass frit of the present invention preferably has a softening point T S ′ of 450 to 600 ° C.
Glass frit of the present invention, T S 'is 450 to 600 ° C., and, alpha' and more preferably is 50 × 10 -7 ~87 × 10 -7 / ℃.
[0020]
Next, the composition of the glass frit of the present invention will be described using mass percentage display.
The glass powder of the present invention is essential. If it is less than 65%, the sinterability decreases. Preferably it is 70% or more.
[0021]
The inorganic pigment is not essential, but may be contained up to 35% in order to color the fired body. If it exceeds 35%, the sinterability deteriorates. Preferably it is 30% or less.
The inorganic pigment is appropriately selected according to the desired color. For example, black inorganic pigments include iron manganese complex oxide, copper chromium manganese complex oxide, cobalt chromium complex oxide, cobalt oxide, chromium oxide and the like. The main component is exemplified.
[0022]
The ceramic filler is not essential, but may be contained up to 35% in order to reduce the α ′ or improve the strength of the fired body. If it exceeds 35%, the sinterability deteriorates. Preferably it is 30% or less.
[0023]
Ceramic fillers are inorganic powders such as oxides, borides and silicides having a melting point or glass transition point of 700 ° C. or higher, α-alumina, α-quartz, zircon, cordierite, β-eucryptite. It is preferably a powder of one or more oxides selected from the group consisting of forsterite, mullite, steatite, aluminum borate and quartz glass.
[0024]
The glass frit of the present invention consists essentially of the above components, but other components may be contained within a range not impairing the object of the present invention. The total content of the other components is preferably 10% or less, more preferably 5% or less.
[0025]
The glass paste of the present invention is produced by kneading the glass frit of the present invention with a binder and a solvent. Examples of the binder include ethyl cellulose, acrylic resin, styrene resin, phenol resin, and butyral resin, and examples of the solvent include α-terpineol, butyl carbitol acetate, and phthalate ester. In addition, you may contain components other than a binder or a solvent in the range which does not impair the objective of this invention.
[0026]
The electronic circuit component of the present invention has a conductive paste containing the glass powder of the present invention as a binder, a paste such as a resistive paste, a conductive element obtained by baking, an electronic circuit element such as a resistive element, The electronic circuit element contains the glass of the present invention.
[0027]
The electronic circuit of the present invention is an electronic circuit having an electrical insulating layer obtained by firing the glass paste of the present invention, and the HIC is exemplified as the electronic circuit, and the HIC overcoat is exemplified as the use of the electrical insulating layer. Is done.
[0028]
【Example】
The raw materials were prepared and mixed so as to have a glass composition represented by mass percentage in the columns of Bi 2 O 3 to F in Table 1, and 0.5 to 2 at 1000 to 1300 ° C. using a platinum crucible or a ceramic crucible. It melt | dissolved for time and it was set as the molten glass. Glasses A to G are examples. Both the glasses H and I, which are comparative examples, were devitrified during melting.
Next, the molten glass was rapidly cooled to obtain a flaky glass, which was pulverized with a ball mill to obtain a glass powder having a mass average particle diameter of 1 to 6 μm.
[0029]
Α of glass A to G , glass transition point T G (unit: ° C.), softening point T S (unit: ° C.), and crystallization peak temperature T C (unit: ° C.) were measured as follows. The results are shown in Table 1.
α: The average linear expansion coefficient at 50 to 350 ° C. was measured for a fired body obtained by firing the glass powder at 600 ° C. for 15 minutes after dry pressing. Glass B was not measured.
T G , T S , T C : Glass powder was measured by differential thermal analysis at a temperature rising rate of 10 ° C./min.
[0030]
Next, it prepared and mixed so that it might become a composition shown by the mass percentage display in the column from the glass powder of Table 2 to an inorganic pigment, and obtained glass frits 1-7.
As the glass powder, the glass powder shown in the glass column of the same table was used.
[0031]
As the ceramic filler, quartz glass powder is used for glass frits 2 and 7, cordierite powder is used for glass frit 3, zircon powder is used for glass frit 4, aluminum borate powder is used for glass frit 5, and glass frit. For α, α-alumina powder was used.
As inorganic pigments, copper-chromium-manganese double oxide pigments were used for glass frits 2, 5, and 6, cobalt oxide pigments were used for glass frit 3, and chromium oxide pigments were used for glass frits 4 and 7, respectively.
[0032]
The glass frits 1 to 7 were fired at 600 ° C. for 15 minutes, and α ′ of the obtained fired body was measured. Further, the differential heat of glass transition point T G ′ (unit: ° C.), softening point T S ′ (unit: ° C.), and crystallization peak temperature T C ′ (unit: ° C.) was set at a rate of temperature increase of 10 ° C./min. It was measured by analysis. The results are shown in Table 2.
[0033]
[Table 1]
[Table 2]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the lead-free binder of the paste for electronic circuit components and the lead-free paste for the overcoat of an electronic circuit are obtained. It is also possible to obtain lead-free electronic circuit components and lead-free electronic circuit elements.
Claims (7)
Ｂｉ２Ｏ３ ５６〜７５％、
Ｂ２Ｏ３ １９〜３０％、
ＳｎＯ２＋ＣｅＯ２ ０．２〜５％、
ＺｎＯ ０〜１５％、
ＳｉＯ２ ０〜２％、
Ａｌ２Ｏ３ ０〜１０％、
ＴｉＯ２ ０〜１０％、
ＺｒＯ２ ０〜５％、
Ｌｉ２Ｏ ０〜８％、
Ｎａ２Ｏ ０〜８％、
Ｋ２Ｏ ０〜８％、
ＭｇＯ ０〜１０％、
ＣａＯ ０〜１０％、
ＳｒＯ ０〜１０％、
ＢａＯ ０〜１０％、
ＣｕＯ ０〜５％、
Ｖ２Ｏ５ ０〜５％、
Ｆ ０〜５％、
からなる無鉛ガラス。In the mass percentage display based on the following ingredients,
Bi 2 O 3 56~ 75%,
B 2 O 3 19 ~30%,
SnO 2 + CeO 2 0 . 2-5%,
ZnO 0~ 15%,
SiO 2 0~ 2%,
Al 2 O 3 0-10%,
TiO 2 0-10%,
ZrO 2 0-5%,
Li 2 O 0-8%,
Na 2 O 0-8%,
K 2 O 0-8%,
MgO 0-10%,
CaO 0-10%,
SrO 0-10%,
BaO 0-10%,
CuO 0-5%,
V 2 O 5 0~5%,
F 0-5%,
Lead-free glass consisting of
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| JP2001222935A JP4839539B2 (en) | 2001-07-24 | 2001-07-24 | Lead-free glass, glass frit, glass paste, electronic circuit components and electronic circuits |
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