JP2005324969A - Low-melting point glass adhesive - Google Patents

Low-melting point glass adhesive Download PDF

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JP2005324969A
JP2005324969A JP2004138506A JP2004138506A JP2005324969A JP 2005324969 A JP2005324969 A JP 2005324969A JP 2004138506 A JP2004138506 A JP 2004138506A JP 2004138506 A JP2004138506 A JP 2004138506A JP 2005324969 A JP2005324969 A JP 2005324969A
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low
mol
glass
melting point
glass adhesive
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Takanobu Nojima
隆信 野島
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Toyo Glass Co Ltd
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Toyo Glass Co Ltd
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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
    • 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
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • 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
    • C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Glass Compositions (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To develop a low-melting point glass adhesive which contains no harmful substances such as lead and cadmium, and also is sufficiently low in melting point and high in weatherability. <P>SOLUTION: The low-melting point glass adhesive which contains no harmfull substances, and also is sufficiently low in melting point and high in weatherability, can be obtained by incorporating 60-90 mol% of TeO<SB>2</SB>, 5-20 mol% of R<SB>2</SB>O, (where, R is one or two or more kinds selected from among Li, Na and K), 0-25 mol% of R'O, (where R' is one or two or more kinds selected from the group consisting of Mg, Ca, Zn, Sr, and Ba), and 0-10 mol% of B<SB>2</SB>O<SB>3</SB>. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、電子材料、セラミックス、合金などの接着・封止に用いて好適な低融点ガラス接着剤に関する。   The present invention relates to a low-melting-point glass adhesive suitable for use in bonding / sealing electronic materials, ceramics, alloys, and the like.

低融点ガラス接着剤としては、一般に鉛やカドミウムを含むものが知られている（特許文献１、２等）。また、無鉛の低融点ガラスとして、りん酸塩系ガラス組成物が特許文献３に開示されている。さらにテルル酸化物をガラス構造の骨格とした低融点の無アルカリガラス組成物が特許文献４に開示されている。
特開平７−１２６０３７号公報 特開平１−１６０８４５号公報 特開平７−６９６７２号公報 特開平１０−２９８３４号公報 As low-melting glass adhesives, those containing lead or cadmium are generally known (Patent Documents 1, 2 and the like). Moreover, Patent Document 3 discloses a phosphate glass composition as a lead-free low-melting glass. Further, Patent Document 4 discloses a low-melting-point alkali-free glass composition having tellurium oxide as a glass structure skeleton.
Japanese Patent Application Laid-Open No. 7-126037 JP-A-1-160845 JP-A-7-69672 JP-A-10-29834

鉛、カドミウム等の有害物質を含む組成は安全性、環境保全の観点から問題があり、リサイクルの処理も難しく、好ましくない。無鉛の低融点ガラスにおいては、接着温度の指標となるガラス転移温度は３００℃以下になるが耐候性が非常に悪い。また、従来のテルル酸化物を主成分とする低融点ガラスは、転移温度（Ｔｇ）が３５７〜３７６℃程度であり、融点の低さが不十分である。   Compositions containing harmful substances such as lead and cadmium have problems from the viewpoint of safety and environmental protection, and are difficult to recycle, which is not preferable. In the lead-free low melting point glass, the glass transition temperature as an index of the adhesion temperature is 300 ° C. or less, but the weather resistance is very poor. Moreover, the low melting glass which has the conventional tellurium oxide as a main component has a transition temperature (Tg) of about 357 to 376 ° C., and the melting point is insufficient.

本発明は、鉛、カドミウム等の有害物質を含まず、しかも融点の十分に低く耐候性の高い低融点ガラス接着剤を開発することを課題としてなされたものである。   An object of the present invention is to develop a low-melting-point glass adhesive that does not contain harmful substances such as lead and cadmium and that has a sufficiently low melting point and high weather resistance.

（構成１）本発明は、ＴｅＯ２を６０〜９０mol％、Ｒ２Ｏを５〜２０mol％（但し、ＲはＬｉ、Ｎａ又はＫから選択される１種又は２種以上）、Ｒ’Ｏを０〜２５mol％（但し、Ｒ’はＭｇ、Ｃａ、Ｚｎ、Ｓｒ又はＢａから選択される１種又は２種以上）及びＢ２Ｏ３を０〜１０mol％含有することを特徴とする低融点ガラス接着剤である。 (Configuration 1) In the present invention, TeO 2 is 60 to 90 mol%, R 2 O is 5 to 20 mol% (where R is one or more selected from Li, Na or K), and R′O is Low-melting glass characterized by containing 0 to 25 mol% (where R ′ is one or more selected from Mg, Ca, Zn, Sr or Ba) and 0 to 10 mol% of B 2 O 3 It is an adhesive.

（構成２）また本発明は、前記構成１のガラス接着剤であって、ガラス転移温度が３００℃以下であることを特徴とする低融点ガラス接着剤である。 (Configuration 2) The present invention is also the glass adhesive of Configuration 1, wherein the glass transition temperature is 300 ° C. or lower.

（構成３）また本発明は、前記構成１又は２のガラス接着剤において、Ｐ２Ｏ５、ＴｉＯ２、ＳｉＯ２、ＷＯ３、Ａｌ２Ｏ３又はＺｒＯ２から選択される１種又は２種以上を含有することを特徴とする低融点ガラス接着剤である。 (Configuration 3) In the glass adhesive of Configuration 1 or 2, the present invention provides one or two selected from P 2 O 5 , TiO 2 , SiO 2 , WO 3 , Al 2 O 3, or ZrO 2. It is a low melting glass adhesive characterized by containing the above.

（構成４）また本発明は、前記構成１、２又は３のガラス接着剤において、低膨張の無機充填材を混合したことを特徴とする低融点ガラス接着剤である。 (Configuration 4) The present invention is also a low-melting glass adhesive characterized in that a low expansion inorganic filler is mixed in the glass adhesive of the above configuration 1, 2 or 3.

本発明の低融点ガラス接着剤は、鉛、カドミウム等の有害物質を含まないので安全であり、十分な低融点性能を有し、耐久性にも優れたものである。   The low-melting-point glass adhesive of the present invention is safe because it does not contain harmful substances such as lead and cadmium, has sufficient low-melting-point performance, and is excellent in durability.

ＴｅＯ２はガラス構造の骨格を成す網目形成酸化物であり、６０mol％未満だとガラスの形成が困難となる。９０mol％より多いと、化学耐久性が落ちる。Ｒ２Ｏは融点を下げる効果があるが、５mol％未満だと融点を下げる効果がない。２０mol％より多くなると、化学耐久性が劣化する。Ｒ’Ｏは化学耐久性を上げる効果があるが、２０mol％以上になると融点が高くなる。望ましくは５mol％〜２０mol％の範囲である。Ｂ２Ｏ３は化学耐久性を上げる効果があるが、１０mol％より多くなると融点が高くなる。 TeO 2 is a network-forming oxide that forms a skeleton having a glass structure. If the amount is less than 60 mol%, glass formation becomes difficult. When it is more than 90 mol%, chemical durability is lowered. R 2 O has an effect of lowering the melting point, but if it is less than 5 mol%, there is no effect of lowering the melting point. When it exceeds 20 mol%, chemical durability deteriorates. R′O has the effect of increasing chemical durability, but the melting point increases when it is 20 mol% or more. Desirably, it is in the range of 5 mol% to 20 mol%. B 2 O 3 has the effect of increasing the chemical durability, but if it exceeds 10 mol%, the melting point becomes high.

本発明のガラス接着剤は、Ｐ２Ｏ５、ＴｉＯ２、ＳｉＯ２、ＷＯ３、Ａｌ２Ｏ３又はＺｒＯ２から選択される１種又は２種以上を補助添加成分として含有させることができる。Ｐ２Ｏ５は融点を下げる効果がある。ただし入れすぎると化学耐久性は劣化する。ＴｉＯ２、ＳｉＯ２、ＷＯ３、Ａｌ２Ｏ３及びＺｒＯ２は化学耐久性の改善や膨張係数を調節するのに使用する。入れすぎると融点を高くする。これらの補助添加成分の添加量は合計で５mol％以下が望ましい。 The glass adhesive of the present invention can contain one or more selected from P 2 O 5 , TiO 2 , SiO 2 , WO 3 , Al 2 O 3 or ZrO 2 as an auxiliary additive component. P 2 O 5 has the effect of lowering the melting point. However, chemical durability deteriorates if it is added too much. TiO 2 , SiO 2 , WO 3 , Al 2 O 3 and ZrO 2 are used to improve chemical durability and adjust the expansion coefficient. If too much is added, the melting point is raised. The total amount of these auxiliary additive components is preferably 5 mol% or less.

上記組成の低融点ガラス接着剤は、ガラス転移温度（Ｔｇ）がほぼ全て３００℃以下となるが、設計した組成のものの転移温度（Ｔｇ）が万一３００℃を超えた場合でも、Ｒ２Ｏを増量する、Ｐ２Ｏ５を添加又は増量するなどの調整を行うことで、容易にガラス転移温度を３００℃以下とすることができる。転移温度(Ｔｇ)が３００℃以下であれば、接着温度を４００℃以下にすることができ、きわめて有用である。 The low melting point glass adhesive having the above composition has a glass transition temperature (Tg) of almost 300 ° C. or less. Even if the transition temperature (Tg) of the designed composition exceeds 300 ° C., R 2 O The glass transition temperature can be easily adjusted to 300 ° C. or less by adjusting the amount of P 2 O 5 or increasing the amount of P 2 O 5 . If the transition temperature (Tg) is 300 ° C. or lower, the adhesion temperature can be 400 ° C. or lower, which is extremely useful.

無機充填材とは、ガラス接着剤と接着する材料との熱膨張率を一致するよう添加する無機粉末材料であり、β-ユークリプトタイトや溶融石英、β-スポジュメン、コージエライトなどから一種および二種以上選ばれる。これら充填材は接着剤に１０〜７０体積％含有させることができる。 An inorganic filler is an inorganic powder material that is added so that the thermal expansion coefficient of the glass adhesive and the material to be bonded is the same. It is chosen above. These fillers can be contained in the adhesive in an amount of 10 to 70% by volume.

表１に示す組成の実施例１〜９を製造し、転移温度（Ｔｇ）、軟化点（Ｔｆ）及び耐水性を調べた。また、表２に示す無鉛のりん酸塩系低融点ガラス組成の比較例１〜９を製造し、同様に転移温度（Ｔｇ）、軟化点（Ｔｆ）及び耐水性を調べた。   Examples 1 to 9 having the compositions shown in Table 1 were produced, and the transition temperature (Tg), softening point (Tf) and water resistance were examined. Further, Comparative Examples 1 to 9 having lead-free phosphate-based low-melting glass compositions shown in Table 2 were produced, and the transition temperature (Tg), softening point (Tf) and water resistance were similarly examined.

Figure 2005324969
Figure 2005324969

Figure 2005324969
Figure 2005324969

転移温度（Ｔｇ）は示差熱分析法（ＤＴＡ）で測定した。すなわち、ガラス粉末を試験容器に入れ、装置を一定速度で昇温する。ＤＴＡ曲線におけるベースラインの接線及びガラス転移による吸熱領域の急峻な下降位置の接線との交点を調べ、Ｔｇとした。軟化点（Ｔｆ）は２番目の吸熱領域の温度である。
耐水性は、粒度１０６〜３００μｍｍのガラス粉末を９０℃の湯に１時間浸漬し、減少した重量を％で表示した。 The transition temperature (Tg) was measured by differential thermal analysis (DTA). That is, glass powder is put into a test container and the apparatus is heated at a constant speed. The intersection point between the tangent line of the base line in the DTA curve and the tangent line of the steeply descending position of the endothermic region due to the glass transition was examined and set as Tg. The softening point (Tf) is the temperature of the second endothermic region.
For water resistance, glass powder having a particle size of 106 to 300 μm was immersed in hot water at 90 ° C. for 1 hour, and the reduced weight was expressed in%.

実施例１〜９は、いずれも転移温度（Ｔｇ）が３００℃以下であり、無鉛のりん酸塩系ガラスとほぼ同等の優れた低融点ガラス接着剤であることが立証された。また、耐水性は概ね無鉛のりん酸塩系ガラスよりも優れたものであった。   Each of Examples 1 to 9 has a transition temperature (Tg) of 300 ° C. or lower, and was proved to be an excellent low-melting-point glass adhesive almost equivalent to a lead-free phosphate glass. In addition, the water resistance was generally superior to that of lead-free phosphate glass.

Claims (4)

ＴｅＯ２を６０〜９０mol％、Ｒ２Ｏを５〜２０mol％（但し、ＲはＬｉ、Ｎａ又はＫから選択される１種又は２種以上）、Ｒ’Ｏを０〜２５mol％（但し、Ｒ’はＭｇ、Ｃａ、Ｚｎ、Ｓｒ又はＢａから選択される１種又は２種以上）及びＢ２Ｏ３を０〜１０mol％含有することを特徴とする低融点ガラス接着剤。 TeO 2 is 60 to 90 mol%, R 2 O is 5 to 20 mol% (where R is one or more selected from Li, Na or K), and R′O is 0 to 25 mol% (where R 'Is one or more selected from Mg, Ca, Zn, Sr or Ba) and 0 to 10 mol% of B 2 O 3 . 請求項１のガラス接着剤であって、ガラス転移温度が３００℃以下であることを特徴とする低融点ガラス接着剤。   The glass adhesive according to claim 1, wherein the glass transition temperature is 300 ° C or lower. 請求項１又は２のガラス接着剤において、Ｐ２Ｏ５、ＴｉＯ２、ＳｉＯ２、ＷＯ３、Ａｌ２Ｏ３又はＺｒＯ２から選択される１種又は２種以上を含有することを特徴とする低融点ガラス接着剤。 The glass adhesive according to claim 1 or 2, comprising one or more selected from P 2 O 5 , TiO 2 , SiO 2 , WO 3 , Al 2 O 3 or ZrO 2. Low melting glass adhesive. 請求項１、２又は３のガラス接着剤において、低膨張の無機充填材を混合したことを特徴とする低融点ガラス接着剤。   The glass adhesive according to claim 1, 2, or 3, wherein a low-expansion inorganic filler is mixed.
JP2004138506A 2004-04-13 2004-05-07 Low-melting point glass adhesive Pending JP2005324969A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012235387A (en) * 2011-05-06 2012-11-29 Nippon Dempa Kogyo Co Ltd Manufacturing method of piezoelectric device
WO2015091374A1 (en) * 2013-12-19 2015-06-25 Osram Gmbh Glass composition, component, and method for producing a component

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012235387A (en) * 2011-05-06 2012-11-29 Nippon Dempa Kogyo Co Ltd Manufacturing method of piezoelectric device
WO2015091374A1 (en) * 2013-12-19 2015-06-25 Osram Gmbh Glass composition, component, and method for producing a component
JP2017502902A (en) * 2013-12-19 2017-01-26 オスラム ゲーエムベーハーＯＳＲＡＭ ＧｍｂＨ Glass composition, part, and method for manufacturing part
US10233114B2 (en) 2013-12-19 2019-03-19 Osram Gmbh Glass composition, component, and method for producing a component

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