JP4016507B2 - Bismuth glass composition - Google Patents

Bismuth glass composition Download PDF

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Publication number
JP4016507B2
JP4016507B2 JP29971298A JP29971298A JP4016507B2 JP 4016507 B2 JP4016507 B2 JP 4016507B2 JP 29971298 A JP29971298 A JP 29971298A JP 29971298 A JP29971298 A JP 29971298A JP 4016507 B2 JP4016507 B2 JP 4016507B2
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Prior art keywords
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JP2000128574A (en
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俊郎 山中
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Nippon Electric Glass Co Ltd
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Nippon Electric 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
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/14—Silica-free oxide glass compositions containing boron

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

Description

【０００１】
【産業上の利用分野】
本発明は電子部品の接着、封着、被覆等に好適なビスマス系ガラス組成物に関するものである。
【０００２】
【従来の技術】
従来から電子部品の接着や封着材料として、或いは電子部品に形成された電極や抵抗体の保護や絶縁のための被覆材料としてガラスが用いられている。
【０００３】
これらのガラスは、その用途に応じて化学耐久性、機械的強度、流動性、電気絶縁性等種々の特性が要求されるが、何れの用途にも共通する特性として、低温で焼成可能であることが挙げられる。それゆえ何れの用途においても、ガラスの融点を下げる効果が極めて大きいＰｂＯを多量に含有した低融点ガラスが広く用いられている。
【０００４】
【発明が解決しようとする課題】
しかしながら最近、ＰｂＯ含有ガラスに対して環境上の問題が指摘されており、ＰｂＯを含まないガラスに置換することが望まれている。またＰｂＯを多量に含有するガラスを用いて電気絶縁膜を形成すると、Ｐｂ2+イオンが拡散して電気絶縁性が低下し易いという不都合もある。
【０００５】
本発明は上記事情に鑑みなされたものであり、５００℃以下の温度で焼成が可能であるとともに、ＰｂＯを含有しないために環境問題が生じたり、電気絶縁性が低下する恐れがないガラス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】
本発明のビスマス系ガラスは、モル分率で、Ｂｉ2Ｏ3 ３０〜５０％、Ｂ2Ｏ3 １０〜４０％、ＢａＯ＋ＳｒＯ １〜１０％、ＺｎＯ ０〜３０％、ＣｕＯ ０〜２０％、Ｆｅ2Ｏ3 ０〜５％、ＳｉＯ2＋Ａｌ2Ｏ3 ０〜５％、Ｃｓ2Ｏ ０〜５％、Ｆ2 ０〜２０％の組成を有し、かつ、Ｂｉ2Ｏ3／（ＢａＯ＋ＳｒＯ）が３．５〜３５．０の関係を満たし、ガラス転移点が３６３℃以下であることを特徴とする。
【０００７】
【作用】
本発明のビスマス系ガラス組成物の組成を上記のように限定した理由は次のとおりである。
【０００８】
Ｂｉ2Ｏ3はガラスの軟化点を下げるための主要成分であり、その含有量は３０〜５０％、好ましくは３５〜４５％である。Ｂｉ2 Ｏ3 の含有量が３０％より少ないと転移点が高くなり過ぎて５００℃以下で焼成できなくなり、５０％より多いと安定なガラスが得られなくなる。
【０００９】
Ｂ2Ｏ3はガラス形成成分として必須であり、その含有量は１０〜４０％、好ましくは１８〜４０％である。Ｂ2Ｏ3の含有量が１０％より少ないとガラスが不安定になって失透し易くなる。また失透を生じない場合でも、焼成時に結晶の析出速度が極めて大きく、接着、封着、被覆等の作業に必要な流動性が得られない。一方、Ｂ2Ｏ3が４０％より多くなるとガラスの粘性が高くなり過ぎて５００℃以下の温度で焼成が困難になる。
【００１０】
ＢａＯとＳｒＯはガラスの安定化に大きな効果があり、これらを合量で１〜１０％、好ましくは２〜９％含有する。これらの成分の合量が１％より少ないとその効果がなく、一方、１０％より多くなると転移点が高くなる。なおＢａＯの含有量は０〜１０％、特に２〜９％であることが好ましく、またＳｒＯの含有量は０〜５％、特に０〜３％であることが好ましい。
【００１１】
また、Ｂｉ2Ｏ3と（ＢａＯ＋ＳｒＯ）の割合は、低融点でかつ安定なガラスを得る上で重要な要素であり、モル比でＢｉ2Ｏ3／（ＢａＯ＋ＳｒＯ）が３．５〜３５．０、好ましくは４．０〜１５．０、さらに好ましくは５．０〜１０．０である。Ｂｉ2Ｏ3／（ＢａＯ＋ＳｒＯ）が３．５未満になると、ガラスの転移点が高くなり、５００℃以下の温度で封着し難くなる。また３５．０を超えると結晶の析出速度が極めて大きくなって流動性が悪くなる。
【００１２】
ＺｎＯはガラスの安定化に大きな効果があり、その含有量は０〜３０％、好ましくは１５〜２５％である。その含有量が３０％より多くなるとガラスが結晶化しやすくなって流動性が悪くなる。
【００１３】
ＣｕＯはガラスを安定化するための成分であり、その含有量は０〜２０％、好ましくは０〜１５％である。ＣｕＯが２０％を超えると結晶の析出速度が極めて大きくなって流動性が悪くなる。
【００１４】
Ｆｅ2Ｏ3はガラスを安定化するための成分であり、その含有量は０〜５％、好ましくは０〜２％である。Ｆｅ2Ｏ3が５％を超えると逆にガラスが不安定になる。
【００１５】
ＳｉＯ2及びＡｌ2Ｏ3は何れもガラスをより安定化させるために含有させる成分であり、合量で５％以下、好ましくは２％以下使用する。これらの成分が上記範囲を超えるとガラスの粘性が高くなり過ぎて好ましくない。なおＳｉＯ2及びＡｌ2Ｏ3の含有量はそれぞれ０〜２％であることが好ましい。
【００１６】
Ｃｓ2ＯとＦ2はガラスをより低粘性化する成分であり、Ｃｓ2Ｏの含有量は０〜５％、好ましくは０〜３％、Ｆ2の含有量は０〜２０％、好ましくは０〜１０％である。これらの成分が上記範囲を超えるとガラスの化学耐久性が低下する。
【００１７】
なお上記成分以外にも、ガラスの粘性や熱膨張係数の調整のために、ＭｇＯ、Ｌａ2Ｏ3、ＴｉＯ2、ＺｒＯ2、Ｖ2Ｏ5、Ｎｂ2Ｏ5、ＭｏＯ3、ＷＯ3、ＴｅＯ2、Ａｇ2Ｏ、Ｎａ2Ｏ、Ｋ2Ｏ、Ｌｉ2Ｏ等を５％以下添加することが可能である。ただしＰｂＯ等、環境上問題のある成分の添加は避けるべきである。
【００１８】
以上の組成を有するガラスは、ガラス転移点が３６３℃以下であり、５００℃以下の温度で良好な流動性を示す非結晶性又は結晶性のガラスである。また３０〜３００℃における熱膨張係数が約１００×１０-7／℃以上であり、これと適合する高膨張材料を５００℃以下の温度で接着、封着又は被覆することが可能である。
【００１９】
一方、熱膨張係数の適合しない材料の接着、封着又は被覆を行う場合、対象物との熱膨張係数差を是正するために、耐火性フィラーを混合して使用することが可能である。また機械的強度が不足する場合も耐火性フィラーを混合して使用することができる。
【００２０】
耐火性フィラーを混合する場合、その混合割合はガラス４５〜９５体積％と耐火性フィラー５５〜５体積％であることが好ましい。両者の割合をこのように規定した理由は、耐火性フィラーが５体積％より少ないとその効果がなく、５５体積％より多くなると流動性が悪くなり易いためである。
【００２１】
耐火性フィラーとしては、チタン酸鉛系セラミック、ウイレマイト系セラミック、β−ユークリプタイト、コーディエライト、ジルコン系セラミック、酸化錫系セラミック、ムライト、石英ガラス、アルミナ等の粉末を単独、或は組み合わせて使用することが好ましい。
【００２２】
なお本発明のビスマス系ガラス組成物の具体的な用途としては、▲１▼蛍光表示管用パッケージの封着、絶縁層の形成、▲２▼プラズマディスプレイ−パネルの気密封着、絶縁層や誘電体層の形成、バリアリブの形成、▲３▼磁気ヘッド−コア同士又はコアとスライダーの封着、等が挙げられる。また使用時の形態は特に制限はなく、粉末状、板状、棒状等、その用途に応じて種々の形態に成形して使用することができる。
【００２３】
【実施例】
以下、本発明のビスマス系ガラス組成物を実施例に基づいて詳細に説明する。
【００２４】
表１〜３は、本発明の参考例（試料Ｎｏ．１）、実施例（試料Ｎｏ．２〜１２）及び比較例（試料Ｎｏ．１３〜１５）を示すものである。
【００２５】
【表１】

Figure 0004016507
【００２６】
【表２】
Figure 0004016507
【００２７】
【表３】
Figure 0004016507
Figure 0004016507
【００２８】
表の各試料は次のようにして調製した。
【００２９】
まず表に示したガラス組成となるように各種酸化物、炭酸塩等を調合したガラスバッチを準備し、これを白金坩堝に入れて９００〜１０００℃で２時間溶融した後、溶融ガラスをステンレス製の金型に流しだして成形した。得られた各試料について、ガラス転移点、３０〜３００℃における熱膨張係数、焼成温度、及び結晶性か非結晶性かを評価した。結果を表に示す。
【００３０】
表から明らかなように、本発明の実施例であるＮｏ．２〜１２の各試料は、ガラス転移点が３４５〜３６３℃、３０〜３００℃の温度範囲における熱膨張係数が１０９〜１１９×１０-7／℃であり、焼成温度が５００℃以下であった。また試料Ｎｏ．３、４、７、９、１２は結晶性であり、試料Ｎｏ．２、５、６、８、１０、１１は非結晶性であった。
【００３１】
一方、比較例であるＮｏ．１３の試料はＢａＯとＳｒＯの含有量が１％未満であり、またＢｉ2Ｏ3／（ＢａＯ＋ＳｒＯ）が３５．０を超える。このためガラスの結晶化傾向が著しく、その結果、流動性が悪く、５００℃以下で焼成できなかった。Ｎｏ．１４の試料はＢａＯとＳｒＯが合量で１０％を超え、Ｂｉ2Ｏ3／（ＢａＯ＋ＳｒＯ）が３．５未満であるために、またＮｏ．１５の試料はＢｉ2Ｏ3が３０％未満であるために、ガラス転移点が高くなり、何れも５００℃以下の温度で焼成できなかった。
【００３２】
なお転移点は示差熱分析装置（ＤＴＡ）により求めた。熱膨張係数は、成形したガラス体を直径４ｍｍ、長さ４０ｍｍの円柱状に研磨加工し、押し棒式熱膨張係数測定装置を用いて測定した。焼成温度は、次のようにして求めた。まずガラス体を粉砕してガラス粉末を得、ガラスの真比重に相当する重量のガラス粉末を金型を用いて外径２０ｍｍ、高さ約５ｍｍのボタン状に加圧成形した。次いでこのボタンを板ガラスの上に載せて電気炉に入れ、１０℃／分の速度で昇温し、種々の温度で１０分間保持した。このようにして得られたボタンの外径が２１〜２２ｍｍの範囲にある温度を焼成温度とした。また結晶性か非結晶性かの判定は、焼成温度で１０分間加熱された後の試料の外観を顕微鏡で観察し、結晶の析出状態から評価した。
【００３３】
【発明の効果】
以上のように本発明のビスマス系ガラス組成物は、ＰｂＯを含有しないため、環境問題を引き起こす心配がない。また５００℃以下の温度で焼成できるため、従来のＰｂＯを含有する低融点ガラスの代替材料として、電子部品の接着、封着、被覆等の用途に使用することが可能である。[0001]
[Industrial application fields]
The present invention relates to a bismuth-based glass composition suitable for bonding, sealing, coating, etc. of electronic components.
[0002]
[Prior art]
Conventionally, glass has been used as an adhesive or sealing material for electronic components, or as a coating material for protecting and insulating electrodes and resistors formed on electronic components.
[0003]
These glasses are required to have various properties such as chemical durability, mechanical strength, fluidity, and electrical insulation depending on the application, but can be fired at a low temperature as a property common to all applications. Can be mentioned. Therefore, in any application, low-melting glass containing a large amount of PbO that has an extremely large effect of lowering the melting point of glass is widely used.
[0004]
[Problems to be solved by the invention]
Recently, however, environmental problems have been pointed out with respect to PbO-containing glasses, and it is desired to replace them with glass containing no PbO. In addition, when an electrical insulating film is formed using glass containing a large amount of PbO, there is also a disadvantage that Pb 2+ ions diffuse and electrical insulation properties are liable to deteriorate.
[0005]
The present invention has been made in view of the above circumstances, and can be fired at a temperature of 500 ° C. or less, and does not contain PbO, so that there is no risk of environmental problems or a decrease in electrical insulation. The purpose is to provide.
[0006]
[Means for Solving the Problems]
The bismuth-based glass of the present invention has a mole fraction of Bi 2 O 3 30-50%, B 2 O 3 10-40%, BaO + SrO 1-10%, ZnO 0-30%, CuO 0-20%, Fe 2 O 3 0-5%, SiO 2 + Al 2 O 3 0-5%, Cs 2 O 0-5%, F 2 0-20%, and Bi 2 O 3 / (BaO + SrO) is 3.5-3 5 . It meets 0 relationships, and a glass transition point of 363 ° C. or less.
[0007]
[Action]
The reason for limiting the composition of the bismuth-based glass composition of the present invention as described above is as follows.
[0008]
Bi 2 O 3 is a main component for lowering the softening point of the glass, and its content is 30 to 50%, preferably 35 to 45%. If the content of Bi 2 O 3 is less than 30%, the transition point becomes too high to be fired at 500 ° C. or less, and if it exceeds 50%, stable glass cannot be obtained.
[0009]
B 2 O 3 is essential as a glass forming component, and its content is 10 to 40%, preferably 18 to 40%. If the content of B 2 O 3 is less than 10%, the glass becomes unstable and tends to devitrify. Even when devitrification does not occur, the crystal deposition rate is extremely high at the time of firing, and the fluidity necessary for operations such as adhesion, sealing, and coating cannot be obtained. On the other hand, if B 2 O 3 exceeds 40%, the viscosity of the glass becomes too high and firing at a temperature of 500 ° C. or less becomes difficult.
[0010]
BaO and SrO have a great effect on the stabilization of the glass, and contain them in a total amount of 1 to 10%, preferably 2 to 9%. If the total amount of these components is less than 1%, the effect is not obtained, while if it exceeds 10%, the transition point becomes high. The BaO content is preferably 0 to 10%, particularly preferably 2 to 9%, and the SrO content is preferably 0 to 5%, particularly preferably 0 to 3%.
[0011]
The ratio of Bi 2 O 3 and (BaO + SrO) is an important factor for obtaining a stable glass having a low melting point, and Bi 2 O 3 / (BaO + SrO) is 3.5 to 35.0 in terms of molar ratio. Preferably, it is 4.0-15.0, More preferably, it is 5.0-10.0. When Bi 2 O 3 / (BaO + SrO) is less than 3.5, the glass transition point becomes high and sealing becomes difficult at a temperature of 500 ° C. or lower. On the other hand, if it exceeds 35.0, the deposition rate of crystals becomes extremely high and the fluidity becomes poor.
[0012]
ZnO has a great effect on glass stabilization, and its content is 0 to 30%, preferably 15 to 25%. When the content exceeds 30%, the glass is easily crystallized and the fluidity is deteriorated.
[0013]
CuO is a component for stabilizing the glass, and its content is 0 to 20%, preferably 0 to 15%. When CuO exceeds 20%, the precipitation rate of crystals becomes extremely high and the fluidity becomes poor.
[0014]
Fe 2 O 3 is a component for stabilizing the glass, and its content is 0 to 5%, preferably 0 to 2%. If Fe 2 O 3 exceeds 5%, the glass becomes unstable.
[0015]
Both SiO 2 and Al 2 O 3 are components that are added to stabilize the glass, and the total amount is 5% or less, preferably 2% or less. If these components exceed the above range, the viscosity of the glass becomes too high, which is not preferable. Note it is preferable that the content of SiO 2 and Al 2 O 3 is 0-2%, respectively.
[0016]
Cs 2 O and F 2 are components that lower the viscosity of the glass. The content of Cs 2 O is 0 to 5%, preferably 0 to 3%, and the content of F 2 is 0 to 20%, preferably 0 to 10%. When these components exceed the above range, the chemical durability of the glass is lowered.
[0017]
In addition to the above components, MgO, La 2 O 3 , TiO 2 , ZrO 2 , V 2 O 5 , Nb 2 O 5 , MoO 3 , WO 3 , TeO are used to adjust the viscosity and thermal expansion coefficient of the glass. 2 , Ag 2 O, Na 2 O, K 2 O, Li 2 O or the like can be added at 5% or less. However, addition of environmentally problematic components such as PbO should be avoided.
[0018]
The glass having the above composition is a non-crystalline or crystalline glass having a glass transition point of 363 ° C. or lower and good fluidity at a temperature of 500 ° C. or lower. Further, the coefficient of thermal expansion at 30 to 300 ° C. is about 100 × 10 −7 / ° C. or higher, and a high expansion material compatible therewith can be bonded, sealed or coated at a temperature of 500 ° C. or lower.
[0019]
On the other hand, when bonding, sealing, or coating a material that does not match the thermal expansion coefficient, it is possible to mix and use a refractory filler in order to correct the difference in thermal expansion coefficient from the object. Also, when the mechanical strength is insufficient, a refractory filler can be mixed and used.
[0020]
When mixing a refractory filler, the mixing ratio is preferably 45 to 95% by volume of glass and 55 to 5% by volume of refractory filler. The reason for defining the ratio of the two in this way is that if the refractory filler is less than 5% by volume, there is no effect, and if it exceeds 55% by volume, the fluidity tends to deteriorate.
[0021]
As the refractory filler, powders of lead titanate ceramics, willemite ceramics, β-eucryptite, cordierite, zircon ceramics, tin oxide ceramics, mullite, quartz glass, alumina, etc., alone or in combination Are preferably used.
[0022]
Specific uses of the bismuth-based glass composition of the present invention include (1) sealing of fluorescent display tube packages, formation of insulating layers, (2) hermetic sealing of plasma display panels, insulating layers and dielectrics. Examples include formation of a layer, formation of a barrier rib, and (3) sealing of a magnetic head-core or between a core and a slider. Moreover, the form at the time of use does not have a restriction | limiting in particular, According to the use, it can shape | mold and use it in various forms, such as powder form, plate shape, and rod shape.
[0023]
【Example】
Hereinafter, the bismuth-based glass composition of the present invention will be described in detail based on examples.
[0024]
Tables 1 to 3 show reference examples (sample No. 1), examples (sample Nos. 2 to 12) and comparative examples (sample Nos. 13 to 15) of the present invention.
[0025]
[Table 1]
Figure 0004016507
[0026]
[Table 2]
Figure 0004016507
[0027]
[Table 3]
Figure 0004016507
Figure 0004016507
[0028]
Each sample in the table was prepared as follows.
[0029]
First, a glass batch prepared by preparing various oxides, carbonates and the like so as to have the glass composition shown in the table was prepared, put in a platinum crucible and melted at 900 to 1000 ° C. for 2 hours, and then the molten glass was made of stainless steel. The mold was poured into a mold. About each obtained sample, the glass transition point, the thermal expansion coefficient in 30-300 degreeC, a calcination temperature, and crystalline or non-crystalline were evaluated. The results are shown in the table.
[0030]
As is apparent from the table, No. 1 as an example of the present invention. 2-12 of each sample, the glass transition point three hundred forty-five to three 6 3 ° C., the thermal expansion coefficient in a temperature range of 30 to 300 ° C. is 109~119 × 10 -7 / ℃, the firing temperature is 500 ° C. or less there were. Sample no . 3 , 4, 7, 9, and 12 are crystalline. 2, 5, 6, 8, 10, and 11 were non-crystalline.
[0031]
On the other hand, No. which is a comparative example. Sample No. 13 has a BaO and SrO content of less than 1%, and Bi 2 O 3 / (BaO + SrO) exceeds 35.0. For this reason, the crystallization tendency of the glass was remarkable, and as a result, the fluidity was poor, and the glass could not be fired at 500 ° C. or lower. No. In the sample No. 14, the total amount of BaO and SrO exceeds 10%, and Bi 2 O 3 / (BaO + SrO) is less than 3.5. Since the sample No. 15 had Bi 2 O 3 of less than 30%, the glass transition point was high and none of the samples could be fired at a temperature of 500 ° C. or lower.
[0032]
The transition point was determined by a differential thermal analyzer (DTA). The thermal expansion coefficient was measured using a push rod type thermal expansion coefficient measuring device after polishing the molded glass body into a cylindrical shape having a diameter of 4 mm and a length of 40 mm. The firing temperature was determined as follows. First, a glass body was pulverized to obtain a glass powder, and a glass powder having a weight corresponding to the true specific gravity of the glass was press-molded into a button shape having an outer diameter of 20 mm and a height of about 5 mm using a mold. Next, this button was placed on a plate glass, placed in an electric furnace, heated at a rate of 10 ° C./min, and held at various temperatures for 10 minutes. The temperature at which the outer diameter of the button thus obtained was in the range of 21 to 22 mm was defined as the firing temperature. The crystallinity or non-crystallinity was determined by observing the appearance of the sample after being heated at the firing temperature for 10 minutes with a microscope and evaluating from the crystal precipitation state.
[0033]
【The invention's effect】
As described above, since the bismuth-based glass composition of the present invention does not contain PbO, there is no concern of causing environmental problems. Moreover, since it can bake at the temperature of 500 degrees C or less, it can be used for uses, such as adhesion | attachment of an electronic component, sealing, and coating | cover, as an alternative material of the low melting glass containing conventional PbO.

Claims (2)

モル分率で、Ｂｉ2Ｏ3 ３０〜５０％、Ｂ2Ｏ3 １０〜４０％、ＢａＯ＋ＳｒＯ １〜１０％、ＺｎＯ ０〜３０％、ＣｕＯ ０〜２０％、Ｆｅ2Ｏ3 ０〜５％、ＳｉＯ2＋Ａｌ2Ｏ3 ０〜５％、Ｃｓ2Ｏ ０〜５％、Ｆ2 ０〜２０％の組成を有し、かつ、Ｂｉ2Ｏ3／（ＢａＯ＋ＳｒＯ）が３．５〜３５．０の関係を満たし、ガラス転移点が３６３℃以下であることを特徴とするビスマス系ガラス組成物。Mole fraction, Bi 2 O 3 30~50%, B 2 O 3 10~40%, BaO + SrO 1~10%, 0~30% ZnO, 0~20% CuO, Fe 2 O 3 0~5%, It has a composition of SiO 2 + Al 2 O 3 0-5%, Cs 2 O 0-5%, F 2 0-20%, and Bi 2 O 3 / (BaO + SrO) is 3.5-35.0. meets a relationship, bismuth glass composition, wherein the glass transition point of 363 ° C. or less. 本質的にＰｂＯを含有しないことを特徴とする請求項１のビスマス系ガラス組成物。  The bismuth-based glass composition according to claim 1, which essentially contains no PbO.
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