JP3417066B2 - Sealing material - Google Patents
Sealing materialInfo
- Publication number
- JP3417066B2 JP3417066B2 JP17542694A JP17542694A JP3417066B2 JP 3417066 B2 JP3417066 B2 JP 3417066B2 JP 17542694 A JP17542694 A JP 17542694A JP 17542694 A JP17542694 A JP 17542694A JP 3417066 B2 JP3417066 B2 JP 3417066B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- low
- sealing material
- weight
- pbo
- 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 - Fee Related
Links
- 239000003566 sealing material Substances 0.000 title claims description 18
- 239000011521 glass Substances 0.000 claims description 50
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 34
- 238000002844 melting Methods 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- 239000011787 zinc oxide Substances 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 14
- 238000010304 firing Methods 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 229910052845 zircon Inorganic materials 0.000 claims description 6
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 6
- 238000005187 foaming Methods 0.000 description 12
- 239000000945 filler Substances 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000005361 soda-lime glass Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 239000005394 sealing glass Substances 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229910020617 PbO—B2O3—SiO2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052644 β-spodumene Inorganic materials 0.000 description 1
Classifications
-
- 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
- C03C8/245—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 containing more than 50% lead oxide, by weight
Landscapes
- 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)
- Vessels, Lead-In Wires, Accessory Apparatuses For Cathode-Ray Tubes (AREA)
Description
【０００１】本発明は、各種ディスプレー用ガラスの封
着に好適な封着用材料に関する。The present invention relates to a sealing material suitable for sealing glass for various displays.
【０００２】従来からブラウン管を始めとする各種ディ
スプレー材料の封着や、ＩＣ用のアルミナパッケージ等
の封着に、低融点ガラスが用いられてきた。一般には、
ＰｂＯ−Ｂ2Ｏ3系、ＰｂＯ−Ｂ2Ｏ3−ＺｎＯ系の低融点
ガラスが多く使用される。これらのガラスは膨張係数が
大きく、被封着材のそれとうまく整合しない場合が多
い。そこで、低融点ガラスに低膨張性のフィラー（無機
結晶の充填剤）を混ぜることによって、低温での接着性
などの特性を保ったまま膨張係数を小さくすることに成
功している。例えば、米国特許第３２５０６３１号公
報、同第３２５８３５０号公報、特開昭４９ー２４２０
８号公報等はその代表的な例で、低融点ガラスにβーユ
ークリプタイト、βースポジュメン、チタン酸鉛、石
英、ジルコン等を添加したものである。また、他にもそ
れぞれの目的にあわせて、ガラス組成、フィラーの種
類、量を変え、各種用途に対応させたものが多数発明さ
れている。例えば特開昭５２ー５６８６７号公報は半導
体装置のハーメチックコーティングと表面安定化のた
め、コージェライトやチタン酸鉛をフィラーとして含む
低融点ガラスを提案し、硫酸含有の電解錫メッキ浴に対
して良好な化学抵抗を有するようにしてある。特公昭５
４ー２３９２８号公報では、低融点ガラスにチタン酸鉛
とジルコンを含有させることによって半導体素子の気密
封着に適した、とくにリード線のメッキ工程で酸に侵さ
れないような材料を提案している。特公昭６１ー４３２
９８、特開昭５６ー６９２４２号公報にはＩＣ用のアル
ミナ質パッケージの封着に好適な低融点ガラスとして、
ＰｂＯ−Ｂ2Ｏ3−ＺｎＯ−ＳｉＯ2（−Ａｌ2Ｏ3−ＲＯ
−ＳｎＯ2ーＲ2０）系の低融点ガラスにコージェライト
等のフィラーを添加したものを提案している。特公昭６
２ー４７８２４号公報にはＰｂＯ−Ｂ2Ｏ3−ＳｉＯ2−
Ａｌ2Ｏ3系の低融点ガラスにジルコンを添加することに
よって、直流電圧の印加の下にも黒化しない表示管の封
着用ガラスを提案している。Conventionally, low melting point glass has been used for sealing various display materials such as cathode ray tubes and sealing alumina packages for ICs. In general,
PbO-B 2 O 3 -based low melting glass PbO-B 2 O 3 -ZnO system is often used. These glasses have a large expansion coefficient and often do not match well with that of the material to be sealed. Therefore, by mixing a low-melting glass with a low-expansion filler (inorganic crystal filler), the expansion coefficient has been successfully reduced while maintaining properties such as adhesiveness at low temperatures. For example, U.S. Pat. Nos. 3,250,631 and 3,258,350, JP-A-49-2420.
No. 8 and the like are typical examples thereof, and low melting glass to which β-eucryptite, β-spodumene, lead titanate, quartz, zircon and the like are added. In addition, in addition to the above, many glass compositions have been invented in which the glass composition, the kind and the amount of the filler are changed according to the respective purposes, so as to meet various purposes. For example, Japanese Unexamined Patent Publication (Kokai) No. 52-56867 proposes a low melting point glass containing cordierite or lead titanate as a filler for hermetic coating and surface stabilization of a semiconductor device, and is suitable for an electrolytic tin plating bath containing sulfuric acid. It has a good chemical resistance. Japanese Patent Office Sho 5
JP-A-4-23928 proposes a material suitable for hermetically sealing a semiconductor element by containing lead titanate and zircon in a low-melting glass, which is particularly resistant to acid in the lead wire plating process. . Japanese Patent Publication Sho 61-432
98, JP-A-56-69242 discloses a low melting glass suitable for sealing an alumina package for ICs.
PbO-B 2 O 3 -ZnO- SiO 2 (-Al 2 O 3 -RO
It has been proposed to add a filler such as cordierite to a low-melting-point glass of --SnO 2 --R 2 0) system. Tokusho Sho 6
The No. 2-47824 Publication PbO-B 2 O 3 -SiO 2 -
By adding zircon to an Al 2 O 3 -based low melting point glass, a glass for sealing a display tube which is not blackened even when a DC voltage is applied is proposed.
【０００３】フラットディスプレー、蛍光表示管に使わ
れるガラスは、ソーダ石灰ガラス或いはそれに類似の組
成のガラスであり、膨張係数は80〜100×10ー7/℃程度で
あることが多い。封着は、４３０〜５５０℃の温度域で
行われることが多く、十分な接着を短時間で行うために
は、例えば５５０℃、５分の焼成条件などが用いられて
いる。しかし、従来使用されてきたＰｂＯ−Ｂ2Ｏ3系、
あるいはＰｂＯ−ＺｎＯ−Ｂ2Ｏ3系ガラスを用いたフリ
ットでは、発泡が多く、緻密な封着を行うには不十分な
ものであった。また発泡が多い焼成体は強度が低下しや
すいという問題があった。[0003] Flat display, glass used in fluorescent display tube is a glass of similar composition to the soda-lime glass or it expansion coefficient is often about 80 to 100 × 10 over 7 / ° C.. The sealing is often performed in a temperature range of 430 to 550 ° C., and in order to perform sufficient adhesion in a short time, for example, firing conditions of 550 ° C. for 5 minutes are used. However, conventionally used have PbO-B 2 O 3 -based,
Or in the frit using a PbO-ZnO-B 2 O 3 based glass, foaming often was insufficient to do dense sealing. In addition, there is a problem that the strength of a fired body with a large amount of foaming tends to decrease.
【０００４】そこで、本発明の目的は、５５０℃まで温
度で焼しても発泡が少なく、短時間で緻密な封着が可能
な強度の高い封着用材料を提供することにある。Therefore, an object of the present invention is to provide a high-strength sealing material which has a small amount of foaming even if it is fired at a temperature of up to 550 ° C. and can be densely sealed in a short time.
【０００５】本発明の封着材料は、低融点ガラス粉末に
酸化亜鉛結晶のウィスカーを含む結晶粉末を混合したも
のからなり、低融点ガラス粉末及び結晶粉末が以下の組
成割合からなることを特徴とする。
低融点ガラス粉末組成
ＰｂＯ：７０〜８２重量％
Ｂ2Ｏ3：７〜１４重量％
ＺｎＯ：３〜１４重量％
ＳｉＯ2：０．１〜４．０重量％
Ａｌ2Ｏ3：０〜２．０重量％
混合割合
低融点ガラス粉末：６５〜９８重量％
ジルコン：０〜１５重量％
酸化亜鉛ウィスカー：２〜２０重量％
酸化亜鉛結晶のウイスカーとしては、針状または２方向
以上に分岐した形状を有するものが好んで用いられる。The sealing material of the present invention comprises a mixture of low-melting glass powder and crystal powder containing zinc oxide crystal whiskers, wherein the low-melting glass powder and the crystal powder have the following composition ratios. To do. Low melting point glass powder Composition PbO: 70 to 82 wt% B 2 O 3: 7~14 wt% ZnO: 3 to 14 wt% SiO 2: 0.1 to 4.0 wt% Al 2 O 3: 0~2. 0% by weight Mixing ratio Low melting point glass powder: 65 to 98% by weight Zircon: 0 to 15% by weight Zinc oxide whiskers: 2 to 20% by weight As whiskers for zinc oxide crystals, needle-like or branched shapes in two or more directions. Those that have are preferred.
【０００６】酸化亜鉛の結晶ウィスカーは、ウィスカー
でない酸化亜鉛の結晶粉末を混合した場合よりも流動性
の低下が小さく、また低融点ガラスとの反応性も低く、
低膨張のフィラーとして働くと同時に焼成時の発泡を抑
制することができる。発泡が少ないこととウィスカーと
しての強化の効果により焼成体の強度が向上する。流動
性の低下が少ないのは、ウィスカーでない粉末の場合に
比べて、みかけの粒径が大きくなるためと考えられる。
すなわち、細く延びた結晶体の占める体積が増加するた
めと推定される。また、低融点ガラスとして焼成時に結
晶化するガラスを用いた場合、より強度を高めることが
できる。[0006] Zinc oxide crystal whiskers have a smaller decrease in fluidity and a lower reactivity with a low-melting glass than those obtained by mixing non-whisker zinc oxide crystal powders.
It can act as a low-expansion filler and at the same time suppress foaming during firing. The strength of the fired body is improved due to the small amount of foaming and the effect of strengthening as whiskers. It is considered that the decrease in fluidity is small because the apparent particle size is larger than that in the case of non-whisker powder.
That is, it is presumed that the volume occupied by the thinly elongated crystal body increases. Further, when glass that crystallizes during firing is used as the low melting point glass, the strength can be further increased.
【０００７】以下では、低融点ガラスおよび結晶粉末の
組成限定の理由を述べる。ＰｂＯはガラスを低融点化す
る最も重要な成分である。８２％より多いとガラスが失
透しやすくなり、また、耐水、耐湿性も悪くなる。７０
％より少ないとガラスの軟化点が高くなり、４５０℃以
下での封着が困難になる。焼成時に結晶化する組成とし
ては７２〜８０％が適しており、より好ましくは７４〜
７９％である。Ｂ2Ｏ3は１４％より多いとガラスの軟化
点が高くなり、４５０℃以下での封着が困難になる。７
％より少ないとガラスが失透し易くなる。結晶化する組
成としては、７〜１０％が適しており、より好ましくは
８〜１０％である。ＺｎＯは１４％より多いとフリット
焼成時の結晶化速度が大きくなりすぎ、流動性が悪くな
る。３％より少ないと耐水、耐湿性が悪くなり、強度も
低くなる。結晶化する組成としては１０〜１４％が好ま
しい。ＳｉＯ2は４．０％より多いとフリットとしての
流動性が悪くなり、同時に封着物の耐圧強度が低い。
０．１％より少ないと焼成時に結晶化しやすくなり、流
動性が悪くなる。また、耐水、耐湿性も悪くなる。より
好ましくは０．５〜４．０％である。Ａｌ2Ｏ3はガラス
を安定化し耐水性、耐湿性を向上させる成分であるが、
２．０％より多いとガラスの軟化点が高くなり、また失
透し易くなる。結晶する組成では１．０％以下が適して
おり、より好ましくは０．５％以下である。ＺｒＯ2は
ガラスの耐水性、耐湿性を向上させ、焼成時の着色を薄
くする成分である。結晶化する組成において１．０％以
下の量を添加するのが適しており、より好ましくは０．
５％以下である。結晶粉末は、ガラスの膨張係数を調整
（小さくする）するために必要なものである。ジルコン
は強度を上げるが、１５％より多いと流動性が悪くな
る。酸化亜鉛結晶ウイスカー粉末は、本発明の必須成分
であり、結晶が針状または２方向以上に分岐した構造を
持つウィスカーが用いられる。低融点ガラスの流動性の
低下が少なく、発泡を抑制し、また強度を向上すること
ができる。４％以下では効果が少なく、２０％以上では
ガラスの流動性が悪くなる。The reasons for limiting the composition of the low melting point glass and the crystal powder will be described below. PbO is the most important component for lowering the melting point of glass. If it is more than 82%, the glass tends to devitrify, and the water resistance and moisture resistance also deteriorate. 70
If it is less than 100%, the softening point of the glass becomes high and it becomes difficult to seal at 450 ° C or lower. 72-80% is suitable as a composition that crystallizes during firing, and more preferably 74-
79%. If the content of B 2 O 3 is more than 14%, the softening point of the glass becomes high, and sealing at 450 ° C. or lower becomes difficult. 7
If it is less than%, the glass tends to devitrify. The composition for crystallization is preferably 7 to 10%, more preferably 8 to 10%. If ZnO is more than 14%, the crystallization rate during frit firing becomes too high, resulting in poor fluidity. If it is less than 3%, water resistance and moisture resistance are deteriorated and strength is also lowered. The composition for crystallization is preferably 10 to 14%. If the SiO 2 content is more than 4.0%, the fluidity as a frit becomes poor, and at the same time, the pressure resistance of the sealed material is low.
If it is less than 0.1%, crystallization tends to occur during firing, resulting in poor fluidity. In addition, water resistance and moisture resistance are also deteriorated. It is more preferably 0.5 to 4.0%. Al 2 O 3 is a component that stabilizes glass and improves water resistance and moisture resistance,
If it exceeds 2.0%, the softening point of the glass tends to be high, and devitrification tends to occur. A suitable composition for crystallization is 1.0% or less, and more preferably 0.5% or less. ZrO 2 is a component that improves the water resistance and moisture resistance of glass and reduces the coloring during firing. It is suitable to add an amount of 1.0% or less in the composition to be crystallized, and more preferably 0.
It is 5% or less. The crystal powder is necessary for adjusting (decreasing) the expansion coefficient of glass. Zircon increases the strength, but if it exceeds 15%, the fluidity becomes poor. The zinc oxide crystal whisker powder is an essential component of the present invention, and whiskers having a structure in which crystals are needle-shaped or branched in two or more directions are used. The flowability of the low-melting glass is not significantly reduced, foaming can be suppressed, and the strength can be improved. If it is 4% or less, the effect is small, and if it is 20% or more, the fluidity of the glass is deteriorated.
【０００８】以下に本発明の封着用材料を、実施例、お
よび比較例に基づいて詳細に説明する。表１に示した組
成になるように調合した原料を、白金坩堝に入れ、１０
００〜１２００℃で１〜２時間溶融する。溶融ガラスは
水砕した後、ボールミルで１００μ以下に粉砕する。こ
の粉末ガラスに１００μ以下に粉砕したフィラー（無機
結晶の充填剤）を加えて均質に混合し、本発明の封着用
ガラスとする。通常の封着には、封着用ガラスにビーク
ル（ニトロセルロースを酢酸イソアミル溶液で溶かした
物）を適量混合し、ペースト状にしたものを接着面に塗
布して使用される。表１に示した各特性は以下のように
して評価した。
〔ボタンフロー径〕封着用材料粉末１０ｇを秤取り、こ
れを直径１２．５ｍｍの円柱状にプレス成形する（プレ
ス圧力約１００Ｋｇ／ｃｍ2）。これをソーダ石灰ガラ
ス板の上において、４５０℃、５０分間焼成する。また
は同様に８ｇの試料を５５０℃で５分間焼成する。通常
サンプルは軟化流動し、ほぼ円盤状に広がる。この円盤
の直径をもってフロー径とし、流動性の尺度とする。
〔熱膨張係数〕熱膨張計を用いて測定し、３０℃〜ガラ
ス転移点までの平均の値で表した。
〔発泡性〕ボタンフローを行った試料を切断し、その断
面における発泡の状態を目視で観察した。
〔三点曲げ強度〕４５０℃で５０分間焼成した試料の強
度を三点曲げ強度試験により、測定した。
〔衝撃強度〕φ１２×６の大きさの金属製円筒をソーダ
石灰ガラス板に封着用材料を用い４５０℃、５０分間焼
成して垂直に固定し、その試料の衝撃強度をＪＩＳ Ｃ
−５０２６に準じて測定し、破壊する限界の衝撃加速度
で示した。The sealing material of the present invention will be described in detail below with reference to Examples and Comparative Examples. The raw materials prepared so as to have the composition shown in Table 1 were put in a platinum crucible, and 10
Melt at 00 to 1200 ° C for 1 to 2 hours. The molten glass is pulverized with water and then pulverized with a ball mill to 100 μ or less. A filler (filler of inorganic crystals) pulverized to 100 μm or less is added to this powdered glass and mixed homogeneously to obtain the glass for sealing of the present invention. For ordinary sealing, a suitable amount of a vehicle (nitrocellulose dissolved in an isoamyl acetate solution) is mixed with sealing glass, and a paste is applied to the adhesive surface for use. Each property shown in Table 1 was evaluated as follows. [Button flow diameter] 10 g of the powder for sealing material is weighed and press-molded into a column having a diameter of 12.5 mm (pressing pressure of about 100 Kg / cm 2 ). This is baked on a soda-lime glass plate at 450 ° C. for 50 minutes. Alternatively, similarly, 8 g of the sample is baked at 550 ° C. for 5 minutes. Normally, the sample softens and flows, and spreads out in a substantially disc shape. The diameter of this disk is used as the flow diameter and is used as a measure of fluidity. [Thermal expansion coefficient] It was measured using a thermal expansion meter and expressed as an average value from 30 ° C to the glass transition point. [Foamability] The sample subjected to the button flow was cut and the state of foaming in the cross section was visually observed. [Three-Point Bending Strength] The strength of the sample fired at 450 ° C. for 50 minutes was measured by a three-point bending strength test. [Impact strength] A metal cylinder having a size of φ12 × 6 is fired at 450 ° C. for 50 minutes using a sealing material on a soda-lime glass plate and fixed vertically, and the impact strength of the sample is measured according to JIS C.
It was measured according to -5026 and shown as the impact acceleration at the limit of breaking.
【表１】
表１の実施例１、２は非晶質のＰｂＯ−Ｂ2Ｏ3−ＺｎＯ
系ガラスに酸化亜鉛のウィスカーを混合した封着用材料
である。また実施例３、４は結晶質のＰｂＯ−Ｂ2Ｏ3−
ＺｎＯ系ガラスに酸化亜鉛のウィスカーを混合した封着
用材料である。実施例１から実施例４においては、４５
０℃−５０分間および５５０℃−５分間の焼成のいずれ
の場合も発泡が少なく、強度も比較的高い焼成体が得ら
れた。比較例１は非晶質のＰｂＯ−Ｂ2Ｏ3系ガラスにチ
タン酸鉛を混合した封着用材料である。この封着用材料
は、４５０℃、５５０℃いずれの温度においても実施例
の材料に比べて発泡が多い。そのため特に衝撃強度が低
くなっている。比較例２は、実施例１と同じ結晶質のガ
ラス粉末に炭化けい素の結晶粉末をフィラーとして混合
したものである。この場合は、焼成温度を高くしていく
とある温度から急激に発泡が激しくなり、５５０℃の焼
成では非常に脆い材料になってしまい、封着用材料に適
さない。表１に示したように、本発明の範囲のガラス組
成、フィラー割合の封着物は、発泡が少なく、緻密で強
度の高い封着物が得られる。[Table 1] Table 1 Examples 1 and 2 of an amorphous PbO-B 2 O 3 -ZnO
It is a sealing material in which whisker of zinc oxide is mixed with a base glass. The Examples 3 and 4 Crystalline PbO-B 2 O 3 -
It is a sealing material in which ZnO whiskers are mixed with ZnO glass. In Examples 1 to 4, 45
In both cases of firing at 0 ° C. for 50 minutes and at 550 ° C. for 5 minutes, a fired body with little foaming and a relatively high strength was obtained. Comparative Example 1 is a sealing material obtained by mixing lead titanate to PbO-B 2 O 3 -based glass amorphous. This sealing material has more foaming than the material of the example at any temperature of 450 ° C and 550 ° C. Therefore, the impact strength is particularly low. Comparative Example 2 is a mixture of the same crystalline glass powder as that of Example 1 with silicon carbide crystal powder as a filler. In this case, when the firing temperature is increased, the foaming rapidly becomes violent from a certain temperature, and the firing at 550 ° C. results in a very brittle material, which is not suitable as a sealing material. As shown in Table 1, the sealing material having the glass composition and the filler ratio within the range of the present invention has a small amount of foaming and is dense and has high strength.
【０００９】本発明の封着用材料を用いると、５５０℃
以下の焼成において、ガラスの封着を発泡が少なく、高
い強度で行うことができる。When the sealing material of the present invention is used, it is 550 ° C.
In the following firing, the glass can be sealed with a small amount of foaming and high strength.
フロントページの続き (56)参考文献 特開 平８−26770（ＪＰ，Ａ) 特開 平８−12371（ＪＰ，Ａ) 特開 平７−69670（ＪＰ，Ａ) 特開 平６−127976（ＪＰ，Ａ) 特開 昭60−204637（ＪＰ，Ａ) Ｄ．Ｗ．Ａ．Ｆｏｒｂｅｓ，Ｓｏｌｄ ｅｒ ｇｌａｓｓ ｓｅａｌｓ ｉｎ ｓｅｍｉ−ｃｏｎｄｕｃｔｏｒ ｐａｃ ｋａｇｉｎｇ，Ｇｌａｓｓ Ｔｅｃｈｎ ｏｌｏｇｙ，1967年 ４月，ｖｏｌ．８ ｎｏ．２，ｐ．32−42 Ｉ．Ｗ．Ｄｏｎａｌｄ，Ｐｒｅｐａｒ ａｔｉｏｎ，ｐｒｏｐｅｒｔｉｅｓ ａ ｎｄ ｃｈｅｍｉｓｔｒｙ ｏｆ ｇｌ ａｓｓ−ａｎｄ ｇｌａｓｓ−ｃｅｒａ ｍｉｃ−ｔｏ−ｍｅｔａｌ ｓｅａｌｓ ａｎｄ ｃｏａｔｉｎｇｓ，Ｊｏｕｒ ｎａｌ ｏｆ Ｍａｔｅｒｉａｌｓ Ｓ ｃｉｅｎｃｅ，1993年 ６月 １日，ｖ ｏｌ．28 ｎｏ．11，ｐ．2841−2886 (58)調査した分野(Int.Cl.7，ＤＢ名) C03C 1/00 - 14/00 ＷＰＩContinuation of front page (56) Reference JP-A-8-26770 (JP, A) JP-A-8-12371 (JP, A) JP-A-7-69670 (JP, A) JP-A-6-127976 (JP , A) JP-A-60-204637 (JP, A) D.I. W. A. Forbes, Solder glass seals in semi-conductor package packaging, Glass Technology, April 1967, vol. 8 no. 2, p. 32-42 I. W. Donald, Preparation, properties and chemistry of gl ass-and glass-cera mic-to-metal seals and coatings, Journal of Materials, October 6, 1993. 28 no. 11, p. 2841-2886 (58) Fields investigated (Int.Cl. 7 , DB name) C03C 1/00-14/00 WPI
Claims (3)
カーを含む結晶粉末を混合した封着用材料であり、前記
低融点ガラス粉末及び前記結晶粉末は、以下の組成割合
からなることを特徴とする封着用材料。 低融点ガラス粉末組成 ＰｂＯ：７０〜８２重量％ Ｂ2Ｏ3：７〜１４重量％ ＺｎＯ：３〜１４重量％ ＳｉＯ2：０．１〜４．０重量％ Ａｌ2Ｏ3：０〜２．０重量％ 混合割合 低融点ガラス粉末：６５〜９６重量％ ジルコン：０〜１５重量％ 酸化亜鉛ウィスカー：４〜２０重量％1. A sealing material in which low-melting glass powder is mixed with crystal powder containing zinc oxide crystal whiskers, wherein the low-melting glass powder and the crystal powder have the following composition ratios. Sealing material. Low melting point glass powder Composition PbO: 70 to 82 wt% B 2 O 3: 7~14 wt% ZnO: 3 to 14 wt% SiO 2: 0.1 to 4.0 wt% Al 2 O 3: 0~2. 0% by weight Low melting point glass powder: 65 to 96% by weight Zircon: 0 to 15% by weight Zinc oxide whiskers: 4 to 20% by weight
する以下の組成割合からなることを特徴とする請求項１
に記載の封着用材料。 ＰｂＯ：７２〜８０重量％ Ｂ2Ｏ3：７〜１０重量％ ＺｎＯ：１０〜１４重量％ ＳｉＯ2：０．５〜４．０重量％ Ａｌ2Ｏ3：０〜１．０重量％ ＺｒＯ2： ０〜１．０重量％2. The low-melting-point glass powder is composed of the following composition ratio that crystallizes during firing.
The sealing material described in. PbO: 72 to 80 wt% B 2 O 3: 7~10 wt% ZnO: 10 to 14 wt% SiO 2: 0.5 to 4.0 wt% Al 2 O 3: 0~1.0 wt% ZrO 2 : 0 to 1.0% by weight
からなることを特徴とする請求項２に記載の封着用材
料。 ＰｂＯ：７４〜７９重量％ Ｂ2Ｏ3：８〜１０重量％ ＺｎＯ：１０〜１４重量％ ＳｉＯ2：０．５〜４．０重量％ Ａｌ2Ｏ3：０〜０．５重量％ ＺｒＯ2： ０〜０．５重量％3. The sealing material according to claim 2, wherein the low melting point glass powder has the following composition ratio. PbO: 74 to 79 wt% B 2 O 3: 8~10 wt% ZnO: 10 to 14 wt% SiO 2: 0.5 to 4.0 wt% Al 2 O 3: 0~0.5 wt% ZrO 2 : 0 to 0.5% by weight
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17542694A JP3417066B2 (en) | 1994-07-27 | 1994-07-27 | Sealing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17542694A JP3417066B2 (en) | 1994-07-27 | 1994-07-27 | Sealing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0834641A JPH0834641A (en) | 1996-02-06 |
| JP3417066B2 true JP3417066B2 (en) | 2003-06-16 |
Family
ID=15995899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17542694A Expired - Fee Related JP3417066B2 (en) | 1994-07-27 | 1994-07-27 | Sealing material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3417066B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997036836A1 (en) * | 1996-04-02 | 1997-10-09 | Techneglas, Inc. | Sealing glass modifier for use with voc-free or low-voc vehicle |
| US6287996B1 (en) | 1998-09-14 | 2001-09-11 | Asahi Glass Company Ltd. | Ceramic color composition and process for producing a curved glass plate |
| JP2008303075A (en) * | 2007-06-05 | 2008-12-18 | Central Glass Co Ltd | Insulating coating material |
-
1994
- 1994-07-27 JP JP17542694A patent/JP3417066B2/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| Ｄ．Ｗ．Ａ．Ｆｏｒｂｅｓ，Ｓｏｌｄｅｒ ｇｌａｓｓ ｓｅａｌｓ ｉｎ ｓｅｍｉ−ｃｏｎｄｕｃｔｏｒ ｐａｃｋａｇｉｎｇ，Ｇｌａｓｓ Ｔｅｃｈｎｏｌｏｇｙ，１９６７年 ４月，ｖｏｌ．８ ｎｏ．２，ｐ．３２−４２ |
| Ｉ．Ｗ．Ｄｏｎａｌｄ，Ｐｒｅｐａｒａｔｉｏｎ，ｐｒｏｐｅｒｔｉｅｓ ａｎｄ ｃｈｅｍｉｓｔｒｙ ｏｆ ｇｌａｓｓ−ａｎｄ ｇｌａｓｓ−ｃｅｒａｍｉｃ−ｔｏ−ｍｅｔａｌ ｓｅａｌｓ ａｎｄ ｃｏａｔｉｎｇｓ，Ｊｏｕｒｎａｌ ｏｆ Ｍａｔｅｒｉａｌｓ Ｓｃｉｅｎｃｅ，１９９３年 ６月 １日，ｖｏｌ．２８ ｎｏ．１１，ｐ．２８４１−２８８６ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0834641A (en) | 1996-02-06 |
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