JP2009073729A - Sealing material - Google Patents

Sealing material Download PDF

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JP2009073729A
JP2009073729A JP2008220977A JP2008220977A JP2009073729A JP 2009073729 A JP2009073729 A JP 2009073729A JP 2008220977 A JP2008220977 A JP 2008220977A JP 2008220977 A JP2008220977 A JP 2008220977A JP 2009073729 A JP2009073729 A JP 2009073729A
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sealing material
glass
alumina
powder
refractory filler
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JP5476691B2 (en
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Kentaro Ishihara
健太郎 石原
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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
    • C03C3/04—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
    • 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

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a sealing material satisfactory fluidized at ≤530°C and further hard to be deformed in an evacuation stage at 450 to 500°C, so as to improve the characteristics of a PDP (plasma display panel) or the like and production efficiency in a sealing material comprising bismuth based glass powder and refractory filler powder. <P>SOLUTION: In the sealing material comprising bismuth-based glass powder and a refractory filler powder, the bismuth-based glass powder comprises, as a glass composition, by mass% expressed in terms of oxide, 67 to 90% Bi<SB>2</SB>O<SB>3</SB>, 2 to 12% B<SB>2</SB>O<SB>3</SB>, 0 to 5% Al<SB>2</SB>O<SB>3</SB>, 1 to 15% ZnO, 0 to 10% BaO, 0 to 5% CuO, 0 to 3% Fe<SB>2</SB>O<SB>3</SB>, 0 to 5% CeO<SB>2</SB>and 0 to 5% Sb<SB>2</SB>O<SB>3</SB>, in which the value of mass ratio Bi<SB>2</SB>O<SB>3</SB>/B<SB>2</SB>O<SB>3</SB>is ≤11, and, as the refractory filler powder, alumina is contained by 1 to 25 vol%. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、電子部品または平面表示装置等に好適な封着材料に関するものである。特に、本発明は、プラズマディスプレイパネル（ＰＤＰ）の前面ガラス基板と背面ガラス基板の封着に好適な封着材料に関するものである。   The present invention relates to a sealing material suitable for an electronic component or a flat display device. In particular, the present invention relates to a sealing material suitable for sealing a front glass substrate and a back glass substrate of a plasma display panel (PDP).

従来から平面表示装置等の封着材料としてガラスが用いられている。ガラスは、樹脂系の接着剤に比べ、化学的耐久性および耐熱性に優れるとともに、平面表示装置等の気密性を確保するのに適している。   Conventionally, glass has been used as a sealing material for flat display devices and the like. Glass is excellent in chemical durability and heat resistance as compared with a resin-based adhesive, and is suitable for ensuring airtightness of a flat display device or the like.

これらのガラスは、用途によっては機械的強度、流動性、電気絶縁性等様々な特性が要求されるが、少なくとも平面表示装置等に使用される蛍光体の蛍光特性を劣化させない温度で使用可能であることが要求される。それゆえ、上記特性を満足するガラスとして、低融点の鉛ホウ酸系ガラスが広く用いられてきた（特許文献１参照）。   These glasses require various properties such as mechanical strength, fluidity, and electrical insulation depending on the application, but they can be used at temperatures that do not deteriorate the fluorescent properties of phosphors used in flat display devices. It is required to be. Therefore, a low melting point lead borate glass has been widely used as a glass satisfying the above characteristics (see Patent Document 1).

ところが、最近、鉛ホウ酸系ガラスに含まれるＰｂＯに対して環境上の問題が指摘されており、鉛ホウ酸系ガラスから無鉛ガラスに置き換えることが望まれている。そのため、鉛ホウ酸系ガラスの代替品として、様々な低融点の無鉛ガラスが開発されている。その中でも特許文献２等に記載されているビスマス系ガラス（Ｂｉ２Ｏ３−Ｂ２Ｏ３系ガラス、Ｂｉ２Ｏ３、Ｂ２Ｏ３を必須成分として含有するガラス）は、熱膨張係数等の諸特性が鉛ホウ酸系ガラスと略同等であるため、その代替候補として期待されているが、流動性および熱的安定性等の特性において、依然として鉛ホウ酸系ガラスに及ばないのが実情である。 However, recently, environmental problems have been pointed out with respect to PbO contained in lead borate glass, and it is desired to replace lead borate glass with lead-free glass. Therefore, various low-melting lead-free glasses have been developed as substitutes for lead borate glasses. Among them, bismuth-based glass (Bi 2 O 3 —B 2 O 3 -based glass, glass containing Bi 2 O 3 , B 2 O 3 as an essential component) described in Patent Document 2 and the like has a coefficient of thermal expansion, etc. These properties are almost equivalent to lead borate glass, so they are expected as alternatives. However, in reality, they are not as good as lead borate glass in terms of fluidity and thermal stability. It is.

さらに、封着材料は、一般的に、ガラス粉末と耐火性フィラー粉末を含有する複合材料であり、従来、耐火性フィラー粉末として、低膨張のチタン酸鉛等が使用されてきた。しかし、ガラスの場合と同様にして、チタン酸鉛等も無鉛の耐火性フィラーに置き換えることが望まれている。   Furthermore, the sealing material is generally a composite material containing glass powder and refractory filler powder, and conventionally, low expansion lead titanate or the like has been used as the refractory filler powder. However, as in the case of glass, it is desirable to replace lead titanate and the like with lead-free refractory fillers.

ところで、ＰＤＰは、以下のような製造工程で作製され、ＰＤＰの作製に使用される封着材料は、以下のような熱処理工程を経る。まず、ＰＤＰの背面ガラス基板の外周縁部にビークル内に分散された封着材料を塗布した後、ビークル成分を熱分解または焼却して、一次焼成（グレーズ工程、仮焼成工程）を行う。封着材料を均一に分散させるビークルは、有機溶媒や樹脂等を含有している。一般的に、樹脂は、ガラスの軟化点以下の温度で良好に熱分解するニトロセルロースまたはアクリル樹脂等が使用されている。封着材料とビークルは、三本ロールミル等の混練装置を用いて、均一に混練することにより、ペーストに加工される。一次焼成は、樹脂が完全に熱分解する温度条件で行われる。一次焼成において、仮に樹脂の熱分解が不完全であると、その後に供される二次焼成（封着工程、シール工程）でガラス中に樹脂の残渣が残存し、その結果、ガラスに失透または泡等の致命的な欠陥が生じやすくなる。次に、前面ガラス基板と背面ガラス基板の位置合わせを行った上で、二次焼成を行い、前面ガラス基板と背面ガラス基板を封着する。最後に、排気管を通してＰＤＰ内部を真空排気した後、希ガスを必要量注入して排気管を封止する。このようにしてＰＤＰは作製される。
特開昭６３−３１５５３６号公報 特開平６−２４７９７号公報 By the way, the PDP is manufactured by the following manufacturing process, and the sealing material used for manufacturing the PDP undergoes the following heat treatment process. First, a sealing material dispersed in a vehicle is applied to the outer peripheral edge of the rear glass substrate of the PDP, and then the vehicle components are pyrolyzed or incinerated to perform primary firing (glazing process, pre-baking process). A vehicle that uniformly disperses the sealing material contains an organic solvent, a resin, and the like. In general, as the resin, nitrocellulose, an acrylic resin, or the like that is thermally decomposed well at a temperature below the softening point of glass is used. The sealing material and the vehicle are processed into a paste by uniformly kneading using a kneading apparatus such as a three-roll mill. The primary firing is performed under temperature conditions where the resin is completely thermally decomposed. In the primary firing, if the thermal decomposition of the resin is incomplete, a resin residue remains in the glass in the subsequent secondary firing (sealing step, sealing step), and as a result, the glass is devitrified. Or, fatal defects such as bubbles are likely to occur. Next, after aligning the front glass substrate and the back glass substrate, secondary firing is performed to seal the front glass substrate and the back glass substrate. Finally, the inside of the PDP is evacuated through the exhaust pipe, and then a necessary amount of rare gas is injected to seal the exhaust pipe. In this way, the PDP is manufactured.
Japanese Unexamined Patent Publication No. Sho 63-315536 JP-A-6-24797

既述の通り、ＰＤＰは、一次焼成工程、二次焼成工程、真空排気工程を経て、製造される。通常、一次焼成工程、二次焼成工程は、大気中で行われ、真空排気工程は、高真空の減圧雰囲気で行われる。真空排気工程は、装置内部を高真空にするために、長時間（通常、４３０℃で７〜１０時間）を要する工程となっており、ＰＤＰの製造効率を低下させる一因となっている。このような事情に鑑み、近年、ＰＤＰの製造効率を高めるために、真空排気工程を高温で行う試みが検討されている。真空排気工程を高温、具体的には４５０〜５００℃で行うと、装置内部を短時間で高真空状態にすることができるため、ＰＤＰの製造効率を大幅に高めることができる。   As described above, the PDP is manufactured through a primary firing process, a secondary firing process, and a vacuum exhaust process. Usually, the primary firing process and the secondary firing process are performed in the air, and the vacuum exhaust process is performed in a high vacuum reduced pressure atmosphere. The evacuation process is a process that requires a long time (usually 7 to 10 hours at 430 ° C.) in order to make the inside of the apparatus into a high vacuum, which is a cause of reducing the production efficiency of the PDP. In view of such circumstances, in recent years, attempts have been made to perform the evacuation process at a high temperature in order to increase the production efficiency of the PDP. When the evacuation process is performed at a high temperature, specifically 450 to 500 ° C., the inside of the apparatus can be brought into a high vacuum state in a short time, and thus the production efficiency of the PDP can be greatly increased.

また、真空排気工程を４５０〜５００℃で行うと、装置内部の残存ガス量や不純物の含有量を低減できるため、換言すれば装置内部の真空度を高めることができるため、装置内部の希ガスの純度を高めることができ、その結果、ＰＤＰの輝度特性を高めることができる。   Further, when the vacuum exhaust process is performed at 450 to 500 ° C., the residual gas amount and impurity content inside the apparatus can be reduced. In other words, the degree of vacuum inside the apparatus can be increased. As a result, the luminance characteristics of the PDP can be improved.

しかし、真空排気工程を４５０〜５００℃で行うと、以下のような問題が生じる。   However, when the evacuation process is performed at 450 to 500 ° C., the following problems occur.

ＰＤＰの前面ガラス基板と背面ガラス基板の封着には、一般的に、非晶質のガラス粉末を用いた封着材料が使用される。ＰＤＰの一次焼成工程、二次焼成工程は、蛍光体等の劣化を防止するために、５３０℃以下、好ましくは５１０℃以下の温度で行う必要があり、これに伴って、封着材料は、５３０℃以下の温度で良好に流動することが要求される。封着材料を５３０℃以下の温度で良好に流動させるためには、ガラスの軟化点を低下させる必要があるが、このような場合において、真空排気工程を４５０℃以上で行うと、真空排気工程でガラスが再軟化し、封着材料が装置内部に引き込まれて、ＰＤＰの気密信頼性が損なわれやすくなる。また、装置内部に引き込まれた封着部位は、機械的衝撃により、破損しやすく、ＰＤＰの気密信頼性が損なわれやすくなる。   Generally, a sealing material using amorphous glass powder is used for sealing the front glass substrate and the rear glass substrate of the PDP. The primary firing step and the secondary firing step of the PDP need to be performed at a temperature of 530 ° C. or lower, preferably 510 ° C. or lower in order to prevent deterioration of the phosphor and the like. It is required to flow well at a temperature of 530 ° C. or lower. In order to allow the sealing material to flow well at a temperature of 530 ° C. or lower, it is necessary to lower the softening point of the glass. In such a case, if the vacuum evacuation step is performed at 450 ° C. or higher, the vacuum evacuation step As a result, the glass is softened again, and the sealing material is drawn into the apparatus, so that the airtight reliability of the PDP tends to be impaired. In addition, the sealing portion drawn into the apparatus is easily damaged by mechanical impact, and the airtight reliability of the PDP is easily impaired.

また、ビスマス系ガラスは、鉛ホウ酸系ガラスに比べて、ガラスの軟化点が高いため、ビスマス系ガラス粉末と耐火性フィラー粉末を含有する封着材料において、従来、ビスマス系ガラス粉末の軟化点を低下させることにより、封着材料の流動性を向上させることが主な技術的課題であった。しかし、従来の手法で、封着材料の流動性を高めると、真空排気工程で封着材料が装置内部に引き込まれやすくなり、真空排気工程を高温化することが困難になる。   In addition, bismuth-based glass has a higher softening point than lead borate-based glass. Therefore, in sealing materials containing bismuth-based glass powder and refractory filler powder, the softening point of bismuth-based glass powder has been conventionally used. It has been a main technical problem to improve the fluidity of the sealing material by lowering. However, when the fluidity of the sealing material is increased by a conventional method, the sealing material is easily drawn into the apparatus in the vacuum exhaust process, and it is difficult to increase the temperature of the vacuum exhaust process.

そこで、本発明は、ビスマス系ガラス粉末と耐火性フィラー粉末を含有する封着材料において、５３０℃以下の温度で良好に流動するとともに、４５０〜５００℃の真空排気工程で変形し難い封着材料を得ることにより、ＰＤＰ等の特性および製造効率を向上させることを技術的課題とする。   Accordingly, the present invention provides a sealing material containing a bismuth-based glass powder and a refractory filler powder, which flows well at a temperature of 530 ° C. or less and hardly deforms in a vacuum exhaust process at 450 to 500 ° C. Therefore, it is a technical subject to improve the characteristics and manufacturing efficiency of PDP and the like.

本発明者は、鋭意努力の結果、ビスマス系ガラス粉末と耐火性フィラー粉末を含有する封着材料において、ビスマス系ガラス粉末のガラス組成範囲を、下記酸化物換算の質量％表示で、Ｂｉ２Ｏ３ ６７〜９０％、Ｂ２Ｏ３ ２〜１２％、Ａｌ２Ｏ３ ０〜５％、ＺｎＯ １〜２０％、ＢａＯ ０〜１０％、ＣｕＯ ０〜５％、Ｆｅ２Ｏ３ ０〜３％、ＣｅＯ２ ０〜５％、Ｓｂ２Ｏ３ ０〜５％に規制するとともに、ビスマス系ガラス粉末のガラス組成において質量比Ｂｉ２Ｏ３／Ｂ２Ｏ３の値を１１以下に規制し、且つ耐火性フィラー粉末として、アルミナ（Ａｌ２Ｏ３、Ａｌｕｍｉｎａ）を１〜２５体積％含有させることで、上記技術的課題を解決できることを見出し、本発明として、提案するものである。すなわち、本発明の封着材料は、ビスマス系ガラス粉末と耐火性フィラー粉末を含有する封着材料において、ビスマス系ガラス粉末は、ガラス組成として、下記酸化物換算の質量％表示で、Ｂｉ２Ｏ３ ６７〜９０％、Ｂ２Ｏ３ ２〜１２％、Ａｌ２Ｏ３ ０〜５％、ＺｎＯ １〜１５％、ＢａＯ ０〜１０％、ＣｕＯ ０〜５％、Ｆｅ２Ｏ３ ０〜３％、ＣｅＯ２ ０〜５％、Ｓｂ２Ｏ３ ０〜５％を含有し、質量比Ｂｉ２Ｏ３／Ｂ２Ｏ３の値が１１以下であり、且つ耐火性フィラー粉末として、アルミナを１〜２５体積％含有することを特徴とする。 As a result of diligent efforts, the present inventor, in a sealing material containing a bismuth-based glass powder and a refractory filler powder, shows the glass composition range of the bismuth-based glass powder in terms of mass% in terms of the following oxide, Bi 2 O. 3 67~90%, B 2 O 3 2~12%, Al 2 O 3 0~5%, ZnO 1~20%, BaO 0~10%, 0~5% CuO, Fe 2 O 3 0~3% , CeO 2 0 to 5%, Sb 2 O 3 0 to 5%, the value of the mass ratio Bi 2 O 3 / B 2 O 3 in the glass composition of the bismuth-based glass powder is regulated to 11 or less, and The present inventors have found that the above technical problem can be solved by containing 1 to 25% by volume of alumina (Al 2 O 3 , Allumina) as the refractory filler powder, and proposes the present invention. That is, the sealing material of the present invention is a sealing material containing bismuth glass powder and the refractory filler powder, bismuth glass powder is a glass composition including, in mass% in terms of oxide, Bi 2 O 3 67~90%, B 2 O 3 2~12%, Al 2 O 3 0~5%, 1~15% ZnO, BaO 0~10%, 0~5% CuO, Fe 2 O 3 0~3% , CeO 2 0 to 5%, Sb 2 O 3 0 to 5%, the mass ratio Bi 2 O 3 / B 2 O 3 is 11 or less, and refractory filler powder is alumina 1 to It is characterized by containing 25% by volume.

本発明の封着材料は、耐火性フィラー粉末として、アルミナを１〜２５体積％含有している。封着材料中にアルミナを１体積％以上含有させると、熱処理工程でガラスが変形し難くなり、真空排気工程で封着材料が装置内部に引き込まれにくくなる。その一方で、アルミナの含有量を２５体積％以下に規制すれば、二次焼成工程で封着材料の流動性を確保することができる。つまりアルミナの含有量を１〜２５体積％に規制すれば、一次焼成工程で封着材料の流動性が損なわれる事態を防止できるとともに、真空排気工程を４５０〜５００℃で行っても、封着材料が装置内部に引き込まれにくくなり、装置内部を短時間で高真空状態にすることができる。その結果、ＰＤＰの製造効率および輝度特性を高めることができる。   The sealing material of the present invention contains 1 to 25% by volume of alumina as a refractory filler powder. When the sealing material contains 1% by volume or more of alumina, the glass is hardly deformed in the heat treatment process, and the sealing material is not easily drawn into the apparatus in the vacuum exhaust process. On the other hand, if the alumina content is regulated to 25% by volume or less, the fluidity of the sealing material can be secured in the secondary firing step. In other words, if the alumina content is regulated to 1 to 25% by volume, it is possible to prevent a situation where the fluidity of the sealing material is impaired in the primary firing step, and even if the evacuation step is performed at 450 to 500 ° C., sealing is performed. It becomes difficult for the material to be drawn into the apparatus, and the inside of the apparatus can be brought into a high vacuum state in a short time. As a result, the manufacturing efficiency and luminance characteristics of the PDP can be improved.

本発明の封着材料は、ビスマス系ガラス粉末のガラス組成範囲およびガラス組成比を上記のように規制している。このようにすれば、ガラスの熱的安定性を高めることができ、一次焼成工程および二次焼成工程でビスマス系ガラスが失透し難くなり、ＰＤＰの前面ガラス基板と背面ガラス基板の封着強度を高めることができる。   The sealing material of the present invention regulates the glass composition range and glass composition ratio of the bismuth-based glass powder as described above. In this way, the thermal stability of the glass can be enhanced, and the bismuth-based glass is less likely to be devitrified in the primary firing step and the secondary firing step, and the sealing strength of the front glass substrate and the rear glass substrate of the PDP. Can be increased.

また、ビスマス系ガラス粉末のガラス組成範囲を上記のように規制すれば、ガラスの軟化点を低下できるため、封着材料の流動性を高めることができ、封着材料を５３０℃以下の温度で良好に流動させることができる。さらに、このようにすれば、ガラス組成中にＰｂＯを含有しなくても、ガラスの軟化点を低下できるため、近年の環境的要請を満たすことができる。また、ビスマス系ガラス粉末のガラス組成比Ｂｉ２Ｏ３／Ｂ２Ｏ３の値を上記のように規制すれば、真空排気工程で封着材料の引き込みを的確に防止することができる。 In addition, if the glass composition range of the bismuth-based glass powder is regulated as described above, the softening point of the glass can be lowered, so that the fluidity of the sealing material can be increased, and the sealing material can be heated at a temperature of 530 ° C. or lower. It can flow well. Further, in this way, even if PbO is not contained in the glass composition, the softening point of the glass can be lowered, so that recent environmental demands can be satisfied. Moreover, if the value of the glass composition ratio Bi 2 O 3 / B 2 O 3 of the bismuth-based glass powder is regulated as described above, the entrainment of the sealing material can be accurately prevented in the vacuum exhaust process.

第二に、本発明の封着材料は、アルミナの平均粒子径Ｄ５０が３〜２５μｍであることに特徴付けられる。ここで、「平均粒子径Ｄ５０」は、レーザー回折法で測定した値を指す。 Secondly, the sealing material of the present invention has an average particle diameter D 50 of the alumina is characterized in that it is 3～25Myuemu. Here, “average particle diameter D 50 ” refers to a value measured by a laser diffraction method.

第三に、本発明の封着材料は、アルミナの１０％粒子径Ｄ１０が１〜５μｍおよび／または９０％粒子径Ｄ９０が１０〜３５μｍであることに特徴付けられる。ここで、「１０％粒子径Ｄ１０」および「９０％粒子径Ｄ９０」は、レーザー回折法で測定した値を指す。また、「１０％粒子径Ｄ１０」は、積算粒子量が１０％になる粒子径（体積）であり、「９０％粒子径Ｄ９０」は、積算粒子量が９０％になる粒子径（体積）である。 Third, the sealing material of the present invention, the 10% particle size D 10 of alumina 1~5μm and / or 90% particle diameter D 90 of characterized in that it is 10 to 35 [mu] m. Here, “10% particle diameter D 10 ” and “90% particle diameter D 90 ” indicate values measured by a laser diffraction method. Further, “10% particle diameter D 10 ” is a particle diameter (volume) at which the accumulated particle amount is 10%, and “90% particle diameter D 90 ” is a particle diameter (volume) at which the accumulated particle amount is 90%. ).

第四に、本発明の封着材料は、非結晶性であることに特徴付けられる。ここで、「非結晶性」とは、示差熱分析（ＤＴＡ）で５５０℃以上、好ましくは５７０℃以上の温度で結晶化ピークが発現しないものを指す。なお、ＤＴＡは、大気中で行い、昇温速度１０℃／分、室温から測定を開始する。   Fourth, the sealing material of the present invention is characterized as being amorphous. Here, “non-crystalline” refers to a substance in which a crystallization peak does not appear at a temperature of 550 ° C. or higher, preferably 570 ° C. or higher, by differential thermal analysis (DTA). In addition, DTA is performed in air | atmosphere and a temperature increase rate starts at 10 degree-C / min and room temperature.

結晶性の封着材料は、一旦、ガラスに結晶が析出すると、ガラスが軟化変形し難くなり、真空排気工程で封着材料が装置内部に引き込まれる事態を防止することができる。しかし、結晶性の封着材料は、ガラスの溶融工程、粉砕工程、耐火性フィラー粉末の混合工程等で発生する不純物により、結晶の析出時期が容易に変動し、封着材料の製造ロットによって、結晶の析出時期が変動しやすい性質を有している。ＰＤＰ等の平面表示装置は、既述の通り、複数回の熱処理工程を経るため、結晶性の封着材料を使用すると、前面ガラス基板と背面ガラス基板を安定して封着することが困難になる。具体的には、一次焼成工程でガラスに結晶が析出すれば、二次焼成工程でガラスに析出した結晶が成長して、封着材料の流動性が低下し、その結果、前面ガラス基板と背面ガラス基板の封着強度が低下しやすくなり、ＰＤＰの気密信頼性も確保し難くなる。その点、封着材料が非結晶性であれば、上記の問題は生じず、封着材料の製造工程で発生する不純物により、封着材料の特性が変動し難く、前面ガラス基板と背面ガラス基板の封着強度を確保することができる。   In the crystalline sealing material, once crystals are deposited on the glass, the glass is difficult to be softened and deformed, and the sealing material can be prevented from being drawn into the apparatus in the vacuum exhaust process. However, the crystalline sealing material can easily change the crystal deposition time due to impurities generated in the glass melting process, pulverization process, refractory filler powder mixing process, etc., depending on the production lot of the sealing material, It has the property that the precipitation time of crystals tends to fluctuate. As described above, since a flat display device such as a PDP undergoes a plurality of heat treatment steps, it is difficult to stably seal the front glass substrate and the rear glass substrate when a crystalline sealing material is used. Become. Specifically, if crystals are deposited on the glass in the primary firing step, the crystals deposited on the glass in the secondary firing step grow, and the fluidity of the sealing material is reduced. The sealing strength of the glass substrate tends to decrease, and it becomes difficult to ensure the airtight reliability of the PDP. In that respect, if the sealing material is non-crystalline, the above-mentioned problem does not occur, and the characteristics of the sealing material hardly change due to impurities generated in the manufacturing process of the sealing material. The sealing strength can be ensured.

第五に、本発明の封着材料は、実質的にＰｂＯを含有しないことに特徴付けられる。ここで、本発明でいう「実質的にＰｂＯを含有しない」とは、ガラス組成中のＰｂＯの含有量が１０００ｐｐｍ以下の場合を指す。このようにすれば、近年の環境的要請を満たすことができる。   Fifth, the sealing material of the present invention is characterized by being substantially free of PbO. Here, “substantially not containing PbO” in the present invention refers to a case where the content of PbO in the glass composition is 1000 ppm or less. In this way, environmental demands in recent years can be satisfied.

第六に、本発明の封着材料は、ＰＤＰの前面ガラス基板と背面ガラス基板の封着に用いることに特徴付けられる。   Sixth, the sealing material of the present invention is characterized by being used for sealing the front glass substrate and the rear glass substrate of PDP.

第七に、本発明の封着材料は、ビスマス系ガラス粉末と耐火性フィラー粉末を含有する封着材料において、（１）耐火性フィラー粉末として、アルミナを１〜２５体積％含有し、（２）軟化点が５３０℃以下であり、（３）封着材料を緻密に焼結させたものを測定試料とし、室温から４５０℃まで昇温速度３℃／分で昇温した後、４５０℃で２０分間保持したときの粘度が１０６．０ｄＰａ・ｓ以上であることを特徴とする。ここで、「軟化点」は、マクロ型示差熱分析（マクロ型ＤＴＡ）装置で測定した第四変局点を指す。なお、マクロ型ＤＴＡは、大気中で室温から測定を開始し、昇温速度を１０℃／分とする。また、「緻密に焼結させたもの」は、焼結体の表面に結晶が析出しておらず、光沢がある状態のもの（例えば、軟化点＋５０℃で２０分間焼結させたもの）を用い、「４５０℃で２０分間保持したときの粘度」は、平行板粘度計で測定することができる。 Seventh, the sealing material of the present invention contains (1) 1 to 25% by volume of alumina as the refractory filler powder in the sealing material containing the bismuth-based glass powder and the refractory filler powder. ) The softening point is 530 ° C. or less, and (3) a sample obtained by densely sintering the sealing material is used as a measurement sample, and the temperature is raised from room temperature to 450 ° C. at a rate of temperature rise of 3 ° C./min. Viscosity when held for 20 minutes is 10 6.0 dPa · s or more. Here, the “softening point” refers to a fourth inflection point measured with a macro type differential thermal analysis (macro type DTA) apparatus. The macro type DTA starts measurement from room temperature in the atmosphere, and the temperature rising rate is 10 ° C./min. In addition, the “sintered densely” means that a crystal is not deposited on the surface of the sintered body and is glossy (for example, sintered at a softening point + 50 ° C. for 20 minutes). The “viscosity when held at 450 ° C. for 20 minutes” can be measured with a parallel plate viscometer.

本発明の封着材料において、アルミナの含有量を１〜２５体積％に規制すれば、封着材料の流動性が損なわれる事態を防止できるとともに、真空排気工程を４５０〜５００℃で行っても、封着材料が装置内部に引き込まれにくくなり、装置内部を短時間で高真空状態にすることができる。その結果、ＰＤＰの製造効率および輝度特性を高めることができる。また、本発明の封着材料において、ガラスの軟化点を５３０℃以下に規制すれば、封着材料の流動性を高めることができ、５３０℃以下の温度で封着材料を良好に流動させることができる。さらに、本発明の封着材料において、４５０℃で２０分間保持したときの粘度を１０６．０ｄＰａ・ｓ以上に規制すれば、真空排気工程で封着材料の変形を抑制することができ、封着材料の引き込みを防止しやすくなる。 In the sealing material of the present invention, if the content of alumina is restricted to 1 to 25% by volume, the fluidity of the sealing material can be prevented from being impaired, and the evacuation step can be performed at 450 to 500 ° C. The sealing material is less likely to be drawn into the apparatus, and the inside of the apparatus can be brought into a high vacuum state in a short time. As a result, the manufacturing efficiency and luminance characteristics of the PDP can be improved. Further, in the sealing material of the present invention, if the softening point of the glass is regulated to 530 ° C. or lower, the fluidity of the sealing material can be improved, and the sealing material can be flowed well at a temperature of 530 ° C. or lower. Can do. Furthermore, in the sealing material of the present invention, if the viscosity when held at 450 ° C. for 20 minutes is regulated to 10 6.0 dPa · s or more, deformation of the sealing material can be suppressed in the vacuum exhaust process, It becomes easy to prevent the sealing material from being pulled in.

第八に、本発明の封着材料は、４５０℃で２０分保持したときの粘度変化が１００．５ｄＰａ・ｓ以下であることを特徴とする。このようにすれば、真空排気工程で、封着材料の変形を抑制することができ、封着材料の引き込みを防止しやすくなる。ここで、「４５０℃２０分保持したときの粘度変化」は、平行板粘度計で測定することができる。 Eighth, the sealing material of the present invention is characterized in that the viscosity change when held at 450 ° C. for 20 minutes is 10 0.5 dPa · s or less. If it does in this way, a deformation | transformation of sealing material can be suppressed at a vacuum exhaustion process, and it will become easy to prevent entrainment of sealing material. Here, “change in viscosity when held at 450 ° C. for 20 minutes” can be measured with a parallel plate viscometer.

本発明の封着材料において、ビスマス系ガラス粉末のガラス組成範囲を上記のように限定した理由を以下に示す。   The reason for limiting the glass composition range of the bismuth-based glass powder as described above in the sealing material of the present invention will be described below.

Ｂｉ２Ｏ３は、軟化点を下げるための主要成分である。その含有量は６７〜９０％、好ましくは７０〜８４％、より好ましくは７３〜８２％、更に好ましくは７５〜７７％未満である。Ｂｉ２Ｏ３の含有量が６７％より少ないと、ガラスの軟化点が高くなり過ぎ、５３０℃以下の温度で封着しにくくなる。一方、Ｂｉ２Ｏ３の含有量が９０％より多いと、ガラスが熱的に不安定になり、溶融時または焼成時にガラスが失透しやすくなる。 Bi 2 O 3 is a main component for lowering the softening point. Its content is 67-90%, preferably 70-84%, more preferably 73-82%, and still more preferably less than 75-77%. When the content of Bi 2 O 3 is less than 67%, the softening point of the glass becomes too high and it becomes difficult to seal at a temperature of 530 ° C. or lower. On the other hand, when the content of Bi 2 O 3 is more than 90%, the glass becomes thermally unstable, and the glass tends to devitrify during melting or firing.

Ｂ２Ｏ３は、ビスマス系ガラスのガラスネットワークを形成する成分であり、必須成分である。その含有量は２〜１２％、好ましくは３〜１０％、より好ましくは４〜１０％、更に好ましくは５〜９．６％である。Ｂ２Ｏ３の含有量が２％より少ないと、ガラスが熱的に不安定になり、溶融時または焼成時にガラスが失透しやすくなる。一方、Ｂ２Ｏ３の含有量が１２％より多いと、ガラスの粘性が高くなり過ぎ、５３０℃以下の温度で封着しにくくなる。 B 2 O 3 is a component that forms a glass network of bismuth-based glass and is an essential component. Its content is 2 to 12%, preferably 3 to 10%, more preferably 4 to 10%, still more preferably 5 to 9.6%. If the content of B 2 O 3 is less than 2%, the glass becomes thermally unstable, and the glass tends to devitrify during melting or firing. On the other hand, if the content of B 2 O 3 is more than 12%, the viscosity of the glass becomes too high and sealing becomes difficult at a temperature of 530 ° C. or lower.

質量比Ｂｉ２Ｏ３／Ｂ２Ｏ３は、ビスマス系ガラスの熱的安定性および軟化特性に大きく影響を及ぼす成分比率である。また、ビスマス系ガラスにおいて、Ｂｉ２Ｏ３とＢ２Ｏ３は、ガラスの骨格を形成する主要成分であるとともに、両成分はガラス組成中の含有比率が高いことから、ビスマス系ガラスの特性を決定付ける成分と考えられる。Ｂｉ２Ｏ３は、ガラスの軟化点を低下させる成分であり、Ｂ２Ｏ３に対しＢｉ２Ｏ３の含有量が多くなるにつれて、ガラスの軟化点が低下する傾向がある。その一方、ガラスの熱的安定性が乏しくなり、ガラスに失透が生じやすくなる。また、Ｂ２Ｏ３は、ガラスの熱的安定性を向上させる成分であり、Ｂｉ２Ｏ３に対しＢ２Ｏ３の含有量が多くなるにつれて、ガラスの熱的安定性が向上する。その一方、ガラスの軟化点が上昇する傾向がある。したがって、Ｂｉ２Ｏ３とＢ２Ｏ３は、その特性がトレードオフの関係にあり、質量比Ｂｉ２Ｏ３／Ｂ２Ｏ３の値を所定範囲に規制すれば、ガラスの軟化点と熱的安定性を最適化することが可能になり、二次焼成工程で封着材料の流動性を確保しつつ、真空排気工程で封着材料が装置内部に引き込まれる事態を防止しやすくなる。質量比Ｂｉ２Ｏ３／Ｂ２Ｏ３は１１以下、好ましくは１０．８以下、より好ましくは６〜１０．２、更に好ましくは７．８〜９．９である。質量比Ｂｉ２Ｏ３／Ｂ２Ｏ３の値が１１より大きいと、ガラスの軟化点は低下するが、一次焼成工程でガラスが失透しやすくなる、或いは真空排気工程で封着材料が装置内部に引き込まれやすくなる。 The mass ratio Bi 2 O 3 / B 2 O 3 is a component ratio that greatly affects the thermal stability and softening characteristics of the bismuth-based glass. In the bismuth-based glass, Bi 2 O 3 and B 2 O 3 are the main components forming the glass skeleton, and both components have a high content ratio in the glass composition, so that the characteristics of the bismuth-based glass are improved. It is considered as a determinative component. Bi 2 O 3 is a component that lowers the softening point of the glass, and as the content of Bi 2 O 3 increases with respect to B 2 O 3 , the softening point of the glass tends to decrease. On the other hand, the thermal stability of the glass becomes poor and the glass tends to be devitrified. Further, B 2 O 3 is a component for improving the thermal stability of the glass, as to Bi 2 O 3 becomes large content of B 2 O 3, they improve the thermal stability of the glass. On the other hand, the softening point of glass tends to increase. Therefore, Bi 2 O 3 and B 2 O 3 have a trade-off characteristic, and if the mass ratio Bi 2 O 3 / B 2 O 3 is regulated within a predetermined range, the glass softening point and heat It is possible to optimize the mechanical stability, and it is easy to prevent the sealing material from being drawn into the apparatus in the vacuum exhaust process while ensuring the fluidity of the sealing material in the secondary firing process. The mass ratio Bi 2 O 3 / B 2 O 3 is 11 or less, preferably 10.8 or less, more preferably 6 to 10.2, and still more preferably 7.8 to 9.9. If the value of the mass ratio Bi 2 O 3 / B 2 O 3 is larger than 11, the softening point of the glass is lowered, but the glass is easily devitrified in the primary firing process, or the sealing material is used in the vacuum exhaust process. It becomes easy to be drawn inside.

Ａｌ２Ｏ３は、ガラスの耐候性を向上させる成分である。その含有量は０〜５％、好ましくは０〜２％である。Ａｌ２Ｏ３の含有量が５％より多いと、ガラスの軟化点が高くなり過ぎ、５３０℃以下の温度で封着することが困難になる。 Al 2 O 3 is a component that improves the weather resistance of the glass. Its content is 0-5%, preferably 0-2%. When the content of Al 2 O 3 is more than 5%, too high softening point of the glass, it is difficult to seal at 530 ° C. or lower.

ＺｎＯは、溶融時または焼成時にガラスの失透を抑制する効果がある成分である。その含有量は１〜１５％、好ましくは２〜１１％、より好ましくは３〜９％、更に好ましくは４〜８％である。ＺｎＯの含有量が１％より少ないと、溶融時または焼成時にガラスの失透を抑制する効果が得られにくくなる。ＺｎＯの含有量が１５％より多いと、ガラス組成内のバランスを欠き、逆にガラスの熱的安定性が損なわれ、その結果、ガラスが失透しやすくなる。   ZnO is a component that has an effect of suppressing devitrification of the glass during melting or firing. Its content is 1 to 15%, preferably 2 to 11%, more preferably 3 to 9%, still more preferably 4 to 8%. When the content of ZnO is less than 1%, it becomes difficult to obtain an effect of suppressing devitrification of the glass during melting or firing. When the content of ZnO is more than 15%, the balance in the glass composition is lost, and conversely, the thermal stability of the glass is impaired, and as a result, the glass is easily devitrified.

ＢａＯ、ＳｒＯ、ＭｇＯ、ＣａＯは、溶融時または焼成時にガラスの失透を抑制する効果がある成分である。これらの成分は合量で１５％までガラス組成中に添加することができる。これらの成分の合量が１５％より多いと、ガラスの軟化点が高くなり過ぎ、５３０℃以下の温度で封着し難くなる。   BaO, SrO, MgO, and CaO are components that have an effect of suppressing devitrification of the glass during melting or firing. These components can be added to the glass composition up to 15% in total. When the total amount of these components is more than 15%, the softening point of the glass becomes too high and it becomes difficult to seal at a temperature of 530 ° C. or lower.

ＢａＯの含有量は０〜１０％が好ましく、０〜８％がより好ましく、１〜７％が更に好ましい。ＢａＯの含有量が１０％より多いと、ガラス組成内のバランスを欠き、逆にガラスの熱的安定性が損なわれ、その結果、ガラスが失透しやすくなる。また、ガラスの熱的安定性を向上させる観点から、ＢａＯの含有量を１％以上（望ましくは３％以上）とするのが好ましい。   The content of BaO is preferably 0 to 10%, more preferably 0 to 8%, and still more preferably 1 to 7%. When the content of BaO is more than 10%, the balance in the glass composition is lost, and conversely, the thermal stability of the glass is impaired, and as a result, the glass is easily devitrified. Further, from the viewpoint of improving the thermal stability of the glass, the BaO content is preferably 1% or more (desirably 3% or more).

ＳｒＯ、ＭｇＯ、ＣａＯのそれぞれの含有量は０〜５％が好ましく、０〜２％がより好ましい。各成分の含有量が５％より多いと、ガラスが失透、或いは分相しやすくなる。   Each content of SrO, MgO, and CaO is preferably 0 to 5%, and more preferably 0 to 2%. When the content of each component is more than 5%, the glass is easily devitrified or phase-separated.

ＣｕＯは、溶融時または焼成時にガラスの失透を抑制する効果があり、５％まで添加することができる。ＣｕＯの含有量が５％より多いと、ガラスが失透しやすくなり、ガラスの流動性が損なわれやすくなる。また、ガラスの熱的安定性を向上させる観点から、ＣｕＯを微量添加するのが好ましく、具体的には、ＣｕＯの含有量を０．０１％以上（望ましくは０．１％以上、より望ましくは１％以上）とするのが好ましい。   CuO has an effect of suppressing devitrification of the glass at the time of melting or firing, and can be added up to 5%. If the content of CuO is more than 5%, the glass tends to devitrify and the fluidity of the glass tends to be impaired. Further, from the viewpoint of improving the thermal stability of the glass, it is preferable to add a small amount of CuO. Specifically, the content of CuO is 0.01% or more (desirably 0.1% or more, more desirably 1% or more).

Ｆｅ２Ｏ３は、溶融時または焼成時にガラスの失透を抑制する効果があり、その含有量は０〜３％が好ましく、０〜２％がより好ましい。Ｆｅ２Ｏ３の含有量が３％より多いと、ガラス組成内のバランスを欠き、逆にガラスの熱的安定性が損なわれ、その結果、ガラスが失透しやすくなる。また、ガラスの熱的安定性を向上させる観点から、Ｆｅ２Ｏ３を微量添加するのが好ましく、具体的には、Ｆｅ２Ｏ３の含有量を０．０１％以上（望ましくは０．１％以上）とするのが好ましい。 Fe 2 O 3 has an effect of suppressing devitrification of the glass at the time of melting or firing, and its content is preferably 0 to 3%, more preferably 0 to 2%. When the content of Fe 2 O 3 is more than 3%, the balance in the glass composition is lost, and conversely, the thermal stability of the glass is impaired, and as a result, the glass is easily devitrified. From the viewpoint of improving the thermal stability of the glass, it is preferable to add a small amount of Fe 2 O 3. Specifically, the content of Fe 2 O 3 is 0.01% or more (preferably 0.1%). % Or more).

ＣｅＯ２は、溶融時または焼成時にガラスの失透を抑制する効果があり、その含有量は０〜５％、好ましくは０〜２％、より好ましくは０〜１％である。ＣｅＯ２の含有量が５％より多いと、ガラス組成内のバランスを欠き、逆にガラスの熱的安定性が損なわれ、ガラスが失透しやすくなる。また、ガラスの熱的安定性を向上させる観点から、ＣｅＯ２を微量添加するのが好ましく、具体的には、ＣｅＯ２の含有量を０．０１％以上とするのが好ましい。 CeO 2 has an effect of suppressing devitrification of the glass at the time of melting or firing, and its content is 0 to 5%, preferably 0 to 2%, more preferably 0 to 1%. When the content of CeO 2 is more than 5%, the balance in the glass composition is lost, and conversely, the thermal stability of the glass is impaired, and the glass is easily devitrified. Further, from the viewpoint of improving the thermal stability of the glass, it is preferable to add a small amount of CeO 2 , and specifically, the content of CeO 2 is preferably 0.01% or more.

Ｓｂ２Ｏ３は、ガラスの失透を抑制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％、より好ましくは０．１〜１％である。Ｓｂ２Ｏ３は、ビスマス系ガラスのネットワーク構造を安定化させる効果があり、ビスマス系ガラスにおいて、Ｓｂ２Ｏ３を適宜添加すれば、Ｂｉ２Ｏ３の含有量が多い場合、例えばＢｉ２Ｏ３の含有量が７６％以上であっても、ガラスの熱的安定性が低下し難くなる。ただし、Ｓｂ２Ｏ３の含有量が５％より多いと、ガラス組成内のバランスを欠き、逆にガラスの熱的安定性が損なわれ、その結果、ガラスが失透しやすくなる。また、ガラスの熱的安定性を向上させる観点から、Ｓｂ２Ｏ３を微量添加するのが好ましく、具体的には、Ｓｂ２Ｏ３の含有量を０．１％以上（望ましくは０．４％以上）とするのが好ましい。 Sb 2 O 3 content of a component for suppressing the devitrification of the glass, the content thereof is 0 to 5%, preferably 0 to 2%, more preferably 0.1% to 1%. Sb 2 O 3 has an effect of stabilizing the network structure of the bismuth-based glass. If Sb 2 O 3 is appropriately added to the bismuth-based glass, when the content of Bi 2 O 3 is large, for example, Bi 2 O 3 Even if the content of 3 is 76% or more, the thermal stability of the glass is hardly lowered. However, when the content of Sb 2 O 3 is more than 5%, the balance in the glass composition is lost, and conversely, the thermal stability of the glass is impaired, and as a result, the glass is easily devitrified. Further, from the viewpoint of improving the thermal stability of the glass, it is preferable to add a small amount of Sb 2 O 3. Specifically, the Sb 2 O 3 content is 0.1% or more (preferably 0.4%). % Or more).

なお、ビスマス系ガラス粉末は、ガラス組成として、上記成分以外にも、例えば以下の成分を合量で２０％、好ましくは１０％までガラス組成中に含有させることができる。   The bismuth-based glass powder can contain, for example, the following components in addition to the above components in the glass composition in a total amount of 20%, preferably 10% in addition to the above components.

ＳｉＯ２は、ガラスの耐候性を向上させる成分である。その含有量は０〜１０％、好ましくは０〜３％である。ＳｉＯ２の含有量が１０％より多いと、ガラスの軟化点が高くなり過ぎ、５３０℃以下の温度で封着することが困難になる。 SiO 2 is a component that improves the weather resistance of glass. Its content is 0 to 10%, preferably 0 to 3%. If the content of SiO 2 is more than 10%, the softening point of the glass becomes too high, and it becomes difficult to seal at a temperature of 530 ° C. or lower.

ＷＯ３は、ガラスの失透を抑制するための成分であり、その含有量は０〜１０％が好ましく、０〜２％がより好ましい。ただし、ＷＯ３の含有量が１０％より多いと、ガラス組成内のバランスを欠き、逆にガラスの熱的安定性が損なわれ、その結果、ガラスが失透しやすくなる。 WO 3 is a component for suppressing devitrification of the glass, and its content is preferably 0 to 10%, more preferably 0 to 2%. However, when the content of WO 3 is more than 10%, the balance in the glass composition is lost, and conversely, the thermal stability of the glass is impaired, and as a result, the glass is easily devitrified.

Ｉｎ２Ｏ３、Ｇａ２Ｏ３は必須成分ではないが、ガラスの失透を抑制するための成分であり、その含有量は合量で０〜５％が好ましく、０〜３％がより好ましい。ただし、Ｉｎ２Ｏ３、Ｇａ２Ｏ３の含有量が合量で５％より多いと、ガラス組成内のバランスを欠き、逆にガラスの熱的安定性が損なわれ、その結果、ガラスが失透しやすくなる。なお、Ｉｎ２Ｏ３の含有量は０〜１％がより好ましく、Ｇａ２Ｏ３の含有量は０〜０．５％がより好ましい。 In 2 O 3 and Ga 2 O 3 are not essential components, but are components for suppressing devitrification of the glass, and the total content is preferably 0 to 5%, more preferably 0 to 3%. . However, if the total content of In 2 O 3 and Ga 2 O 3 is more than 5%, the balance in the glass composition is lost, and conversely, the thermal stability of the glass is impaired, resulting in the loss of the glass. It becomes easy to see through. In addition, the content of In 2 O 3 is more preferably 0 to 1%, and the content of Ga 2 O 3 is more preferably 0 to 0.5%.

Ｌｉ、Ｎａ、ＫおよびＣｓの酸化物は、ガラスの軟化点を低くする成分であるが、溶融
時にガラスの失透を促進する作用を有するため合量で２％以下とするのが好ましい。 The Li, Na, K, and Cs oxides are components that lower the softening point of the glass. However, since they have an action of promoting devitrification of the glass during melting, the total amount is preferably 2% or less.

Ｐ２Ｏ５は、溶融時にガラスの失透を抑制する成分であるが、その添加量が１％より多いと、溶融時にガラスが分相しやすくなるため好ましくない。 P 2 O 5 is a component that suppresses the devitrification of the glass at the time of melting. However, if the amount added is more than 1%, the glass tends to phase-separate at the time of melting, which is not preferable.

ＭｏＯ３、Ｌａ２Ｏ３、Ｙ２Ｏ３およびＧｄ２Ｏ３は、溶融時にガラスの分相を抑制する成分であるが、これらの合量が３％より多いと、ガラスの軟化点が高くなり過ぎ、５３０℃以下の温度で焼成しにくくなる。 MoO 3 , La 2 O 3 , Y 2 O 3 and Gd 2 O 3 are components that suppress the phase separation of the glass at the time of melting. However, if the total amount of these is more than 3%, the softening point of the glass is high. It becomes too difficult to fire at a temperature of 530 ° C. or lower.

また、その他の成分であっても、ガラスの特性を損なわない範囲で１５％（好ましくは５％）までガラス組成中に添加することができる。   Moreover, even if it is another component, it can add to a glass composition to 15% (preferably 5%) in the range which does not impair the characteristic of glass.

以上のガラス組成を有するビスマス系ガラスは、５３０℃以下の温度で良好な流動性を示す非晶質のガラスであり、３０〜３００℃における熱膨張係数が約１００〜１２０×１０−７／℃である。 The bismuth glass having the above glass composition is an amorphous glass exhibiting good fluidity at a temperature of 530 ° C. or less, and has a thermal expansion coefficient of about 100 to 120 × 10 −7 / ° C. at 30 to 300 ° C. It is.

本発明の封着材料は、耐火性フィラー粉末として、アルミナを１〜２５体積％、好ましくは２〜１８体積％、より好ましくは３〜１４体積％含有する。アルミナは、焼成後の封着部位の形状維持に顕著な効果がある成分である。アルミナが１体積％より少ないと、形状維持効果が乏しくなり、真空排気工程で封着材料が装置内部に引き込まれやすくなる。一方、アルミナが２５体積％より多いと、封着材料が流動し難くなり、一次焼成工程および二次焼成工程で所望の流動性を確保し難くなる。   The sealing material of the present invention contains 1 to 25% by volume, preferably 2 to 18% by volume, more preferably 3 to 14% by volume of alumina as a refractory filler powder. Alumina is a component that has a significant effect on maintaining the shape of the sealed part after firing. When the amount of alumina is less than 1% by volume, the shape maintaining effect is poor, and the sealing material is easily drawn into the apparatus in the vacuum exhaust process. On the other hand, when there is more alumina than 25 volume%, it becomes difficult for a sealing material to flow and it becomes difficult to ensure desired fluidity | liquidity in a primary baking process and a secondary baking process.

本発明の封着材料において、アルミナの１０％粒子径Ｄ１０は１〜５μｍが好ましく、２〜４μｍがより好ましい。アルミナの１０％粒子径Ｄ１０が１μｍより小さいと、焼成時にアルミナがガラス中に溶け込みやすくなるため、封着材料が流動し難くなり、一次焼成工程および二次焼成工程で所望の流動性を確保し難くなる。一方、アルミナの１０％粒子径Ｄ１０が５μｍより大きいと、アルミナの形状維持効果が乏しくなり、真空排気工程で封着材料が装置内部に引き込まれやすくなる。 In the sealing material of the present invention, the 10% particle size D 10 of the alumina 1~5μm preferably, 2-4 [mu] m is more preferable. Securing 10% particle diameter D 10 of the 1μm smaller than alumina, since alumina during firing tends penetration in glass, the sealing material is difficult to flow, the desired fluidity in the primary firing process and secondary firing step It becomes difficult to do. On the other hand, a 5μm greater than the 10% particle size D 10 of the alumina, the shape maintaining effect of alumina is poor, the sealing material is easily pulled into the apparatus by the vacuum exhaust process.

本発明の封着材料において、アルミナの平均粒子径Ｄ５０は３〜２５μｍが好ましく、５〜１５μｍがより好ましい。アルミナの平均粒子径Ｄ５０が３μｍより小さいと、焼成時にアルミナがガラス中に溶け込みやすくなるため、封着材料が流動し難くなり、一次焼成工程および二次焼成工程で所望の流動性を確保し難くなる。一方、アルミナの平均粒子径Ｄ５０が２５μｍより大きいと、アルミナの形状維持効果が乏しくなり、真空排気工程で封着材料が装置内部に引き込まれやすくなる。 In the sealing material of the present invention, the average particle diameter D 50 of the alumina is preferably 3～25Myuemu, 5 to 15 [mu] m is more preferable. If the average particle diameter D 50 of alumina is smaller than 3 μm, the alumina easily dissolves in the glass at the time of firing, so that the sealing material becomes difficult to flow, and the desired fluidity is ensured in the primary firing step and the secondary firing step. It becomes difficult. On the other hand, a 25μm larger average particle diameter D 50 of the alumina, the shape maintaining effect of alumina is poor, the sealing material is easily pulled into the apparatus by the vacuum exhaust process.

本発明の封着材料において、アルミナの９０％粒子径Ｄ９０は１０〜３５μｍが好ましく、１７〜３０μｍがより好ましい。アルミナの９０％粒子径Ｄ９０が１０μｍより小さいと、焼成時にアルミナがガラス中に溶け込みやすくなるため、封着材料が流動し難くなり、一次焼成工程および二次焼成工程で所望の流動性を確保し難くなる。一方、アルミナの９０％粒子径Ｄ９０が３５μｍより大きいと、アルミナの形状維持効果が乏しくなり、真空排気工程で封着材料が装置内部に引き込まれやすくなる。 In the sealing material of the present invention, the 90% particle diameter D 90 of alumina is preferably 10 to 35 μm, and more preferably 17 to 30 μm. If the 90% particle diameter D 90 of alumina is smaller than 10 μm, the alumina easily dissolves in the glass during firing, so that the sealing material is difficult to flow, and the desired fluidity is ensured in the primary firing process and the secondary firing process. It becomes difficult to do. On the other hand, if the 90% particle diameter D 90 of alumina is larger than 35 μm, the shape maintaining effect of alumina is poor, and the sealing material is easily drawn into the apparatus in the vacuum exhaust process.

本発明の封着材料において、アルミナの比表面積は０．１〜３ｍ２／ｇが好ましく、０．５〜２ｍ２／ｇがより好ましい。ここで、本発明でいう「比表面積」とは、気体吸着ＢＥＴ法で測定した値を指し、ＪＩＳ Ｒ１６２６に準拠した方法により測定した値を指す。アルミナの比表面積が０．１ｍ２／ｇより小さいと、アルミナの形状維持効果が乏しくなり、真空排気工程で封着材料が装置内部に引き込まれやすくなる。一方、アルミナの比表面積が３ｍ２／ｇより大きいと、焼成時にアルミナがガラス中に溶け込みやすくなるため、封着材料の流動性が低下し、５３０℃以下の温度で封着し難くなる。 In the sealing material of the present invention, the specific surface area of the alumina is preferably 0.1~3m 2 / g, 0.5~2m 2 / g is more preferable. Here, the “specific surface area” in the present invention refers to a value measured by a gas adsorption BET method, and a value measured by a method based on JIS R1626. When the specific surface area of alumina is smaller than 0.1 m 2 / g, the shape maintaining effect of alumina becomes poor, and the sealing material is easily drawn into the apparatus in the vacuum exhaust process. On the other hand, when the specific surface area of alumina is larger than 3 m 2 / g, alumina easily dissolves in the glass at the time of firing, so that the fluidity of the sealing material is lowered and sealing becomes difficult at a temperature of 530 ° C. or lower.

耐火性フィラー粉末として、アルミナ以外に、ウイレマイト、ジルコン、リン酸ジルコニウム、リン酸タングステン酸ジルコニウム、タングステン酸ジルコニウム、酸化スズ、コーディエライト、β−ユークリプタイト、チタン酸アルミニウム、セルシアン、石英ガラス、ムライト、β−スポジュメン、アルミナ−シリカ系セラミックス等の種々の材料を使用することができる。これらの耐火性フィラー粉末は、熱膨張係数が低く、且つ機械的強度が高く、好ましい。特に、耐火性フィラー粉末として、ウイレマイトおよびコーディエライトは、ビスマス系ガラスを失透させにくく、低膨張であり、更には機械的強度に優れているため、より好ましい。   As refractory filler powder, besides alumina, willemite, zircon, zirconium phosphate, zirconium tungstate phosphate, zirconium tungstate, tin oxide, cordierite, β-eucryptite, aluminum titanate, celsian, quartz glass, Various materials such as mullite, β-spodumene, and alumina-silica ceramics can be used. These refractory filler powders are preferable because they have a low thermal expansion coefficient and high mechanical strength. In particular, as the refractory filler powder, willemite and cordierite are more preferable because they are less likely to devitrify bismuth-based glass, have low expansion, and are excellent in mechanical strength.

本発明の封着材料において、ガラス粉末と耐火性フィラー粉末の混合割合は、ガラス粉末４０〜９０体積％、耐火性フィラー粉末１０〜６０体積％が好ましく、ガラス粉末５０〜７５体積％、耐火性フィラー粉末２５〜５０体積％がより好ましい。両者の割合をこのように規定した理由は、耐火性フィラー粉末が１０体積％より少ないと、封着材料の熱膨張係数をガラス基板等の被封着物の熱膨張係数に整合させにくくなり、残留応力により封着部位およびガラス基板等の被封着物が破壊しやすくなる。一方、耐火性フィラー粉末が６０体積％より多いと、相対的にガラス粉末の含有量が少なくなるため、封着材料の流動性が低下し、一次焼成工程および二次焼成工程で所望の流動性を確保し難くなる。   In the sealing material of the present invention, the mixing ratio of the glass powder and the refractory filler powder is preferably 40 to 90% by volume of glass powder and 10 to 60% by volume of refractory filler powder, 50 to 75% by volume of glass powder, and refractory. The filler powder is more preferably 25 to 50% by volume. The reason for defining the ratio of the two in this way is that when the refractory filler powder is less than 10% by volume, it becomes difficult to match the thermal expansion coefficient of the sealing material to the thermal expansion coefficient of the sealed object such as a glass substrate, and the residual The sealed part and the sealed object such as the glass substrate are easily broken by the stress. On the other hand, when the amount of the refractory filler powder is more than 60% by volume, the content of the glass powder is relatively reduced, so that the fluidity of the sealing material is lowered, and the desired fluidity in the primary firing process and the secondary firing process. It becomes difficult to secure.

本発明の封着材料において、封着材料の軟化点は５３０℃以下が好ましく、５１０℃以下がより好ましく、４９０℃以下が更に好ましい。封着材料の軟化点が５３０℃より高いと、５３０℃以下の温度で封着材料が流動し難くなり、所望の封着強度を確保できないおそれがある。   In the sealing material of the present invention, the softening point of the sealing material is preferably 530 ° C. or less, more preferably 510 ° C. or less, and further preferably 490 ° C. or less. If the softening point of the sealing material is higher than 530 ° C., the sealing material becomes difficult to flow at a temperature of 530 ° C. or less, and a desired sealing strength may not be ensured.

本発明の封着材料は、非晶質であることが好ましい。このようにすれば、５３０℃以下の温度でガラスの表面に結晶が析出し難く、つまりガラスが流動する前に、ガラスが失透し難く、所望の流動性を確保しやすくなる。また、封着材料が非晶質であると、被封着物と封着材料の反応が促進されるため、封着強度が高まり、ＰＤＰの気密信頼性を確保しやすくなる。   The sealing material of the present invention is preferably amorphous. This makes it difficult for crystals to precipitate on the surface of the glass at a temperature of 530 ° C. or lower, that is, it is difficult for the glass to devitrify before the glass flows, and it becomes easy to ensure the desired fluidity. Further, when the sealing material is amorphous, the reaction between the object to be sealed and the sealing material is promoted, so that the sealing strength is increased and it is easy to ensure the airtight reliability of the PDP.

本発明の封着材料は、ＰｂＯを含有する態様を排除するものではないが、既述の通り、環境上の理由からＰｂＯを実質的に含有しないことが好ましい。また、ガラス組成中にＰｂＯを含有させると、ガラス中に存在するＰｂ２＋が拡散して、封着材料の電気絶縁性を低下させる場合がある。 The sealing material of the present invention does not exclude the embodiment containing PbO, but as described above, it is preferable that the sealing material does not substantially contain PbO for environmental reasons. Moreover, when PbO is contained in the glass composition, Pb 2+ present in the glass diffuses, and the electrical insulation of the sealing material may be lowered.

封着材料は、粉末のまま使用してもよいが、封着材料とビークルを均一に混練し、ペースト材料として使用すると取り扱いやすい。ビークルは、主に有機溶媒と樹脂とからなり、樹脂はペースト材料の粘性を調整する目的で添加される。また、必要に応じて、界面活性剤、増粘剤等を添加することもできる。作製されたペースト材料は、ディスペンサーやスクリーン印刷機等の塗布機を用いて、ガラス基板等の被封着物上に塗布される。   The sealing material may be used as a powder, but it is easy to handle when the sealing material and the vehicle are uniformly kneaded and used as a paste material. The vehicle is mainly composed of an organic solvent and a resin, and the resin is added for the purpose of adjusting the viscosity of the paste material. Moreover, surfactant, a thickener, etc. can also be added as needed. The produced paste material is applied onto an object to be sealed such as a glass substrate using an applicator such as a dispenser or a screen printer.

有機溶媒としては、Ｎ、Ｎ’−ジメチルホルムアミド（ＤＭＦ）、α−ターピネオール、高級アルコール、γ−ブチルラクトン（γ−ＢＬ）、テトラリン、ブチルカルビトールアセテート、酢酸エチル、酢酸イソアミル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ベンジルアルコール、トルエン、３−メトキシ−３−メチルブタノール、水、トリエチレングリコールモノメチルエーテル、トリエチレングリコールジメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノブチルエーテル、プロピレンカーボネート、ジメチルスルホキシド（ＤＭＳＯ）、Ｎ−メチル−２−ピロリドン等が使用可能である。特に、α−ターピネオールは、高粘性であり、樹脂等の溶解性も良好であるため、好ましい。   As organic solvents, N, N′-dimethylformamide (DMF), α-terpineol, higher alcohol, γ-butyllactone (γ-BL), tetralin, butyl carbitol acetate, ethyl acetate, isoamyl acetate, diethylene glycol monoethyl ether , Diethylene glycol monoethyl ether acetate, benzyl alcohol, toluene, 3-methoxy-3-methylbutanol, water, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl Ether, tripropylene glycol monobutyl ether, propylene carbonate, dimethyl sulfoxide (DMSO) N- methyl-2-pyrrolidone and the like can be used. In particular, α-terpineol is preferable because it is highly viscous and has good solubility in resins and the like.

樹脂としては、アクリル樹脂、エチルセルロ−ス、ポリエチレングリコール誘導体、ニトロセルロース、ポリメチルスチレン、ポリエチレンカーボネート、メタクリル酸エステル等が使用可能である。特に、アクリル樹脂、ニトロセルロースは、ペースト材料の粘性を確保しやすく、熱分解性が良好であるため、好ましい。   As the resin, acrylic resin, ethyl cellulose, polyethylene glycol derivative, nitrocellulose, polymethylstyrene, polyethylene carbonate, methacrylic acid ester and the like can be used. In particular, acrylic resin and nitrocellulose are preferable because the viscosity of the paste material is easily secured and the thermal decomposability is good.

本発明の封着材料は、ＰＤＰの前面ガラス基板と背面ガラス基板の封着に使用することが好ましい。既述の通り、本発明の封着材料は、５３０℃以下の温度で良好に流動するとともに、真空排気工程が４５０〜５００℃であっても、封着材料が装置内部に引き込まれにくいため、本用途に好適である。   The sealing material of the present invention is preferably used for sealing the front glass substrate and the rear glass substrate of the PDP. As described above, the sealing material of the present invention flows well at a temperature of 530 ° C. or lower, and even if the evacuation process is 450 to 500 ° C., the sealing material is not easily drawn into the apparatus, Suitable for this application.

本明細書は、ＰＤＰを中心にして、本発明を説明したが、蛍光表示管、フィールドエミッションディスプレイ（以下、ＦＥＤ）も装置内部を高真空にする真空排気工程が存在するため、ＰＤＰの場合と同様に真空排気工程を高温化できれば、製造効率および輝度特性を高めることができる。なお、ＦＥＤには、各種電子放出素子を有する各種形式のＦＥＤが含まれる点は言うまでもない。   Although this specification has described the present invention centering on the PDP, the fluorescent display tube and the field emission display (hereinafter referred to as FED) also have a vacuum evacuation process in which the inside of the apparatus is evacuated. Similarly, if the temperature of the evacuation process can be increased, manufacturing efficiency and luminance characteristics can be improved. Needless to say, the FED includes various types of FEDs having various electron-emitting devices.

本発明の封着材料は、ビスマス系ガラス粉末と耐火性フィラー粉末を含有する封着材料において、（１）耐火性フィラー粉末として、アルミナを１〜２５体積％含有し、（２）軟化点が５３０℃以下であり、（３）封着材料を緻密に焼結させたものを測定試料とし、室温から４５０℃まで昇温速度３℃／分で昇温した後、４５０℃で２０分間保持したときの粘度が１０６．０ｄＰａ・ｓ以上（好ましくは１０６．３ｄＰａ・ｓ以上）であることを特徴とする。４５０℃で２０分間保持したときの粘度が１０６．０ｄＰａ・ｓ未満であると、真空排気工程で封着材料が変形しやすくなり、真空排気工程で封着材料が装置内部に引き込まれやすくなる。なお、アルミナの含有量および軟化点について、好適な数値範囲および効果は、既に記載した内容と同等であるため、ここではその記載を省略する。 The sealing material of the present invention is a sealing material containing bismuth-based glass powder and refractory filler powder. (1) As a refractory filler powder, 1 to 25% by volume of alumina is contained. (2) Softening point The temperature was 530 ° C. or less, and (3) a sample obtained by densely sintering the sealing material was used as a measurement sample, and the temperature was raised from room temperature to 450 ° C. at a rate of temperature rise of 3 ° C./min, and then held at 450 ° C. for 20 minutes. The viscosity is 10 6.0 dPa · s or more (preferably 10 6.3 dPa · s or more). If the viscosity when held at 450 ° C. for 20 minutes is less than 10 6.0 dPa · s, the sealing material is likely to be deformed in the evacuation process, and the sealing material is easily drawn into the apparatus in the evacuation process. Become. In addition, about the content and softening point of an alumina, since the suitable numerical range and effect are equivalent to the content already described, the description is abbreviate | omitted here.

本発明の封着材料は、ビスマス系ガラス粉末と耐火性フィラー粉末を含有する封着材料において、封着材料を緻密に焼結させたものを測定試料とし、室温から４５０℃まで昇温速度３℃／分で昇温した後、４５０℃２０分保持したときの粘度変化が１００．５ｄＰａ・ｓ以下（好ましくは１００．３ｄＰａ・ｓ以下）であることを特徴とする。４５０℃２０分保持したときの粘度変化が１００．５ｄＰａ・ｓより大きいと、真空排気工程で封着材料が変形しやすくなり、真空排気工程で封着材料が装置内部に引き込まれやすくなる。 The sealing material of the present invention is a sealing material containing a bismuth-based glass powder and a refractory filler powder, in which the sealing material is densely sintered, and the temperature rise rate from room temperature to 450 ° C. is 3 It is characterized in that the viscosity change is 10 0.5 dPa · s or less (preferably 10 0.3 dPa · s or less) when kept at 450 ° C. for 20 minutes after the temperature is raised at ° C./min. If the change in viscosity when held at 450 ° C. for 20 minutes is greater than 10 0.5 dPa · s, the sealing material is likely to be deformed in the evacuation process, and the sealing material is easily drawn into the apparatus in the evacuation process. .

以下、実施例に基づいて本発明を詳細に説明する。   Hereinafter, the present invention will be described in detail based on examples.

表１、２は、本発明の実施例（試料Ｎｏ．２〜７、９〜１４）および本発明の比較例（試料Ｎｏ．１、８、１５〜１７）を示している。   Tables 1 and 2 show Examples of the present invention (Sample Nos. 2 to 7, 9 to 14) and Comparative Examples of the present invention (Sample Nos. 1, 8, and 15 to 17).

まず、表中に示したガラス組成となるように各種酸化物、炭酸塩等の原料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１０００〜１２００℃で２時間溶融した。次に、水冷ローラーにより、溶融ガラスを薄片状に成形した。最後に、薄片状のガラスをボールミルにて粉砕後、目開き２００メッシュの篩いを通過させて、平均粒径Ｄ５０が１０μｍの各ガラス粉末試料を得た。 First, a glass batch in which raw materials such as various oxides and carbonates were prepared so as to have the glass composition shown in the table was prepared, and this was put in a platinum crucible and melted at 1000 to 1200 ° C. for 2 hours. Next, the molten glass was formed into a thin piece with a water-cooled roller. Finally, after grinding the flaky glass ball mill, passed through a sieve of mesh 200 mesh, average particle diameter D 50 to obtain each glass powder sample of 10 [mu] m.

耐火性フィラー粉末として、平均粒子径Ｄ５０が８μｍのアルミナ粉末（表中ではＡＬＭと表記）、ウイレマイト粉末（表中ではＷＩＬと表記）、コーディエライト粉末（表中ではＣＤＲと表記）、酸化スズ粉末（表中ではＳｎＯ２と表記）を使用した。 As refractory filler powder, alumina powder having an average particle diameter D 50 of 8 μm (indicated in the table as ALM), willemite powder (in the table as WIL), cordierite powder (in the table as CDR), oxidation Tin powder (indicated as SnO 2 in the table) was used.

以上の粉末試料を用いて、試料Ｎｏ．１〜１７を作製し、流動径、失透状態、残留応力および引き込み性を評価した。   Using the above powder sample, Sample No. 1-17 were produced and the flow diameter, the devitrification state, the residual stress, and the retractability were evaluated.

流動径は、封着材料の真比重に相当する重量の粉末を金型により外径２０ｍｍのボタン状に乾式プレスして、そのボタン試料を高歪点ガラス基板（日本電気硝子株式会社製ＰＰ−８Ｃ）上に載置し、流気式熱処理炉に投入した後に空気中で１０℃／分の速度で昇温し、５１０℃で２０分間保持して、その後１０℃／分の速度で室温まで降温し、得られた焼成ボタンの直径を測定することで評価した。なお、流動径が２０ｍｍ以上であれば、流動性が良好であることを意味する。   The flow diameter was dry-pressed into a button shape having an outer diameter of 20 mm using a mold with a weight corresponding to the true specific gravity of the sealing material, and the button sample was subjected to a high strain point glass substrate (PP-made by Nippon Electric Glass Co., Ltd.). 8C), placed in an air-flow heat treatment furnace, heated in air at a rate of 10 ° C / min, held at 510 ° C for 20 minutes, and then brought to room temperature at a rate of 10 ° C / min. The temperature was lowered, and evaluation was performed by measuring the diameter of the fired button obtained. In addition, if a flow diameter is 20 mm or more, it means that fluidity | liquidity is favorable.

耐失透性は、次のようにして評価した。まず、各試料とビークル（アクリル樹脂含有のα−ターピネオール）を三本ロールミルで均一に混錬し、ペースト化した後、高歪点ガラス基板（日本電気硝子株式会社製ＰＰ−８Ｃ）の端部に線状（長さ４０×幅３×１．５ｍｍ厚）に塗布し、乾燥オーブンで１５０℃１０分間乾燥した。次に、室温から１０℃／分で昇温し、基板を５１０℃で２０分間焼成した後、室温まで１０℃／分で降温した。最後に、得られた焼成体の表面を光学顕微鏡（５０倍）で観察して、表面に結晶が認められなかったものを「○」とし、表面に結晶が認められたものを「×」とした。   The devitrification resistance was evaluated as follows. First, after each sample and vehicle (acrylic resin-containing α-terpineol) were uniformly kneaded with a three-roll mill and formed into a paste, the end of a high strain point glass substrate (PP-8C manufactured by Nippon Electric Glass Co., Ltd.) Was applied in a linear shape (length 40 × width 3 × 1.5 mm thickness) and dried in a drying oven at 150 ° C. for 10 minutes. Next, the temperature was raised from room temperature at 10 ° C./min, the substrate was baked at 510 ° C. for 20 minutes, and then lowered to room temperature at 10 ° C./min. Finally, the surface of the fired body obtained was observed with an optical microscope (50 times), and “◯” was given when no crystal was observed on the surface, and “X” when crystal was found on the surface. did.

残留応力は、次のようにして評価した。まず封着材料の真比重に相当する重量の粉末を金型により外径２０ｍｍのボタン状に乾式プレスし、そのボタン試料を高歪点ガラス基板（日本電気硝子株式会社製ＰＰ−８Ｃ）上に載置した。次に、これを流気式熱処理炉に投入した後に空気中で１０℃／分の速度で昇温し、５１０℃で２０分間保持し、その後１０℃／分の速度で室温まで降温した。最後に、得られたボタン直下のガラス基板にクラックが発生していないものを「○」とし、クラックが発生しているものを「×」とした。   Residual stress was evaluated as follows. First, a powder having a weight corresponding to the true specific gravity of the sealing material is dry-pressed into a button shape having an outer diameter of 20 mm using a mold, and the button sample is placed on a high strain point glass substrate (PP-8C manufactured by Nippon Electric Glass Co., Ltd.). Placed. Next, this was put into an air-flow type heat treatment furnace, heated in air at a rate of 10 ° C./min, held at 510 ° C. for 20 minutes, and then cooled to room temperature at a rate of 10 ° C./min. Finally, “O” indicates that no crack was generated on the obtained glass substrate immediately below the button, and “X” indicates that the crack was generated.

引き込み性は、次のようにして評価した。まず、各試料とビークル（アクリル樹脂含有のα−ターピネオール）を三本ロールミルで均一に混錬し、ペースト化した後、５ｍｍφの排気孔を有する１００×１００×１．８ｍｍ厚の高歪点ガラス基板（日本電気硝子株式会社製ＰＰ−８Ｃ）の外周縁に線状（長さ４０×幅３×１．５ｍｍ厚）に塗布し、乾燥オーブンで１５０℃１０分間乾燥した。次に、得られた乾燥膜上に１００×１００×１．８ｍｍ厚の高歪点ガラス基板（日本電気硝子株式会社製ＰＰ−８Ｃ）を正確に重ね合わせた後、クリップ等で加圧しながら、室温から１０℃／分で昇温し、５１０℃２０分間焼成した後、室温まで１０℃／分で降温した。そして、排気孔を通じて、得られたガラス容器内を真空ポンプで真空排気した。真空排気は、４８０℃４０分間行い、装置内部が１０−６Ｔｏｒｒとなるように調整した。その後、ガラス容器内を観察し、封着部位の一部に引き込みによる貫通孔（気密リーク）が発生していないものを「○」、封着部位の一部が装置内部に引き込まれて、貫通孔が発生しているものを「×」として評価した。 The pullability was evaluated as follows. First, each sample and vehicle (acrylic resin-containing α-terpineol) were uniformly kneaded with a three-roll mill and made into a paste, and then 100 × 100 × 1.8 mm thick high strain point glass having 5 mmφ exhaust holes. The substrate (PP-8C manufactured by Nippon Electric Glass Co., Ltd.) was applied linearly (length 40 × width 3 × 1.5 mm thickness) to the outer peripheral edge and dried in a drying oven at 150 ° C. for 10 minutes. Next, a 100 × 100 × 1.8 mm thick high strain point glass substrate (PP-8C manufactured by Nippon Electric Glass Co., Ltd.) was accurately superimposed on the obtained dried film, and then pressed with a clip or the like, The temperature was raised from room temperature at 10 ° C./minute, baked at 510 ° C. for 20 minutes, and then lowered to room temperature at 10 ° C./minute. And the inside of the obtained glass container was evacuated with the vacuum pump through the exhaust hole. The evacuation was performed at 480 ° C. for 40 minutes, and the inside of the apparatus was adjusted to 10 −6 Torr. Then, the inside of the glass container is observed, “○” indicates that there is no through hole (airtight leak) due to pulling in part of the sealing part, and part of the sealing part is drawn into the apparatus and penetrates. The thing which the hole generate | occur | produced was evaluated as "x".

試料Ｎｏ．２〜７、９〜１４は、ガラス粉末のガラス組成範囲およびガラス組成比が所定範囲内に規制されているとともに、封着材料中にアルミナを所定量含有しているため、流動径、失透状態、残留応力および引き込み性の評価が良好であった。   Sample No. 2-7 and 9-14, the glass composition range and glass composition ratio of the glass powder are regulated within a predetermined range, and a predetermined amount of alumina is contained in the sealing material. The evaluation of the state, residual stress, and retractability was good.

試料Ｎｏ．１は、封着材料中にアルミナを含有していないため、引き込み性の評価が不良であった。試料Ｎｏ．８は、アルミナの含有量が過剰であり、流動性の評価が不良であった。試料Ｎｏ．１５は、質量比Ｂｉ２Ｏ３／Ｂ２Ｏ３の値が１１より大きいため、引き込み性の評価が不良であった。試料Ｎｏ．１６は、ガラス粉末中のＢｉ２Ｏ３の含有量が過剰であるため、流動径および失透性の評価が不良であった。試料Ｎｏ．１７は、ガラス粉末中のＺｎＯの含有量が過剰であるため、流動径、失透性および残留応力の評価が不良であった。 Sample No. Since No. 1 did not contain alumina in the sealing material, the evaluation of retractability was poor. Sample No. In No. 8, the alumina content was excessive, and the fluidity evaluation was poor. Sample No. 15, since the value is greater than 11 mass ratio Bi 2 O 3 / B 2 O 3, retraction of the evaluation was poor. Sample No. No. 16 was poor in evaluation of the flow diameter and devitrification because the content of Bi 2 O 3 in the glass powder was excessive. Sample No. No. 17 was poor in evaluation of flow diameter, devitrification, and residual stress because the ZnO content in the glass powder was excessive.

アルミナの粒度分布の影響を調査するために以下の実験を行った。表３は、本発明の実施例（試料Ｎｏ．１８〜２２）を示している。   The following experiment was conducted to investigate the influence of the particle size distribution of alumina. Table 3 shows Examples (Sample Nos. 18 to 22) of the present invention.

まず、表３に示したガラス組成となるように各種酸化物、炭酸塩等の原料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１０００〜１２００℃で２時間溶融した。次に、水冷ローラーにより、溶融ガラスを薄片状に成形した。最後に、薄片状のガラスをボールミルにて粉砕後、目開き２００メッシュの篩いを通過させて、平均粒径Ｄ５０が１０μｍの各ガラス粉末試料を得た。 First, a glass batch in which raw materials such as various oxides and carbonates were prepared so as to have the glass composition shown in Table 3 was prepared, and this was put in a platinum crucible and melted at 1000 to 1200 ° C. for 2 hours. Next, the molten glass was formed into a thin piece with a water-cooled roller. Finally, after grinding the flaky glass ball mill, passed through a sieve of mesh 200 mesh, average particle diameter D 50 to obtain each glass powder sample of 10 [mu] m.

耐火性フィラー粉末として、アルミナ粉末（表中ではＡＬＭと表記）を使用した。アルミナ焼結体の粉砕条件および分級条件等を適宜調整することにより、アルミナ粉末の粒度分布を調整した。また、平均粒子径Ｄ５０が８μｍのウイレマイト粉末（表中ではＷＩＬと表記）を使用した。 As the refractory filler powder, alumina powder (shown as ALM in the table) was used. The particle size distribution of the alumina powder was adjusted by appropriately adjusting the pulverization conditions and classification conditions of the alumina sintered body. The average particle diameter D 50 was used 8μm willemite powder (denoted WIL in the tables).

以上の粉末試料を用いて、試料Ｎｏ．１８〜２２を作製し、流動径、失透状態、残留応力および引き込み性を評価した。流動径、失透状態、残留応力および引き込み性の評価方法は、上記と同様である。   Using the above powder sample, Sample No. 18-22 were produced and the flow diameter, the devitrification state, the residual stress, and the drawing property were evaluated. The evaluation method of the flow diameter, devitrification state, residual stress, and retractability is the same as described above.

試料Ｎｏ．１８〜２２は、ガラス粉末のガラス組成範囲およびガラス組成比が所定範囲内に規制されているとともに、封着材料中にアルミナを所定量含有し、アルミナの粒度分布が所定範囲であるため、流動径、失透状態、残留応力および引き込み性の評価が良好であった。   Sample No. 18-22, since the glass composition range and the glass composition ratio of the glass powder are regulated within the predetermined range, the sealing material contains a predetermined amount of alumina, and the particle size distribution of the alumina is within the predetermined range. The evaluation of diameter, devitrification state, residual stress, and retractability was good.

本発明の封着材料の粘度特性を調査するために以下の実験を行った。   The following experiment was conducted to investigate the viscosity characteristics of the sealing material of the present invention.

５１０℃２０分で試料Ｎｏ．１３（軟化点４７１℃）を緻密に焼結させ、所定形状に加工したものを測定試料とし、平行板粘度計で粘度特性を評価した。その結果を図１に示す。図１から明らかなように、試料Ｎｏ．１３は、室温から４５０℃まで昇温速度３℃／分で昇温した後、４５０℃で２０分間保持したときの粘度が１０６．３ｄＰａ・ｓ以上であり、４５０℃２０分保持したときの粘度変化が１００．３ｄＰａ・ｓ以下であった。また、試料Ｎｏ．２〜７、９〜１２、１４、１８〜２２についても、上記と同様の評価を行ったところ、室温から４５０℃まで昇温速度３℃／分で昇温した後、４５０℃で２０分間保持したときの粘度が１０６．３ｄＰａ・ｓ以上であり、４５０℃２０分保持したときの粘度変化が１００．３ｄＰａ・ｓ以下であった。 Sample No. 5 at 510 ° C. for 20 minutes. 13 (softening point 471 ° C.) was densely sintered and processed into a predetermined shape as a measurement sample, and the viscosity characteristics were evaluated with a parallel plate viscometer. The result is shown in FIG. As is clear from FIG. No. 13 has a viscosity of 10 6.3 dPa · s or more when held at 450 ° C. for 20 minutes after being heated from room temperature to 450 ° C. at a heating rate of 3 ° C./min, and when held at 450 ° C. for 20 minutes The viscosity change was 10 0.3 dPa · s or less. Sample No. 2-7, 9-12, 14, 18-22 were also evaluated in the same manner as described above. After the temperature was increased from room temperature to 450 ° C at a rate of temperature increase of 3 ° C / min, the temperature was maintained at 450 ° C for 20 minutes. The viscosity was 10 6.3 dPa · s or more, and the viscosity change when held at 450 ° C. for 20 minutes was 10 0.3 dPa · s or less.

本発明の封着材料は、ＰＤＰ、ＦＥＤ、蛍光表示管の封着に好適である。その他にも、本発明の封着材料は、有機エレクトロルミネッセンスディスプレイ、無機エレクトロルミネッセンスディスプレイ、ＩＣセラミックパッケージ等の各種セラミックパッケージ、球レンズキャップ部品等の各種金属パッケージの封着に用いることもできる。   The sealing material of the present invention is suitable for sealing PDP, FED, and fluorescent display tube. In addition, the sealing material of the present invention can be used for sealing various ceramic packages such as an organic electroluminescence display, an inorganic electroluminescence display, and an IC ceramic package, and various metal packages such as a spherical lens cap component.

本発明の封着材料の粘度特性を示すデータである。It is data which shows the viscosity characteristic of the sealing material of this invention.

Claims (8)

ビスマス系ガラス粉末と耐火性フィラー粉末を含有する封着材料において、
ビスマス系ガラス粉末は、ガラス組成として、下記酸化物換算の質量％表示で、Ｂｉ２Ｏ３ ６７〜９０％、Ｂ２Ｏ３ ２〜１２％、Ａｌ２Ｏ３ ０〜５％、ＺｎＯ １〜１５％、ＢａＯ ０〜１０％、ＣｕＯ ０〜５％、Ｆｅ２Ｏ３ ０〜３％、ＣｅＯ２ ０〜５％、Ｓｂ２Ｏ３ ０〜５％を含有し、質量比Ｂｉ２Ｏ３／Ｂ２Ｏ３の値が１１以下であり、且つ耐火性フィラー粉末として、アルミナを１〜２５体積％含有することを特徴とする封着材料。 In a sealing material containing bismuth glass powder and refractory filler powder,
The bismuth-based glass powder has a glass composition represented by mass% in terms of the following oxide, Bi 2 O 3 67 to 90%, B 2 O 3 2 to 12%, Al 2 O 3 0 to 5%, ZnO 1 to 15%, BaO 0~10%, 0~5 % CuO, Fe 2 O 3 0~3%, CeO 2 0~5%, contain Sb 2 O 3 0~5%, the mass ratio Bi 2 O 3 / A sealing material characterized in that the value of B 2 O 3 is 11 or less, and contains 1 to 25% by volume of alumina as a refractory filler powder. アルミナの平均粒子径Ｄ５０が３〜２５μｍであることを特徴とする請求項１に記載の封着材料。 The sealing material according to claim 1, wherein the average particle diameter D 50 of alumina is 3 to 25 μm. アルミナの１０％粒子径Ｄ１０が１〜５μｍおよび／または９０％粒子径Ｄ９０が１０〜３５μｍであることを特徴とする請求項１または２に記載の封着材料。 Sealing material according to claim 1 or 2 10% particle size D 10 of the alumina 1~5μm and / or 90% particle size D 90 of characterized in that it is a 10 to 35 [mu] m. 非結晶性であることを特徴とする請求項１〜３のいずれかに記載の封着材料。   The sealing material according to claim 1, which is non-crystalline. 実質的にＰｂＯを含有しないことを特徴とする請求項１〜４のいずれかに記載の封着材料。   The sealing material according to any one of claims 1 to 4, which does not substantially contain PbO. プラズマディスプレイパネルの前面ガラス基板と背面ガラス基板の封着に用いることを特徴とする１〜５のいずれかに記載の封着材料。   The sealing material according to any one of 1 to 5, which is used for sealing a front glass substrate and a back glass substrate of a plasma display panel. ビスマス系ガラス粉末と耐火性フィラー粉末を含有する封着材料において、
（１）耐火性フィラー粉末として、アルミナを１〜２５体積％含有し、
（２）軟化点が５３０℃以下であり、
（３）封着材料を緻密に焼結させたものを測定試料とし、室温から４５０℃まで昇温速度３℃／分で昇温した後、４５０℃で２０分間保持したときの粘度が１０６．０ｄＰａ・ｓ以上であることを特徴とする封着材料。 In a sealing material containing bismuth glass powder and refractory filler powder,
(1) As a refractory filler powder, containing 1 to 25% by volume of alumina,
(2) The softening point is 530 ° C. or lower,
(3) A dense sintered material of the sealing material is used as a measurement sample, the temperature is increased from room temperature to 450 ° C. at a rate of temperature increase of 3 ° C./min, and the viscosity when held at 450 ° C. for 20 minutes is 10 6. 0.0 dPa · s or more, a sealing material. ４５０℃で２０分保持したときの粘度変化が１００．５ｄＰａ・ｓ以下であることを特徴とする請求項７に記載の封着材料。 The sealing material according to claim 7, wherein a change in viscosity when held at 450 ° C. for 20 minutes is 10 0.5 dPa · s or less.
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