JP2004303669A - Paste for forming ceramic rib, ceramic rib and manufacturing method of ceramic rib - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a paste capable of forming a rib having a narrow pitch and a high aspect ratio. <P>SOLUTION: The paste is capable of forming a rib-shaped part 13 on a base plate 10 by elastically deforming a paste membrane 11 by piercing a blade 12 having a prescribed tooth of a comb 12b into the paste membrane 11 formed on the surface of the base plate 10 and moving the blade 12 against the paste membrane 11 in a prescribed direction. The paste contains glass powder or glass/ ceramic mixed powder, resin, one or more kinds of solvent, and at least one or more kinds of organic/inorganic composite thixotropic agents, and the plural kinds of solvent contain a low boiling-point solvent and a high boiling-point solvent selected from a group of solvents having a boiling point different from each other by 30°C or more. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００３０】
【表２】

【００３１】
【表３】

【００３２】
【表４】

【００３３】
溶剤の選択は、選択された１種類以上の低沸点溶剤と、１種類以上の高沸点溶剤の各沸点が３０℃以上異なるように選択される。この低沸点溶剤よりなる群から選ばれた１種類以上の低沸点溶剤に対し、高沸点溶剤よりなる群から選ばれた１種類以上の高沸点溶剤の重量比は、１種類以上の低沸点溶剤：１種類以上の高沸点溶剤＝５０〜５：５０〜９５に調整されることが好ましい。
【００３４】
ペーストは上述した粉末、樹脂及び有機揺変剤と、複数種類の溶剤からなるが、必要である場合これらを主成分として、これら以外に、可塑剤及び分散剤を含ませることもできる。
【００３５】
可塑剤としてはグリセリン、ジブチルフタレート等が挙げられる。
更に、分散剤としては、ポリオキシエチレンアルキルフェニルエーテルリン酸、ポリオキシエチレンジアルキルフェニルエーテルリン酸、ポリオキシエチレンアルキルエーテルリン酸、ポリオキシフェニルエーテルリン酸、ラウリルリン酸、ポリオキシエチレンラウリルエーテルリン酸、ポリオキシエチレンラウリルエーテルリン酸ナトリウム、ポリオキシエチレンオレイルエーテルリン酸ナトリウム、ポリオキシエチレンアルキルフェニルエーテルリン酸ナトリウム、ラウリル硫酸ナトリウム、ラウリル硫酸トリエタノールアミン、ラウリル硫酸アンモニウム、ラウリル硫酸カリウム、ポリオキシエチレンラウリルエーテル硫酸ナトリウム、ポリオキシエチレンラウリル硫酸トリエタノールアミン、ポリオキシエチレンラウリル硫酸アンモニウム、ドデシルベンゼンスルホン酸トリエタノールアミン、オクチルフェノキシジエトキシエチルスルホン酸ナトリウム、テトラデセンスルホン酸ナトリウム、ポリエーテルポリカルボン酸、エステルエーテルポリカルボン酸等の分散剤が挙げられる。
【００３６】
ペーストは、ガラス粉末又はガラス・セラミック混合粉末を５０〜９７重量％、樹脂を０．１〜１５重量％、有機・無機複合揺変剤を０．１〜２０重量％、複数種類の溶剤を３〜６０重量％とをそれぞれ配合して調製される。
【００３７】
ガラス粉末又はガラス・セラミック粉末を５０〜９７重量％の範囲に限定したのは、５０重量％未満では、ブレードを用いて所定の形状のリブ状物を得ることが困難となり、９７重量％を越えるとペーストの製造が困難になるからである。
【００３８】
樹脂を０．１〜１５重量％の範囲に限定したのは、０．１重量％未満では、ブレードを用いて所定の形状のリブ状物を得ることが困難になり、１５重量％を越えると基板表面にペーストを均一に塗布することが困難になり、かつ焼成後のセラミックリブ内に有機物が残存するという不具合があるからである。
【００３９】
また、揺変剤を０．１〜２０重量％の範囲に限定したのは、０．１重量％未満では、充分なチクソ性を得られず、ブレードを用いて所定の形状のリブ状物を得ることが困難となり、２０重量％を越えるとペースト製造が困難になるからである。
【００４０】
更に、複数種類の溶剤を３〜６０重量％の範囲に限定したのは、３重量％未満ではペースト製造が困難もしくは基板表面にペーストを均一に塗布することが困難になるからであり、６０重量％を越えるとブレードを用いて所定の形状のリブ状物を得ることが困難若しくは複数種類の溶剤を後に気化させる時間が長くなるからである。
【００４１】
ペーストを上記のように調製することにより、せん断速度が２０／ｓの時の粘度が０．１〜２００Ｐａ・ｓとなり、基板表面への塗布及び均一厚さに引き延ばすことが容易になる。
更に、１種類以上の低沸点溶剤が揮発した後は、ブレード成型中、ペーストはブレードから受けるせん断応力により粘度が１０〜２００Ｐａ・ｓ程度に急激に低下するため、ブレード開口形状に従って塑性変形し、リブを形成する。成型直後には、ブレードからのせん断応力が除去されるため、粘度が１０００〜３０００Ｐａ・ｓ程度に急激に上昇し、形成されたリブの形状が変化することなく、保持され、狭ピッチ・高アスペクト比のリブを得ることができる。
更に、ブレード成型中は、ペーストの粘度が１０〜２００Ｐａ・ｓ程度に低下しているため、ブレードの走行に対して反力を及ぼすことなく一定の走行速度でのリブ成型が可能となるため、基板内でのリブ高さの偏差（バラツキ）を縮小することができる。
【００４２】
ペーストの製造方法は、表１及び表２に例示する低沸点溶剤よりなる群から１種類以上の低沸点溶剤を選択し、その溶剤と沸点が３０℃以上異なる１種類以上の高沸点溶剤を表３及び表４に例示する高沸点溶剤よりなる群から選択して秤量する。そして、別に秤量されたガラス粉末又はガラス・セラミック混合粉末と、樹脂と、揺変剤と、１種類以上の高沸点溶剤とを調合及び混練する。分散剤及び可塑剤を含ませる場合には、１種類以上の高沸点溶剤を主成分とし、これに可塑剤若しくは分散剤のいずれか一方若しくは双方を予め混練しておき、この混練物に上述した粉末と樹脂と揺変剤と、を調合して更に混練する。上記組成にて混練することにより、製造中のペーストの粘度を量産設備が使用可能範囲まで低下させることができるため、量産レベルでのペースト製造が可能となる。その後、１種類以上の低沸点溶剤を添加して再び混練することによりペーストを得る。
【００４３】
次に、このようにして得られたペーストを用いたリプ状物の形成方法を図１を用いて説明する。
【００４４】
図１（ａ）に示すように先ず基板表面に上述のペーストを塗布してペースト膜１１を形成する。ペーストの基板１０表面への塗布は、ロールコーティング法、スクリーン印刷法、ダイコーティング法、バーコーティング法又は、ドクターブレード法等の既存の手段により行われる。基板１０表面にペーストが塗布されてペースト膜１１が形成された後には、図１（ｂ）に示すようにその基板１０を所定時間放置して基板表面に形成されたペースト膜１１から１種類以上の低沸点溶剤を破線矢印で示すように気化させる。１種類以上の低沸点溶剤を気化させる環境温度及び時間は低沸点溶剤として使用される溶剤の種類により異なるが、沸点が１２０〜１５０℃近辺の１−エトキシー２−プロパノール、４−メチルー２−ペンタノール等を使用した場合には、１５〜２５℃の雰囲気中で１〜５時間放置することが好ましい。
【００４５】
特に、本実施形態におけるペーストは、１種類以上の低沸点溶剤を最後に添加して製造したため、最初に混合された１種類以上の高沸点溶剤のみがガラス粉末又はガラス・セラミック混合粉末における粉体の周囲に馴染み、１種類以上の低沸点溶剤はその粉体の周囲に馴染んだ高沸点溶剤の周囲に馴染んでいるため１種類以上の低沸点溶剤が比較的揮発しやすいペーストになっており、基板を所定時間放置することによりペースト膜から１種類以上の低沸点溶剤を確実に揮発させることができる。
【００４６】
１種類以上の低沸点溶剤を完全に気化させた後、図１（ｃ）に示すように、このペースト膜１１をブレード１２により塑性変形させて所定形状を有するリブ状物１３を形成する。このリブ状物１３は変形した後の形状に保たれ、かつリブ状物１３にはガラス粉末等が均一に分散されている。このペースト膜１１の形成された基板１０表面に接触させるブレード１２には複数のくし歯１２ｂが等間隔にかつ同一方向に形成される。このブレード１２はペーストとの反応やペーストに溶解されることのない金属、セラミック又はブラスチック及びこれらの複合物質等により作られ、特に、寸法精度、耐久性の観点からＦｅ、Ｎｉ、Ｃｏを含む合金もしくはＣｏ、Ｎｉ中にタングステンカーバイト等のセラミックを分散させた超硬合金やセラミックが好ましい。それぞれのくし歯１２ｂの隙間はこのブレード１２により形成されるリブ状物１３の断面形状に相応して形成される。
【００４７】
本実施の形態におけるブレード１２は、図４および図５に示すように、厚さｔ、くし歯１２ｂのピッチｐ、くし歯１２ｂの隙間ｗ、その深さｈが所定の値のステンレススチールもしくは超硬合金により形成される。
また、くし歯１２ｂの隙問の形状は図３に示すように方形状に形成する場合のみならず、最終的に作られるＦＰＤの用途によりくし歯１２ｂの隙問の形状を台形状又は逆台形に形成してもよい。くし歯１２ｂの隙問の形状を台形にすれば、開口部を広くした用途に適したリブ状物１３を形成することができ、くし歯１２ｂの隙間の形状を逆台形にすれば、リブの頂部が広い面積で平坦化したリブ状物１３を形成することができる。
【００４８】
ここで、ブレード１２は、厚さが０．００５ｍｍ以上５ｍｍ以下であって、くし歯１２ｂのピッチをＰとし、くし歯１２ｂの隙間をｗ、その隙間の深さをｈとするとき、０．０５≦ｈ≦５．０ｍｍで、０．０３ｍｍ≦ｗ≦３．０ｍｍであることが好ましい。
【００４９】
これらの条件を満たすブレード１２により形成されたリブ状物１３は、その後の乾燥及び焼成により引き締まり、所定のリブ１４の隙間を有する緻密なセラミックリブ１４を得ることができる。このように形成されたブレード１２によるリブ状物１３の形成は、ブレード１２のくし歯１２ｂをペースト膜１１に突き刺し、エッジを基板１０表面に接触させた状態で、基板１０を固定してブレード１２を一定方向に移動するか、又はブレード１２を固定して基板１０を一定方向に移動させてペースト膜１１を塑性変形させることにより行われる。即ち、上記移動により基板１０表面に塗布されたペーストのブレード１２のくし歯１２ｂに対応する箇所は、くし歯１２ｂの隙間に移動するか若しくは掃き取られ、くし歯１２ｂの隙間に位置するペーストのみが基板１０上に残存して基板１０表面にリブ状物１３が形成される。
【００５０】
くし歯１２ｂの溝の深さがペースト膜１１の厚さより大きい場合にはブレード１２又はガラス基板１０を移動するときに掃き取られたペーストが溝に入り込みペースト膜１１の厚さ以上の高さを有するリブ状物１３を形成できる。この所定形状を有するリブ状物１３を形成した後、大気中１００〜２００℃で１０〜３０分間乾燥し、更に大気中５２０〜５８０℃で１０〜３０分間焼成することにより、セラミックリブ１４が得られる。このセラミックリブ１４を用いて図示しないＰＤＰを作製することができる。
【００５１】
上述のようにして基板１０上に形成されたセラミックリブ１４は、図３の拡大した円内に示すように、リブ１４の高さをＨとし、高さ（１／２）Ｈのところのリブ１４の幅をＷＣ、とするとき、Ｈ、ＷＣの標準偏差がそれぞれ４％以下であって、Ｈ／ＷＣで表されるアスペクト比が１．５〜１０であることが好ましい。リブピッチが小さくかつアスペクト比が１．５〜１０であることにより、極めて高精細なセラミックリブ１４を得ることができる。
【００５２】
本実施形態のペーストにおいては、上記のように少なくとも１種類以上の有機・無機複合揺変剤を、増粘剤、ダレ防止剤、沈降防止剤として加えることにより、ペーストに大きなチクソ性（チクソトロピー：Ｔｈｉｘｏｔｒｏｐｙ）を持たせることが可能となる。このため、ペーストにシェアー（切断：ｓｈｅａｒ）のかかる成形時には粘度が低下し、塑性変形を受けやすくなり、シェアーの無くなる成形後には粘度が高くなる。
このため、成形時にペーストを塑性変形させるため等、切断力のかかった場合には粘度が低下して、容易に塑性変形することが可能になるとともに、切断力のなくなった場合には粘度が高くなり、形成された形状を容易に維持することができる。つまり、ペーストの成形性と保形性とを同時に向上することができる。
【００５３】
これにより、ブレード１２によるリブ状物１３形成時にブレード１２くし歯１２ｂに過大な反力を作用することなく、かつ、ブレード１２の進行を妨げることがなく、ブレード１２速度を一定に維持した状態で不要なペーストを除去することができるため、成形したペースト１１におけるリブ形状を維持し、かつ、ペースト膜１１の成形精度を維持した状態でリブ形成における寸法精度を向上することができるため、成形したペーストにおけるリブ状物１３形状を維持することができる。さらに、ブレード１２くし歯１２ｂにかかる反力を削減することができるため、成形に必要なブレード１２くし歯１２ｂの強度を低下することが可能となるため、ブレード１２におけるくし歯１２ｂの寸法を小さくして、より高精細なリブを形成することが可能となるとともに、リブ状物１３形成における寸法精度を向上し、高保形指数を維持することが可能となる。
【００５４】
同時に、このペーストは、チクソ性の高い有機・無機複合揺変剤を添加したことにより、ペーストの粘度・チクソ性を調整することができる。従って、添加量を調整することにより、所望のリブ形状を得ることができる。これによって、例えば、６０μｍ程度のリブをピッチ寸法１２０μｍ程度で形成する際に、寸法精度を±５μｍ程度以下にすることが可能となる。
【００５５】
なお、上述した実施形態では、ブレード１２のくし歯１２ｂをペースト膜１１につき刺してエッジ１２ａを基板１０表面に接触させた状態で、ブレード１２を移動するか、又は基板１０を移動させて基板の表面に直接リブ状物１３を形成したが、図６に示すように、基板１０の表面に形成されたペースト膜１１にブレード１２のくし歯１２ｂをつき刺し、ブレード１２のエッジ１２ａを基板１０表面から所定の高さ浮上した状態でプレード１２又は基板１０を一定方向に移動してペースト膜１１を塑性変形させてもよい。このように塑性変形させると、基板１０表面に下地層２２とこの下地層２２上にリブ状物２３を形成することができる。
【００５６】
即ち、ブレード１２又は基板１０の移動により基板１０表面から所定の高さまでのペーストは基板表面上に残存して下地層２２を形成し、この下地層２２より上方のペーストにおけるブレード１２のくし歯１２ｂに対応する箇所はくし歯１２ｂの隙間に移動するか若しくは掃き取られ、くし歯１２ｂの隙間に位置するペーストのみが下地層２２上に残存して下地層２２上にリブ状物２３が形成される。次に上記下地層２２及びリブ状物２３を乾燥及び焼成すると、図７に示すように基板１０上に誘電体層２４が形成され、この誘電体層２４上にセラミックリブ２５が形成されることになる。
【００５７】
さらに、本実施形態のペーストでは、上述したようにペーストを配合することにより、剪断速度が２０／秒の時の粘度が０．１〜２００Ｐａ・ｓのペーストを得ることができ、この粘度におけるペーストは比較的流動性があって塗布しやすく、かつ基板上で均一厚さに容易に引き延ばすことができる。
【００５８】
以下、本発明に係るセラミックリブを形成するためのペーストの第２実施形態を図面に基づいて説明する。
【００５９】
本実施形態において、上記の第１実施形態と異なる点は、ペーストの組成における揺変剤として、有機・無機複合揺変剤に加えて無機揺変剤を添加したことである。
【００６０】
本実施形態においては、無機揺変剤として、ベントナイトや、カオリナイト、ハロサイト、加水ハロサイト、セリサイト、イライト、ノントロナイト、モンモリロナイト、ヘクトライト、セピオライト、アタパルジャイト、白雲母、滑石等のうち、単独または複数選択してこれをペーストに添加する。
【００６１】
このとき、セラミックペーストは、揺変剤として、有機・無機複合揺変剤と無機揺変剤とを０．１〜２０重量％それぞれ配合して調製される。揺変剤を０．１〜２０重量％の範囲に設定したのは、０．１重量％より少ないと、十分なチクソ性を発現することができないため好ましくなく、また、２０重量％よりも多い場合には、ペーストの粘度が高くなりすぎるため、ペーストが成形時シェアーでは塑性変形せず、ブレードによりペーストが掻き取られてしまうため、リブを形成することができないという不具合を生じるため好ましくないからである。
【００６２】
本実施形態においては、上記の第１実施形態と同様の効果を奏することができるとともに、さらに、このペーストにおいては、チクソ性の高い有機・無機複合揺変剤と無機揺変剤とを添加したことで、揺変剤の分散程度を混練条件により制御することで、ペーストの増粘・チクソ性を調整することができる。従って、所望のリブ形状を得ることができる。また、揺変剤の有機成分によって調合直後から特性の安定した耐経時変化に優れるとともに、無機揺変剤および無機成分によって調合後の経時変化を低減し、長期にわたってチクソ性を維持することが可能となり、高精細のリブ状物１３を形成可能とすることができる。
【００６３】
さらに、本実施形態のペーストでは、上記の無機複合揺変剤を混入することによって、上記の第１実施形態の場合に比べて、揺変剤の有機成分および溶剤の必要量を減ずることができ、これにより、焼成時に乾燥・揮発・脱離する有機成分を削減し、リブ状物１３に比べてセラミックリブ１４が収縮してしまうことをより一層低減できる。従って、セラミックリブ１４の寸法精度をリブ状物１３の成形時にさらに精密に設定することができる。
【００６４】
なお、上記の各実施形態において、揺変剤は、図８（ａ）に示すように、ペースト中において、溶剤（分散剤・樹脂等を含む）Ｐの内部で、揺変剤Ｔが３次元のネットワークを形成して高粘度化し、ガラス−セラミック粒子Ｓどうしを結びつけている。この状態が、ブレード成形時等において外力がかかることによって、図８（ｂ）に示すように、揺変剤Ｔの接合が崩れ、低粘度化すると考えられる。
【００６５】
次に本発明の実施例を比較例とともに詳しく説明する。
【００６６】
＜実施例１＞
平均粒径１μｍのＰｂＯ−ＳｉＯ_２一Ｂ_２Ｏ_３系ガラス粉末を８０重量％と、セラミックフィラーとして平均粒径Ｏ．５μｍのアルミナ粉末を２０重量％とを用意し、両者を十分に混合した。この混合粉末と、樹脂としてのエチルセルロースと、有機・無機複合揺変剤としての有機ベントナイトと、溶剤として高沸点溶剤としてのα−テレピネオールと低沸点溶剤としての１エトキシ２プロパノールとを重量比で８３／０．５／１／１０．５／５の割合になるように秤量した。この秤量された混合粉末と、樹脂と、揺変剤と高沸点溶剤とを先に配合し、十分に混練して混練物を得た。その混練物に、秤量された低沸点溶剤である１エトロキシ２プロパノ−ルを添加しペーストを得た。
【００６７】
次に、図２に示すように、対角寸法が４２インチであって、厚さが３ｍｍの長方形のソーダライム系ガラス基板１０を固定した状態で、このガラス基板１０上に上記ペーストをロールコーターにより、厚さ１５０μｍで塗布してペースト膜１１を形成した。このようにペースト膜１１が形成された基板１０を室温で１時間放置することにより、ペースト膜１１から低沸点溶剤である１エトキシ２プロパノールを気化させた。
【００６８】
くし歯１２ｂのピッチＰが１２０μｍであって、くし歯１２ｂの隙間ｗが６０μｍ、その深さｈが２００μｍ、厚さｔが０．１ｍｍのステンレス鋼により形成されたブレード１２を用意した。（図４および図５）
【００６９】
ガラス基板１０を固定したまま、このブレード１２のくし歯１２ｂを低沸点溶剤が気化したペースト膜１１に突き刺し、そのエッジ１２ａをガラス基板１０に接触させた状態で、図２の実線矢印で示す方向にブレード１２を一定方向に移動してペースト膜１１を塑性変形させることにより、基板１０表面にリブ状物１３を形成した。
その後、リブ状物１３を大気中１５０℃で２０分間乾燥して高沸点溶剤を脱離させ、更に大気中５５０℃で１０分間焼成してセラミックリブ１４とした。このセラミックリブを実施例１とした。
【００７０】
＜実施例２＞
平均粒径１μｍのＰｂＯ−ＳｉＯ_２一Ｂ_２Ｏ_３系ガラス粉末を８０重量％と、セラミックフィラーとして平均粒径０．５μｍのアルミナ粉末とを２０重量％を用意し、両者を十分に混合した。この混合粉末と、樹脂としてのエチルセルロースと、無機揺変剤としてのベントナイトと、有機・無機複合揺変剤としての有機ベントナイトと、高沸点溶剤としてのα−テルピネオールと、低沸点溶剤としての１エトキシ２プロパノールを重量比で８３／０．５／０．８／０．２／１０．５／５の割合になるように秤量した。この秤量された混合粉末と、樹脂と、揺変剤と、高沸点溶剤とを先に配合し、十分に混練して混練物を得た。
以下、実施例１と同様の手順でリブ状物１３およびセラミックリブ１４を得た。このセラミックリブ１４を実施例２とした。
【００７１】
＜比較例１＞
平均粒径１μｍのＰｂＯ−ＳｉＯ_２一Ｂ_２Ｏ_３系ガラス粉末を８０重量％と、セラミックフィラーとして平均粒径Ｏ．５μｍのアルミナ粉末を２０重量％とを用意し、両者を十分に混合した。この混合粉末と、樹脂としてのエチルセルロースと、溶剤として高沸点溶剤としてのα−テレピネオールと低沸点溶剤としての１エトキシ２プロパノールとを、重量比で８０／１／１４／７の割合で配合し、十分に混練して混練物を得た。その混練物に、秤量された低沸点溶剤である１エトロキシ２プロパノ−ルを添加しペーストを得た。以下、実施例１と同様の手順でリブ状物１３およびセラミックリブ１４を得た。このセラミックリブ１４を比較例１とした。
【００７２】
＜比較試験及び評価＞
このように焼成して得られた各実施例および比較例のセラミックリブ１４のそれぞれ任意の１００本について、その高さＨ及び幅Ｗ_Ｃを以下のようにそれぞれ測定した。
【００７３】
図３に示すように、実施例及び比較例の基板上の任意の１００本のセラミックリブの幅Ｗ_Ｃの測定は、セラミックリブの高さをＨとしたときの高さ（１／２）Ｈのところのリブの幅Ｗ_Ｃとし、これらの高さＨおよび幅Ｗ_Ｃから、それぞれのアスペクト比Ｈ／Ｗ_Ｃを算出した。また、これらの測定値の平均値を算出した後、Ｈ，Ｗ_Ｃ，Ｈ／Ｗ_Ｃのそれぞれの（最大値又は最小値−平均値）／平均値で表されるばらつき値を算出した。
表５に実施例および比較例の結果（リブの高さＨ，幅_Ｃ，アスペクト比Ｈ／Ｗ_Ｃの平均値およびばらつき値）を対比させて示す。
【００７４】
【表５】

【００７５】
表５から明らかなように、比較例と比べて、実施例では、あきらかにアスペクト比が向上しているとともに、リブの高さＨ，幅_Ｃ，アスペクト比Ｈ／Ｗ_Ｃの各データのばらつきが減少しており、セラミックリブ１４における寸法精度が向上していることが解る。
つまり、実施例では比較例に比べて、高精細のＰＤＰに対して対応することが可能であると考えられる。
また、表５から、比較例と比べて、実施例におけるセラミックリブのばらつきが小さいことがわかる。これは、低沸点溶剤を揮発させた後にリブ状物を形成するため、ペーストの粘度が比較的高く、リブ状物のだれが少ないことに起因するものと考えられる。
【００７６】
【発明の効果】
本発明によれば、前記ペーストの組成が、ガラス粉末又はガラス・セラミック混合粉末を５０〜９７重量％、樹脂を０．１〜１５重量％、複数種類の溶剤を３〜６０重量％、を含み、このペースト組成に０．１〜２０重量％の少なくとも一種類以上の有機・無機複合揺変剤，および／または無機揺変剤を、増粘剤、ダレ防止剤、沈降防止剤として加えることにより、ペーストに大きなチクソ性（チクソトロピーＴｈｉｘｏｔｒｏｐｙ）を持たせることが可能となるため、ペーストにシェアー（切断：ｓｈｅａｒ）のかかる成形時には粘度が低下し、塑性変形を受けやすくなり、シェアーの無くなる成形後には粘度が高くなる。つまり、ブレードによるリブ形成時にブレードに過大な反力を作用することなく、かつ、成形精度を維持した状態で不必要なペーストを除去することができるため、成形したペーストにおけるリブ形状を維持し、リブ形成における寸法精度を向上することが可能となる。さらに、比較的流動性があって塗布しやすい所定の粘度のペーストを得ることができ、基板上で均一厚さに容易に引き延ばすことができる一方、ペーストは１種類以上の低沸点溶剤が揮発した状態で粘度が上昇する。その粘度が上昇したペースト膜をブレードで所望の形状に塑性変形させることにより得られたリプ状物は、変形した後の形状に保たれ、リブ状物の形状が歪むことなくその形状を保ったままセラミックリブを作製することができるという効果を奏する。
【図面の簡単な説明】
【図１】本発明のリブ状物の形成手順を示す斜視図である。
【図２】本発明に係るセラミックリブを形成するためのペーストの第１実施形態におけるセラミックキャピラリリブの形成状態を示す斜視図である。
【図３】図２のＡ−Ａ線断面におけるセラミックキャピラリリブを乾燥、加熱及び焼成することにより得たセラミックリブを示す断面図である。
【図４】そのブレードの正面図である。
【図５】図４のＢ−Ｂ線断面図である。
【図６】本発明に係るセラミックリブを形成するためのペーストの第２実施形態におけるセラミックキャピラリリブの形成状態を示す図２に対応する斜視図である。
【図７】図６のＢ−Ｂ線断面におけるセラミックキャピラリ層付リブを乾燥、加熱及び焼成することにより得た絶縁層付セラミックリブを示す図３に対応する断面図である。
【図８】ペースト中における揺変剤の働きを示す模式図で、外力のない状態（ａ）、および外力のある状態（ｂ）を示すものである。
【符号の説明】
１０ ガラス基板
１１ ペースト膜
１２ ブレード
１２ａ エツジ
１２ｂ くし歯
１３，２３ リブ状物
１４，２５ セラミックリブ
２２ 下地層
２４ 絶縁下地層
Ｐ 溶剤（分散剤・樹脂等を含む）
Ｔ 揺変剤
Ｓ ガラス−セラミック粒子[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a process for producing a rib-like material (ceramic library) for producing a flat panel display (FPD) such as a plasma display panel (PDP) or a plasma addressed liquid crystal display (PALC) such as a PALC (plasma display panel). The present invention relates to a method for producing the same, a method for forming a rib-like material used therefor, a ceramic rib made from the rib-like material, and an FPD having the ceramic rib.
[0002]
[Prior art]
Conventionally, a ceramic rib is formed by applying a paste on a glass substrate to form a paste film, and then sticking a blade on the paste film in this state, and moving the blade relative to the paste film in a fixed direction. As a result, the paste film is plastically deformed to form a rib. (Patent Document 1)
The above-mentioned paste is configured so that a rib-like material can be formed by plastic deformation. This paste contains 50 to 98% by weight of a glass powder or a glass / ceramic mixed powder, 0.1 to 10% by weight of a resin, 2 to 50% by weight of a solvent, and has a specific surface area of 10 m ² / g or more. 10% by weight of fine particles.
[0003]
[Patent Document 1]
JP 2000-268729 A
[Problems to be solved by the invention]
However, the viscosity of the conventional paste to which only the ceramic ultrafine particles (inorganic fine particles) are added as described above increases, and a large force is required for stirring, mixing, and kneading. For this reason, it is difficult to produce paste using mass production equipment (apparatus).
Further, in the method for forming a ceramic rib using the above paste, since the viscosity of the paste is high, it is difficult to keep the blade traveling speed constant, and the rib height depending on the blade traveling speed fluctuates, and the There is a problem that the deviation of the rib height becomes large.
[0005]
Furthermore, in the method of forming a rib-like material, the paste is first applied to the surface of the substrate to form a paste film. Therefore, the paste used in the method has good fluidity and can be easily applied to the surface of the substrate. It is desirable to be able to apply and have a uniform thickness. On the other hand, the paste film formed on the substrate surface is plastically deformed to form a rib-like material on the substrate surface, so that the rib-like material formed by plastic deformation is prevented from sagging and then dried and fired. It is necessary to maintain its shape. Therefore, the paste used in the method is required to have low fluidity.
[0006]
An object of the present invention is to provide a paste that has a viscosity in a range that enables production of a paste using mass production equipment (apparatus), and that can form a rib having a narrow pitch and a high aspect ratio. An object of the present invention is to provide a paste which can be easily applied and maintain the shape of a rib-like material after plastic deformation, a method for producing the paste, and a method for forming a rib-like material using the paste.
It is an object of the present invention to provide a ceramic rib made from this paste and an FPD (flat panel display) having the ceramic rib.
[0007]
[Means for Solving the Problems]
The paste for forming the ceramic rib of the present invention is obtained by piercing a blade having predetermined comb teeth into a paste film formed on the substrate surface and moving the blade in a fixed direction relative to the paste film. A paste capable of forming a rib on the surface of the substrate by plastically deforming the paste film,
The composition of the paste is 50 to 97% by weight of glass powder or glass / ceramic mixed powder, 0.1 to 15% by weight of resin, 3 to 60% by weight of plural kinds of solvents, and at least one kind of organic and inorganic 0.1 to 20% by weight of a complex thixotropic agent,
Each of the plurality of types of solvents has a different boiling point of 30 ° C. or more, and the plurality of types of solvents have one or more low-boiling solvents selected from the group consisting of low-boiling solvents having a boiling point of 100 ° C. to 180 ° C. One or more high-boiling solvents selected from the group consisting of high-boiling solvents having a temperature of 190 ° C to 450 ° C,
The above problem was solved by including the following.
Further, in the present invention, it is preferable to include one or both of a plasticizer and a dispersant.
[0008]
By preparing the paste for forming the ceramic rib of the present invention with the above composition, a paste having a viscosity of 0.1 to 200 Pa · s at a shear rate of 20 / s can be obtained. The paste having this viscosity has fluidity, is easy to apply, and can be easily spread to a uniform thickness on the substrate.
The weight ratio of one or more high-boiling solvents to one or more low-boiling solvents is preferably one or more low-boiling solvents: one or more high-boiling solvents = 50 to 5:50 to 95. Most preferably, one or more low-boiling solvents: one or more high-boiling solvents = 25 to 50:75 to 50.
The viscosity at a shear rate of 20 / s is preferably from 0.2 to 100 Pa · s, more preferably from 0.5 to 80 Pa · s.
[0009]
In addition, in this paste, in the state where one or more low-boiling solvents are volatilized, during the blade molding, the viscosity of the paste sharply decreases to about 10 to 200 Pa · s due to the shear stress received from the blade, and therefore, according to the blade opening shape. Plastically deforms to form ribs. Immediately after molding, since the shear stress from the blade is removed, the viscosity rises sharply to about 1000 to 3000 Pa · s, the shape of the formed rib is maintained without change, and the narrow pitch and high aspect ratio are maintained. A ratio rib can be obtained. Further, during blade molding, since the viscosity of the paste is reduced to about 10 to 200 Pa.s, it is possible to perform rib molding at a constant traveling speed without exerting a reaction force on the traveling of the blade, The deviation (variation) of the rib height in the substrate can be reduced.
[0010]
Examples of the organic / inorganic composite thixotropic agent include, for example, those obtained by modifying the layer surface and end surface of a layered clay mineral such as the inorganic thixotropic agent bentonite with an organic substituent, or compounding a polymer or a solvent.
[0011]
The paste for forming the ceramic rib of the present invention is obtained by piercing a blade having predetermined comb teeth into a paste film formed on the substrate surface and moving the blade in a fixed direction relative to the paste film. A paste capable of forming a rib on the surface of the substrate by plastically deforming the paste film,
The composition of the paste is 50 to 95% by weight of a glass powder or a glass-ceramic mixed powder, 0.1 to 15% by weight of a resin, 3 to 60% by weight of a plurality of kinds of solvents, and at least one kind of inorganic whisker. Agent and at least one or more organic / inorganic composite thixotropic agents in an amount of 0.1 to 20% by weight,
Each of the plurality of types of solvents has a different boiling point of 30 ° C. or more, and the plurality of types of solvents have one or more low-boiling solvents selected from the group consisting of low-boiling solvents having a boiling point of 100 ° C. to 180 ° C. One or more high-boiling solvents selected from the group consisting of high-boiling solvents having a temperature of 190 ° C to 450 ° C,
The above problem was solved by including the following.
[0012]
In the present invention, by preparing a paste with the above composition, similarly to the above paste, it is possible to obtain a paste that has fluidity, is easy to apply, and can be easily stretched to a uniform thickness on a substrate. A rib having a high aspect ratio can be obtained, and a deviation (variation) in the rib height within the substrate can be reduced.
Furthermore, in each of the above pastes, by mixing each of the above thixotropic agents, it is possible to reduce the required amount of the above resin and a plurality of types of solvents, thereby forming the ceramic ribs after firing with a blade. Shrinkage of dimensions can be reduced as compared with the rib-shaped material. Therefore, the dimensional accuracy of the ceramic rib can be set more precisely at the time of forming the rib.
[0013]
Further, in the method for producing a paste for forming a ceramic rib according to the present invention, the glass powder or the glass-ceramic mixed powder, the resin, at least one or more organic / inorganic composite thixotropic agent, or at least one or more inorganic thixotropic agent A step of kneading the thixotropic agent, at least one or more organic / inorganic composite thixotropic agents, and one or more high-boiling solvents having a boiling point of 190 ° C to 450 ° C to obtain a kneaded product;
This problem was solved by including a step of adding one or more low-boiling solvents having a boiling point of 100 ° C. or more and 180 ° C. or less to the kneaded material and kneading again.
[0014]
In the above method, in the previous step of kneading the high boiling point solvent, by kneading with the above composition, the viscosity of the paste during the production can be reduced to a range where mass production equipment can be used. Manufacturing becomes possible.
[0015]
In the method for producing a paste for forming a ceramic rib according to the present invention, the kneaded product before adding the low-boiling solvent preferably contains one or both of a plasticizer and a dispersant.
[0016]
In the above method, the high boiling solvent is mixed and kneaded with the powder, the resin, and the thixotropic agent, so that the high boiling solvent is mainly used around the powder in the glass powder or the glass-ceramic mixed powder. Thereafter, one or more low-boiling solvents are added and kneaded again, so that the low-boiling solvents are adapted to the surroundings of the high-boiling solvents that are adapted to the periphery of the powder. For this reason, it is possible to obtain a paste in which one or more low-boiling solvents are relatively easily volatilized.
[0017]
The method for forming a rib-like material of the present invention is the above-mentioned paste, or a step of applying a paste obtained by the above-described method to a substrate surface to form a paste film,
Vaporizing the one or more low-boiling solvents from the paste film formed on the substrate surface;
The one or more low-boiling solvents are vaporized into a paste film, and a blade having predetermined comb teeth is pierced and the blade is moved in a fixed direction relative to the paste film, whereby the paste film is plastically deformed. Forming a rib on the surface of the substrate,
The above problem was solved by including the following.
[0018]
The ceramic rib of the present invention is preferably formed by drying and firing the rib-like material formed by the above method.
[0019]
The FPD of the present invention has the above-mentioned ceramic rib.
[0020]
In the present invention, a rib, a ceramic rib, and an FPD can be manufactured from the above paste.
[0021]
BEST MODE FOR CARRYING OUT THE INVENTION
Next, a first embodiment of a paste for forming a ceramic rib according to the present invention will be described with reference to the drawings.
[0022]
As shown in FIG. 2, in the present embodiment, a rib 13 having a predetermined shape is provided on a paste film 11 formed by applying paste on the surface of a substrate 10, and a comb tooth 12 b formed on a blade 12. Is formed on the surface of the substrate 10 by moving the blade 12 or the substrate 10 in a certain direction with the edge 12a of the blade 12 in contact with the surface of the substrate 10.
[0023]
The paste is a paste containing a glass powder or a glass-ceramic mixed powder, a resin, a solvent (a solvent, a plasticizer and a dispersant), and an organic / inorganic composite thixotropic agent, and the glass powder is SiO ₂ , B ₂ It is preferable that O ₃ , ZnO, PbO, or the like be a main component and have a softening point of 300 ° C. to 600 ° C.
[0024]
The glass-ceramic mixed powder is a glass powder mainly composed of SiO ₂ , B ₂ O ₃ , ZnO, PbO or the like, and a ceramic powder such as alumina, zircon, cordierite, mullite, titania, forsterite, etc. serving as a filler. This ceramic powder is mixed in order to make the thermal expansion coefficient of the rib 13 formed equal to the thermal expansion coefficient of the glass substrate 10 and to improve the strength of the fired ceramic rib. .
[0025]
The content of the ceramic powder is preferably 60% by volume or less. When the content of the ceramic powder exceeds 60% by volume, the ribs become porous, which is not preferable. In addition, it is preferable that the particle diameters of the glass powder and the ceramic powder are each 0.1 to 30 μm. When the particle diameter of the glass powder and the ceramic powder is less than 0.1 μm, the glass powder and the ceramic powder are easily aggregated, and the handling becomes troublesome. On the other hand, if the thickness exceeds 30 μm, a desired rib 13 cannot be formed when the blade 12 described later moves.
[0026]
The resin has a function as a binder, is easily decomposed by heat, is a polymer having a high viscosity when dissolved in a solvent, and is a cellulose resin (ethyl cellulose, methyl cellulose, etc.), an acrylic resin (polymethyl methacrylate, polyethyl methacrylate). Etc.).
[0027]
Here, the organic / inorganic composite thixotropic agent as the thixotropic agent is a thixotropic agent in which the surface or end face of the inorganic thixotropic agent is modified with an organic substance and an inorganic thixotropic agent. A mineral layer surface and end face modified with an organic substituent, or a composite of an inorganic thixotropic agent bentonite, a carboxyvinyl polymer, a solvent, and the like can be used.
In addition, inorganic thixotropic agents modified with organic substances include smectite, beidellite, savonite, bentonite, montmorillonite, nontronite, hectorite, kaolinite, halothite, hydrohalosite, sericite, illite, muscovite, talc, inorganic It can be selected from oxide fine particles (silica, alumina, magnesia, zirconia, etc.).
[0028]
The plurality of types of solvents include one or more low-boiling solvents selected from the group consisting of low-boiling solvents having a boiling point of 100 ° C to 180 ° C, and high-boiling solvents having a boiling point of 190 ° C to 450 ° C.
Tables 1 and 2 show examples of solvents having a boiling point of 100 ° C or more and 180 ° C or less constituting a group consisting of low-boiling solvents, and Table 1 shows solvents having a boiling point of 190 ° C or more and 450 ° C or less constituting a group consisting of high-boiling solvents. 3 and Table 4.
[0029]
[Table 1]

[0030]
[Table 2]

[0031]
[Table 3]

[0032]
[Table 4]

[0033]
The selection of the solvent is selected such that the boiling points of the selected one or more low-boiling solvents and the one or more high-boiling solvents are different by 30 ° C. or more. The weight ratio of one or more high-boiling solvents selected from the high-boiling solvent to one or more low-boiling solvents selected from the low-boiling solvent is one or more low-boiling solvents. : 1 or more high-boiling solvents = 50 to 5: It is preferable to adjust to 50 to 95.
[0034]
The paste is composed of the above-mentioned powder, resin and organic thixotropic agent, and plural kinds of solvents. If necessary, these may be used as main components, and further, a plasticizer and a dispersant may be included.
[0035]
Examples of the plasticizer include glycerin and dibutyl phthalate.
Further, as dispersants, polyoxyethylene alkylphenyl ether phosphoric acid, polyoxyethylene dialkylphenyl ether phosphoric acid, polyoxyethylene alkyl ether phosphoric acid, polyoxyphenyl ether phosphoric acid, lauryl phosphoric acid, polyoxyethylene lauryl ether phosphoric acid Acid, sodium polyoxyethylene lauryl ether phosphate, sodium polyoxyethylene oleyl ether phosphate, sodium polyoxyethylene alkyl phenyl ether phosphate, sodium lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, potassium lauryl sulfate, polyoxyethylene Sodium lauryl ether sulfate, polyoxyethylene lauryl sulfate triethanolamine, polyoxyethylene lauryl sulfate ammonium Um, triethanolamine dodecylbenzenesulfonate, octyl phenoxy Siji sodium ethoxyethyl sulfonate, sodium tetradecene sulfonate, polyether carboxylic acids, dispersants such as esters ether polycarboxylic acids.
[0036]
The paste contains 50 to 97% by weight of glass powder or glass / ceramic mixed powder, 0.1 to 15% by weight of resin, 0.1 to 20% by weight of organic / inorganic composite thixotropic agent, and 3 to 3 kinds of solvents. ６０60% by weight.
[0037]
The reason for limiting the glass powder or glass-ceramic powder to the range of 50 to 97% by weight is that if it is less than 50% by weight, it becomes difficult to obtain a rib having a predetermined shape using a blade, and exceeds 97% by weight. This makes it difficult to produce a paste.
[0038]
The reason why the resin is limited to the range of 0.1 to 15% by weight is that if it is less than 0.1% by weight, it becomes difficult to obtain a rib having a predetermined shape using a blade, and if it exceeds 15% by weight. This is because it is difficult to uniformly apply the paste to the surface of the substrate, and there is a problem that an organic substance remains in the fired ceramic rib.
[0039]
Further, the reason why the thixotropic agent is limited to the range of 0.1 to 20% by weight is that if it is less than 0.1% by weight, sufficient thixotropy cannot be obtained, and a rib having a predetermined shape is formed using a blade. This is because it is difficult to obtain the paste, and if it exceeds 20% by weight, it becomes difficult to produce the paste.
[0040]
Further, the reason why the plural kinds of solvents are limited to the range of 3 to 60% by weight is that if the amount is less than 3% by weight, it is difficult to produce the paste or to uniformly apply the paste on the substrate surface. %, It is difficult to obtain a rib-like material having a predetermined shape using a blade, or it takes a long time to vaporize a plurality of kinds of solvents later.
[0041]
By preparing the paste as described above, the viscosity at a shear rate of 20 / s becomes 0.1 to 200 Pa · s, which facilitates application to the substrate surface and stretching to a uniform thickness.
Further, after one or more low-boiling solvents are volatilized, during the blade molding, the viscosity of the paste is sharply reduced to about 10 to 200 Pas due to shear stress received from the blade, so that the paste is plastically deformed according to the blade opening shape, Form ribs. Immediately after molding, since the shear stress from the blade is removed, the viscosity rises sharply to about 1000 to 3000 Pa · s, the shape of the formed rib is maintained without change, and the narrow pitch and high aspect ratio are maintained. A ratio rib can be obtained.
Further, during blade molding, since the viscosity of the paste is reduced to about 10 to 200 Pa.s, it is possible to perform rib molding at a constant traveling speed without exerting a reaction force on the traveling of the blade, The deviation (variation) of the rib height in the substrate can be reduced.
[0042]
The method for producing the paste is such that one or more low-boiling solvents are selected from the group consisting of the low-boiling solvents exemplified in Tables 1 and 2, and one or more high-boiling solvents having a boiling point different from the solvent by 30 ° C. or more are shown. 3 and selected from the group consisting of high-boiling solvents exemplified in Table 4 and weighed. Then, separately weighed glass powder or mixed glass-ceramic powder, resin, thixotropic agent, and one or more high-boiling solvents are mixed and kneaded. When a dispersant and a plasticizer are contained, one or more high-boiling solvents are used as a main component, and one or both of a plasticizer and a dispersant are kneaded in advance, and the above-described kneaded material is added to the kneaded material. The powder, the resin and the thixotropic agent are mixed and further kneaded. By kneading with the above composition, the viscosity of the paste during production can be reduced to a range where mass production equipment can be used, so that paste production at a mass production level becomes possible. Thereafter, a paste is obtained by adding one or more kinds of low-boiling solvents and kneading again.
[0043]
Next, a method for forming a lip-like object using the paste thus obtained will be described with reference to FIG.
[0044]
As shown in FIG. 1A, the above-mentioned paste is first applied to the surface of the substrate to form a paste film 11. The paste is applied to the surface of the substrate 10 by an existing means such as a roll coating method, a screen printing method, a die coating method, a bar coating method, or a doctor blade method. After the paste is applied to the surface of the substrate 10 to form the paste film 11, the substrate 10 is left for a predetermined time as shown in FIG. Is vaporized as shown by the dashed arrow. The environmental temperature and time for vaporizing one or more low-boiling solvents differ depending on the type of the solvent used as the low-boiling solvent, but the boiling points are 1-ethoxy-2-propanol and 4-methyl-2-pen having a boiling point around 120 to 150 ° C. When using tanol or the like, it is preferable to leave it in an atmosphere at 15 to 25 ° C. for 1 to 5 hours.
[0045]
In particular, since the paste in the present embodiment was manufactured by adding one or more low-boiling solvents last, only the one or more high-boiling solvents initially mixed were powdered in a glass powder or a glass-ceramic mixed powder. And one or more low-boiling solvents have become familiar paste around the high-boiling solvent that has become familiar around the powder, so that one or more low-boiling solvents are relatively easy to volatilize, By leaving the substrate for a predetermined time, one or more low-boiling solvents can be reliably volatilized from the paste film.
[0046]
After one or more low-boiling solvents are completely vaporized, the paste film 11 is plastically deformed by a blade 12 to form a rib 13 having a predetermined shape, as shown in FIG. 1C. The rib 13 is kept in a deformed shape, and glass powder or the like is uniformly dispersed in the rib 13. A plurality of comb teeth 12b are formed at equal intervals and in the same direction on the blade 12 that comes into contact with the surface of the substrate 10 on which the paste film 11 is formed. The blade 12 is made of a metal, ceramic or plastic and a composite material thereof that does not react with the paste or is dissolved in the paste, and particularly includes Fe, Ni, and Co from the viewpoint of dimensional accuracy and durability. An alloy or a cemented carbide or ceramic in which ceramic such as tungsten carbide is dispersed in Co or Ni is preferable. The gap between the respective comb teeth 12b is formed in accordance with the cross-sectional shape of the rib 13 formed by the blade 12.
[0047]
As shown in FIGS. 4 and 5, the blade 12 in the present embodiment has a thickness t, a pitch p of the comb teeth 12b, a gap w between the comb teeth 12b, and a depth h of stainless steel or ultra-thin having a predetermined value. It is formed by a hard alloy.
Further, the shape of the interstices of the comb teeth 12b is not limited to the case of forming a square shape as shown in FIG. May be formed. If the shape of the interstices of the comb teeth 12b is trapezoidal, it is possible to form a rib-like material 13 suitable for applications with a wide opening, and if the shape of the gap of the comb teeth 12b is inverted trapezoidal, The rib-like material 13 whose top is flattened with a large area can be formed.
[0048]
Here, when the blade 12 has a thickness of 0.005 mm or more and 5 mm or less, the pitch of the comb teeth 12 b is P, the gap of the comb teeth 12 b is w, and the depth of the gap is h, the blade pitch is 0. It is preferable that 05 ≦ h ≦ 5.0 mm and 0.03 mm ≦ w ≦ 3.0 mm.
[0049]
The rib-like material 13 formed by the blade 12 satisfying these conditions is tightened by subsequent drying and firing, and a dense ceramic rib 14 having a predetermined rib 14 gap can be obtained. The ribs 13 formed by the blade 12 formed as described above are formed by piercing the comb teeth 12 b of the blade 12 into the paste film 11 and fixing the substrate 10 while keeping the edge in contact with the surface of the substrate 10. Is performed in a certain direction, or the paste film 11 is plastically deformed by fixing the blade 12 and moving the substrate 10 in a certain direction. That is, the portion of the paste applied to the surface of the substrate 10 corresponding to the comb teeth 12b of the blade 12 is moved or swept into the gap between the comb teeth 12b, and only the paste located in the gap between the comb teeth 12b is moved. Are left on the substrate 10 to form the ribs 13 on the surface of the substrate 10.
[0050]
If the depth of the groove of the comb tooth 12b is larger than the thickness of the paste film 11, the paste swept out when moving the blade 12 or the glass substrate 10 enters the groove and increases the height of the paste film 11 to a height greater than the thickness. Can be formed. After forming the rib-like material 13 having the predetermined shape, the ceramic rib 14 is obtained by drying in air at 100 to 200 ° C. for 10 to 30 minutes and further firing in air at 520 to 580 ° C. for 10 to 30 minutes. Can be Using this ceramic rib 14, a PDP (not shown) can be manufactured.
[0051]
As shown in the enlarged circle of FIG. 3, the ceramic rib 14 formed on the substrate 10 as described above has a height H of the rib 14 and a rib at a height (セ ラ ミ ッ ク) H. When the width of 14 is WC, the standard deviation of H and WC is preferably 4% or less, respectively, and the aspect ratio represented by H / WC is preferably 1.5 to 10. When the rib pitch is small and the aspect ratio is 1.5 to 10, an extremely high-definition ceramic rib 14 can be obtained.
[0052]
In the paste of the present embodiment, as described above, at least one or more organic / inorganic composite thixotropic agents are added as a thickening agent, an anti-dripping agent, and an anti-settling agent, so that the paste has a large thixotropic property (thixotropic: (Thixotropic). For this reason, when the paste is subjected to shearing (cutting), the viscosity is reduced at the time of molding, the plastic is liable to undergo plastic deformation, and the viscosity is increased after the molding at which the shear is lost.
For this reason, the viscosity decreases when a cutting force is applied, such as for plastically deforming the paste during molding, and it becomes possible to easily perform plastic deformation. Thus, the formed shape can be easily maintained. That is, the moldability and shape retention of the paste can be simultaneously improved.
[0053]
Thus, when the ribs 13 are formed by the blades 12, the blade 12 does not exert an excessive reaction force on the comb teeth 12 b and does not hinder the advancement of the blades 12. Since unnecessary paste can be removed, the rib shape of the formed paste 11 can be maintained, and the dimensional accuracy in forming the rib can be improved while maintaining the forming accuracy of the paste film 11. The shape of the ribs 13 in the paste can be maintained. Furthermore, since the reaction force applied to the blade 12 comb teeth 12b can be reduced, the strength of the blade 12 comb teeth 12b required for molding can be reduced, so that the dimensions of the comb teeth 12b in the blade 12 are reduced. As a result, it is possible to form ribs with higher definition, improve the dimensional accuracy in forming the ribs 13, and maintain a high shape retention index.
[0054]
At the same time, the viscosity and thixotropy of the paste can be adjusted by adding an organic / inorganic composite thixotropic agent having high thixotropy to the paste. Therefore, a desired rib shape can be obtained by adjusting the amount of addition. Thereby, for example, when forming a rib of about 60 μm with a pitch dimension of about 120 μm, the dimensional accuracy can be reduced to about ± 5 μm or less.
[0055]
In the above-described embodiment, the blade 12 is moved or the substrate 10 is moved while the comb 12b of the blade 12 is pierced into the paste film 11 and the edge 12a is in contact with the surface of the substrate 10. Although the ribs 13 were formed directly on the surface, the comb teeth 12b of the blade 12 were pierced into the paste film 11 formed on the surface of the substrate 10 as shown in FIG. The paste film 11 may be plastically deformed by moving the blade 12 or the substrate 10 in a certain direction while floating above the predetermined height. By plastically deforming in this manner, the underlayer 22 on the surface of the substrate 10 and the ribs 23 on the underlayer 22 can be formed.
[0056]
That is, the paste from the surface of the substrate 10 to a predetermined height remains on the substrate surface due to the movement of the blade 12 or the substrate 10 to form the underlayer 22, and the comb teeth 12b of the blade 12 in the paste above the underlayer 22 Is moved or swept into the gap between the comb teeth 12b, and only the paste located in the gap between the comb teeth 12b remains on the underlayer 22 to form the rib-like material 23 on the underlayer 22. . Next, when the base layer 22 and the ribs 23 are dried and fired, a dielectric layer 24 is formed on the substrate 10 as shown in FIG. 7, and a ceramic rib 25 is formed on the dielectric layer 24. become.
[0057]
Furthermore, in the paste of the present embodiment, by mixing the paste as described above, a paste having a viscosity of 0.1 to 200 Pa · s at a shear rate of 20 / sec can be obtained, and the paste at this viscosity can be obtained. Is relatively fluid and easy to apply, and can be easily stretched to a uniform thickness on a substrate.
[0058]
Hereinafter, a second embodiment of a paste for forming a ceramic rib according to the present invention will be described with reference to the drawings.
[0059]
The present embodiment differs from the first embodiment in that an inorganic thixotropic agent is added in addition to an organic / inorganic composite thixotropic agent as a thixotropic agent in the paste composition.
[0060]
In the present embodiment, among the inorganic thixotropic agents, bentonite, kaolinite, halosite, hydrohalosite, sericite, illite, nontronite, montmorillonite, hectorite, sepiolite, attapulgite, muscovite, talc, etc. , One or more of them and add it to the paste.
[0061]
At this time, the ceramic paste is prepared by mixing 0.1 to 20% by weight of an organic / inorganic composite thixotropic agent and an inorganic thixotropic agent as thixotropic agents. The reason that the thixotropic agent is set in the range of 0.1 to 20% by weight is not preferable because if it is less than 0.1% by weight, sufficient thixotropy cannot be exhibited, and more than 20% by weight. In this case, since the viscosity of the paste becomes too high, the paste is not plastically deformed in the shear during molding, and the paste is scraped off by the blade. It is.
[0062]
In the present embodiment, the same effects as those of the first embodiment can be obtained, and in this paste, an organic / inorganic composite thixotropic agent having a high thixotropic property and an inorganic thixotropic agent are added. Thus, by controlling the degree of dispersion of the thixotropic agent by the kneading conditions, the thickening / thixotropic properties of the paste can be adjusted. Therefore, a desired rib shape can be obtained. In addition, the organic component of the thixotropic agent has excellent stability over time immediately after compounding, and the inorganic thixotropic agent and inorganic component can reduce the time-dependent change after compounding and maintain thixotropy over a long period of time. Thus, it is possible to form the high-definition rib 13.
[0063]
Furthermore, in the paste of the present embodiment, the required amounts of the organic components and the solvent of the thixotropic agent can be reduced by mixing the above inorganic composite thixotropic agent, as compared with the case of the first embodiment. Thus, the organic components that are dried, volatilized, and desorbed during firing are reduced, and the shrinkage of the ceramic ribs 14 as compared with the rib-like material 13 can be further reduced. Therefore, the dimensional accuracy of the ceramic ribs 14 can be set more precisely when the ribs 13 are formed.
[0064]
In each of the above embodiments, as shown in FIG. 8 (a), the thixotropic agent is a three-dimensional thixotropic agent T inside a solvent (including a dispersant / resin) in the paste. Is formed to increase the viscosity and connect the glass-ceramic particles S to each other. It is considered that in this state, when an external force is applied at the time of blade molding or the like, the bonding of the thixotropic agent T is broken as shown in FIG.
[0065]
Next, examples of the present invention will be described in detail together with comparative examples.
[0066]
<Example 1>
80% by weight of PbO-SiO ₂ one _B 2 _{O 3} based glass powder having an average particle diameter of 1 [mu] m, an average particle diameter of O. as ceramic filler 20% by weight of 5 μm alumina powder was prepared, and both were sufficiently mixed. This mixed powder, ethyl cellulose as a resin, organic bentonite as an organic / inorganic composite thixotropic agent, α-terpineol as a solvent having a high boiling point, and 1 ethoxy-2-propanol as a low boiling point solvent were 83 wt%. /0.5/1/10.5/5. The weighed mixed powder, the resin, the thixotropic agent and the high-boiling solvent were first blended and sufficiently kneaded to obtain a kneaded product. To the kneaded product was added 1-ethoxy-2-propanol, which was a weighed low boiling point solvent, to obtain a paste.
[0067]
Next, as shown in FIG. 2, in a state where a rectangular soda lime glass substrate 10 having a diagonal dimension of 42 inches and a thickness of 3 mm is fixed, the paste is roll-coated on the glass substrate 10. Was applied to form a paste film 11 with a thickness of 150 μm. By leaving the substrate 10 on which the paste film 11 was thus formed at room temperature for 1 hour, 1 ethoxy-2-propanol, which is a low boiling point solvent, was vaporized from the paste film 11.
[0068]
A blade 12 made of stainless steel having a pitch P of the comb teeth 12b of 120 μm, a gap w of the comb teeth 12b of 60 μm, a depth h of 200 μm, and a thickness t of 0.1 mm was prepared. (FIGS. 4 and 5)
[0069]
With the glass substrate 10 fixed, the comb teeth 12b of the blade 12 are pierced into the paste film 11 in which the low-boiling-point solvent is vaporized, and the edge 12a is brought into contact with the glass substrate 10 in the direction indicated by the solid arrow in FIG. By moving the blade 12 in a predetermined direction to plastically deform the paste film 11, a rib 13 was formed on the surface of the substrate 10.
Thereafter, the rib-like material 13 was dried in the air at 150 ° C. for 20 minutes to remove the high boiling point solvent, and was further fired in the air at 550 ° C. for 10 minutes to obtain the ceramic rib 14. This ceramic rib was used as Example 1.
[0070]
<Example 2>
80% by weight of PbO-SiO ₂ one _B 2 _{O 3} based glass powder having an average particle diameter of 1 [mu] m, and alumina powder having an average particle diameter of 0.5μm prepared 20% by weight ceramic filler were mixed well both . This mixed powder, ethyl cellulose as a resin, bentonite as an inorganic thixotropic agent, organic bentonite as an organic / inorganic composite thixotropic agent, α-terpineol as a high-boiling solvent, and 1-ethoxy as a low-boiling solvent 2-Propanol was weighed to a weight ratio of 83 / 0.5 / 0.8 / 0.2 / 10.5 / 5. The weighed mixed powder, the resin, the thixotropic agent, and the high-boiling solvent were first blended and sufficiently kneaded to obtain a kneaded product.
Hereinafter, a rib 13 and a ceramic rib 14 were obtained in the same procedure as in Example 1. This ceramic rib 14 was used as Example 2.
[0071]
<Comparative Example 1>
80% by weight of PbO-SiO ₂ one _B 2 _{O 3} based glass powder having an average particle diameter of 1 [mu] m, an average particle diameter of O. as ceramic filler 20% by weight of 5 μm alumina powder was prepared, and both were sufficiently mixed. This mixed powder, ethyl cellulose as a resin, α-terpineol as a solvent as a solvent and α-terpineol as a solvent and 1-ethoxy-2-propanol as a low-boiling solvent were blended at a weight ratio of 80/1/1/7. The mixture was sufficiently kneaded to obtain a kneaded material. To the kneaded product was added 1-ethoxy-2-propanol, which was a weighed low boiling point solvent, to obtain a paste. Hereinafter, a rib 13 and a ceramic rib 14 were obtained in the same procedure as in Example 1. This ceramic rib 14 was used as Comparative Example 1.
[0072]
<Comparison test and evaluation>
Respectively, for any 100 of the ceramic ribs 14 of each of Examples and Comparative Examples obtained by sintering in this manner, the height H and width W _C were measured as follows.
[0073]
As shown in FIG. 3, the examples and the measurement of the width W _C of any 100 ceramic ribs on the substrate of the comparative example, the height when the height of the ceramic ribs and H (1/2) H and the width W _C of the ribs at the from these height H and width W _C, was calculated for each of the aspect ratio H / W _C. Further, after calculating the average value of these measured values, H, W C, respectively (the maximum value or the minimum value - average value) of the _{H /} W _C was calculated variation value represented by / average value.
Table 5 in the Examples and Comparative Examples of the results (rib height H, the width _C, the average value and the variation value of the aspect ratio H / W _C) is contrasted shown.
[0074]
[Table 5]

[0075]
As apparent from Table 5, in comparison with Comparative Example, in the embodiment, together are clearly better aspect ratio rib height H, a width _{C, and} variation in the data of the aspect ratio H / W _C It can be seen that the dimensional accuracy of the ceramic rib 14 has been improved.
That is, it is considered that the embodiment can deal with a high-definition PDP as compared with the comparative example.
Also, from Table 5, it can be seen that the variation of the ceramic rib in the example is smaller than that in the comparative example. This is considered to be due to the fact that the viscosity of the paste is relatively high and the rib-like material is less droopy, since the rib-like material is formed after evaporating the low boiling point solvent.
[0076]
【The invention's effect】
According to the present invention, the composition of the paste includes 50 to 97% by weight of a glass powder or a glass / ceramic mixed powder, 0.1 to 15% by weight of a resin, and 3 to 60% by weight of a plurality of kinds of solvents. By adding 0.1 to 20% by weight of at least one or more organic / inorganic composite thixotropic agent and / or inorganic thixotropic agent to this paste composition as a thickener, an anti-dripping agent and an anti-settling agent. In addition, since the paste can have a large thixotropy (Thixotropic), the viscosity decreases during molding in which the paste is sheared, and the paste is susceptible to plastic deformation. The viscosity increases. In other words, during the rib formation by the blade, without applying excessive reaction force to the blade, and since unnecessary paste can be removed while maintaining the molding accuracy, the rib shape in the molded paste is maintained, It is possible to improve the dimensional accuracy in rib formation. Further, it is possible to obtain a paste having a predetermined viscosity which is relatively fluid and easy to apply, and can be easily stretched to a uniform thickness on a substrate, while the paste has one or more low-boiling solvents volatilized. The viscosity increases in the state. The lip-like material obtained by plastically deforming the paste film whose viscosity has increased to a desired shape with a blade is maintained in the shape after the deformation, and the shape of the rib-like material is maintained without distortion. There is an effect that the ceramic rib can be manufactured as it is.
[Brief description of the drawings]
FIG. 1 is a perspective view showing a procedure for forming a rib-like material of the present invention.
FIG. 2 is a perspective view showing a state of forming a ceramic capillary rib in a first embodiment of a paste for forming a ceramic rib according to the present invention.
FIG. 3 is a cross-sectional view showing a ceramic rib obtained by drying, heating, and firing the ceramic capillary rib in a cross section taken along line AA of FIG. 2;
FIG. 4 is a front view of the blade.
FIG. 5 is a sectional view taken along line BB of FIG. 4;
FIG. 6 is a perspective view corresponding to FIG. 2, showing a state of forming a ceramic capillary rib in a second embodiment of a paste for forming a ceramic rib according to the present invention.
7 is a cross-sectional view corresponding to FIG. 3 showing a ceramic rib with an insulating layer obtained by drying, heating, and firing the rib with a ceramic capillary layer in a cross section taken along line BB of FIG. 6;
FIG. 8 is a schematic diagram showing the action of a thixotropic agent in a paste, showing a state without external force (a) and a state with external force (b).
[Explanation of symbols]
Reference Signs List 10 glass substrate 11 paste film 12 blade 12a edge 12b comb teeth 13,23 rib-like material 14,25 ceramic rib 22 underlayer 24 insulating underlayer P solvent (including dispersant, resin, etc.)
T Thixotropic agent S Glass-ceramic particles

Claims (8)

By piercing a blade having predetermined comb teeth into the paste film formed on the substrate surface and moving the blade relative to the paste film in a fixed direction, the paste film is plastically deformed and the paste film is formed on the substrate surface. A paste capable of forming a rib,
The composition of the paste is 50 to 97% by weight of glass powder or glass / ceramic mixed powder, 0.1 to 15% by weight of resin, 3 to 60% by weight of plural kinds of solvents, and at least one kind of organic and inorganic 0.1 to 20% by weight of a complex thixotropic agent,
Each of the plurality of types of solvents has a different boiling point of 30 ° C. or more, and the plurality of types of solvents have one or more low-boiling solvents selected from the group consisting of low-boiling solvents having a boiling point of 100 ° C. to 180 ° C. One or more high-boiling solvents selected from the group consisting of high-boiling solvents having a temperature of 190 ° C to 450 ° C,
A paste for forming a ceramic rib, comprising: By piercing a blade having predetermined comb teeth into the paste film formed on the substrate surface and moving the blade relative to the paste film in a fixed direction, the paste film is plastically deformed and the paste film is formed on the substrate surface. A paste capable of forming a rib,
The composition of the paste is 50 to 95% by weight of a glass powder or a glass-ceramic mixed powder, 0.1 to 15% by weight of a resin, 3 to 60% by weight of a plurality of kinds of solvents, and at least one kind of inorganic whisker. Agent and at least one or more organic / inorganic composite thixotropic agents in an amount of 0.1 to 20% by weight,
Each of the plurality of types of solvents has a different boiling point of 30 ° C. or more, and the plurality of types of solvents have one or more low-boiling solvents selected from the group consisting of low-boiling solvents having a boiling point of 100 ° C. to 180 ° C. One or more high-boiling solvents selected from the group consisting of high-boiling solvents having a temperature of 190 ° C to 450 ° C,
A paste for forming a ceramic rib, comprising: 3. The paste for forming a ceramic rib according to claim 1, wherein the paste contains one or both of a plasticizer and a dispersant. Glass powder or glass / ceramic mixed powder, resin, at least one or more organic / inorganic composite thixotropic agent, or at least one or more inorganic thixotropic agent and at least one or more organic / inorganic composite thixotropic agent; A step of kneading one or more high-boiling solvents having a boiling point of 190 ° C. or higher and 450 ° C. or lower to obtain a kneaded product;
Adding one or more kinds of low-boiling solvents having a boiling point of 100 ° C. or more and 180 ° C. or less to the kneaded material and kneading the kneaded material again, the method comprising the steps of: The method for producing a paste for forming a ceramic rib according to claim 4, wherein the kneaded product before adding the low boiling point solvent further contains one or both of a plasticizer and a dispersant. Applying a paste according to any one of claims 1 to 3 or a paste obtained by the method according to claim 4 or 5 to a substrate surface to form a paste film;
Vaporizing the low boiling point solvent from the paste film formed on the substrate surface,
The low boiling solvent vaporized paste film is pierced with a blade having predetermined comb teeth, and the paste film is plastically deformed by moving the blade relative to the paste film in a fixed direction. Forming a rib on the surface. A ceramic rib obtained by drying and firing a rib-like material formed by the method according to claim 6. An FPD comprising the ceramic rib according to claim 7.

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