JP4631153B2 - Display member and display - Google Patents

Description

【００２９】
酸化リチウム、酸化ナトリウムまたは酸化カリウムのアルカリ金属酸化物のうち少なくとも１種を用い、その合計量が３〜１５重量％、さらには３〜１０重量％であることが好ましい。
【００３０】
アルカリ金属酸化物は、ガラスの荷重軟化点、熱膨張係数のコントロールを容易にするのみならず、ガラスの屈折率を低くすることができるため、感光性有機成分との屈折率差を小さくすることが容易になる。アルカリ金属酸化物の合計量が３重量％以上とすることでガラスの低融点化の効果を得ることができ、１５重量％以下とすることでガラスの化学的安定性を維持すると共に熱膨張係数を小さく抑えることができる。アルカリ金属としては、ガラスの屈折率を下げることやイオンのマイグレーションを防止することを考慮するならリチウムを選択するのが好ましい。
【００３１】
酸化ケイ素の配合量は５〜３０重量％が好ましく、より好ましくは１０〜３０重量％である。酸化ケイ素は、ガラスの緻密性、強度や安定性の向上に有効であり、また、ガラスの低屈折率化にも効果がある。熱膨張係数をコントロールしてガラス基板とのミスマッチによる剥離などを防ぐこともできる。５重量％以上とすることで、熱膨張係数を小さく抑えガラス基板に焼き付けた時にクラックを生じない。また、屈折率を低く抑えることができる。３０重量％以下とすることで、ガラス転移点、荷重軟化点を低く抑え、ガラス基板への焼き付け温度を低くすることができる。
【００３２】
酸化ホウ素は、鉛などの重金属を含有しないガラスにおいて低融点化のために必要な成分であり、さらに低屈折率化にも有効であり、２０〜４５重量％、さらには２０〜４０重量％の範囲で配合することが好ましい。２０重量％以上とすることで、ガラス転移点、荷重軟化点を低く抑えガラス基板への焼き付けを容易にする。また、４５重量％以上とすることでガラスの化学的安定性を維持することができる。
【００３３】
酸化バリウムおよび酸化ストロンチウムのうち少なくとも１種を用い、その合計量が２〜１５重量％、さらには２〜１０重量％であることが好ましい。これらの成分は、ガラスの低融点化、熱膨張係数の調整に有効であり、焼き付け温度の基板の耐熱性への適用、電気絶縁性、形成される隔壁の安定性や緻密性の点でも好ましい。２重量％以上とすることで低融点化の効果を得ることができると共に結晶化による失透を防ぐこともできる。また、１５重量％以下とすることにより、熱膨張係数を小さく抑え、屈折率も小さく抑えることができる。またガラスの化学的安定性も維持できる。
【００３４】
酸化アルミニウムはガラス化範囲を広げてガラスを安定化する効果があり、ペーストのポットライフ延長にも有効である。１０〜２５重量％の範囲で配合することが好ましく、この範囲内とすることでガラス転移点、荷重軟化点を低く保ち、ガラス基板上への焼き付けを容易とすることができる。
【００３５】
さらに、酸化カルシウムおよび酸化マグネシウムは、ガラスを溶融しやすくすると共に熱膨張係数を制御するために配合されることが好ましい。酸化カルシウムおよび酸化マグネシウムは合計で２〜１５重量％配合するのが好ましい。合計量が２重量％以上とすることで結晶化によるガラスの失透を防ぎ、１５重量％以下とすることでガラスの化学的安定性を維持することができる。
【００３６】
また、上記の組成には表記されていないが、酸化亜鉛はガラスの熱膨張係数を大きく変化させることなく低融点化させる成分でありこれも配合されることが好ましい。多く配合しすぎると屈折率が大きくなる傾向にあるので、１〜２０重量％の範囲で配合するのが好ましい。
【００３７】
感光性ペーストに用いる低融点ガラス粉末は、ペースト形成時の充填性および分散性が良好で、ペーストの均一な厚さでの塗布が可能であると共にパターン形成性を良好に保つためには、平均粒子径が１〜５μｍであり、最大粒子径が３５μｍ以下であることが好ましい。このような粒度分布を有するガラス粉末がペーストへの充填性および分散性の点で優れているが、低融点ガラス粉末の場合は焼成工程でその殆どが溶融し一体化されるので、かなり大きな粒子径の粉末も許容される。しかし、焼成工程での加熱温度以上の荷重軟化点または融点を有するフィラー成分の場合は、そのまま隔壁中または隔壁表面に残留するので、その平均粒子径はより小さいことが好ましく１．５〜４μｍであることが適当である。この範囲であれば、充填性および分散性を満足させて、塗布性およびパターン形成性の優れた感光性ペーストを構成することができる。
【００３８】
本発明のＰＤＰ用部材の隔壁は、上記のナノ粒子やガラス材料の他に、平均粒子径１．５〜５μｍのフィラーを５〜３０重量％含有しても良い。このフィラーを含むことにより、焼成前のパターン形成性を維持しつつ、焼成後の隔壁の強度を保持し、焼成収縮率を抑制し、形状保持性を高める効果がある。さらに隔壁の誘電率を下げるのに効果がある。
【００３９】
平均粒子径１．５〜５μｍのフィラーは、感光性ペーストにおける感光性有機成分や低融点ガラスの平均屈折率との整合をとり、露光光の散乱を抑えるために、平均屈折率が１．４５〜１．６５の範囲内にあることが好ましい。このフィラーの平均屈折率を上記の範囲内とするために、組成を調整した高融点ガラス、結晶化ガラス、セラミックスからなるフィラーやコーディエライトが好ましく用いられる。
【００４０】
フィラーとしては、コーディエライト（２ＭｇＯ・２Ａｌ₂Ｏ₃・５ＳｉＯ₂）、セルジアン（ＢａＯ・Ａｌ₂Ｏ₃・ＳｉＯ₂）、アノーサイト（ＣａＯ・Ａｌ₂Ｏ₃・２ＳｉＯ₂）、ステアタイト（ＭｇＯ−ＳｉＯ₂）、スポジュウメン（ＬｉＯ２・Ａｌ₂Ｏ₃・４ＳｉＯ₂）、フォルステライト（２ＭｇＯ・ＳｉＯ₂）、シリカ（石英）、高融点ガラスが好ましく用られる。
【００４１】
高融点ガラスとしては、ガラス転移点５００〜１２００℃、荷重軟化点５５０〜１２００℃を有するものが好ましく、このような高融点ガラスは、酸化ケイ素および酸化アルミニウムをそれぞれ１５重量％以上含有する組成のものが好ましく、これらの含有量合計が５０重量％以上であることが必要な熱特性を得るのに有効である。高融点ガラスの組成はこれに限定されるものではないが、例えば以下のような酸化物換算組成のものを用いることができる。
酸化珪素 １５〜５０重量％
酸化ホウ素 ５〜２０重量％
酸化バリウム ２〜１０重量％
酸化アルミニウム １５〜５０重量％。
【００４２】
さらに具体的には、例えば、酸化珪素３８重量％、酸化ホウ素１０重量％、酸化バリウム５重量％、酸化アルミニウム３６重量％で、その他の成分として酸化カルシウム、酸化亜鉛、酸化マグネシウムを少量ずつ含有するガラス転移点６２５℃、荷重軟化点７５０℃の高融点ガラスの平均屈折率は１．５９であり、これは本発明で好ましく使用される低融点ガラスの平均屈折率と同等である。
【００４３】
フィラーのもう一つの成分であるコーディエライトの屈折率は１．５８であり、本発明の成分として好適である。
【００４４】
このようなフィラーの平均粒子径は１．５〜５μｍの範囲が好ましい。１．５μｍ以上とすることで形状保持性の効果を得ることができる。また、フィラー成分は焼成工程で溶融することがないので５μｍより大きすぎると、形成された隔壁の頂部の凹凸が大きくなりクロストークの原因となるなどの問題を生じる傾向にある。
【００４５】
隔壁形成に用いる感光性ペーストは、低融点ガラス、ナノ粒子、フィラー、感光性有機成分等を所定の組成となるように調合した後、３本ローラや混練機で均質に混合分散することにより調製される。ペーストの調製の際、ナノ粒子のペーストの段階からの凝集を回避するために、感光性ポリマやモノマーなどの感光性樹脂、光重合開始剤、無機材料から不純物イオンを除去しておくことが好ましい。有機成分に含まれる感光性モノマー、感光性オリゴマーもしくはポリマー、種々の添加剤の熱分解特性とガラス粉末成分の熱特性が不釣り合いになると、隔壁が褐色に着色したり、隔壁が基板から剥がれたりする欠陥が発生する傾向にあるので、これらの整合を図ることも肝要である。
【００４６】
感光性ペーストの粘度は、有機溶媒により１万〜２０万ｃＰ（センチ・ポイズ）程度に調整して使用される。この時使用される有機溶媒としては、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルエチルケトン、ジオキサン、アセトン、シクロヘキサノン、シクロペンタノン、イソブチルアルコール、イソプロピルアルコール、テトラヒドロフラン、ジメチルスルフォキシド、γ-ブチロラクトンなどやこれらのうちの1種以上を含有する有機溶媒混合物が挙げられる。
【００４７】
感光性ペーストの塗布は、スクリーン印刷法、バーコーター法、ロールコータ法、ドクターブレード法などの一般的な方法で行うことができる。塗布厚さは、所望の隔壁の高さとペーストの焼成による収縮率を考慮して決めることができる。
【００４８】
塗布・乾燥した感光性ペースト膜にフォトマスクを介して露光を行って、隔壁パターンを形成する。露光の際、ペースト塗布膜とフォトマスクを密着して行う方法と一定の間隔をあけて行う方法（プロキシミティ露光）のいずれを用いても良い。露光用の光源としては、水銀灯やハロゲンランプが適当であるが、超高圧水銀灯が最もよく使用される。超高圧水銀灯を光源として、プロキシミティ露光を行うのが一般的である。露光条件はペーストの塗布膜厚さによって異なるが、通常は５〜３０ｍＷ／ｃｍ²の出力の超高圧水銀灯を用いて２０秒から１０分間露光を行うのが適当である。
【００４９】
露光後、露光部分と未露光部分の現像液に対する溶解度差を利用して、現像を行うが、この場合、浸漬法、スプレー法、ブラシ法などが用いられる。本発明で好ましく用いられる感光性ペーストの感光性有機成分としては、側鎖にカルボキシル基を有するものが好ましく採用され、この場合にはアルカリ水溶液での現像が可能になる。アルカリとしては、有機アルカリ水溶液を用いた方が焼成時にアルカリ成分を除去し易いので好ましい。有機アルカリとしては、一般的なアミン化合物を用いることができる。具体的には、テトラメチルアンモニウムヒドロキサイド、トリメチルベンジルアンモニウムヒドロキサイド、モノエタノールアミン、ジエタノールアミンなどがあげられる。アルカリ水溶液の濃度は通常０．０５〜１重量％、より好ましくは０．１〜０．６重量％である。アルカリ濃度が低すぎると可溶部が完全に除去されない傾向にあり、アルカリ濃度が高すぎると、露光部のパターンが剥離したり、侵食したりする傾向にある。現像時の温度は、２０〜５０℃で行うことが工程管理上好ましい。
【００５０】
感光性ペーストの塗布膜から露光・現像の工程を経て形成した隔壁パターンを次に焼成炉で焼成し、有機成分を熱分解して除去し、同時に無機成分中の低融点ガラスを溶融させて隔壁を形成する。
【００５１】
焼成の雰囲気や温度は、ペーストや基板の特性によって異なるが、通常は、空気中で焼成される。焼成炉としては、バッチ式の焼成炉やベルト式の連続型焼成炉を用いることができる。バッチ式の焼成を行うには通常、隔壁パターンが形成されたガラス基板を室温から５００℃程度まで数時間掛けてほぼ等速で昇温した後、焼成温度として設定した５５０〜６００℃に３０〜１２０分間で上昇させて、約１５〜３０分間保持して焼成を行う。焼成温度は用いるガラス基板のガラス転移点より低くなければならないので、ガラス基板を用いる場合には自ずから好ましい上限が存在する。焼成温度が高すぎたり、焼成時間が長すぎたりすると隔壁の形状にダレなどの欠陥が発生する傾向にある。
【００５２】
本発明のＰＤＰ用部材の隔壁は全光線反射率が５０％以上、さらには６０％以上、またさらには７０％以上であることが好ましい。全光線反射率が高いことにより、蛍光体層からの発光を高い割合で開口部から外部に放射することになり輝度を高めると共に、また隣合う他の発光色への影響を遮断することができ、それぞれの発光色の色純度を高めることができる。また、全光線反射率は９０％以下であることが好ましい。９０％以下とすることにより、外光の反射による非発光領域への写り込みを防ぐことができる。全光線反射率は、例えば実施例で用いた方法にて測定することができる。
【００５３】
また、隔壁の気孔率は２〜８％、さらには２〜５％であることが好ましい。気孔率を８％以下とすることにより、緻密な構造の隔壁が形成され隔壁強度が向上するとともに、下層部の密着性を高め、隔壁の倒れを防止することができる。また、気孔率をこの程度に抑えることができれば、気孔はほとんど閉気孔の状態で存在するため、輝度低下などの発光特性低下の原因となるガスや水分が放電時に気孔から排出されるのを防ぐことができ、放電寿命や、輝度安定性も向上する。
【００５４】
一方、気孔率を２％以上とすることにより、熱や機械的な衝撃に対する緩衝効果を発揮する。つまり適度な気孔の存在が、熱や、衝撃による亀裂の伝搬を分散させ、隔壁の破損を防ぐことができる。また適度な気孔の存在は、隔壁の高反射率化にも寄与させることができる。気孔率は、例えば実施例で用いた方法にて測定することができる。
【００５５】
隔壁に挟まれたセル内に、赤、緑、青に発光する蛍光体ペーストを塗布して必要に応じて焼成し、本発明のディスプレイ用部材としてプラズマディスプレイパネル用の背面板を製造することができる。この背面板と前面板とを張り合わせた後、封着、ガス封入して本発明のディスプレイとしてプラズマディスプレイが作製される。
【００５６】
これらの技術は、プラズマアドレス液晶ディスプレイならびに電子放出素子あるいは蛍光表示管を用いたディスプレイにおいても、好ましく適用される。
【００５７】
【実施例】
以下、実施例を用いて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、濃度（％）は特に断らない限り重量％である。
【００５８】
（測定方法）
（１）感光性ペーストに添加するナノ粒子の平均粒子径の測定
堀場製作所製の動的光散乱式粒径分布測定装置ＬＢ−５００を用いて測定したが、実施例１１〜１５については、マイクロトラック粒度分析計ＵＰＡ１５０ＭＯＤＥＬ、Ｎｏ．９３４０（日機装株式会社）を用いて測定した。
【００５９】
（２）凝集粒子の粒子径の測定
イオンエッチング法で処理した試料を、透過型電子顕微鏡（ＴＥＭ）を用いて２万倍に拡大して撮影し、その写真の画像処理から凝集粒子を球（画像上は円）に近似し、その直径を算出した。５０個の凝集粒子について観察・画像処理を行い、それらの平均値を凝集粒子の粒子径とした。
【００６０】
（３）隔壁におけるナノ粒子の平均粒子径の測定
上記（２）と同様にＴＥＭを用いて対応箇所を５０万倍に拡大して撮影し、その写真の画像処理から平均粒子径を算出した。
【００６１】
（４）全光線反射率の測定
以下の装置及び測定条件にて行った。
測定装置：ＵＶ−３１０１ＰＣ型自記分光光度計（島津製作所製）
スリット幅：７．５ｎｍ
測定速度：SLOW（約４points/sec）
光源：ハロゲンランプ（340nm以上）
検出器：ＰＭＴ（860nm以下）
副白板：ＢａＳＯ４
入射角：８度
測定に用いた試料は、ガラス基板にペーストをスクリーン印刷法で塗布し乾燥した後、５９０〜６００℃で１５分間焼成した後の厚さ約３０μｍ膜である。全光線反射率（Ｒｔ）は入射角８度で入射した光の全反射を測定したものである。
【００６２】
（５）気孔率の測定
連続自動粉体真密度測定器（（株）セイシン企業製、オートトゥルーデンサーＭＡＴ−７０００）を用いて測定した。気孔率Ｐ（％）は、焼成膜を粉砕した微粉末での値を真密度ｄｔｈ、焼成膜の形態での値を嵩密度ｄｅｘとした時、Ｐ＝｛１−（ｄｅｘ／ｄｔｈ）｝×１００と定義される。
【００６３】
真密度は、塗布・焼成膜を乳鉢で指頭に感じない程度の３２５メッシュ以下くらいまで粉砕して測定する。一方、嵩密度は、塗布・焼成膜の一部を形状を崩さないように削りとり、粉砕を行わないこと以外は真密度の場合と同様にして計測した。
【００６４】
（実施例１）
まず感光性ペーストの調製を行った。感光性ペーストに含まれる各成分の量（重量部）は、低融点ガラス５６、ナノ粒子１４（つまり低融点ガラスとナノ粒子の混合比率は８０：２０）、感光性ポリマー１９、感光性モノマー７．５、光重合開始剤２．４、増感剤２．４とした。
【００６５】
酸化物換算組成が、分析値で酸化リチウム６．７％、酸化ケイ素２２％、酸化ホウ素３２％、酸化バリウム３．９％、酸化アルミニウム１９％、酸化亜鉛２．２％、酸化マグネシウム５．５％、酸化カルシウム４．１％の低融点ガラスを用いた。この低融点ガラスのガラス転移点は４９７℃、荷重軟化点は５３０℃、熱膨張係数は７５×１０^-7／Ｋ、屈折率は１．５８、誘電率８．１であった。ガラス成分は、予めアトラクターで微粉末とし、平均粒子径２．６μｍの非球状粉末として使用した。
【００６６】
このガラス粉末１００重量部に対して、０．０８重量部のアゾ系有機染料スダンIVをアセトンに溶解し、分散剤を加えてホモジナイザーで均質に撹拌し、この溶液中にガラス粉末を添加して均質に分散・混合後、ロータリーエバポレーターを用いてアセトンを蒸発させ、１５０〜２００℃の温度で乾燥した。
【００６７】
一方、γ−ブチロラクトンに感光性ポリマーを４０％溶液になるように混合し、撹拌しながら６０℃まで加熱して全てのポリマーを溶解した。用いた感光性ポリマーは、サイクロマーＰ（ダイセル化学製品ＡＣＡ２１０、分子量２８，０００、酸価１２０）を用いた。室温の感光性ポリマー溶液に、感光性モノマー（ＭＧＰ４００）、光重合開始剤(ＩＣ−３６９）および増感剤(２，４−ジエチルチオキサントン）を加えた後に、超音波攪拌器で３０分間ほど攪拌して均一な１液の状態となるように溶解させた。その後、この溶液を４００メッシュのフィルターを用いて濾過し、有機ビヒクルを作製した。
【００６８】
ナノ粒子として、平均粒子径が０．００５μｍ（５ｎｍ）の酸化チタンをγ−ブチロラクトンに単分散に近い状態で分散した２０％濃度の溶液を用いた。
【００６９】
ナノ粒子の分散溶液と、前述の有機ビヒクルおよび低融点ガラスをスパチュラーで混ぜ、３本ローラで混合・分散して感光性ペーストを得た。
【００７０】
次いで、この感光性ペーストの焼成後の測定用の試料を準備した。感光性ペーストを１００ｍｍ角ガラス基板上に３２５メッシュのスクリーンを用いたスクリーン印刷により塗布した。塗布膜にピンホールなどの発生を回避するために塗布・乾燥を数回繰り返し行い、膜厚の調整を行った。途中の乾燥は８０℃で１０分間行った。その後、８０℃で１時間保持して乾燥した。乾燥後の塗布膜厚さは５０μｍとした。これを６００℃で１５分間焼成したところ、白色を呈し、全光線反射率は７０％、気孔率は６％であった。
【００７１】
また、焼成後における酸化チタンのナノ粒子の平均粒子径は０．０１μｍ、凝集粒子の粒子径は０．５３μｍであった。図１に焼成後の凝集粒子のＴＥＭ写真を示した。従って、後述するディスプレイ用部材の隔壁においても、同等の全光線反射率、気孔率、焼成後のナノ粒子の平均粒子径、凝集粒子の粒子径が得られているものと推察される。
【００７２】
次に、プラズマディスプレイの作製を行った。
ガラス基板（旭硝子社製ＰＤ２００）上に、感光性銀ペーストを用いて、フォトリソグラフィ法により、線幅４０μｍ、ピッチ１５０μｍの５００本のアドレス電極を形成した。
【００７３】
次に、電極上にガラス粉末５０重量％、酸化チタン１５％、エチルセルロース２０％、溶媒１５％からなるガラスペーストをスクリーン印刷により塗布した後に、焼成して誘電体層を形成した。
【００７４】
誘電体層上に、前述の測定用試料の塗膜の形成と同様にして感光性ペーストを塗布し、乾燥後の厚さ１６５μｍの塗膜を形成した。
【００７５】
続いて、１５０μｍピッチ、線幅２０μｍのネガ用のクロムマスクを用いて、上面から２０ｍＷ／ｃｍ²出力の超高圧水銀灯でプロキシミティ露光した。露光量は６００ｍＪ／ｃｍ²とした。
【００７６】
次に、３５℃に保持したモノエタノールアミンの０．２％水溶液をシャワーで３００秒間かけることにより現像し、その後、シャワースプレーを用いて水洗し、光硬化していないスペース部分を除去してガラス基板上にストライプ状の隔壁パターンを形成した。
【００７７】
このようにして得られた隔壁パターンを空気中、６００℃で１５分間焼成して白色隔壁を形成した。形成された隔壁の断面形状を電子顕微鏡で観察したところ、高さ１１５μｍ、隔壁中央部の線幅３０μｍ、ピッチ１５０μｍであった。
【００７８】
隔壁間に蛍光体層を形成し、本発明のディスプレイ用部材としてプラズマディスプレイ用の背面板を得た。
【００７９】
この背面板を別途作製した前面板と合わせた後、封着しガス封入し駆動回路を接続してプラズマディスプレイを作製した。このパネルに電圧を印加して表示を行った。全面点灯時の輝度を大塚電子社製の測光機ＭＣＰＤ−２００を用いて測定した。輝度は４２０ｃｄ／ｍ²であった。
【００８０】
（実施例２）
ナノ粒子として平均粒子径が０．０１μｍの酸化チタンを用い、低融点ガラスの配合量を５９重量部、ナノ粒子の配合量を１０重量部（すなわち低融点ガラスとナノ微粒子との混合割合を８５：１５）とした以外は、実施例１を繰り返した。焼成後の測定において、全光線反射率は６０％であり、気孔率は５％であった。また、焼成後の酸化チタンのナノ粒子の平均粒子径は、０．０２μｍ、凝集粒子の粒子径は０．５μｍであった。さらに、プラズマディスプレイの輝度は３８０ｃｄ／ｍ²であった。
【００８１】
（実施例３）
ナノ粒子として平均粒子径が０．０３μｍの酸化チタンを用い、低融点ガラスの配合量を６３重量部、ナノ粒子の配合量を７重量部（すなわち 低融点ガラスとナノ粒子との混合割合を９０：１０）とし、隔壁の焼成温度を５９０℃とした以外は実施例１を繰り返した。焼成後の測定において、全光線反射率は５５％であり、気孔率は４％であった。また、焼成後の酸化チタンのナノ粒子の平均粒子径は０．０５μｍ、凝集粒子の粒子径は０．７μｍであった。さらに、プラズマディスプレイ用の背面板において白色隔壁を形成することができ、これを用いたプラズマディスプレイの輝度は３５０ｃｄ／ｍ²であった。
【００８２】
（実施例４）
低融点ガラスとして、酸化物換算組成が分析値で、酸化リチウム６．７％、酸化ケイ素２２％、酸化ホウ素３２％、酸化バリウム３．９％、酸化アルミニウム１９％、酸化亜鉛２．２％、酸化マグネシウム５．５％、酸化カルシウム４．１％ののものを用いた。この低融点ガラスのガラス転移点は４９７℃、荷重軟化点は５３０℃、熱膨張係数は７５×１０^-7／Ｋ、屈折率は１．５８であった。ガラス成分は、予めアトラクターで微粉末とし、平均粒子径２．６μｍの非球状粉末にして使用した。
【００８３】
ナノ粒子として粒度分布のピークが０．０５μｍにある酸化チタンを用い、低融点ガラスとして下記のものを用いた。
【００８４】
また、低融点ガラスの配合量を５９重量部、ナノ粒子の配合量を１０重量部（すなわち低融点ガラスとナノ微粒子との混合割合を８５：１５）とした。
【００８５】
これら以外は実施例１を繰り返した。焼成後の測定において、全光線反射率は６５％であり、気孔率は５％であった。また、焼成後の酸化チタンのナノ粒子の平均粒子径は、０．０８μｍ、凝集粒子の粒子径は１．０μｍであった。さらに、プラズマディスプレイ用の背面板において白色隔壁を形成することができ、これを用いたプラズマディスプレイの輝度は４００ｃｄ／ｍ²であった。
【００８６】
（実施例５）
低融点ガラスとして、酸化物組成が分析値で、酸化リチウム８．６％、酸化ケイ素２０．１％、酸化ホウ素３１％、酸化アルミニウム２０．６％、酸化バリウム３．８％、酸化マグネシウム５．９％、酸化カルシウム４．２％、酸化亜鉛２．１％のものを用いた。この低融点ガラスのガラス転移点は４７２℃、荷重軟化点は５１５℃、熱膨張係数は８３×１０^-7／Ｋ、平均屈折率は１．５９であった。ガラス成分は、予めアトラクターで微粉末とし、平均粒子径２．６μｍの非球状粉末にして使用した。
【００８７】
ナノ粒子として平均粒子径が０．０１μｍにある酸化アルミニウムを用た。
【００８８】
また低融点ガラスの配合量を６３重量部、ナノ粒子の配合量を７重量部（すなわち 低融点ガラスとナノ粒子との混合割合を９０：１０）とした。
【００８９】
さらに感光性ポリマーとして、メタクリル酸４０％、メチルメタクリレート３０％およびスチレン３０％からなる共重合体のカルボキシル基に対して０．４当量のグリシジルメタクリレートを付加反応させたもので、その重量平均分子量は４３，０００、酸価は９５のものを用いた。
また隔壁の焼成温度を５９０℃とした。
【００９０】
これら以外は実施例１を繰り返した。焼成後の測定において、全光線反射率は５０％であり、気孔率は４％であった。また、焼成後の酸化アルミニウムのナノ粒子の平均粒子径は、０．０２μｍ、凝集粒子の粒子径は０．４μｍであった。さらに、プラズマディスプレイ用の背面板において白色隔壁を形成することができ、これを用いたプラズマディスプレイの輝度は３３０ｃｄ／ｍ²であった。
【００９１】
（実施例６）
ナノ粒子として平均粒子径が０．０２μｍの酸化ケイ素を用いた以外は実施例５を繰り返した。
【００９２】
焼成後の測定において全光線反射率は５２％であり、気孔率は５％であった。また、焼成後の酸化ケイ素のナノ粒子の平均粒子径は、０．０３５μｍ、凝集粒子の粒子径は０．５μｍであった。さらに、プラズマディスプレイ用の背面板において白色隔壁を形成することができ、これを用いたプラズマディスプレイの輝度は３４０ｃｄ／ｍ²であった。
【００９３】
（実施例７）
ナノ粒子として平均粒子径が０．０２μｍの酸化セリウムを用いた以外は実施例５を繰り返した。
【００９４】
焼成後の測定において全光線反射率は５０％であり、気孔率は４％であった。また、焼成後の酸化セリウムのナノ粒子の平均粒子径は、０．０４５μｍ、凝集粒子の粒子径は０．７μｍであった。さらに、プラズマディスプレイ用の背面板において白色隔壁を形成することができ、これを用いたプラズマディスプレイの輝度は３３０ｃｄ／ｍ²であった。
【００９５】
（実施例８）
電子放出素子を用いたディスプレイは、電子放出素子を作製した電子源を固定する背面基板と、蛍光体層とメタルバックが形成された前面基板を封着して作製した。前面基板と背面基板との間には、支持枠と耐大気圧支持部材として隔壁を作製した。
【００９６】
表面伝導型電子放出素子および電極間配線を形成した基板上に、実施例１で用いた感光性ペーストをスクリーン印刷により全面塗布・乾燥し、これを繰り返して乾燥厚みが約１ｍｍの塗布膜を形成した。この塗布膜に、幅２ｍｍのストライプ状の開口部を１ｃｍピッチで有するフォトマスクを密着させて、出力１５ｍＷ／ｃｍ²の超高圧水銀灯で紫外線露光した。露光量は１．２Ｊ／ｃｍ²とした。次に、２回目の感光性ペーストの塗布・乾燥を行って、最初と同様の厚みの２段目の塗布膜を形成し、今度は開口部幅１．６ｍｍのフォトマスクを最初の露光部に対応するようにアライメントして同様に露光した。この手法を３段目まで繰り返し、３段目には１．２ｍｍの開口部を有するフォトマスクを使用した。このように露光処理の終わった塗布膜を実施例３と同様の手段で現像・水洗して、断面が３段の雛壇状の高さ２．３ｍｍのストライプ状の隔壁パターンを形成した。これを空気中５８０℃で２０分間焼成し、白色隔壁を有する電子放出素子を用いたディスプレイ用の背面基板を得た。ここで得られた隔壁の全光線反射率、気孔率および凝集粒子のサイズは、実施例３の場合と同様と推定することができる。
【００９７】
一方、ブラックマトリクスおよび３原色に発光する蛍光体層を形成しメタルバックを設けた前面基板を別途作製し、上記背面基板と封着して電子放出素子を用いたディスプレイを得た。得られたディスプレイは、白色隔壁の効果により輝度が向上した。
【００９８】
（実施例９）
実施例２の感光性ペーストを用いて、プラズマアドレス液晶ディスプレイ用の隔壁を形成した。実施例２と同様の白色隔壁が形成された。これにより、ディスプレイの輝度および色純度が向上した。
【００９９】
（実施例１０）
実施例３の感光性ペーストを用いて、蛍光表示管を用いたディスプレイ用の隔壁を形成した。実施例３と同様の白色隔壁が形成された。これにより、ディスプレイの輝度および色純度が向上した。
【０１００】
（実施例１１）
低融点ガラス粉末、酸化チタン微粒子およびフィラーとして高融点ガラス粉末からなる無機成分それぞれをを７５％、５％、２０％の割合で用いた。低融点ガラス粉末は、実施例１と同じ粉末を用いた。酸化チタン微粒子（多木化学社製、“タイノック”、酸化チタン濃度１８．５％）は、純度９９％以上で、平均粒子径は０．００４μｍであった。
【０１０１】
フィラーとして用いた高融点ガラスの酸化物換算組成は、酸化ケイ素３８％、酸化ホウ素１０％、酸化バリウム５％、酸化カルシウム４％、酸化アルミニウム３６％、酸化亜鉛２％、酸化マグネシウム５％であり、ガラス転移点６５２℃、荷重軟化点７４６℃を有し、平均粒子径２．４μｍで屈折率は１．５９、誘電率７．０であった。
【０１０２】
感光性ポリマーは、実施例１と同じものを用いた。 感光性ペーストの構成成分は、感光性ポリマー１５％、感光性モノマーＧＭＰＡ７．２％、光重合開始剤（チバ・ガイギー社製、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ブタノン−１：ＩＣ３６９）３．６％、ベンゾトリアゾール（ＢＴ）３．１５％、ノプコスパース（サンノプコ社製）０．５％、ハイドロキノンモノメチルエーテル（ＨＱＭＥ）０．１％、スダンIV０．０３５％、フローノン（共栄社化学社製）０．７％と無機成分７０％つぃた。溶媒にはγ−ブチロラクトンを用いた。ここで、ＧＭＰＡは、ビス（２−ヒドロキシ−３−メタクリロイルオキシプロピル）イソプロピルアミン（以下、ＧＭＰＡと略記）で示されるモノマーである。この感光性ペーストを用い、焼成条件をを５９０℃、３０分保持とした以外は実施例１を繰り返した。
【０１０３】
焼成後の測定において、全光線反射率は５２％であり、気孔率は３％であった。また、焼成後の酸化チタンのナノ粒子の平均粒子径は、０．０１μｍ、凝集粒子の粒子径は０．５μｍであった。さらに、プラズマディスプレイの輝度は４３０ｃｄ／ｍ²であった。
【０１０４】
（実施例１２）
ナノ粒子として、酸化チタン系微粒子（触媒化成製、オプトレイク５０２）を用いた。これは、酸化チタン４２．８％、酸化錫３７．１％、酸化ケイ素２１．１％から構成されており、その平均粒子径は０．００５μｍであった。低融点ガラス粉末、酸化チタン系微粒子およびフィラーとして高融点ガラス粉末からなる無機成分それぞれをを７７％、３％、２０％の割合で用いた以外は実施例１１を繰り返した。
【０１０５】
焼成後の測定において、全光線反射率は５３％であり、気孔率は３％であった。また、焼成後の酸化チタンのナノ粒子の平均粒子径は、０．０２μｍ、凝集粒子の粒子径は０．６μｍであった。さらに、プラズマディスプレイの輝度は４００ｃｄ／ｍ²であった。
【０１０６】
（実施例１３）
実施例１１と同じナノ粒子を用い、フィラーとして誘電率３．８の石英を用いた以外は実施例１１を繰り返した。
【０１０７】
焼成後の測定において、全光線反射率は５８％であり、気孔率は５％であった。また、焼成後の酸化チタンのナノ粒子の平均粒子径は、０．０１μｍ、凝集粒子の粒子径は０．４μｍであった。さらに、プラズマディスプレイの輝度は３８０ｃｄ／ｍ²であった。
【０１０８】
（実施例１４）
実施例１１と同じナノ粒子を用い、フィラーとして誘電率４．５のコーディエライトを用いた以外は実施例１３を繰り返した。
【０１０９】
焼成後の測定において、全光線反射率は６０％であり、気孔率は５％であった。また、焼成後の酸化チタンのナノ粒子の平均粒子径は、０．０２μｍ、凝集粒子の粒子径は０．５μｍであった。さらに、プラズマディスプレイの輝度は３８０ｃｄ／ｍ²であった。
【０１１０】
（実施例１５）
ナノ粒子として、酸化チタン系微粒子（触媒化成製、オプトレイク５０５）を用いた。これは、酸化チタン４１．８％、酸化錫３７．１％、酸化ケイ素２１．１％から構成されており、その平均粒子径は０．００８μｍであった。フィラーとして誘電率６．３のセルジアン（ＢａＯ・Ａｌ₂Ｏ₃・ＳｉＯ₂）を用いた以外は実施例１３を繰り返した。
【０１１１】
焼成後の測定において、全光線反射率は５５％であり、気孔率は５％であった。また、焼成後の酸化チタンのナノ粒子の平均粒子径は、０．０２μｍ、凝集粒子の粒子径は０．５μｍであった。さらに、プラズマディスプレイの輝度は３８０ｃｄ／ｍ²であった。
【０１１２】
（比較例１）
ナノ粒子として平均粒子径が０．００２μｍの酸化チタンを用いた他は実施例１を繰り返した。焼成後の測定において全光線反射率は６５％であるが、気孔率が１０％となった。また、焼成後の酸化チタンのナノ粒子の平均粒子径は、０．００５μｍ、凝集粒子の粒子径は０．２μｍであった。一方、プラズマディスプレイの作製において感光性ペーストの塗布膜を露光・現像したが、ナノ粒子が凝集して、パターン形成が出来なかった。
【０１１３】
（比較例２）
実施例１で用いたナノ粒子の替わりに平均粒子径が０．１μｍの酸化チタンの酸化物粉末を用いた他は実施例１を繰り返した。焼成後の測定において全光線反射率は６５％であり、気孔率は３％であった。また、焼成後の酸化チタンの粒子の平均粒子径は０．２μｍ、凝集粒子の粒子径は０．４μｍであった。しかしながら、プラズマディスプレイの作製において、感光性ペースト塗布膜を露光・現像したが、得られた隔壁パターンの形状が不適であり、良好な隔壁形成ができなかった。
【０１１４】

【０１１５】
【発明の効果】
本発明のディスプレイ用部材における隔壁には、ナノ粒子が凝集して形成された粒子径０．３〜２μｍの凝集粒子が存在するため隔壁の全光線反射率が高く、高輝度で、色純度に優れたディスプレイを得ることができる。
【図面の簡単な説明】
【図１】実施例１における、ナノ粒子の凝集粒子の、透過型電子顕微鏡による観察写真である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a display such as a display using a plasma display (PDP), a plasma addressed liquid crystal display (PALC), an electron-emitting device (field emission, FE), or a fluorescent display tube device (VFD).
[0002]
[Prior art]
Displays using PDPs, electron-emitting devices, and fluorescent display tube devices can produce brighter images than liquid crystal displays (LCDs), have a wider viewing angle, and can meet the demands for larger screens and higher definition. Therefore, the needs are increasing.
[0003]
The electron-emitting device includes a thermal electron-emitting device and a cold cathode electron-emitting device. A display using a cold cathode electron source displays an image by emitting fluorescent light by irradiating a phosphor with an electron beam emitted from an electron-emitting device. In this apparatus, the front glass substrate and the rear glass substrate are used with respective functions, and the rear glass substrate is provided with a matrix-like wiring for connecting a plurality of electron-emitting devices and electrodes of these devices. Since these wirings intersect at the electrode portion of the electron-emitting device, an insulating layer is provided for insulation. Further, a partition wall (spacer) is formed as an atmospheric pressure resistant support member between the two substrates.
[0004]
Unlike the CRT, the structure and electrical operation mechanism of the fluorescent display tube (VFD) excites the phosphor with a slow electron flow of several tens mA at a voltage of several tens V in the VFD. Also in a display using such a VFD element, a grid-like partition is formed to divide the light emitting region.
[0005]
The PDP generates a plasma discharge between an anode electrode and a cathode electrode facing each other in a discharge space partitioned by a partition provided between a front glass substrate and a back glass substrate, and gas enclosed in the space. The display is performed by irradiating the phosphor applied in the discharge space with ultraviolet rays generated from the discharge.
[0006]
The plasma addressed liquid crystal (PALC) display is obtained by replacing the TFT (thin film transistor) array portion of the TFT-LCD with a plasma channel, and basically has the same structure as the TFT-LCD except for the plasma portion. The plasma generating portion is divided by partition walls having a height of about 200 μm and a pitch of about 480 μm. That is, each of the various displays described above requires a partition wall. Hereinafter, the PDP will be described on behalf of these various displays. The partition walls in the PDP are conventionally formed of an insulating glass paste by a screen printing method, but this method is required as the area of the PDP increases and the resolution increases due to the problem of alignment accuracy due to expansion and contraction of the screen plate. In other words, a high-definition partition with a high aspect ratio cannot be obtained. As a method for improving such a problem, a method of forming a partition wall by a photolithography technique using a photosensitive paste is known.
[0007]
On the other hand, the partition wall not only divides the light emitting area, but also affects the display characteristics of the display such as light emission luminance and color purity. In order to improve the efficiency of light emission from the phosphor layer, there is a demand for increasing the reflectance of the barrier ribs. In other words, if the light transmittance of the barrier rib is high and the reflectance is low, the display light emitted from the phosphor layer applied to the side surfaces of the barrier ribs and the bottom surface between the barrier ribs is not sufficiently reflected, and the fluorescence between the adjacent barrier ribs is further reduced. The display light of the body layer leaks, and a display with high brightness and good color purity cannot be obtained.
[0008]
Therefore, as a means for increasing the reflectance of the partition walls and improving the efficiency of light emission from the phosphor layer, for example, Japanese Patent Publication No. 6-44452 discloses that the partition walls contain a white pigment such as titanium oxide. ing.
[0009]
[Problems to be solved by the invention]
However, with the above-described means, when the barrier rib is formed by a photolithography method using a photosensitive paste, good light patternability cannot be obtained because the light transmittance is inhibited by the white pigment.
[0010]
The present invention solves such contradictory problems, and provides a display having barrier ribs formed by good patterning of a photolithography method, having high barrier rib reflectivity, and excellent display characteristics such as light emission luminance. With the goal.
[0011]
[Means for Solving the Problems]
That is, the present invention is a display member in which a partition is formed on a substrate, the partition contains a low-melting glass material, and the partition has an average particle diameter. 0.006 At least one selected from titanium oxide, cerium oxide, silicon oxide, aluminum oxide, and tin oxide, containing aggregated particles having a particle diameter of 0.3 to 2 μm composed of inorganic fine particles of about 0.08 μm. It is the member for a display characterized by being.
[0012]
Moreover, this invention is various displays using said display member.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Although the present invention will be described in accordance with a PDP manufacturing procedure, the present invention can be preferably applied to a plasma addressed liquid crystal display and a display using an electron-emitting device or a fluorescent display tube.
[0014]
As the PDP substrate, soda glass or a glass substrate for PDP (for example, “PD200” manufactured by Asahi Glass Co., Ltd.) is used.
[0015]
An address electrode is formed of a conductive metal on the substrate. As the conductive metal, silver, copper, chromium, aluminum, nickel, gold, or the like can be used. The address electrodes are formed in a stripe shape having a width of 20 to 100 μm. A dielectric layer is then preferably formed to cover the electrode.
[0016]
Next, a partition wall is formed on the dielectric layer or the substrate on which the electrode is formed. In the present invention, the partition walls are formed by a photolithography method using a photosensitive paste. That is, a photosensitive paste is applied, exposed, developed using the difference in solubility between the exposed portion and the unexposed portion in the developer, and then baked to form partition walls.
[0017]
In the display member of the present invention, the partition wall has an average particle size of 0.003 to 0.08 μm, preferably 0.006 to 0.08 μm, more preferably 0.008 to 0.08 μm, and extremely fine inorganic fine particles (hereinafter, It is important to contain 0.3 to 2 μm agglomerated particles composed of such ultrafine inorganic fine particles called nanoparticles. By adopting this configuration, it is possible to obtain both contradictory characteristics of exhibiting good light transmittance in patterning by a photolithography method and showing high reflectance as a partition wall after baking. .
[0018]
That is, the nanoparticles as described above are finer than the wavelength of ultraviolet light 350 to 420 nm used for exposure, and are relatively uniformly dispersed in the photosensitive paste and its coating film. The exposure can be performed without affecting the transparency, that is, the patterning property.
[0019]
On the other hand, in the baking after exposure / development, the nanoparticles are aggregated to form aggregated particles having a particle diameter of 0.3 to 2 μm. Then, the aggregated particles can improve the reflectance of the partition walls, and can improve the light emission efficiency from the phosphor layer. A more preferable size as the aggregated particles is 0.5 to 1.0 μm in particle diameter. The particle diameter of the aggregated particles here refers to a diameter when an observation photograph of the aggregated particles by an electron microscope or the like is image-processed and converted into a circle having the same area as the apparent area of the aggregated particles.
[0020]
As described above, it is important that the nanoparticles are sufficiently small so as not to inhibit the transmission of exposure light. Specifically, the average particle diameter is 0.08 μm or less. However, if it is too small, it will also aggregate in the photosensitive paste and its coating film, impeding the transmission of exposure light. Therefore, the average particle diameter of the nanoparticles contained in the partition formed by the photosensitive paste method is 0.003 μm or more in consideration of the sintering growth described later.
[0021]
As such nanoparticles, it is preferable to use at least one selected from the group consisting of titanium oxide, cerium oxide, silicon oxide, aluminum oxide, and tin oxide. By using these oxides, a high reflectance can be exhibited when agglomerated by firing. In particular, titanium oxide-based fine particles containing at least 30% by weight of titanium oxide are preferable.
[0022]
Titanium oxide-based fine particles are preferably used because they can provide both contradictory required properties such as good light transmission in pattern formation and high reflectivity as the partition walls after firing. In addition, it may be effective to avoid the aggregation of the titanium oxide fine particles by combining the fine particles of silicon oxide, tin oxide, aluminum oxide, zirconium oxide, cerium oxide and the like in the titanium oxide fine particles. Therefore, it is preferable.
[0023]
As content with respect to the partition wall formation material of the nanoparticle which exists in the member for display after baking, 5 to 30 weight%, Furthermore, 10 to 20 weight% is preferable. By setting the content to 5% by weight or more, the effect of improving the reflectance by addition can be obtained. Moreover, by setting it as 30 weight% or less, a desired partition wall pattern can be formed without inhibiting the transmission of exposure light.
[0024]
In order to contain the nanoparticles as described above in the partition after firing, the size of the nanoparticles at the stage of preparing the photosensitive paste (paste preparation stage) is set to the desired size in the partition after firing. It is preferable to make it a little smaller than the size of. This is because nanoparticles have a property of being easily sintered even at a low temperature compared to particles of the order of several μm, and may sinter and grow during firing of partition walls. The nanoparticles at the stage of charging preferably have an average particle diameter of 0.002 to 0.06 μm, more preferably 0.005 to 0.03 μm. If the nanoparticles in the preparation stage (paste preparation stage) are too small, it tends to be difficult to suppress aggregation in the photosensitive paste and its coating film, and if it is too large, the efficiency of aggregation after firing tends to decrease. If it is too large, the patterning property at the time of exposure tends to be hindered.
[0025]
In addition, it is also preferable to subject the nanoparticles in this preparation stage to a surface treatment with a surfactant. By doing so, it can prevent that the said nanoparticle interacts with the photosensitive resin component and the organic solvent, and aggregates.
[0026]
Moreover, the partition of the member for PDP of this invention contains low melting glass. By using the low melting point glass, as will be described later, it becomes easy to control the difference in refractive index with the photosensitive organic component, and does not hinder the patterning property at the time of exposure, and can form a strong partition by baking. it can.
[0027]
The low melting point glass preferably has a glass transition point of 400 to 550 ° C and a load softening point of 450 to 600 ° C. By setting the load softening point to 450 ° C. or higher, the partition walls are not deformed in the subsequent process of display formation, and by setting the load softening point to 600 ° C. or lower, it is possible to obtain a high strength partition wall that melts during firing. it can.
[0028]
In addition, the average refractive index of the low-melting glass is in the range of 1.5 to 1.65 in order to match the average refractive index of the photosensitive organic component in the photosensitive paste and suppress exposure light scattering. It is preferable. The low melting glass powder satisfying such characteristics preferably has the following composition in terms of oxide.

[0029]
It is preferable that at least one of alkali metal oxides of lithium oxide, sodium oxide or potassium oxide is used, and the total amount is 3 to 15% by weight, more preferably 3 to 10% by weight.
[0030]
Alkali metal oxide not only facilitates control of the glass load softening point and thermal expansion coefficient, but also reduces the refractive index of the glass, thus reducing the refractive index difference from the photosensitive organic component. Becomes easier. By making the total amount of alkali metal oxides 3% by weight or more, the effect of lowering the melting point of the glass can be obtained, and by making it 15% by weight or less, the chemical stability of the glass is maintained and the thermal expansion coefficient. Can be kept small. As the alkali metal, lithium is preferably selected in consideration of lowering the refractive index of the glass and preventing ion migration.
[0031]
The blending amount of silicon oxide is preferably 5 to 30% by weight, more preferably 10 to 30% by weight. Silicon oxide is effective in improving the denseness, strength and stability of glass, and is effective in lowering the refractive index of glass. The thermal expansion coefficient can be controlled to prevent peeling due to mismatch with the glass substrate. By setting the content to 5% by weight or more, the thermal expansion coefficient is kept small, and no cracks occur when baked on a glass substrate. Further, the refractive index can be kept low. By setting it to 30% by weight or less, the glass transition point and the load softening point can be kept low, and the baking temperature on the glass substrate can be lowered.
[0032]
Boron oxide is a component necessary for lowering the melting point in glass containing no heavy metal such as lead, and is also effective for lowering the refractive index, and is 20 to 45% by weight, further 20 to 40% by weight. It is preferable to mix in a range. By setting it to 20% by weight or more, the glass transition point and the load softening point are kept low, and baking onto the glass substrate is facilitated. Moreover, the chemical stability of glass can be maintained by setting it as 45 weight% or more.
[0033]
It is preferable that at least one of barium oxide and strontium oxide is used, and the total amount is 2 to 15% by weight, more preferably 2 to 10% by weight. These components are effective for lowering the melting point of glass and adjusting the thermal expansion coefficient, and are also preferable in terms of application of the baking temperature to the heat resistance of the substrate, electrical insulation, and stability and denseness of the formed partition walls. . When the content is 2% by weight or more, an effect of lowering the melting point can be obtained and devitrification due to crystallization can be prevented. Moreover, by setting it as 15 weight% or less, a thermal expansion coefficient can be restrained small and a refractive index can also be restrained small. Also, the chemical stability of the glass can be maintained.
[0034]
Aluminum oxide has the effect of expanding the vitrification range and stabilizing the glass, and is effective in extending the pot life of the paste. It is preferable to mix | blend in the range of 10-25 weight%, By making it in this range, a glass transition point and a load softening point can be kept low and baking on a glass substrate can be made easy.
[0035]
Furthermore, it is preferable that calcium oxide and magnesium oxide are blended for facilitating melting of the glass and controlling the thermal expansion coefficient. Calcium oxide and magnesium oxide are preferably blended in a total of 2 to 15% by weight. When the total amount is 2% by weight or more, devitrification of the glass due to crystallization can be prevented, and when the total amount is 15% by weight or less, the chemical stability of the glass can be maintained.
[0036]
Although not described in the above composition, zinc oxide is a component that lowers the melting point without greatly changing the thermal expansion coefficient of the glass, and it is preferable that this is also blended. If too much is added, the refractive index tends to increase, so it is preferable to add in the range of 1 to 20% by weight.
[0037]
The low melting point glass powder used for the photosensitive paste has good filling properties and dispersibility during paste formation, and can be applied with a uniform thickness of the paste and in order to maintain good pattern forming properties, The particle diameter is preferably 1 to 5 μm, and the maximum particle diameter is preferably 35 μm or less. The glass powder having such a particle size distribution is excellent in terms of filling and dispersibility in the paste, but in the case of a low melting glass powder, most of it is melted and integrated in the firing step, so that considerably large particles Diameter powders are also acceptable. However, in the case of a filler component having a load softening point or a melting point higher than the heating temperature in the firing step, it remains as it is in the partition wall or on the partition wall surface, so the average particle diameter is preferably smaller and is 1.5 to 4 μm. It is appropriate to be. If it is this range, the filling property and dispersibility can be satisfied, and the photosensitive paste excellent in applicability | paintability and pattern formation property can be comprised.
[0038]
The partition of the member for PDP of the present invention may contain 5 to 30% by weight of a filler having an average particle diameter of 1.5 to 5 μm in addition to the above-mentioned nanoparticles and glass material. By including this filler, there is an effect that the strength of the partition walls after firing is maintained, the firing shrinkage rate is suppressed, and the shape retainability is enhanced while maintaining the pattern formability before firing. Further, it is effective for lowering the dielectric constant of the partition wall.
[0039]
The filler having an average particle diameter of 1.5 to 5 μm has an average refractive index of 1.45 in order to match the photosensitive organic component in the photosensitive paste and the average refractive index of the low-melting glass and to suppress exposure light scattering. It is preferable to be in the range of ˜1.65. In order to make the average refractive index of the filler within the above range, a filler or cordierite made of a high melting point glass, a crystallized glass, or a ceramic whose composition is adjusted is preferably used.
[0040]
As the filler, cordierite (2MgO · 2Al ₂ O _Three ・ 5SiO ₂ ), Celsian (BaO · Al ₂ O _Three ・ SiO ₂ ), Anorthite (CaO · Al ₂ O _Three ・ 2SiO ₂ ), Steatite (MgO-SiO) ₂ ), Spodumene (LiO2 · Al ₂ O _Three ・ 4SiO ₂ ), Forsterite (2MgO · SiO ₂ ), Silica (quartz), and high melting point glass are preferably used.
[0041]
As the refractory glass, those having a glass transition point of 500 to 1200 ° C. and a load softening point of 550 to 1200 ° C. are preferable. Such a refractory glass has a composition containing 15% by weight or more of silicon oxide and aluminum oxide, respectively. Those having a total content of 50% by weight or more are effective for obtaining necessary thermal characteristics. The composition of the high melting point glass is not limited to this, but for example, the following oxide conversion composition can be used.
Silicon oxide 15-50% by weight
Boron oxide 5-20% by weight
Barium oxide 2-10% by weight
Aluminum oxide 15-50% by weight.
[0042]
More specifically, for example, 38% by weight of silicon oxide, 10% by weight of boron oxide, 5% by weight of barium oxide, 36% by weight of aluminum oxide, and other components containing calcium oxide, zinc oxide, and magnesium oxide in small amounts. The average refractive index of the high melting point glass having a glass transition point of 625 ° C. and a load softening point of 750 ° C. is 1.59, which is equivalent to the average refractive index of the low melting point glass preferably used in the present invention.
[0043]
Cordierite, another component of the filler, has a refractive index of 1.58 and is suitable as a component of the present invention.
[0044]
The average particle diameter of such a filler is preferably in the range of 1.5 to 5 μm. By setting the thickness to 1.5 μm or more, an effect of shape retention can be obtained. In addition, since the filler component does not melt in the firing step, if it is larger than 5 μm, the unevenness at the top of the formed partition wall tends to increase and cause problems such as crosstalk.
[0045]
The photosensitive paste used to form the barrier ribs is prepared by mixing low-melting glass, nanoparticles, filler, photosensitive organic components, etc. so as to have a predetermined composition, and then uniformly mixing and dispersing with a three-roller or kneader. Is done. In preparing the paste, it is preferable to remove impurity ions from a photosensitive resin such as a photosensitive polymer or monomer, a photopolymerization initiator, or an inorganic material in order to avoid aggregation of the nanoparticles from the paste stage. . If the thermal decomposition characteristics of the photosensitive monomer, photosensitive oligomer or polymer contained in the organic component, and the thermal properties of the glass powder component are disproportionate, the partition walls may be colored brown or the partition walls may be peeled off from the substrate. Therefore, it is important to match these defects.
[0046]
The viscosity of the photosensitive paste is adjusted to about 10,000 to 200,000 cP (centipoise) with an organic solvent. Examples of the organic solvent used at this time include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, and the like. Examples thereof include organic solvent mixtures containing one or more of them.
[0047]
The photosensitive paste can be applied by a general method such as a screen printing method, a bar coater method, a roll coater method, or a doctor blade method. The coating thickness can be determined in consideration of the desired partition wall height and the shrinkage ratio caused by baking of the paste.
[0048]
The coated and dried photosensitive paste film is exposed through a photomask to form a partition pattern. In the exposure, either a method in which the paste coating film and the photomask are in close contact with each other or a method (proximity exposure) in which the paste coating film and the photomask are spaced apart may be used. As a light source for exposure, a mercury lamp or a halogen lamp is suitable, but an ultra-high pressure mercury lamp is most often used. Generally, proximity exposure is performed using an ultra-high pressure mercury lamp as a light source. The exposure conditions vary depending on the coating thickness of the paste, but usually 5-30 mW / cm. ² It is appropriate to perform the exposure for 20 seconds to 10 minutes using an ultrahigh pressure mercury lamp of the following output.
[0049]
After the exposure, development is performed using the difference in solubility between the exposed portion and the unexposed portion in the developer. In this case, an immersion method, a spray method, a brush method, or the like is used. As the photosensitive organic component of the photosensitive paste preferably used in the present invention, those having a carboxyl group in the side chain are preferably employed, and in this case, development with an aqueous alkaline solution becomes possible. As the alkali, it is preferable to use an organic alkali aqueous solution because an alkali component can be easily removed during firing. As the organic alkali, a general amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine and the like. The concentration of the alkaline aqueous solution is usually 0.05 to 1% by weight, more preferably 0.1 to 0.6% by weight. If the alkali concentration is too low, the soluble portion tends to be not completely removed, and if the alkali concentration is too high, the pattern of the exposed portion tends to peel or erode. The temperature during development is preferably 20 to 50 ° C. for process control.
[0050]
The barrier rib pattern formed from the coating film of the photosensitive paste through the process of exposure and development is then baked in a baking furnace to thermally decompose and remove the organic component, and at the same time, the low melting glass in the inorganic component is melted to separate the barrier rib. Form.
[0051]
The firing atmosphere and temperature vary depending on the characteristics of the paste and the substrate, but are usually fired in air. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used. In order to perform batch-type firing, the glass substrate on which the partition pattern is formed is usually heated from room temperature to about 500 ° C. over several hours at a substantially constant speed, and then set to 550 to 600 ° C. set as the firing temperature to 30 to 30 ° C. Raise for 120 minutes and hold for about 15-30 minutes for firing. Since the firing temperature must be lower than the glass transition point of the glass substrate to be used, there is a preferable upper limit when using the glass substrate. If the firing temperature is too high or the firing time is too long, defects such as sagging tend to occur in the shape of the partition walls.
[0052]
The partition of the PDP member of the present invention preferably has a total light reflectance of 50% or more, more preferably 60% or more, and even more preferably 70% or more. The high total light reflectance means that the light emitted from the phosphor layer is emitted from the aperture at a high rate to the outside, increasing the brightness and blocking the influence on other adjacent light emission colors. The color purity of each luminescent color can be increased. The total light reflectance is preferably 90% or less. By setting it to 90% or less, it is possible to prevent reflection in a non-light emitting region due to reflection of external light. The total light reflectance can be measured by, for example, the method used in the examples.
[0053]
Moreover, it is preferable that the porosity of a partition is 2 to 8%, Furthermore, it is 2 to 5%. By setting the porosity to 8% or less, the partition wall having a dense structure is formed, the partition wall strength is improved, the adhesion of the lower layer portion is increased, and the partition wall can be prevented from falling down. In addition, if the porosity can be suppressed to this level, the pores are almost closed, so that gas and moisture that cause a reduction in luminous characteristics such as luminance are prevented from being discharged from the pores during discharge. In addition, the discharge life and luminance stability are improved.
[0054]
On the other hand, by setting the porosity to 2% or more, a buffering effect against heat and mechanical shock is exhibited. That is, the presence of appropriate pores can disperse the propagation of cracks due to heat and impact, and can prevent the partition wall from being damaged. In addition, the presence of appropriate pores can contribute to an increase in the reflectance of the partition walls. The porosity can be measured, for example, by the method used in the examples.
[0055]
A phosphor paste that emits red, green, and blue light is applied in cells sandwiched between barrier ribs and fired as necessary to produce a back plate for a plasma display panel as a display member of the present invention. it can. After the back plate and the front plate are bonded together, sealing and gas sealing are performed to produce a plasma display as the display of the present invention.
[0056]
These techniques are also preferably applied to plasma addressed liquid crystal displays and displays using electron-emitting devices or fluorescent display tubes.
[0057]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not limited to these. The concentration (%) is% by weight unless otherwise specified.
[0058]
(Measuring method)
(1) Measurement of average particle diameter of nanoparticles added to photosensitive paste
Measurement was performed using a dynamic light scattering particle size distribution measuring apparatus LB-500 manufactured by HORIBA, Ltd., but in Examples 11 to 15, a microtrack particle size analyzer UPA150MODEL, No. It measured using 9340 (Nikkiso Co., Ltd.).
[0059]
(2) Measurement of particle diameter of aggregated particles
A sample processed by the ion etching method was photographed at a magnification of 20,000 times using a transmission electron microscope (TEM), and the aggregated particles were approximated to a sphere (circle on the image) from the image processing of the photograph. The diameter was calculated. Observation and image processing were performed on 50 aggregated particles, and the average value thereof was defined as the particle size of the aggregated particles.
[0060]
(3) Measurement of average particle diameter of nanoparticles in partition walls
In the same manner as in (2) above, the corresponding part was magnified 500,000 times using TEM, and the average particle size was calculated from the image processing of the photograph.
[0061]
(4) Measurement of total light reflectance
The following apparatus and measurement conditions were used.
Measuring apparatus: UV-3101PC self-recording spectrophotometer (manufactured by Shimadzu Corporation)
Slit width: 7.5nm
Measurement speed: SLOW (about 4 points / sec)
Light source: Halogen lamp (over 340nm)
Detector: PMT (860nm or less)
Secondary white board: BaSO4
Incident angle: 8 degrees
The sample used for the measurement is a film having a thickness of about 30 μm after a paste is applied to a glass substrate by a screen printing method and dried and then baked at 590 to 600 ° C. for 15 minutes. The total light reflectivity (Rt) is obtained by measuring the total reflection of light incident at an incident angle of 8 degrees.
[0062]
(5) Measurement of porosity
The measurement was performed using a continuous automatic powder true density measuring device (manufactured by Seishin Co., Ltd., Auto True Densor MAT-7000). The porosity P (%) is P = {1- (dex / dth)} ×, where the value of the fine powder obtained by pulverizing the fired film is the true density dth and the value in the form of the fired film is the bulk density dex. 100.
[0063]
The true density is measured by pulverizing the coated / fired film to about 325 mesh or less so that it does not feel on the fingertips with a mortar. On the other hand, the bulk density was measured in the same manner as in the case of the true density except that a part of the coated / fired film was scraped so as not to lose the shape and not pulverized.
[0064]
Example 1
First, a photosensitive paste was prepared. The amount (parts by weight) of each component contained in the photosensitive paste is the low melting point glass 56, the nanoparticles 14 (that is, the mixing ratio of the low melting point glass and the nanoparticles is 80:20), the photosensitive polymer 19, and the photosensitive monomer 7. 0.5, photopolymerization initiator 2.4, and sensitizer 2.4.
[0065]
The composition in terms of oxide was 6.7% lithium oxide, 22% silicon oxide, 32% boron oxide, 3.9% barium oxide, 19% aluminum oxide, 2.2% zinc oxide, and 5.5% magnesium oxide. %, Calcium oxide 4.1% low melting point glass was used. This low-melting glass has a glass transition point of 497 ° C., a load softening point of 530 ° C., and a thermal expansion coefficient of 75 × 10. ^-7 / K, refractive index was 1.58, and dielectric constant was 8.1. The glass component was previously made into a fine powder by an attractor and used as a non-spherical powder having an average particle size of 2.6 μm.
[0066]
To 100 parts by weight of this glass powder, 0.08 part by weight of azo-based organic dye Sudan IV is dissolved in acetone, a dispersant is added, and the mixture is stirred homogeneously with a homogenizer, and the glass powder is added to this solution. After homogeneously dispersing and mixing, acetone was evaporated using a rotary evaporator and dried at a temperature of 150 to 200 ° C.
[0067]
On the other hand, a photosensitive polymer was mixed with γ-butyrolactone so as to be a 40% solution, and heated to 60 ° C. with stirring to dissolve all the polymers. Cyclomer P (Daicel chemical product ACA210, molecular weight 28,000, acid value 120) was used as the photosensitive polymer used. After adding a photosensitive monomer (MGP400), a photopolymerization initiator (IC-369) and a sensitizer (2,4-diethylthioxanthone) to a photosensitive polymer solution at room temperature, the mixture is stirred with an ultrasonic stirrer for about 30 minutes. Then, it was dissolved so as to obtain a uniform one-liquid state. Thereafter, this solution was filtered using a 400 mesh filter to prepare an organic vehicle.
[0068]
As the nanoparticles, a 20% concentration solution in which titanium oxide having an average particle diameter of 0.005 μm (5 nm) was dispersed in γ-butyrolactone in a state close to monodispersion was used.
[0069]
The dispersion solution of nanoparticles, the above-described organic vehicle and low-melting glass were mixed with a spatula and mixed and dispersed with a three roller to obtain a photosensitive paste.
[0070]
Next, a sample for measurement after baking of the photosensitive paste was prepared. The photosensitive paste was applied on a 100 mm square glass substrate by screen printing using a 325 mesh screen. In order to avoid the occurrence of pinholes in the coating film, coating and drying were repeated several times to adjust the film thickness. Intermediate drying was performed at 80 ° C. for 10 minutes. Then, it hold | maintained at 80 degreeC for 1 hour, and dried. The coating film thickness after drying was 50 μm. When this was baked at 600 ° C. for 15 minutes, it was white and had a total light reflectance of 70% and a porosity of 6%.
[0071]
The average particle diameter of the titanium oxide nanoparticles after firing was 0.01 μm, and the particle diameter of the aggregated particles was 0.53 μm. FIG. 1 shows a TEM photograph of the aggregated particles after firing. Therefore, it is presumed that the same total light reflectance, porosity, average particle diameter of the nanoparticles after firing, and particle diameter of the aggregated particles are obtained in the partition walls of the display member described later.
[0072]
Next, a plasma display was manufactured.
On a glass substrate (PD200 manufactured by Asahi Glass Co., Ltd.), 500 address electrodes having a line width of 40 μm and a pitch of 150 μm were formed by photolithography using a photosensitive silver paste.
[0073]
Next, a glass paste consisting of 50% by weight of glass powder, 15% of titanium oxide, 20% of ethyl cellulose, and 15% of solvent was applied on the electrode by screen printing, and then baked to form a dielectric layer.
[0074]
On the dielectric layer, a photosensitive paste was applied in the same manner as the coating film of the above-described measurement sample, and a coating film having a thickness of 165 μm after drying was formed.
[0075]
Subsequently, using a negative chrome mask with a pitch of 150 μm and a line width of 20 μm, 20 mW / cm from the top surface. ² Proximity exposure was performed with an ultra-high pressure mercury lamp. Exposure amount is 600mJ / cm ² It was.
[0076]
Next, a 0.2% aqueous solution of monoethanolamine kept at 35 ° C. was developed by applying it for 300 seconds in a shower, and then washed with water using a shower spray to remove the uncured space and remove the glass. A striped barrier rib pattern was formed on the substrate.
[0077]
The partition wall pattern thus obtained was baked in air at 600 ° C. for 15 minutes to form white partition walls. When the cross-sectional shape of the formed partition wall was observed with an electron microscope, the height was 115 μm, the line width at the center of the partition wall was 30 μm, and the pitch was 150 μm.
[0078]
A phosphor layer was formed between the barrier ribs to obtain a back plate for plasma display as a display member of the present invention.
[0079]
After this back plate was combined with a separately prepared front plate, it was sealed and sealed with gas, and a driving circuit was connected to produce a plasma display. A voltage was applied to this panel for display. The brightness when the entire surface was lit was measured using a photometer MCPD-200 manufactured by Otsuka Electronics. Luminance is 420 cd / m ² Met.
[0080]
(Example 2)
Titanium oxide having an average particle diameter of 0.01 μm is used as nanoparticles, the blending amount of the low melting glass is 59 parts by weight, and the blending amount of the nanoparticles is 10 parts by weight (that is, the mixing ratio of the low melting point glass and the nanoparticles is 85). Example 1 was repeated except that: In the measurement after firing, the total light reflectance was 60%, and the porosity was 5%. The average particle diameter of the titanium oxide nanoparticles after firing was 0.02 μm, and the particle diameter of the aggregated particles was 0.5 μm. Furthermore, the brightness of the plasma display is 380 cd / m. ² Met.
[0081]
(Example 3)
Titanium oxide having an average particle diameter of 0.03 μm is used as the nanoparticles, the blending amount of the low melting glass is 63 parts by weight, and the blending amount of the nanoparticles is 7 parts by weight (that is, the mixing ratio of the low melting point glass and the nanoparticles is 90%). 10), and Example 1 was repeated except that the firing temperature of the partition walls was 590 ° C. In the measurement after firing, the total light reflectance was 55%, and the porosity was 4%. The average particle size of the titanium oxide nanoparticles after firing was 0.05 μm, and the particle size of the aggregated particles was 0.7 μm. Furthermore, a white barrier rib can be formed on the back plate for the plasma display, and the brightness of the plasma display using this can be 350 cd / m. ² Met.
[0082]
Example 4
As low-melting glass, the oxide conversion composition is an analytical value, lithium oxide 6.7%, silicon oxide 22%, boron oxide 32%, barium oxide 3.9%, aluminum oxide 19%, zinc oxide 2.2%, Magnesium oxide 5.5% and calcium oxide 4.1% were used. This low-melting glass has a glass transition point of 497 ° C., a load softening point of 530 ° C., and a thermal expansion coefficient of 75 × 10. ^-7 / K, refractive index was 1.58. The glass component was made into a fine powder with an attractor in advance and used as a non-spherical powder having an average particle size of 2.6 μm.
[0083]
Titanium oxide having a particle size distribution peak of 0.05 μm was used as the nanoparticles, and the following glass was used as the low-melting glass.
[0084]
The blending amount of the low-melting glass was 59 parts by weight, and the blending amount of the nanoparticles was 10 parts by weight (that is, the mixing ratio of the low-melting glass and the nanoparticles was 85:15).
[0085]
Except these, Example 1 was repeated. In the measurement after firing, the total light reflectance was 65% and the porosity was 5%. The average particle diameter of the titanium oxide nanoparticles after firing was 0.08 μm, and the particle diameter of the aggregated particles was 1.0 μm. Furthermore, a white barrier rib can be formed on the back plate for the plasma display, and the brightness of the plasma display using this can be 400 cd / m. ² Met.
[0086]
(Example 5)
As a low melting glass, the oxide composition is analytical value, lithium oxide 8.6%, silicon oxide 20.1%, boron oxide 31%, aluminum oxide 20.6%, barium oxide 3.8%, magnesium oxide 5. 9%, calcium oxide 4.2%, and zinc oxide 2.1% were used. This low-melting glass has a glass transition point of 472 ° C., a load softening point of 515 ° C., and a thermal expansion coefficient of 83 × 10 8. ^-7 / K, average refractive index was 1.59. The glass component was made into a fine powder with an attractor in advance and used as a non-spherical powder having an average particle size of 2.6 μm.
[0087]
As the nanoparticles, aluminum oxide having an average particle diameter of 0.01 μm was used.
[0088]
The blending amount of the low melting point glass was 63 parts by weight, and the blending amount of the nanoparticles was 7 parts by weight (that is, the mixing ratio of the low melting point glass and the nanoparticles was 90:10).
[0089]
Furthermore, as a photosensitive polymer, 0.4 equivalent of glycidyl methacrylate was added and reacted with the carboxyl group of a copolymer consisting of 40% methacrylic acid, 30% methyl methacrylate and 30% styrene, and its weight average molecular weight was 43,000 and an acid value of 95 were used.
The firing temperature of the partition walls was 590 ° C.
[0090]
Except these, Example 1 was repeated. In the measurement after firing, the total light reflectance was 50% and the porosity was 4%. The average particle size of the aluminum oxide nanoparticles after firing was 0.02 μm, and the particle size of the aggregated particles was 0.4 μm. Furthermore, a white barrier rib can be formed on the back plate for the plasma display, and the brightness of the plasma display using this can be 330 cd / m. ² Met.
[0091]
(Example 6)
Example 5 was repeated except that silicon oxide having an average particle size of 0.02 μm was used as the nanoparticles.
[0092]
In the measurement after firing, the total light reflectance was 52%, and the porosity was 5%. The average particle diameter of the silicon oxide nanoparticles after firing was 0.035 μm, and the particle diameter of the aggregated particles was 0.5 μm. Furthermore, a white barrier rib can be formed on the back plate for the plasma display, and the brightness of the plasma display using this can be 340 cd / m. ² Met.
[0093]
(Example 7)
Example 5 was repeated except that cerium oxide having an average particle size of 0.02 μm was used as the nanoparticles.
[0094]
In the measurement after firing, the total light reflectance was 50%, and the porosity was 4%. The average particle size of the cerium oxide nanoparticles after firing was 0.045 μm, and the particle size of the aggregated particles was 0.7 μm. Furthermore, a white barrier rib can be formed on the back plate for the plasma display, and the brightness of the plasma display using this can be 330 cd / m. ² Met.
[0095]
(Example 8)
A display using an electron-emitting device was manufactured by sealing a back substrate for fixing an electron source from which the electron-emitting device was manufactured and a front substrate on which a phosphor layer and a metal back were formed. A partition wall was produced as a support frame and an atmospheric pressure resistant support member between the front substrate and the back substrate.
[0096]
On the substrate on which the surface conduction electron-emitting device and the inter-electrode wiring are formed, the photosensitive paste used in Example 1 is applied to the entire surface by screen printing and dried, and this is repeated to form a coating film having a dry thickness of about 1 mm. did. A photomask having striped openings with a width of 2 mm at a pitch of 1 cm is adhered to this coating film, and the output is 15 mW / cm. ² Were exposed to UV light using an ultra high pressure mercury lamp. Exposure amount is 1.2 J / cm ² It was. Next, a second photosensitive paste is applied and dried to form a second-stage coating film having the same thickness as the first, and this time a photomask having an opening width of 1.6 mm is applied to the first exposed portion. Aligned to correspond and exposed in the same way. This technique was repeated up to the third stage, and a photomask having an opening of 1.2 mm was used for the third stage. The coating film after the exposure treatment was developed and washed with the same means as in Example 3 to form a stripe-like partition wall pattern having a three-step cross section with a height of 2.3 mm. This was baked in air at 580 ° C. for 20 minutes to obtain a rear substrate for display using an electron-emitting device having white barrier ribs. The total light reflectance, porosity, and aggregate particle size of the partition walls obtained here can be estimated as in the case of Example 3.
[0097]
On the other hand, a front substrate provided with a black matrix and phosphor layers emitting light of three primary colors and provided with a metal back was separately prepared and sealed with the rear substrate to obtain a display using an electron-emitting device. The brightness of the obtained display was improved by the effect of the white partition.
[0098]
Example 9
Using the photosensitive paste of Example 2, partition walls for a plasma addressed liquid crystal display were formed. A white barrier rib similar to that in Example 2 was formed. This improved the brightness and color purity of the display.
[0099]
(Example 10)
Using the photosensitive paste of Example 3, a partition wall for a display using a fluorescent display tube was formed. A white barrier rib similar to that in Example 3 was formed. This improved the brightness and color purity of the display.
[0100]
(Example 11)
The low melting glass powder, the titanium oxide fine particles and the inorganic components composed of the high melting glass powder as fillers were used in proportions of 75%, 5% and 20%, respectively. As the low melting point glass powder, the same powder as in Example 1 was used. Titanium oxide fine particles (manufactured by Taki Chemical Co., Ltd., “Tynoch”, titanium oxide concentration 18.5%) had a purity of 99% or more and an average particle size of 0.004 μm.
[0101]
The oxide equivalent composition of the high melting point glass used as the filler is 38% silicon oxide, 10% boron oxide, 5% barium oxide, 4% calcium oxide, 36% aluminum oxide, 2% zinc oxide and 5% magnesium oxide. The glass transition point was 652 ° C., the load softening point was 746 ° C., the average particle size was 2.4 μm, the refractive index was 1.59, and the dielectric constant was 7.0.
[0102]
The same photosensitive polymer as in Example 1 was used. The constituents of the photosensitive paste were: 15% photosensitive polymer, 7.2% photosensitive monomer GMPA, photopolymerization initiator (manufactured by Ciba-Geigy, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) Butanone-1: IC369) 3.6%, benzotriazole (BT) 3.15%, Nop Cospers (manufactured by San Nopco) 0.5%, hydroquinone monomethyl ether (HQME) 0.1%, Sudan IV 0.035%, Flownon (manufactured by Kyoeisha Chemical Co., Ltd.) 0.7% and inorganic components 70%. Γ-butyrolactone was used as the solvent. Here, GMPA is a monomer represented by bis (2-hydroxy-3-methacryloyloxypropyl) isopropylamine (hereinafter abbreviated as GMPA). Example 1 was repeated except that this photosensitive paste was used and the firing conditions were maintained at 590 ° C. for 30 minutes.
[0103]
In the measurement after firing, the total light reflectance was 52% and the porosity was 3%. The average particle size of the titanium oxide nanoparticles after firing was 0.01 μm, and the particle size of the aggregated particles was 0.5 μm. Furthermore, the brightness of the plasma display is 430 cd / m. ² Met.
[0104]
(Example 12)
As the nanoparticles, titanium oxide-based fine particles (catalytic conversion, Optlake 502) were used. This was composed of 42.8% titanium oxide, 37.1% tin oxide, and 21.1% silicon oxide, and the average particle size was 0.005 μm. Example 11 was repeated except that low-melting glass powder, titanium oxide-based fine particles, and inorganic components composed of high-melting glass powder as fillers were used in proportions of 77%, 3%, and 20%, respectively.
[0105]
In the measurement after firing, the total light reflectance was 53% and the porosity was 3%. The average particle diameter of the titanium oxide nanoparticles after firing was 0.02 μm, and the particle diameter of the aggregated particles was 0.6 μm. Furthermore, the brightness of the plasma display is 400 cd / m. ² Met.
[0106]
(Example 13)
Example 11 was repeated except that the same nanoparticles as in Example 11 were used and quartz having a dielectric constant of 3.8 was used as the filler.
[0107]
In the measurement after firing, the total light reflectance was 58% and the porosity was 5%. The average particle size of the titanium oxide nanoparticles after firing was 0.01 μm, and the particle size of the aggregated particles was 0.4 μm. Furthermore, the brightness of the plasma display is 380 cd / m. ² Met.
[0108]
(Example 14)
Example 13 was repeated except that the same nanoparticles as in Example 11 were used and cordierite with a dielectric constant of 4.5 was used as the filler.
[0109]
In the measurement after firing, the total light reflectance was 60%, and the porosity was 5%. The average particle diameter of the titanium oxide nanoparticles after firing was 0.02 μm, and the particle diameter of the aggregated particles was 0.5 μm. Furthermore, the brightness of the plasma display is 380 cd / m. ² Met.
[0110]
(Example 15)
As the nanoparticles, titanium oxide-based fine particles (catalytic conversion, Optlake 505) were used. This was composed of 41.8% titanium oxide, 37.1% tin oxide, and 21.1% silicon oxide, and the average particle size was 0.008 μm. Serbian with a dielectric constant of 6.3 (BaO.Al ₂ O _Three ・ SiO ₂ Example 13 was repeated except that
[0111]
In the measurement after firing, the total light reflectance was 55%, and the porosity was 5%. The average particle diameter of the titanium oxide nanoparticles after firing was 0.02 μm, and the particle diameter of the aggregated particles was 0.5 μm. Furthermore, the brightness of the plasma display is 380 cd / m. ² Met.
[0112]
(Comparative Example 1)
Example 1 was repeated except that titanium oxide having an average particle size of 0.002 μm was used as the nanoparticles. In the measurement after firing, the total light reflectance was 65%, but the porosity was 10%. The average particle diameter of the titanium oxide nanoparticles after firing was 0.005 μm, and the particle diameter of the aggregated particles was 0.2 μm. On the other hand, in the production of the plasma display, the coating film of the photosensitive paste was exposed and developed, but the nanoparticles aggregated and the pattern could not be formed.
[0113]
(Comparative Example 2)
Example 1 was repeated except that instead of the nanoparticles used in Example 1, an oxide powder of titanium oxide having an average particle size of 0.1 μm was used. In the measurement after firing, the total light reflectance was 65%, and the porosity was 3%. The average particle size of the titanium oxide particles after firing was 0.2 μm, and the particle size of the aggregated particles was 0.4 μm. However, in the production of the plasma display, the photosensitive paste coating film was exposed and developed, but the shape of the obtained partition wall pattern was inappropriate, and satisfactory partition wall formation was not possible.
[0114]

[0115]
【The invention's effect】
The barrier ribs in the display member of the present invention have aggregated particles with a particle diameter of 0.3-2 μm formed by aggregation of nanoparticles, so the total light reflectance of the barrier ribs is high, high brightness, and high color purity. An excellent display can be obtained.
[Brief description of the drawings]
1 is a photograph of agglomerated nanoparticles of Example 1 observed with a transmission electron microscope in Example 1. FIG.

Claims (8)

A display member in which partition walls are formed on a substrate, wherein the partition walls include a low-melting glass material, and the partition walls are composed of inorganic fine particles having an average particle diameter of 0.006 to 0.08 μm. A member for display, comprising 2 μm aggregated particles, wherein the inorganic fine particles are at least one selected from titanium oxide, cerium oxide, silicon oxide, aluminum oxide, and tin oxide. 2. The display member according to claim 1, wherein the low-melting-point glass material has a glass transition point of 400 to 550 ° C. and a load softening point of 450 to 600 ° C. 3. The display member according to claim 1, wherein the low-melting glass material has an average refractive index of 1.5 to 1.65. The partition wall contains a filler selected from the group consisting of cordierite, serdian, anorthite, steatite, spodumene, forsterite, silica, and high melting point glass. The display member as described. A plasma display comprising the display member according to claim 1. A plasma addressed liquid crystal display using the display member according to claim 1. A display using an electron-emitting device, wherein the display member according to claim 1 is used. A display using a fluorescent display tube element, wherein the display member according to claim 1 is used.

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