JP3956889B2 - Plasma display - Google Patents

Description

（光重合開始剤）
ＩＣ−３６９：Ｉｒｇａｃｕｒｅ−３６９（チバ・ガイギー製品）；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
（増感剤）
ＤＥＴＸ−Ｓ：２，４−ジエチルチオキサントン
（有機染料）
スダン ；アゾ系有機染料、化学式Ｃ₂₄Ｈ₂₀Ｎ₄Ｏ、分子量３８０．４５
（実施例１）
表１に示すような組成からなる隔壁用感光性ペーストを作製した。ガラス粉末（ガラス(1) ）７０重量部に対して、有機染料（スダン）０．０８重量部の割合で秤量した。スダンをアセトンに溶解させ、分散剤を加えてホモジナイザで均質に攪拌した。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を用いて、１００℃の温度で乾燥し、アセトンを蒸発させた。こうして有機染料の膜でガラス粉末の表面が均質にコーティングされた粉末を作製した。
【０１１８】
ポリマー、モノマー、光重合開始剤、増感剤を表１に示す割合で混合し、均質に溶解させた。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。
【０１１９】
上記有機ビヒクルと上記ガラス粉末を表１に示す組成になるように添加し、３本ローラで混合・分散して、隔壁形成用の感光性ペーストを調整した。有機成分の屈折率は１．５９、ガラス粉末のそれは１．５９であった。
【０１２０】
電極、誘電体層をあらかじめ形成したＡ４サイズの旭ガラス社製ＰＤ−２００基板上に、前記隔壁用感光性ペーストを３２５メッシュのスクリーンを用いてスクリーン印刷により、均一に塗布した。塗布膜にピンホールなどの発生を回避するために塗布・乾燥を数回以上繰り返し行い、膜厚みの調整を行った。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。乾燥後の厚みは１７０μｍであった。続いて、１４０μｍピッチのネガ型のクロムマスクを通して、上面から５０ｍＪ／ｃｍ²出力の超高圧水銀灯で紫外線照射した。露光量は０．７Ｊ／ｃｍ²であった。
【０１２１】
次に、３５℃に保持したモノエタノールアミンの０．２重量％の水溶液をシャワーで１７０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浄した。これにより、光硬化していない部分が除去され、ガラス基板上にストライプ状の隔壁パターンが形成された。このようにして隔壁パターンが形成されたガラス基板を、空気中で５６０℃で１５分間焼成し、隔壁を形成した。
【０１２２】
隔壁を形成したガラス基板の隔壁内の所定の溝に感光性ペースト法で蛍光体層を形成した。すなわち、赤（Ｒ）、緑（Ｇ）、青（Ｂ）の３種類の感光性蛍光体ペーストを作製し、１種ずつ印刷、乾燥、フォトマスクによる露光、現像を繰り返すことにより、所定の箇所に蛍光体パターンを形成した。この操作を各色について行った後、５００℃で２０分間一括焼成して蛍光体層を形成した。これにより、ＰＤＰ用背面板が得られた。
【０１２３】
形成した隔壁の断面形状を、走査型電子顕微鏡（ＨＩＴＡＣＨＩ製 Ｓ−２４００）で観察した。図１、図３、図４、図５のような形状の場合は上面幅、半値幅、下面幅を、図２および図６のように上面部、下面部の測定の困難な場合は上面幅、下面幅の代わりにＬ９０、Ｌ１０を測定した。また、図２のように底面にアール形状を持つ場合は曲率半径も測定した。各値は、３サンプルの平均値により算出した。本実施例の形状は図３であった。
【０１２４】
隔壁および蛍光体層の欠陥については、(1)焼成前の隔壁の倒れ、剥がれの有無、(2)焼成後の隔壁の剥がれ、断線の有無、(3)蛍光体層の塗布均一性を評価した。それぞれ欠陥のない場合は○とした。さらに、各隔壁の開口率を１−（半値幅／ピッチ）と定義し、算出した。結果を表６に示す。焼成前後ともに剥がれ、倒れ、断線がなく、また蛍光体の塗布均一性も良好である優れたものであった。
【０１２５】
次に、電極、誘電体、保護層を前もって配した前面板と前記背面板にシール剤となる低融点ガラスペーストを設け、所定の配置になるよう位置あわせして対向配置し、４５０℃、３０分間処理して封止した。その後、表示領域内部を排気し、Ｈｅ９９％、Ｘｅ１％の混合ガスの封入を行ってプラズマディスプレイパネルを完成させ、発光特性を調べた。輝度ムラ、輝度に問題のない場合は○とした。結果を表６に示す。輝度ムラが少なく、高輝度で優れた特性を有していた。
実施例２
隔壁用ペーストの組成を表１に示すように変え、露光量を１Ｊ／ｃｍ²に変えた以外は、実施例１と同様にして検討を行った。結果を表６に示す。
実施例３
隔壁用ペーストの組成を表１に示すように変え、露光量を１Ｊ／ｃｍ²に変えた以外は、実施例１と同様にして検討を行った。結果を表６に示す。
実施例４
隔壁用ペーストの組成を表１に示すように変え、隔壁用ペーストの塗布厚みを１５０μｍにし、露光量を０．３Ｊ／ｃｍ²、現像時間を１５０秒に変えた以外は、実施例１と同様にして検討を行った。結果を表６に示す。
実施例５
隔壁用ペーストの組成を表１に示すように変え、隔壁用ペーストの塗布厚みを１５０μｍにし、露光量を１．５Ｊ／ｃｍ²、現像時間を１５０秒にした以外は、実施例１と同様にして検討を行った。結果を表６に示す。
実施例６
隔壁用ペーストの組成を表１のように変え、隔壁用ペーストの塗布厚みを１５０μｍにし、露光量を１．２Ｊ／ｃｍ²、現像時間を１５０秒にした以外は、実施例１と同様にして検討を行った。結果を表６に示す。
実施例７
隔壁用ペーストの組成を表２のように変え、隔壁用ペーストの塗布厚みを１９０μｍにし、現像時間を２００秒にし、焼成温度を５８０℃にした以外は、実施例１と同様にして検討を行った。結果を表７に示す。
実施例８
隔壁用ペーストの組成を表２のように変え、隔壁パターンの焼成温度を５８０℃にした以外は、実施例１と同様にして検討を行った。結果を表７に示す。
実施例９
隔壁用ペーストの組成を表２のように変え、隔壁用ペーストの塗布厚みを２３０μｍにし、隔壁用フォトマスクのピッチを１５０μｍ、現像時間を２３０秒、焼成温度を５８０℃にした以外は、実施例１と同様にして検討を行った。結果を表７に示す。
実施例１０
隔壁用ペーストの組成を表２のように変え、隔壁用ペーストの塗布厚みを１４０μｍにし、隔壁用フォトマスクのピッチを１５０μｍ、露光量を１．２Ｊ／ｃｍ²、現像時間を１５０秒、焼成温度を５８０℃にした以外は実施例１と同様にして検討を行った。結果を表７に示す。
実施例１１
隔壁用ペーストの組成を表２のように変え、隔壁用ペーストの塗布厚みを２３０μｍにし、隔壁用フォトマスクのピッチを１５０μｍ、露光量を０．５Ｊ／ｃｍ²、現像時間を２３０秒、焼成温度を５８０℃にした以外は実施例１と同様にして検討を行った。結果を表７に示す。
実施例１２
隔壁用ペーストの組成を表２のように変え、隔壁用フォトマスクのピッチを１００μｍ、露光波長をｇ線（４３６ｎｍ）のみで露光量を０．８Ｊ／ｃｍ²、焼成温度を５８０℃にした以外は実施例１と同様にして検討を行った。結果を表７に示す。
実施例１３
隔壁用ペーストの組成を表３のように変え、隔壁用ペーストの塗布厚みを２００μｍにし、隔壁用フォトマスクのピッチを１５０μｍ、露光量を０．７Ｊ／ｃｍ²、現像時間を２００秒、焼成温度を５８０℃にした以外は実施例１と同様にして検討を行った。結果を表８に示す。
実施例１４
隔壁用ペーストの組成を表３のように変え、隔壁用ペーストの塗布厚みを２３０μｍにし、隔壁用フォトマスクのピッチを２３０μｍ、露光量を１．２Ｊ／ｃｍ²、現像時間を２３０秒、焼成温度を５８０℃にした以外は実施例１と同様にして検討を行った。結果を表８に示す。
実施例１５
隔壁用ペーストの組成を表３のように変え、隔壁用ペーストの塗布厚みを２１０μｍにし、隔壁用パターンの露光量を０．９Ｊ／ｃｍ²、現像時間を２００秒、焼成温度を５８０℃にした以外は実施例１と同様にして検討を行った。結果を表８に示す。
実施例１６
隔壁用ペーストの組成を表３のように変え、隔壁用パターンの露光量を０．７Ｊ／ｃｍ²、焼成温度を５８０℃にした以外は実施例１と同様にして検討を行った。結果を表８に示す。
実施例１７
隔壁用ペーストの組成を表３のように変え、隔壁用ペーストの塗布厚みを２３０μｍにし、隔壁用フォトマスクのピッチを２３０μｍ、露光量を１．３Ｊ／ｃｍ²、現像時間を２３０秒、焼成温度を５８０℃にした以外は実施例１と同様にして検討を行った。結果を表８に示す。
実施例１８
隔壁用ペーストの組成を表３のように変え、隔壁用ペーストの塗布厚みを１５０μｍにし、隔壁用フォトマスクのピッチを１５０μｍ、露光量を０．６Ｊ／ｃｍ²、現像時間を１５０秒、焼成温度を５６０℃にした以外は実施例１と同様にして検討を行った。結果を表８に示す。
比較例１
隔壁用ペーストの組成を表４のように変え、隔壁用ペーストの塗布厚みを１５０μｍにし、隔壁用フォトマスクのピッチを１５０μｍ、露光量を０．６Ｊ／ｃｍ²、現像時間を１５０秒、焼成温度を５６０℃にした以外は実施例１と同様にして検討を行った。結果を表９に示す。隔壁用ガラス粉末の粒度が小さかったため、隔壁底部まで露光せず、Ｌｔ／Ｌｈ＞１、Ｌｂ／Ｌｈ＜１となり、隔壁の倒れ、剥がれが著しかった。
比較例２
隔壁用ペーストの組成を表４のように変え、隔壁用ペーストの塗布厚みを１９０μｍにし、隔壁用フォトマスクのピッチを１５０μｍ、露光量を０．１Ｊ／ｃｍ²、現像時間を２００秒、焼成温度を５８０℃にした以外は実施例１と同様にして検討を行った。結果を表９に示す。この組成の隔壁用ペーストでは、Ｌ９０／Ｌｈ＞１、Ｌ１０／Ｌｈ＞２の隔壁しか得られず、隔壁の蛇行も大きく、輝度ムラが大きかった。
比較例３
隔壁用ペーストの組成を表４のように変え、隔壁用ペーストの塗布厚みを１３０μｍにし、隔壁用フォトマスクのピッチを１５０μｍ、露光量を０．２Ｊ／ｃｍ²、現像時間を１２０秒、焼成温度を５８０℃にした以外は実施例１と同様にして検討を行った。結果を表９に示す。有機染料の添加量を少なくしたところ、Ｌｂ／Ｌｈ＞２となり、発光輝度が低くなった。
比較例４
隔壁用ペーストの組成を表４のように変え、隔壁用ペーストの塗布厚みを１５０μｍにし、隔壁用フォトマスクのピッチを１５０μｍ、現像時間を１６０秒にした以外は実施例１と同様にして検討を行った。結果を表９に示す。隔壁用ペースト中のガラス粉末の含量が多かったため、隔壁底部まで露光せず、Ｌｔ／Ｌｈ＜０．６５、Ｌｂ／Ｌｈ＜１となり、隔壁の倒れが起こり、輝度が低くなった。
比較例５
隔壁用ペーストの組成を表４のように変え、隔壁用ペーストの塗布厚みを７５μｍにし、隔壁用フォトマスクのピッチを１５０μｍ、露光量を０．６Ｊ／ｃｍ²、現像時間を５０秒にした以外は実施例１と同様にして検討を行った。結果を表９に示す。隔壁用ペースト中のガラス粉末の含量が少なかったため、Ｌ１０／Ｌｈ＞２となり、輝度が低くなった。
比較例６
隔壁用ペーストの組成を表４のように変え、隔壁用ペーストの塗布厚みを９０μｍにし、隔壁用フォトマスクのピッチを１５０μｍ、露光量を０．６Ｊ／ｃｍ²、現像時間を７０秒、焼成温度を５７０℃にした以外は実施例１と同様にして検討を行った。結果を表９に示す。隔壁用ペースト中のガラス粉末の屈折率が１．７３、有機成分の屈折率が１．５９であり、屈折率の整合が悪くて露光がうまく行かず、Ｌｔ／Ｌｈ＞１の隔壁しか得られず、隔壁の蛇行も大きく、輝度ムラが大きかった。
比較例７
隔壁用ペーストの組成を表５のように変え、隔壁用ペーストの塗布厚みを１００μｍにし、露光量を０．６Ｊ／ｃｍ²、現像時間を９０秒にした以外は実施例１と同様にして検討を行った。結果を表１０に示す。隔壁用ガラス粉末の粒度が小さかったため、隔壁底部まで露光せず、Ｌｂ／Ｌｈ＜１となり、隔壁の倒れ、剥がれが著しかった。
比較例８
隔壁用ペーストの組成を表５のように変え、隔壁用ペーストの塗布厚みを１００μｍにし、隔壁用フォトマスクのピッチを１５０μｍ、露光量を３Ｊ／ｃｍ²、現像時間を１００秒、焼成温度を５７０℃にした以外は実施例１と同様にして検討を行った。結果を表１０に示す。有機染料の添加量を多くしたところ、Ｌｂ／Ｌｈ＜１となり、隔壁の倒れが起こり、輝度が低くなった。
比較例９
隔壁用ペーストの組成を表５のように変え、隔壁用ペーストの塗布厚みを１８０μｍにし、隔壁用フォトマスクのピッチを２３０μｍ、現像時間を１９０秒、焼成温度を５８０℃にした以外は実施例１と同様にして検討を行った。結果を表１０に示す。光重合開始剤、増感剤の添加量を減らしたため、露光がうまく行かず、Ｌｔ／Ｌｈ＜０．６５、Ｌｂ／Ｌｈ＜１となり、隔壁の倒れが起こり、輝度ムラが大きかった。
【０１２６】
【表１】

【０１２７】
【表２】

【０１２８】
【表３】

【０１２９】
【表４】

【０１３０】
【表５】

【０１３１】
【表６】

【０１３２】
【表７】

【０１３３】
【表８】

【０１３４】
【表９】

【０１３５】
【表１０】

【０１３６】
【発明の効果】
特定形状を有する隔壁を用いることにより、強度、基板との密着性をあげ、隔壁の蛇行、倒れ、はがれ、断線の少ない高精細プラズマディスプレイが得られた。また、蛍光体の塗布均一性がよく、輝度ムラの少ない高精細プラズマディスプレイが得られた。さらには、発光特性の優れた高輝度、高精細のプラズマディスプレイが得られた。
【図面の簡単な説明】
【図１】本発明の隔壁形状を示す簡単な隔壁断面図である。
【図２】本発明の隔壁形状を示す簡単な隔壁断面図である。
【図３】本発明の隔壁形状を示す簡単な隔壁断面図である。
【図４】本発明の隔壁形状を示す簡単な隔壁断面図である。
【図５】本発明の比較例に挙げた隔壁形状の簡単な断面図である。
【図６】本発明の比較例に挙げた隔壁形状の簡単な断面図である。
【図７】プラズマディスプレイの簡単な構成図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a plasma display. Plasma displays can be used for large televisions and computer monitors.
[0002]
[Prior art]
A plasma display panel (PDP) can display at a higher speed than a liquid crystal panel and can be easily increased in size, and thus is used in fields such as OA equipment and public information display devices. In addition, application to the field of high-definition television is highly expected.
[0003]
With such expansion of applications, a color PDP having a delicate and large number of display cells has attracted attention. The PDP generates a plasma discharge between the anode and cathode electrodes opposed to each other in a discharge space provided between the front glass substrate and the rear glass substrate, and emits ultraviolet rays generated from the gas sealed in the discharge space. The display is performed by touching the phosphor provided in the discharge space. A simple configuration diagram of an AC PDP is shown in FIG. In this case, barrier ribs (also referred to as barriers or ribs) are provided in order to suppress the spread of the discharge to a certain area, perform display in a prescribed cell, and ensure a uniform discharge space. In the case of an AC type PDP, the partition walls are formed in a stripe shape.
[0004]
The shape of the partition wall is about 30 to 80 μm in width and 100 to 200 μm in height. Usually, the barrier ribs are printed and dried in a stripe shape by a screen printing method using a glass powder paste on the front glass substrate or the rear glass substrate, and this printing / drying process is repeated 10 to 20 times to a predetermined height. It is formed by firing. However, in the screen printing method, particularly when the panel size is increased, it is difficult to align the discharge electrode previously formed on the front transparent flat plate and the printing place of the glass paste, and it is difficult to obtain the position accuracy. There is. In addition, since the glass paste is overprinted 10 to 20 times, the undulations of the partition walls and the hem are disturbed, and the accuracy of the height cannot be obtained, resulting in poor display quality, poor workability, and low yield. There's a problem. In particular, when the pattern width is 50 μm and the pitch is 100 μm or less, there is a problem that the bottom of the partition wall tends to bleed due to the thixotropy of the paste, making it difficult to form a sharp and residue-free partition wall.
[0005]
With the increase in area and resolution of PDPs, it is becoming more technically difficult and costly to produce high aspect ratio and high definition partition walls by using this screen printing method. .
[0006]
As a method for improving these problems, JP-A-1-296534, JP-A-2-165538, JP-A-5-342992, and JP-A-6-295676 use a photosensitive paste as a partition. A method of forming by photolithography technology has been proposed. However, these methods have a problem that a dense partition wall cannot be obtained after firing because the glass content of the photosensitive paste is small, and the sensitivity and resolution of the photosensitive paste are low. Therefore, it is necessary to obtain a high aspect ratio partition wall by repeating the steps of applying, exposing and developing the photosensitive paste. However, since application, exposure, and development are repeated, there are problems in alignment and there is a limit to cost reduction.
[0007]
Japanese Patent Application Laid-Open No. 8-50811 proposes a method of forming a partition wall by a single exposure using a photosensitive glass paste method. However, in this method, when a pattern with a narrow line width is formed, the pattern meanders, falls and peels after exposure and development, and when the formed pattern is baked to obtain a partition, disconnection or peeling occurs. There was a problem that occurred. Furthermore, depending on the cross-sectional shape of the barrier ribs, there is a problem that the uniformity of the phosphor coating is deteriorated.
[0008]
[Problems to be solved by the invention]
It is an object of the present invention to provide a high-definition plasma display that increases the strength of the partition walls and the adhesion to the substrate, and has few meandering, falling, peeling and disconnection of the partition walls. Another object of the present invention is to provide a high-definition plasma display with good phosphor uniformity and less luminance unevenness. A further object of the present invention is to provide a high-luminance, high-definition plasma display having excellent light emission characteristics. In addition, the plasma display in the present invention refers to a display that performs display by discharging in a discharge space partitioned by a partition wall. In addition to the AC type PDP, various displays including a plasma address liquid crystal display are used. Can be used.
[0009]
[Means for Solving the Problems]
  The purpose of the present invention is toBy applying a paste containing glass powder and a photosensitive organic component on a substrate, exposing and developing to form a barrier rib pattern, and then baking the substrate and barrier rib patternA plasma display in which partition walls are formed on a substrate, wherein the ratio of the top surface width (Lt), half-value width (Lh), and bottom surface width (Lb) of the partition walls is
        Lt / Lh = 0.65-1
        Lb / Lh = 1-2
        However, except when Lt = Lh = Lb.
And the pitch (P), half width (Lh), and height (H) are
    When P = 100-140 μm
        Lh = 15-40 μm, H = 100-140 μm
    When P = 140-160 μm
        Lh = 20-50 μm, H = 120-170 μm
It is achieved by the plasma display in the relationship.
[0011]
  The object of the present invention is toBy applying a paste containing glass powder and a photosensitive organic component on a substrate, exposing and developing to form a barrier rib pattern, and then baking the substrate and barrier rib patternA plasma display in which partition walls are formed on a substrate, wherein the ratio of 90% height width (L90), half width (Lh), and 10% height width (L10) of the partition walls is
        L90 / Lh = 0.65-1
        L10 / Lh = 1-2
        However, except when L90 = Lh = L10.
And the pitch (P), half width (Lh), and height (H) are
    When P = 100-140 μm
        Lh = 15-40 μm, H = 100-140 μm
    When P = 140-160 μm
        Lh = 20-50 μm, H = 120-170 μm
It is achieved by the plasma display in the relationship.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
In the plasma display of the present invention, since the partition wall has a tapered shape on the side surface, the partition wall has high strength and can be prevented from falling down.
[0014]
The plasma display partition wall of the present invention has a bottom surface width of Lb, a half-value width of Lh, and a top surface width of Lt.
Lt / Lh = 0.65-1
Lb / Lh = 1-2
It is in the range. An example of the present invention is shown in FIG.
[0015]
Note that Lb is the width of the bottom of the partition, Lh is a half width (a line width of 50 height from the bottom when the partition height is 100), and Lt is the width of the top of the partition.
[0016]
If Lt / Lh is greater than 1, the shape of the constriction occurs in the center of the barrier rib, and the ratio of the discharge space to the pitch of the barrier rib, that is, the aperture ratio decreases, so the luminance decreases. In addition, unevenness of coating, that is, unevenness of thickness or nonuniformity occurs when forming the phosphor. On the other hand, if it is less than 0.65, the upper surface becomes too thin, the strength to withstand the atmospheric pressure applied at the time of panel formation is insufficient, and the tip tends to collapse.
[0017]
If Lb / Lh is less than 1, the strength is low, and the partition wall collapses and causes meandering. On the other hand, if it is larger than 2, the discharge space is reduced and the luminance is lowered. More preferably, the ranges of Lt / Lh = 0.8 to 1 and Lb / Lh = 1 to 1.5 are preferable from the viewpoint of securing the aperture ratio. However, Lt = Lh = Lb is not preferable because the strength is weakened and tilting easily occurs. As the shape, a trapezoidal shape or a rectangular shape with no constriction on the lower surface of the partition wall is preferable from the viewpoint of strength.
[0018]
When the top of the partition wall is rounded or the bottom of the partition wall is skirted and it is difficult to define the top surface width and the bottom surface width of the partition wall, the 90% height width (L90) instead of the top surface width, A 10% height width (L10) is measured instead of the bottom surface width. L10, Lh, L90 are
L90 / Lh = 0.65-1
L10 / Lh = 1-2
It is in the range. An example of the present invention is shown in FIG.
[0019]
Note that L90 is a line width having a height of 90 from the bottom surface, and L10 is a line width having a height of 10 from the bottom surface when the partition wall height is 100. However, L90 = Lh = L10 is not preferable for the same reason as Lt = Lh = Lb.
[0020]
In the present invention, when a high-definition partition having a pitch of 230 μm or less and a line width of 50 μm or less is formed on a large panel having a size of 32 inches or more, the above-described shape prevents the meandering, swinging, and disconnection of the partition after firing. Can do. Moreover, by making the partition pattern before firing into the above-mentioned shape, the contact area with the substrate glass and the dielectric layer is particularly widened, and the shape retention and stability are improved. As a result, peeling and disconnection after firing are eliminated.
[0021]
A method for measuring the partition line width is not particularly limited, but it is preferably measured using an optical microscope, a scanning electron microscope, or a laser microscope.
[0022]
For example, when a scanning electron microscope (for example, HITACHI S-2400) is used, the following method is preferable. Cut so that the cross section of the partition wall is exactly as shown in FIG. At that time, since accurate evaluation cannot be performed if the cross section is inclined, the cross section is set to be perpendicular to the stripe direction of the partition walls. The measurement magnification is selected so that 2 to 5 partition walls are in the field of view. For example, when the pitch is 150 μm, a magnification of 200 to 300 times is used. Then, after the scale is calibrated with a standard sample having a size equivalent to the partition line width, a photograph is taken, and the line width is calculated from the scale.
[0023]
Further, when it is desired to perform nondestructive measurement, a laser focus displacement meter (for example, LT-8010 manufactured by Keyence Corporation) may be used. In this case as well, it is preferable to perform the measurement after calibrating with a standard sample. At this time, it is preferable to confirm that the measurement surface of the laser is perpendicular to the stripe direction of the partition wall in order to perform accurate measurement.
[0024]
The inclined surface is not limited to a planar structure, and may have a curved surface shape. In particular, as shown in FIG. 3, it is preferable to have a curved surface shape from the center of the partition wall height to the bottom surface, because even if Lb / Lh is increased, the discharge space can be increased and the luminance does not decrease. It is particularly preferable that the curved surface shape has the following relationship when the radius of curvature of the curved surface shape of the partition wall is R and the half-value width is Lh because the effect is high.
[0025]
R ≦ Lh / 2
In the present invention, the line width of the partition walls is preferably 15 to 50 μm because a high aperture ratio and high luminance can be obtained. If it is larger than 50 μm, the aperture ratio is lowered, so that sufficient luminance cannot be obtained, and if it is smaller than 15 μm, the strength is insufficient and the partition walls are destroyed at the time of sealing, which is not preferable.
[0026]
Furthermore, the pitch of the partition walls is preferably 100 to 250 μm. More preferably, it is 100-160 micrometers. By satisfying this range, a high-definition plasma display can be obtained.
[0027]
Further, the height of the partition walls is preferably 60 to 170 μm because it is advantageous in terms of discharge stability and luminance. More preferably, it is 100-170 micrometers. Outside this range, it is not preferable because a malfunction such as erroneous discharge occurs or luminance is low.
[0028]
  The shape of each part of the partition wall of the present invention is such that the pitch is P,Half widthTheLhWhen the height is H, it is more preferable that the following relationship is satisfied in terms of panel luminance and discharge life.
[0029]
  ・ When P = 100-140μm
        Lh= 15-40 μm, H = 100-140 μm
  ・ When P = 140-160μm
        Lh= 20-50 μm, H = 120-170 μm
  Half widthIf is smaller than the above lower limit, peeling and falling during pattern formation are likely to occur, and disconnection and peeling are likely to occur after firing. If the value is larger than the above upper limit, the luminance is lowered due to a decrease in the aperture ratio, which is not preferable. If the height is smaller than the above lower limit, the discharge space is narrowed, the plasma region is close to the phosphor layer, and the phosphor layer is sputtered, which is not preferable in terms of life. If it exceeds the above upper limit, the ultraviolet rays generated by the discharge are absorbed before reaching the phosphor layer, so that the luminance is lowered, which is not preferable.
[0030]
In the present invention, the porosity of the partition wall is preferably 10% or less, more preferably 3% or less, because the partition wall is prevented from falling down and has excellent adhesion to the substrate. The porosity (P) is expressed as follows: the true specific gravity of the partition wall material is dth, and the measured density of the partition wall is dex.
P = (dth−dex) / dth × 100
It is defined as
[0031]
The true specific gravity of the partition wall material is preferably calculated using the so-called Archimedes method as follows. The partition material is pulverized to a level not exceeding 325 mesh using a mortar. And true specific gravity is calculated | required as described in JIS-R2205. Next, the measurement density is measured using the Archimedes method in the same manner as described above except that the partition wall portion is scraped without breaking the shape and pulverization is not performed.
[0032]
If the porosity is larger than 10%, the adhesion strength is lowered, and in addition, the strength is insufficient, and the emission characteristics are lowered such as luminance reduction due to adsorption of gas and moisture discharged from the pores during discharge. Considering the light emission characteristics such as the discharge life and luminance stability of the panel, it is more preferably 1% or less.
[0033]
A method for manufacturing the partition wall of the present invention is not particularly limited, but it is preferable that the partition wall be manufactured by a photosensitive paste method with few steps and capable of forming a fine pattern. In the sandblasting method, the partition wall pattern is formed by blowing sand and scraping. Therefore, it is difficult to control, the tailing becomes large due to insufficient shaving, or conversely, the bottom surface tends to be thinner than the top surface due to excessive shaving. Further, in the screen printing method, since printing is repeated 10 to 20 times, the bottom of the partition wall is crushed and the upper part of the partition wall tends to hang down.
[0034]
The photosensitive paste method uses a photosensitive paste mainly composed of an inorganic component composed of glass powder and an organic component having photosensitivity, and a photomask pattern is exposed and baked, and a partition pattern is formed by development, followed by firing. Thus, the partition wall is obtained.
[0035]
When used as a partition for a plasma display or a plasma addressed liquid crystal display, a pattern is formed on a glass substrate having a low glass transition point and softening point. Therefore, as a partition material, a glass transition point is 430 to 500 ° C., and a softening point is 470 to 580. It is preferable to use a glass material at 0 ° C. When the glass transition point is 500 ° C. and the softening point is higher than 580 ° C., the glass must be fired at a high temperature, and the substrate is distorted during firing. In addition, a material having a glass transition point of 430 ° C. and a softening point lower than 470 ° C. cannot provide a dense partition layer, which causes separation of the partition wall, disconnection, and meandering.
[0036]
The glass transition point and softening point are preferably measured as follows. Using a differential thermal analysis (DTA) method, about 100 mg of a glass sample is heated in air at 20 ° C./min, temperature is plotted on the horizontal axis, and the amount of heat is plotted on the vertical axis to draw a DTA curve. The glass transition point and softening point are read from the DTA curve.
[0037]
The general high strain point glass used for the substrate glass has a thermal expansion coefficient of 80 to 90 × 10 × 10.^-7Therefore, in order to prevent substrate warpage and cracking during panel sealing, the coefficient of thermal expansion (α₅₀~₄₀₀) Is 50-90 × 10^-7Furthermore, 60 to 90 × 10^-7It is preferable to use the glass material. By using a glass material having the above characteristics, separation of the partition walls and disconnection can be prevented.
[0038]
The amount of the glass powder used for the photosensitive paste method is preferably 65 to 85% by weight based on the sum of the glass powder and the organic component. If it is less than 65% by weight, the shrinkage rate at the time of firing is increased, which causes disconnection and peeling of the partition walls, which is not preferable. Moreover, drying as a paste becomes difficult, stickiness is generated, and printing characteristics are deteriorated. Furthermore, pattern thickening and residual film are likely to occur during development. For this reason, Lb / Lh tends to be larger than 2. If it is larger than 85% by weight, the photosensitive component is small, so that the bottom of the partition pattern is not photocured. For this reason, Lb / Lh tends to be smaller than 1.
[0039]
As a composition of the partition wall material, silicon oxide is preferably blended in the glass in a range of 3 to 60% by weight. If it is less than 3% by weight, the denseness, strength and stability of the glass layer are lowered, the coefficient of thermal expansion deviates from a desired value, and mismatching with the glass substrate tends to occur. Moreover, by making it 60 weight% or less, there exists an advantage that a thermal softening point becomes low and baking to a glass substrate is attained.
[0040]
Boron oxide can improve electrical, mechanical, and thermal properties such as electrical insulation, strength, thermal expansion coefficient, and denseness of the insulating layer by blending in the glass in the range of 5 to 50% by weight. . If it exceeds 50% by weight, the stability of the glass decreases.
[0041]
By using a glass powder containing 5 to 50% by weight of at least one of bismuth oxide, lead oxide, and zinc oxide in glass, a photosensitive paste having temperature characteristics that can be patterned on a glass substrate can be obtained. . If it exceeds 50% by weight, the heat-resistant temperature of the glass becomes too low and baking onto the glass substrate becomes difficult. In particular, the use of glass containing 5 to 50% by weight of bismuth oxide has advantages such as a long pot life of the paste.
[0042]
As a glass composition containing bismuth oxide,
10 to 40 parts by weight of bismuth oxide
3-50 parts by weight of silicon oxide
10 to 40 parts by weight of boron oxide
8-20 parts by weight of barium oxide
10-30 parts by weight of aluminum oxide
It is preferable to contain 50 wt% or more of the composition containing
[0043]
A photosensitive paste having temperature characteristics that can be patterned on a glass substrate can also be obtained by using glass powder containing 2 to 20% by weight of at least one of lithium oxide, sodium oxide, and potassium oxide. By adding 20% by weight or less, preferably 15% by weight or less of an alkali metal oxide such as lithium, sodium or potassium, the stability of the paste can be improved.
[0044]
As a glass composition containing lithium oxide,
Lithium oxide         2 to 15 parts by weight
15-50 parts by weight of silicon oxide
Boron oxide 15-40 parts by weight
2-15 parts by weight of barium oxide
6-25 parts by weight of aluminum oxide
It is preferable to contain 70% by weight or more of the composition containing In the above composition, sodium oxide or potassium oxide may be used instead of lithium oxide, but lithium oxide is preferable in terms of paste stability.
[0045]
Also, the glass containing both metal oxides such as lead oxide, bismuth oxide, zinc oxide and alkali metal oxides such as lithium oxide, sodium oxide, potassium oxide, softening point and wire with lower alkali content The thermal expansion coefficient can be easily controlled.
[0046]
In addition, by adding aluminum oxide, barium oxide, calcium oxide, magnesium oxide, zinc oxide, zirconium oxide, etc., especially aluminum oxide, barium oxide, zinc oxide, etc. to the glass powder, the altitude and workability can be improved. However, the content is preferably 40% by weight or less, more preferably 25% by weight or less from the viewpoint of control of the softening point, thermal expansion coefficient, and refractive index.
[0047]
Furthermore, glass generally used as an insulator has a refractive index of about 1.5 to 1.9, but when using the photosensitive paste method, the average refractive index of the organic component is the average refractive index of the glass powder. When the difference is significantly different from the above, reflection / scattering at the interface between the glass powder and the photosensitive organic component increases, and a fine pattern cannot be obtained. Since the refractive index of a general organic component is 1.45 to 1.7, in order to match the refractive index of the glass powder and the organic component, the average refractive index of the glass powder is set to 1.5 to 1.7. It is preferable to do. More preferably, it is good to set to 1.5-1.65.
[0048]
By using a glass containing a total of 2 to 20% by weight of alkali metal oxides such as sodium oxide, lithium oxide, and potassium oxide, not only the softening point and thermal expansion coefficient can be easily controlled, but also the average of the glass Since the refractive index can be lowered, it is easy to reduce the difference in refractive index from the organic substance. When it is less than 2%, it becomes difficult to control the softening point. When it is larger than 20%, the luminance is lowered by evaporation of the alkali metal oxide during discharge. Further, the addition amount of the alkali metal oxide is preferably less than 10% by weight, more preferably 8% by weight or less in order to improve the stability of the paste.
[0049]
In particular, it is preferable to use lithium oxide among alkali metals because the stability of the paste can be relatively increased. In addition, when potassium oxide is used, there is an advantage that the refractive index can be controlled even with a relatively small amount of addition. As a result, it has a softening point that can be baked on the glass substrate, can have an average refractive index of 1.5 to 1.7, and can easily reduce the difference in refractive index from the organic component.
[0050]
Glass containing bismuth oxide is preferable from the viewpoint of softening point and improvement of water resistance, but glass containing 10% by weight or more of bismuth oxide often has a refractive index of 1.6 or more. Therefore, by using an alkali metal oxide such as sodium oxide, lithium oxide, or potassium oxide in combination with bismuth oxide, the softening point, thermal expansion coefficient, water resistance, and refractive index can be easily controlled.
[0051]
In measuring the refractive index of the glass material in the present invention, it is accurate to confirm the effect by measuring at the wavelength of light exposed by the photosensitive glass paste method. In particular, it is preferable to measure with light having a wavelength in the range of 350 to 650 nm. Furthermore, refractive index measurement with i-line (365 nm) or g-line (436 nm) is preferable.
[0052]
Since the partition wall of the present invention is excellent in increasing the contrast, it may be colored black. By adding various metal oxides, the fired partition walls can be colored. For example, a black pattern can be formed by including 1 to 10% by weight of a black metal oxide in the photosensitive paste.
[0053]
By including at least one, preferably three or more of Cr, Fe, Co, Mn, and Cu as the black metal oxide used at this time, blackening can be achieved. In particular, a black pattern can be formed by containing 0.5 wt% or more of Fe and Mn oxides.
[0054]
In addition to black, a pattern of each color can be formed by using a paste to which an inorganic pigment that develops red, blue, green, or the like is added. These colored patterns can be suitably used for a color filter of a plasma display.
[0055]
The dielectric constant of the partition glass member is preferably 4 to 10 at a frequency of 1 MHz and a temperature of 20 ° C. from the viewpoint of excellent panel power consumption and discharge life. In order to make it 4 or less, a large amount of silicon oxide having a dielectric constant of about 3.8 must be contained, and the glass transition point becomes high and the firing temperature becomes high. If it is 10 or more, a loss of power due to an increase in the amount of charge occurs, causing an increase in power consumption, which is not preferable.
[0056]
Moreover, it is preferable that the specific gravity of the partition of this invention is 2-3. In order to make it 2 or less, the glass material must contain a large amount of alkali metal oxides such as sodium oxide and potassium oxide, which is not preferable because it evaporates during discharge and deteriorates discharge characteristics. . If it becomes 3.3 or more, the display becomes heavy when the screen is enlarged, or the substrate is distorted by its own weight, which is not preferable.
[0057]
The particle diameter of the glass powder used in the above is selected in consideration of the line width and height of the partition wall to be produced. The 50 volume% particle diameter (average particle diameter D50) is 1 to 6 μm, and the maximum particle diameter size. 30 μm or less, specific surface area 1.5 to 4 m²/ G is preferable. More preferably, 10 volume% particle diameter (D10) 0.4-2 μm, 50 volume% particle diameter (D50) 1.5-6 μm, 90 volume% particle diameter (D90): 4-15 μm, and maximum particle diameter size is 25 μm. Hereinafter, specific surface area of 1.5 to 3.5 m²/ G is preferred. More preferably, D50 is 2 to 3.5 μm and the specific surface area is 1.5 to 3 m.²/ G. Here, D10, D50, and D90 are glass particle diameters of 10% by volume, 50% by volume, and 90% by volume from glass powder having a small particle diameter, respectively.
[0058]
By using the glass powder having the particle size distribution as described above, the filling property of the powder is improved, and even if the powder ratio in the photosensitive paste is increased, the occurrence of bubbles is reduced, and extra light scattering is small. Therefore, a preferable partition pattern shape can be formed. When the particle size of the glass powder is smaller than the above range, the specific surface area is increased, so that the agglomeration of the powder is increased and the dispersibility in the organic component is decreased, so that bubbles are easily involved. For this reason, light scattering increases, the center of the partition wall becomes thicker, the bottom portion is insufficiently cured, and Lb / Lh tends to be smaller than 1. Further, even if the particle size of the glass powder is larger than the above range, the bulk density of the powder is lowered, so that the filling property is lowered, the amount of the photosensitive organic component is insufficient, bubbles are easily involved, and light scattering is also easily caused. Furthermore, when the particle size distribution of the glass powder is in the above range, the powder filling ratio is high, so the firing shrinkage ratio is low, the pattern shape does not collapse during firing, and the partition wall shape of the present invention can be obtained stably.
[0059]
The method for measuring the particle diameter is not particularly limited, but it is preferable to use a laser diffraction / scattering method because it can be easily measured. For example, the measurement conditions in the case of using a particle size distribution meter HRA9320-X100 manufactured by Microtrack Co. are as follows.
[0060]
Sample amount: 1g
Dispersion condition: Ultrasonic dispersion in purified water for 1 to 1.5 minutes, and in a case where it is difficult to disperse, it is carried out in a 0.2% sodium hexametaphosphate aqueous solution.
[0061]
Particle refractive index: Varies depending on glass type (1.6 lithium, 1.88 bismuth)
Solvent refractive index: 1.33
Number of measurements: 2 times
The partition wall of the present invention may contain 3 to 60% by weight of a filler having a softening point of 550 to 1200 ° C, more preferably 650 to 800 ° C. Thereby, in the photosensitive paste method, the shrinkage rate at the time of baking after pattern formation becomes small, the pattern formation becomes easy, and the shape retention at the time of baking improves.
[0062]
As the filler, ceramics such as titania, alumina, barium titanate, zirconia, and high melting point glass powder containing 15% by weight or more of silicon oxide and aluminum oxide are preferable. As an example, it is preferable to use glass powder containing the following composition.
[0063]
Silicon oxide: 25 to 50% by weight
Boron oxide: 5 to 20% by weight
Aluminum oxide: 25 to 50% by weight
Barium oxide: 2 to 10% by weight
When a high melting point glass powder is used as a filler, if the refractive index difference from the base glass material (low melting point glass) is large, matching with an organic component becomes difficult, and pattern formability deteriorates.
[0064]
Therefore, when the average refractive index N1 of the low-melting glass powder and the average refractive index N2 of the high-melting glass powder are in the following ranges, the refractive index matching with the organic component is facilitated.
[0065]
−0.05 ≦ N1-N2 ≦ 0.05
A small variation in the refractive index of the inorganic powder is also important for reducing light scattering. The variation in refractive index is ± 0.05 (95% by volume or more of the inorganic powder is in the range of average refractive index N1 ± 0.05), which is preferable for light scattering reduction.
[0066]
As the particle diameter of the filler to be used, those having an average particle diameter of 1 to 6 μm are preferable. Also, D10 (10 volume% particle diameter) 0.4-2 μm, D50 (50 volume% particle diameter): 1-3 μm, D90 (90 volume% particle diameter): 3-8 μm, maximum particle size: 10 μm or less. Use of a material having a distribution is preferable for pattern formation. Even more preferably, D90 is 3 to 5 μm and the maximum particle size is 5 μm or less. It is preferable that D90 is a fine powder having a particle size of 3 to 5 μm because it is excellent in terms of producing a partition wall having a low porosity and a low porosity. Further, the unevenness in the longitudinal direction of the upper part of the partition wall can be made ± 2 μm or less. When a powder having a large particle size is used as the filler, not only the porosity is increased, but also the unevenness at the upper part of the partition wall is increased, thereby causing an erroneous discharge.
[0067]
The organic component contains a photosensitive component selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer, and further, if necessary, a binder, a photopolymerization initiator, an ultraviolet absorber, and a sensitizer. Addition components such as a sensitization aid, a polymerization inhibitor, a plasticizer, a thickener, an organic solvent, an antioxidant, a dispersant, and an organic or inorganic precipitation inhibitor are also added.
[0068]
As the photosensitive component, there are a light-insolubilized type and a light-solubilized type,
(A) containing a functional monomer, oligomer or polymer having one or more unsaturated groups in the molecule
(B) Containing photosensitive compounds such as aromatic diazo compounds, aromatic azide compounds, and organic halogen compounds
(C) There are so-called diazo resins such as a condensate of diazo amine and formaldehyde.
[0069]
In addition, as a light-soluble type,
(D) Containing inorganic salts of diazo compounds and organic acids, quinonediazos
(E) For example, naphthoquinone-1,2-diazide-5-sulfonic acid ester of phenol, novolak resin, or the like in which quinonediazos are bonded to a suitable polymer binder.
[0070]
As the photosensitive component used in the present invention, all of the above can be used. As the photosensitive paste, the photosensitive component that can be easily used by mixing with inorganic fine particles is preferably (A).
[0071]
The photosensitive monomer is a compound containing a carbon-carbon unsaturated bond, and specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, sec. -Butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2 -Ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2 Hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl Acrylate, trifluoroethyl acrylate, allylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate , Dipen Erythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate, tri Methylolpropane triacrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct, bisphenol A- Diacrylates of propylene oxide adducts, acrylates such as thiophenol acrylate, benzyl mercaptan acrylate, etc., and monomers obtained by substituting 1 to 5 of these aromatic ring hydrogen atoms with chlorine or bromine atoms, or styrene, p -Methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α-methylstyrene, brominated α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene, carboxy Methyl styrene, vinyl naphthalene, vinyl anthracene, vinyl carbazole, and those obtained by changing some or all of the acrylates in the molecule of the above compounds to methacrylate, γ-methacryloxypropyltrimethoxysilane, 1-vinyl Such as 2-pyrrolidone, and the like. In the present invention, one or more of these can be used.
[0072]
In addition to these, the development property after exposure can be improved by adding an unsaturated acid such as an unsaturated carboxylic acid. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof.
[0073]
The content of these monomers is preferably 5 to 30% by weight with respect to the sum of the glass powder and the photosensitive component. In other ranges, the pattern formability is deteriorated and the hardness after curing is not preferable.
[0074]
Examples of the binder include polyvinyl alcohol, polyvinyl butyral, methacrylic ester polymer, acrylic ester polymer, acrylic ester-methacrylic ester copolymer, α-methylstyrene polymer, and butyl methacrylate resin.
[0075]
Moreover, the oligomer and polymer obtained by superposing | polymerizing at least 1 type among the compounds which have the above-mentioned carbon-carbon double bond can be used. In the polymerization, it can be copolymerized with other photosensitive monomers so that the content of these photoreactive monomers is 10% by weight or more, more preferably 35% by weight or more.
[0076]
As a monomer to be copolymerized, the developability after exposure can be improved by copolymerizing an unsaturated acid such as an unsaturated carboxylic acid. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof.
[0077]
The acid value (AV) of the polymer or oligomer having an acidic group such as a carboxyl group in the side chain thus obtained is preferably 50 to 180, more preferably 70 to 140. If the acid value is less than 50, the solubility of the unexposed area in the developing solution is lowered. Therefore, if the concentration of the developing solution is increased, the exposed area is peeled off, and it is difficult to obtain a high-definition pattern. In addition, when the acid value is 180, the allowable development width becomes narrow.
[0078]
When imparting developability with a monomer such as an unsaturated acid, it is preferable that the acid value of the polymer be 50 or less because gelation due to the reaction between the glass powder and the polymer can be suppressed.
[0079]
By adding a photoreactive group to the side chain or molecular end of the polymer or oligomer described above, it can be used as a photosensitive polymer or photosensitive oligomer having photosensitivity. Preferred photoreactive groups are those having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group.
[0080]
Such a side chain can be added to an oligomer or polymer by using an ethylenically unsaturated compound having a glycidyl group or an isocyanate group relative to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. There is a method of making an acid chloride or allyl chloride by addition reaction.
[0081]
Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonic acid, glycidyl ether of isocrotonic acid, and the like.
[0082]
Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) acryloyl isocyanate and (meth) acryloylethyl isocyanate.
[0083]
In addition, the ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride is 0.05 to 1 molar equivalent with respect to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. It is preferable to add.
[0084]
The amount of the polymer component consisting of the photosensitive polymer, photosensitive oligomer and binder in the photosensitive glass paste is excellent in terms of pattern formability and shrinkage after baking, so the sum of the glass powder and the photosensitive component. The content is preferably 5 to 30% by weight. Outside this range, it is not preferable because pattern formation is impossible or the pattern becomes thick.
[0085]
Specific examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4 -Benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p -T-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethylketanol, benzylmethoxyethyl acetal, benzoy , Benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6- Bis (p-azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl- Propanedion-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) ) Oxime, Michler's ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyro Photoreducing dyes such as nitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabrominated, tribromophenylsulfone, benzoin peroxide and eosin, methylene blue and reduction of ascorbic acid, triethanolamine, etc. Combinations of agents are included. In the present invention, one or more of these can be used.
[0086]
A photoinitiator is added in 0.05-30 weight% with respect to the photosensitive component, More preferably, it is 0.1-20 weight%. If the amount of the polymerization initiator is too small, the photosensitivity will be poor, and if the amount of the photopolymerization initiator is too large, the residual ratio of the exposed area may be too small.
[0087]
It is also effective to add a UV absorber. High aspect ratio, high definition, and high resolution can be obtained by adding a compound having a high ultraviolet absorption effect. As the ultraviolet absorber, an organic dye, particularly an organic dye having a high UV absorption coefficient in a wavelength range of 350 to 450 nm is preferably used. Specifically, azo dyes, amino ketone dyes, xanthene dyes, quinoline dyes, amino ketone dyes, anthraquinone dyes, benzophenone dyes, diphenyl cyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes, and the like can be used. . Even when an organic dye is added as a light-absorbing agent, it is preferable because it does not remain in the insulating film after baking and the deterioration of the insulating film characteristics due to the light-absorbing agent can be reduced. Of these, azo dyes and benzophenone dyes are preferable.
[0088]
The addition amount of the organic dye is preferably 0.05 to 1% by weight with respect to the glass powder. If it is 0.05% by weight or less, the effect of adding an ultraviolet light absorber is low, and if it exceeds 1% by weight, the photosensitivity becomes poor or the insulating film properties after firing are unfavorable. More preferably, it is 0.1 to 0.18% by weight.
[0089]
An example of a method for adding an ultraviolet light absorber composed of an organic dye will be given. A solution in which an organic dye is previously dissolved in an organic solvent is prepared and kneaded at the time of preparing the paste. Alternatively, there is a method in which glass fine particles are mixed in the organic dye solution and then dried. By this method, so-called capsule-shaped fine particles in which the surface of each glass fine particle is coated with an organic dye film can be produced.
[0090]
In the present invention, metals such as Pb, Fe, Cd, Mn, Co, and Mg contained in the inorganic fine particles and oxides react with photosensitive components contained in the paste, and the paste gels in a short time and cannot be applied. There is a case. In order to prevent such a reaction, it is preferable to add a stabilizer to prevent gelation. As a stabilizer to be used, a triazole compound is preferably used. As the triazole compound, a benzotriazole derivative is preferably used. Of these, benzotriazole is particularly effective. As an example of the surface treatment of glass fine particles with benzotriazole used in the present invention, a predetermined amount of benzotriazole with respect to inorganic fine particles was dissolved in an organic solvent such as methyl acetate, ethyl acetate, ethyl alcohol, and methyl alcohol. Thereafter, it is immersed in the solution for 1 to 24 hours so that the fine particles can be sufficiently immersed. After soaking, it is preferably air-dried at 20 to 30 ° C. to evaporate the solvent to produce triazole-treated fine particles. The proportion of the stabilizer used (stabilizer / inorganic fine particles) is preferably 0.05 to 5% by weight.
[0091]
A sensitizer is added in order to improve sensitivity. Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (diethylamino) -benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) ) Chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) -isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone 1,3-carbonyl-bis (4-diethylamino) Benzal) acetone, 3,3-carbonyl-bis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate And isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole and the like. In the present invention, one or more of these can be used. Some sensitizers can also be used as photopolymerization initiators. When adding a sensitizer to the photosensitive paste of this invention, the addition amount is 0.05-30 weight% normally with respect to the photosensitive component, More preferably, it is 0.1-20 weight%. If the amount of the sensitizer is too small, the effect of improving the photosensitivity is not exhibited, and if the amount of the sensitizer is too large, the residual ratio of the exposed portion may be too small.
[0092]
In addition, a sensitizer having absorption at the exposure wavelength is used. In this case, since the refractive index becomes extremely high in the vicinity of the absorption wavelength, the organic component can be added by adding a large amount of the sensitizer. The refractive index can be improved. In this case, the sensitizer can be added in an amount of 3 to 10% by weight.
[0093]
A polymerization inhibitor is added to improve the thermal stability during storage. Specific examples of the polymerization inhibitor include hydroquinone, monoesterified hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p- Examples include methylphenol, chloranil, and pyrogallol. When adding a polymerization inhibitor, the addition amount is 0.001 to 1 weight% normally in the photosensitive paste.
[0094]
Specific examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, glycerin and the like.
[0095]
The antioxidant is added to prevent oxidation of the acrylic copolymer during storage. Specific examples of antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-4-ethylphenol, 2,2-methylene-bis- ( 4-methyl-6-tert-butylphenol), 2,2-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4-bis- (3-methyl-6-tert-butylphenol), 1 , 1,3-Tris- (2-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-tert-butylphenyl) butane, bis [3,3-bis -(4-Hydroxy-3-t-butylphenyl) butyric acid] glycol ester, dilauryl thiodipropionate, triphenyl phosphite and the like. When adding an antioxidant, the addition amount is usually 0.001 to 1% by weight in the paste.
[0096]
An organic solvent may be added to the photosensitive paste of the present invention in order to adjust the viscosity of the solution. As an organic solvent used at this time, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, bromobenzene, Chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, and the like, and organic solvent mixtures containing one or more of these are used.
[0097]
The refractive index of the organic component is the refractive index of the organic component in the paste at the time when the photosensitive component is exposed by exposure. That is, when the paste is applied and the exposure is performed after the drying process, this is the refractive index of the organic component in the paste after the drying process. For example, after apply | coating a paste on a glass substrate, there exists the method of drying at 50-100 degreeC for 1 to 30 minutes, and measuring a refractive index.
[0098]
The measurement of the refractive index in the present invention is preferably performed by an ellipsometry method or a V block method which are generally performed, and it is accurate to confirm the effect that the measurement is performed at the wavelength of light to be exposed. In particular, it is preferable to measure with light having a wavelength in the range of 350 to 650 nm. Furthermore, refractive index measurement with i-line (365 nm) or g-line (436 nm) is preferable.
[0099]
Moreover, in order to measure the refractive index after an organic component superposes | polymerizes by light irradiation, it can measure by irradiating only the organic component with the same light as the case where light is irradiated with respect to the inside of a paste.
[0100]
The photosensitive paste is usually prepared by blending various components such as inorganic fine particles, ultraviolet light absorber, photosensitive polymer, photosensitive monomer, photopolymerization initiator, glass frit and solvent so as to have a predetermined composition, and then a three-roller. Or by mixing and dispersing homogeneously with a kneader.
[0101]
The viscosity of the paste is appropriately adjusted depending on the addition ratio of inorganic fine particles, thickener, organic solvent, plasticizer, precipitation inhibitor, etc., but the range is 2000 to 200,000 cps (centipoise). For example, when applying to a glass substrate by a spin coat method, 200-5000 cps is preferable. In order to obtain a film thickness of 10 to 20 μm by a single screen printing method, 50,000 to 200,000 cps is preferable.
[0102]
Next, an example of performing pattern processing using a photosensitive paste will be described, but the present invention is not limited to this.
[0103]
A photosensitive paste is applied over the entire surface or partially on a glass substrate, a ceramic substrate, or a polymer film. As a coating method, methods such as screen printing, bar coater, roll coater, die coater, and blade coater can be used. The coating thickness can be adjusted by selecting the number of coatings, screen mesh, and paste viscosity.
[0104]
Here, when the paste is applied onto the substrate, surface treatment of the substrate can be performed in order to improve the adhesion between the substrate and the coating film. As the surface treatment liquid, silane coupling agents such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, tris- (2-methoxyethoxy) vinylsilane, γ-glycidoxypropyltrimethoxysilane, γ- (methacryloxy) Propyl) trimethoxysilane, γ (2-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, or organic metals such as organic titanium, Organic aluminum, organic zirconium and the like. A silane coupling agent or an organic metal diluted with an organic solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl alcohol, ethyl alcohol, propyl alcohol, or butyl alcohol to a concentration of 0.1 to 5% is used. . Next, this surface treatment liquid is uniformly applied onto the substrate with a spinner or the like, and then dried at 80 to 140 ° C. for 10 to 60 minutes, whereby the surface treatment can be performed.
[0105]
Moreover, when apply | coating on a film, there exists the method of performing the exposure process, after sticking on the board | substrate of glass or a ceramic, when performing the next exposure process after drying on a film.
[0106]
After coating, exposure is performed using an exposure apparatus. In general, the exposure is performed by mask exposure using a photomask, as in normal photolithography. As the mask to be used, either a negative type or a positive type is selected depending on the type of the photosensitive organic component. Alternatively, a method of directly drawing with a red or blue laser beam or the like without using a photomask may be used.
[0107]
As the exposure apparatus, a stepper exposure machine, a proximity exposure machine or the like can be used. Moreover, when performing exposure of a large area, a large area can be exposed with an exposure machine having a small exposure area by applying a photosensitive paste on a substrate such as a glass substrate and then performing exposure while transporting. it can.
[0108]
Examples of the active light source used in this case include visible light, near ultraviolet light, ultraviolet light, electron beam, X-ray, and laser light. Among these, ultraviolet light is preferable. Mercury lamps, ultra-high pressure mercury lamps, halogen lamps, germicidal lamps, etc. can be used. Among these, an ultrahigh pressure mercury lamp is suitable. The exposure conditions vary depending on the coating thickness, but 1-100 mW / cm²The exposure is performed for 20 seconds to 30 minutes using an ultra-high pressure mercury lamp of
[0109]
The pattern shape can be improved by providing an oxygen shielding film on the surface of the coated photosensitive paste. As an example of the oxygen shielding film, a film such as polyvinyl alcohol (PVA) or cellulose, or a film such as polyester can be used.
[0110]
In order to form a PVA film, a PVA aqueous solution having a concentration of 0.5 to 5% by weight is uniformly applied on a substrate by a method such as a spinner, and then dried at 70 to 90 ° C. for 10 to 60 minutes to evaporate water. Do it. In addition, it is preferable to add a small amount of alcohol to the aqueous solution because it improves the paintability with the insulating film and facilitates evaporation. A more preferable solution concentration of PVA is 1 to 3% by weight. Within this range, the sensitivity is further improved. The following reasons are presumed that the sensitivity is improved by application of PVA. That is, when the photosensitive component undergoes a photoreaction, if there is oxygen in the air, it is considered that the sensitivity of photocuring is hindered. . When a transparent film such as polyester, polypropylene, or polyethylene is used, there is a method in which these films are pasted on the photosensitive paste after application.
[0111]
After exposure, development is performed using the difference in solubility between the photosensitive portion and the non-photosensitive portion in the developer. In this case, the immersion method, the shower method, the spray method, and the brush method are used. As the developer to be used, an organic solvent in which an organic component in the photosensitive paste can be dissolved can be used. Further, water may be added to the organic solvent as long as its dissolving power is not lost. When a compound having an acidic group such as a carboxyl group is present in the photosensitive paste, development can be performed with an aqueous alkaline solution. A metal alkali aqueous solution such as sodium hydroxide, sodium carbonate, calcium hydroxide aqueous solution or the like can be used as the alkali aqueous solution. However, it is preferable to use an organic alkali aqueous solution because an alkaline component can be easily removed during firing.
[0112]
As the organic alkali, an amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, and diethanolamine. The concentration of the alkaline aqueous solution is usually 0.01 to 10% by weight, more preferably 0.1 to 5% by weight. If the alkali concentration is too low, the soluble portion is not removed, and if the alkali concentration is too high, the pattern portion may be peeled off and the non-soluble portion may be corroded. The development temperature during development is preferably 20 to 50 ° C. in terms of process control.
[0113]
Next, firing is performed in a firing furnace. The firing atmosphere and temperature vary depending on the type of paste and substrate, but firing is performed in an atmosphere of air, nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.
[0114]
In the case of patterning on a glass substrate, firing is carried out by holding at a temperature increase rate of 200 to 400 ° C./hour and a temperature of 540 to 610 ° C. for 10 to 60 minutes. The firing temperature is determined by the glass powder to be used, but it is preferable to fire at an appropriate temperature that does not break the shape after pattern formation and does not leave the shape of the glass powder. When the temperature is lower than the appropriate temperature, the porosity and the unevenness at the upper part of the partition wall are increased, so that the discharge life is shortened and erroneous discharge is easily caused. On the other hand, when the temperature is higher than the appropriate temperature, the shape at the time of pattern formation collapses, and the upper part of the partition wall becomes round or extremely low, and a desired height cannot be obtained.
[0115]
Moreover, you may introduce | transduce a 50-300 degreeC heating process for the purpose of drying and a preliminary reaction in each process of the above application | coating, exposure, image development, and baking.
[0116]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to this. The concentration (%) in Examples and Comparative Examples is% by weight unless otherwise specified.
[0117]
The materials used in the examples of the present invention are shown below.
(Glass powder for partition walls)
Glass (1);
Composition: Li₂O 9%, SiO₂20%, B₂O_Three  31%, BaO 4%, Al₂O_Three24%, ZnO 2%, MgO 6%, CaO 4%
Thermophysical properties: Glass transition point 474 ° C., softening point 515 ° C., thermal expansion coefficient 83 × 10^-7/ K
Particle size: D10 0.9 μm, D50 2.5 μm, D90 6.5 μm, maximum particle size 18.5 μm
Specific surface area: 2.56m²/ G
Refractive index: 1.59 (g line 436 nm)
Specific gravity: 2.55
Glass (2);
Composition, thermophysical properties, refractive index, specific gravity are the same as glass (1)
Particle size: D10 0.7 μm, D50 1.6 μm, D90 2.4 μm, maximum particle size 5.2 μm
Specific surface area: 5.8 m²/ G
Glass (3);
Composition: Li₂O 7%, SiO₂22%, B₂O_Three  32%, BaO 4%, Al₂O_Three22%, ZnO 2%, MgO 6%, CaO 4%
Thermophysical properties: Glass transition point 491 ° C., softening point 528 ° C., thermal expansion coefficient 74 × 10^-7/ K
Particle size: D10 0.9 μm, D50 2.6 μm, D90 7.5 μm, maximum particle size 22.0 μm
Specific surface area: 1.92m²/ G
Refractive index: 1.59 (g line 436 nm)
Specific gravity: 2.54
Glass (4);
Composition and thermophysical properties are the same as glass (3)
Particle size: D10 0.8 μm, D50 1.5 μm, D90 2.5 μm, maximum particle size 4.6 μm
Specific surface area: 5.9m²/ G
Refractive index: 1.59 (g line 436 nm)
Specific gravity: 2.54
Glass (5);
Composition: Li₂O 4%, K₂O 5%, SiO₂15%, B₂O_Three  33%, BaO 4%, Al₂O_Three20%, ZnO 13%, MgO 1%, CaO 5%
Thermophysical properties: glass transition point 470 ° C., softening point 511 ° C., thermal expansion coefficient 76 × 10^-7/ K
Particle size: D10 0.9 μm, D50 2.7 μm, D90 6.0 μm, maximum particle size 13.1 μm
Specific surface area: 2.29m²/ G
Refractive index: 1.58 (g line 436 nm)
Specific gravity: 2.67
Glass (6);
Composition: Bi₂O_Three  27%, SiO₂14%, B₂O_Three  18% Na₂O 2%, BaO 14%, Al₂O_Three4%, ZnO 21%
Thermophysical properties: Glass transition point 483 ° C., softening point 523 ° C., thermal expansion coefficient 79 × 10^-7/ K
Particle size: D10 1.4 μm, D50 3.4 μm, D90 7.4 μm, maximum particle size 22.0 μm
Specific surface area: 3.26 m²/ G
Refractive index: 1.73 (g line 436 nm)
Specific gravity: 4.13
(polymer)
Polymer (1): 0.4 equivalent of glycidyl meta to the carboxyl group of a copolymer comprising 40% methacrylic acid (MAA), 30% methyl methacrylate (MMA) and 30% styrene (St) A 40% γ-butyrolactone solution of a photopolymer having a weight average molecular weight of 43,000 and an acid value of 95 obtained by addition reaction of acrylate (GMA)
Polymer (2): 40% γ-butyrolactone solution of a photosensitive polymer having the same structure as the polymer (1), a weight average molecular weight of 18000 and an acid value of 100
Polymer (3): 0.8 equivalent of glycidyl meta to the carboxyl group of a copolymer comprising 40% methacrylic acid (MAA), 30% methyl methacrylate (MMA) and 30% styrene (St) A 40% γ-butyrolactone solution of a photopolymer having a weight average molecular weight of 30,000 and an acid value of 50 obtained by addition reaction of acrylate (GMA)
(monomer)

(Photopolymerization initiator)
IC-369: Irgacure-369 (Ciba-Geigy product); 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1
(Sensitizer)
DETX-S: 2,4-diethylthioxanthone
(Organic dye)
Sudan: Azo-based organic dye, chemical formula C_{twenty four}H₂₀N_FourO, molecular weight 380.45
Example 1
A photosensitive paste for barrier ribs having the composition shown in Table 1 was prepared. Weighed at a ratio of 0.08 parts by weight of organic dye (Sudan) to 70 parts by weight of glass powder (glass (1)). Sudan was dissolved in acetone, a dispersant was added, and the mixture was stirred uniformly with a homogenizer. Glass powder was added to this solution and uniformly dispersed and mixed, and then dried at a temperature of 100 ° C. using a rotary evaporator to evaporate acetone. Thus, a powder in which the surface of the glass powder was uniformly coated with an organic dye film was produced.
[0118]
A polymer, a monomer, a photopolymerization initiator, and a sensitizer were mixed at a ratio shown in Table 1 and dissolved uniformly. Thereafter, this solution was filtered using a 400 mesh filter to prepare an organic vehicle.
[0119]
The organic vehicle and the glass powder were added so as to have the composition shown in Table 1, and mixed and dispersed with three rollers to prepare a photosensitive paste for forming a partition wall. The refractive index of the organic component was 1.59, and that of the glass powder was 1.59.
[0120]
The photosensitive paste for barrier ribs was uniformly applied by screen printing using a 325 mesh screen on an A4 size PD-200 substrate manufactured by Asahi Glass Co., which had electrodes and dielectric layers formed in advance. In order to avoid the occurrence of pinholes in the coating film, coating and drying were repeated several times or more 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 thickness after drying was 170 μm. Subsequently, 50 mJ / cm from the upper surface through a negative chrome mask with a pitch of 140 μm.²Ultraviolet light was irradiated with an output ultra high pressure mercury lamp. Exposure amount is 0.7 J / cm²Met.
[0121]
Next, a 0.2 wt% aqueous solution of monoethanolamine maintained at 35 ° C. was developed for 170 seconds by showering, and then washed with water using a shower spray. Thereby, the part which is not photocured was removed and the stripe-shaped partition wall pattern was formed on the glass substrate. Thus, the glass substrate in which the partition pattern was formed was baked for 15 minutes at 560 degreeC in the air, and the partition was formed.
[0122]
A phosphor layer was formed by a photosensitive paste method in a predetermined groove in the partition of the glass substrate on which the partition was formed. That is, three types of photosensitive phosphor pastes of red (R), green (G), and blue (B) are prepared, and printing, drying, exposure with a photomask, and development are repeated one by one. A phosphor pattern was formed. After this operation was performed for each color, the phosphor layer was formed by baking at 500 ° C. for 20 minutes. Thereby, the back plate for PDP was obtained.
[0123]
The cross-sectional shape of the formed partition wall was observed with a scanning electron microscope (HITACHI S-2400). 1, 3, 4, and 5, the top surface width, the half-value width, and the bottom surface width are measured. When the top surface and the bottom surface are difficult to measure as illustrated in FIGS. L90 and L10 were measured instead of the bottom surface width. Further, when the bottom surface has a round shape as shown in FIG. 2, the radius of curvature was also measured. Each value was calculated by the average value of 3 samples. The shape of this example was FIG.
[0124]
Regarding defects in barrier ribs and phosphor layers, (1) Evaluation of barrier wall collapse and peeling before firing, (2) Separation of barrier ribs after firing, presence or absence of disconnection, and (3) Uniformity of phosphor layer coating did. When there was no defect, it was marked as “good”. Furthermore, the aperture ratio of each partition was defined as 1- (half width / pitch) and calculated. The results are shown in Table 6. It was excellent in that there was no peeling, falling or disconnection both before and after firing, and the phosphor coating uniformity was also good.
[0125]
Next, a low melting point glass paste as a sealant is provided on the front plate and the back plate on which electrodes, a dielectric, and a protective layer are arranged in advance. Treated for minutes and sealed. Thereafter, the inside of the display area was evacuated and sealed with a mixed gas of He 99% and Xe 1% to complete a plasma display panel, and the light emission characteristics were examined. In the case where there was no problem in luminance unevenness and luminance, it was marked as ◯. The results are shown in Table 6. There was little brightness unevenness, high brightness and excellent characteristics.
Example 2
The composition of the partition wall paste was changed as shown in Table 1, and the exposure amount was 1 J / cm.²Except for changing to, examination was performed in the same manner as in Example 1. The results are shown in Table 6.
Example 3
The composition of the partition wall paste was changed as shown in Table 1, and the exposure amount was 1 J / cm.²Except for changing to, examination was performed in the same manner as in Example 1. The results are shown in Table 6.
Example 4
The composition of the partition wall paste was changed as shown in Table 1, the coating thickness of the partition wall paste was 150 μm, and the exposure amount was 0.3 J / cm.²The examination was performed in the same manner as in Example 1 except that the development time was changed to 150 seconds. The results are shown in Table 6.
Example 5
The composition of the partition wall paste was changed as shown in Table 1, the coating thickness of the partition wall paste was 150 μm, and the exposure amount was 1.5 J / cm.²The examination was conducted in the same manner as in Example 1 except that the development time was 150 seconds. The results are shown in Table 6.
Example 6
The composition of the partition wall paste was changed as shown in Table 1, the coating thickness of the partition wall paste was 150 μm, and the exposure amount was 1.2 J / cm.²The examination was conducted in the same manner as in Example 1 except that the development time was 150 seconds. The results are shown in Table 6.
Example 7
Examination was conducted in the same manner as in Example 1 except that the composition of the partition wall paste was changed as shown in Table 2, the coating thickness of the partition wall paste was 190 μm, the development time was 200 seconds, and the baking temperature was 580 ° C. It was. The results are shown in Table 7.
Example 8
Examination was performed in the same manner as in Example 1 except that the composition of the partition wall paste was changed as shown in Table 2 and the partition pattern firing temperature was 580 ° C. The results are shown in Table 7.
Example 9
Example except that the composition of the partition wall paste was changed as shown in Table 2, the partition wall paste coating thickness was 230 μm, the partition wall photomask pitch was 150 μm, the development time was 230 seconds, and the baking temperature was 580 ° C. The examination was performed in the same manner as in 1. The results are shown in Table 7.
Example 10
The composition of the partition wall paste is changed as shown in Table 2, the partition wall paste coating thickness is 140 μm, the partition wall photomask pitch is 150 μm, and the exposure dose is 1.2 J / cm.²The examination was conducted in the same manner as in Example 1 except that the development time was 150 seconds and the baking temperature was 580 ° C. The results are shown in Table 7.
Example 11
The composition of the partition wall paste is changed as shown in Table 2, the partition wall paste coating thickness is 230 μm, the partition wall photomask pitch is 150 μm, and the exposure dose is 0.5 J / cm.²The examination was conducted in the same manner as in Example 1 except that the development time was 230 seconds and the baking temperature was 580 ° C. The results are shown in Table 7.
Example 12
The composition of the partition wall paste is changed as shown in Table 2, the partition wall photomask pitch is 100 μm, the exposure wavelength is only g-line (436 nm), and the exposure amount is 0.8 J / cm.²The examination was performed in the same manner as in Example 1 except that the firing temperature was 580 ° C. The results are shown in Table 7.
Example 13
The composition of the partition wall paste is changed as shown in Table 3, the partition wall paste coating thickness is 200 μm, the partition wall photomask pitch is 150 μm, and the exposure amount is 0.7 J / cm.²The examination was conducted in the same manner as in Example 1 except that the development time was 200 seconds and the baking temperature was 580 ° C. The results are shown in Table 8.
Example 14
The composition of the partition wall paste is changed as shown in Table 3, the partition wall paste coating thickness is 230 μm, the partition wall photomask pitch is 230 μm, and the exposure dose is 1.2 J / cm.²The examination was conducted in the same manner as in Example 1 except that the development time was 230 seconds and the baking temperature was 580 ° C. The results are shown in Table 8.
Example 15
The composition of the partition wall paste was changed as shown in Table 3, the coating thickness of the partition wall paste was 210 μm, and the exposure amount of the partition wall pattern was 0.9 J / cm.²The examination was conducted in the same manner as in Example 1 except that the development time was 200 seconds and the baking temperature was 580 ° C. The results are shown in Table 8.
Example 16
The composition of the partition wall paste was changed as shown in Table 3, and the exposure amount of the partition wall pattern was 0.7 J / cm.²The examination was performed in the same manner as in Example 1 except that the firing temperature was 580 ° C. The results are shown in Table 8.
Example 17
The composition of the partition wall paste is changed as shown in Table 3, the partition wall paste coating thickness is 230 μm, the partition wall photomask pitch is 230 μm, and the exposure dose is 1.3 J / cm.²The examination was conducted in the same manner as in Example 1 except that the development time was 230 seconds and the baking temperature was 580 ° C. The results are shown in Table 8.
Example 18
The composition of the partition wall paste is changed as shown in Table 3, the partition wall paste coating thickness is 150 μm, the partition wall photomask pitch is 150 μm, and the exposure dose is 0.6 J / cm.²The study was conducted in the same manner as in Example 1 except that the development time was 150 seconds and the baking temperature was 560 ° C. The results are shown in Table 8.
Comparative Example 1
The composition of the partition wall paste is changed as shown in Table 4, the partition wall paste coating thickness is 150 μm, the partition wall photomask pitch is 150 μm, and the exposure amount is 0.6 J / cm.²The study was conducted in the same manner as in Example 1 except that the development time was 150 seconds and the baking temperature was 560 ° C. The results are shown in Table 9. Since the particle size of the partition wall glass powder was small, the bottom of the partition wall was not exposed, and Lt / Lh> 1 and Lb / Lh <1, and the partition wall collapsed and peeled off.
Comparative Example 2
The composition of the partition wall paste was changed as shown in Table 4, the partition wall paste coating thickness was 190 μm, the partition wall photomask pitch was 150 μm, and the exposure amount was 0.1 J / cm.²The examination was conducted in the same manner as in Example 1 except that the development time was 200 seconds and the baking temperature was 580 ° C. The results are shown in Table 9. With the partition wall paste having this composition, only the partition walls of L90 / Lh> 1 and L10 / Lh> 2 were obtained, the partition wall meandering was large, and the luminance unevenness was large.
Comparative Example 3
The composition of the partition wall paste is changed as shown in Table 4, the partition wall paste coating thickness is 130 μm, the partition wall photomask pitch is 150 μm, and the exposure dose is 0.2 J / cm.²The examination was conducted in the same manner as in Example 1 except that the development time was 120 seconds and the baking temperature was 580 ° C. The results are shown in Table 9. When the addition amount of the organic dye was decreased, Lb / Lh> 2 was obtained, and the emission luminance was lowered.
Comparative Example 4
Examination was performed in the same manner as in Example 1 except that the composition of the partition wall paste was changed as shown in Table 4, the partition wall paste coating thickness was 150 μm, the partition wall photomask pitch was 150 μm, and the development time was 160 seconds. went. The results are shown in Table 9. Since the content of the glass powder in the partition wall paste was large, the bottom of the partition wall was not exposed, and Lt / Lh <0.65 and Lb / Lh <1, resulting in collapse of the partition wall and low brightness.
Comparative Example 5
The composition of the partition wall paste was changed as shown in Table 4, the partition wall paste coating thickness was 75 μm, the partition wall photomask pitch was 150 μm, and the exposure amount was 0.6 J / cm.²The examination was conducted in the same manner as in Example 1 except that the development time was 50 seconds. The results are shown in Table 9. Since the content of the glass powder in the partition wall paste was small, L10 / Lh> 2 and the luminance was low.
Comparative Example 6
The composition of the partition wall paste is changed as shown in Table 4, the partition wall paste coating thickness is 90 μm, the partition wall photomask pitch is 150 μm, and the exposure amount is 0.6 J / cm.²The examination was conducted in the same manner as in Example 1 except that the development time was 70 seconds and the baking temperature was 570 ° C. The results are shown in Table 9. The refractive index of the glass powder in the partition wall paste is 1.73, the refractive index of the organic component is 1.59, the refractive index is poorly matched and the exposure is not successful, and only the partition wall of Lt / Lh> 1 is obtained. In addition, the meandering of the partition walls was large and the luminance unevenness was large.
Comparative Example 7
The composition of the partition wall paste was changed as shown in Table 5, the coating thickness of the partition wall paste was 100 μm, and the exposure amount was 0.6 J / cm.²The examination was conducted in the same manner as in Example 1 except that the development time was 90 seconds. The results are shown in Table 10. Since the particle size of the partition wall glass powder was small, the bottom of the partition wall was not exposed and Lb / Lh <1, and the partition wall collapsed and peeled off.
Comparative Example 8
The composition of the partition wall paste was changed as shown in Table 5, the partition wall paste coating thickness was 100 μm, the partition wall photomask pitch was 150 μm, and the exposure amount was 3 J / cm.²The examination was conducted in the same manner as in Example 1 except that the development time was 100 seconds and the baking temperature was 570 ° C. The results are shown in Table 10. When the amount of the organic dye added was increased, Lb / Lh <1, the partition wall collapsed and the luminance was lowered.
Comparative Example 9
Example 1 except that the composition of the partition wall paste was changed as shown in Table 5, the partition wall paste coating thickness was 180 μm, the partition wall photomask pitch was 230 μm, the development time was 190 seconds, and the baking temperature was 580 ° C. It examined in the same way. The results are shown in Table 10. Since the addition amount of the photopolymerization initiator and the sensitizer was reduced, the exposure was not successful, Lt / Lh <0.65, Lb / Lh <1, and the partition wall collapsed, resulting in large luminance unevenness.
[0126]
[Table 1]

[0127]
[Table 2]

[0128]
[Table 3]

[0129]
[Table 4]

[0130]
[Table 5]

[0131]
[Table 6]

[0132]
[Table 7]

[0133]
[Table 8]

[0134]
[Table 9]

[0135]
[Table 10]

[0136]
【The invention's effect】
By using a partition having a specific shape, a high-definition plasma display with improved strength and adhesion to the substrate, and with less meandering, falling, peeling, and disconnection of the partition was obtained. Also, a high-definition plasma display with good phosphor coating uniformity and less luminance unevenness was obtained. Furthermore, a high-luminance and high-definition plasma display having excellent light emission characteristics was obtained.
[Brief description of the drawings]
FIG. 1 is a simple sectional view of a partition wall showing the shape of the partition wall according to the present invention.
FIG. 2 is a simple partition sectional view showing a partition shape of the present invention.
FIG. 3 is a simple sectional view of a partition showing the shape of the partition according to the present invention.
FIG. 4 is a simple sectional view showing the shape of a partition wall according to the present invention.
FIG. 5 is a simple cross-sectional view of a partition wall shape given as a comparative example of the invention.
FIG. 6 is a simple cross-sectional view of a partition shape given as a comparative example of the present invention.
FIG. 7 is a simple configuration diagram of a plasma display.

Claims (5)

A plasma display in which a paste containing glass powder and a photosensitive organic component is applied on a substrate, exposed and developed to form a partition pattern, and then the substrate and the partition pattern are baked to form a partition on the substrate. The ratio of the upper surface width (Lt), half-value width (Lh), and lower surface width (Lb) of the partition wall is Lt / Lh = 0.65-1
Lb / Lh = 1-2
However, when Lt = Lh = Lb, and the pitch (P), half width (Lh), and height (H) are P = 100 to 140 μm, Lh = 15 to 40 μm, H = 100 ~ 140μm
When P = 140 to 160 μm Lh = 20 to 50 μm, H = 120 to 170 μm
Plasma display in the relationship. A plasma display in which a paste containing glass powder and a photosensitive organic component is applied on a substrate, exposed and developed to form a partition pattern, and then the substrate and the partition pattern are baked to form a partition on the substrate. The ratio of 90% height width (L90), half width (Lh), 10% height width (L10) of the partition wall is L90 / Lh = 0.65-1
L10 / Lh = 1-2
However, except when L90 = Lh = L10.
And when the pitch (P), half width (Lh), and height (H) are P = 100 to 140 μm, Lh = 15 to 40 μm, H = 100 to 140 μm
When P = 140 to 160 μm Lh = 20 to 50 μm, H = 120 to 170 μm
Plasma display in the relationship. The plasma display according to claim 1 or 2, wherein the partition wall has a curved shape from the height center portion to the bottom surface. The glass powder is made of a glass material having a glass transition point of 430 to 500 ° C, a softening point of 470 to 580 ° C, and a thermal expansion coefficient (α 50 to ₄₀₀ ) of 50 to 90 × 10 ^-7 / K. 2. The plasma display according to 2. The plasma display according to claim 1 or 2, wherein the glass powder comprises a glass material having the following composition.
Lithium oxide: 2-15 parts by weight Silicon oxide: 15-50 parts by weight Boron oxide: 15-40 parts by weight Barium oxide: 2-15 parts by weight Aluminum oxide: 6-25 parts by weight

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