TW200535564A - Photosensitive inorganic paste composition, sheet-shaped unbaked body, and method of producing plasma display front plate - Google Patents

Photosensitive inorganic paste composition, sheet-shaped unbaked body, and method of producing plasma display front plate Download PDF

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TW200535564A
TW200535564A TW94102507A TW94102507A TW200535564A TW 200535564 A TW200535564 A TW 200535564A TW 94102507 A TW94102507 A TW 94102507A TW 94102507 A TW94102507 A TW 94102507A TW 200535564 A TW200535564 A TW 200535564A
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Taiwan
Prior art keywords
unbaked
photopolymerization initiator
layer
dielectric layer
plasma display
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TW94102507A
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Chinese (zh)
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TWI342981B (en
Inventor
Hiroyuki Obiya
Kiminori Oshio
Akira Kumazawa
Hitoshi Setsuda
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Tokyo Ohka Kogyo Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/24—Manufacture or joining of vessels, leading-in conductors or bases
    • H01J9/241—Manufacture or joining of vessels, leading-in conductors or bases the vessel being for a flat panel display
    • H01J9/242—Spacers between faceplate and backplate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/20—Constructional details
    • H01J2211/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J2211/36—Spacers, barriers, ribs, partitions or the like

Abstract

A photosensitive inorganic paste composition capable of improving pattern accuracy to such an extent to be sufficiently adapted to fine patterning required of plasma displays, a sheet-shaped unbaked body for production of a plasma display front plate using the same, and a method of producing a plasma display front plate. A Norish type I photopolymerization initiator and a hydrogen-withdrawing photopolymerization initiator are used in combination as a photopolymerization initiator in a photosensitive inorganic paste composition comprising at least a photopolymerization initiator, a photopolymerizable monomer and inorganic powders.

Description

200535564 (1) 九、發明說明 【發明所屬之技術領域】 本發明有關一種光敏性無機糊料組成物，其藉微影術 產生優越之圖案形狀，及有關〜種使用該組成物製得而用 以製is電漿顯不則板的薄板型未烘烤还體，且有關一種製 造電漿顯示前板之方法。 φ 【先前技術】 利用電子排出現象由許多精細構件自身發射形成影像 的電漿顯示器具有優越之特性，即其爲習用顯示器無法得 到之大型、薄、質輕且平坦之顯示器，且其寬度係所企求 〇 習用電漿顯示器主要包含直線結構之構件，其具有位 於顯示器垂直方向上之肋條（rib )。然而，近年來，已發 展不僅於垂直方向具有肋條且在水平方向亦有肋條之薄餅 φ 型結構構件，以嘗試有效地將光自發射部位導向電漿顯示 器之前面。該構件之薄餅型結構可藉著防止光自相鄰構件 洩漏，而極有效地將光導向前面。 具有薄餅型構件之電漿顯示器的分解必要部分的透視 圖係出示於圖1中。電漿顯示器具有前板1，其上形成有 彼此平行而各由透明電極1 1 0及匯流排電極1 1 2所構成之 結合電極1 1 ;且具有背板2，其上形成有彼此平行而與結 合電極]1交叉之位址電極2 1。該前板1及背板2係配置 成彼此面對，且整合以構成顯示元件。前板1具有作爲顯 200535564 (2) 不平面之透明玻璃基板1 0，該結合電極1 1係配置於玻璃 基板1 〇之內側，即，位在其面向該背板2之側面。形成 介電層1 2以覆蓋結合電極1 1，介電層1 2上具有經圖案化 之間隔器層16，由MgO等製得之保護膜19係形成於間隔 器層16及介電層12上。另一方面，組合板2係具有基板 2 0 ’其具有配置於基板2 0面向前板1之側面上的位址電 極21。形成介電層22以覆蓋該位址電極21，發光部分係 φ 如下所述般地形成於該介電層22上。 發光部分係由數個構件所構成，各構件各位於結合電 極1 1與位址電極2 1交叉之間隔中。各構件各由在介電層 2 2上沿顯示器之垂直及水平方向形成的肋條2 4來分界。 提供螢光層26以覆蓋肋條之側壁及肋條中介電層22之表 面’即各構件之內壁及底部。電漿顯示器中，來自交流電 源之預定電壓係施加於位在前板上之結合電極以形成電場 ，而於該構件中導致放電。此種放電導致紫外光之生成， φ 進一步導致螢光層26之光發射。 圖2係爲具有薄餅型構件之電漿顯示器自背板側面觀 看之前板1透視圖。圖3係爲具有薄餅型構件之電漿顯示 器之剖面圖。如圖2所示，具有薄餅型結構之電漿顯示器 具有大量位於介電層1 2上之間隔器層1 6，使其排列成等 間隔線之形式。如圖3所示，前面板1中之間隔器層16 係與肋條24接觸’因而於各個被肋條24包圍之構件的頂 部中的間隙X，而稀有氣體可經由間隙X導入各構件內。 使用網版印刷之製造方法係爲製造前板之已知方法。 -6- 200535564 (3) 使用網版印刷之製造方法包括於玻璃基板1 0上形成玻璃 糊膜，於400至70(TC烘烤以形成介電層12，之後藉網版 印刷將玻璃糊組成物依圖案層積於該介電層1 2上，之後 於4 00至7 00 °C二次烘烤，以形成間隔器層16。 然而，使用網版印刷之製造方法需要兩個烘烤步驟， 因而增加製造成本。該方法亦具有圖案位置之準確度較差 的問題。 φ 前述先前技術係描述於例如專利文件1 (日本專利 公開申請案編號2002- 1 50949 )及專利文件2 (日本專利 公開申請案編號2002-3 2 8467 )中。 至於*解決網版印刷方法中之問題的方法，已提供使用 微影術製造電漿顯示前板的新穎方法。採用微影術之製造 方法係參照圖4A至4 C加以描述。首先，於玻璃基板1〇 上形成由非光敏性玻璃糊膜所構成之未烘烤介電層1 2 A及 由光敏性玻璃糊膜所構成之光敏性未曝光未烘烤間隔器材 φ 料層1 6 A。間隔器材料層1 6 A係經由光罩3使用紫外線等 來照射（圖4 A )。該層隨後顯影而出現抗蝕劑圖案1 6 A， (圖4B )。形成之產物於400至70(TC烘烤以同時形成介 電層12及間隔器層16 (圖4C )。 使用微影術之製造方法的優點爲介電層1 2及間隔器 1 6可僅藉著進行單一烘烤步驟而同時烘烤。因此，製造成 本可較使用網版印刷之製造方法降低。 前述製造方法中，使用含有玻璃料、光聚合起始劑、 光可聚合單體及黏合劑樹脂之光敏性玻璃糊組成物來作爲 -7- 200535564 (4) 用以形成間隔器材料層1 6a之材料。至於此種光敏性玻璃 糊組成物中所使用之光聚合起始劑，使用所謂之Norish 類型I光聚合起始劑，其於α碳位置裂解生成自由基。 該No rish類型I光聚合起始劑之特徵爲高固化速度及 優越之內部固化性質。使用內部固化性質優越之Norish 類型I光聚合起始劑，該光敏性玻璃糊膜之固化充分進行 至其底部，產生具有剖面略爲梯形之形狀的高安定性圖案 •。 然而，近年來，對較精細圖案之需求愈益增加，故產 生習用光敏性玻璃糊組成物無法充分應付電漿顯示器所需 之精細圖案化的問題。 例如，當光敏性玻璃糊膜曝光以形成圖4 A中之圖案 時，曝照光相對於光敏性玻璃糊膜之表面以直角進入。然 而，曝照光被光敏性玻璃糊膜中所含之玻璃料所反射而導 致暈影，使得曝照光到達較寬之區域。是故，形成之圖案 # 16A’之剖面成爲圖5所示之梯形。因此，當電漿顯示器所 需之較精細圖案化導致圖案之間隔變窄時，產生該種梯形 之影響變得愈來愈明顯地破壞圖案準確度的問題。 尤其是前述使用微影術之製造方法，由非光敏性玻璃 糊膜構成之未烘烤介電層1 2 A係配置在光敏性玻璃糊膜 16A下方作爲底層且曝光。是故，其中暈影之影響不僅因 爲光敏性玻璃糊膜中所含之玻璃料所反射之光而變得明顯 ，亦因爲作爲底層之未烘烤介電層1 2 A中所含之玻璃料所 反射的光而變得明顯。是故，使圖案底部寬度Wbtm較頂 200535564 (5) 部寬度Wt()p增寬之傾向變得更明顯。 經圖案化之間隔器材料層16A’及未烘烤介電層12A 因爲後續烘烤處理而稍微收縮。當介於圖案與未烘烤介電 層1 2 A之間的接觸區（即，經圖案化間隔器材料層1 6 A ’ 之底部區域）大時，作爲底層之介電層1 2因爲個別經圖 案化間隔器材料1 6 A ’收縮而被拉扯，如同圖6 A所示，使 得經圖案化區中之介電層12提高，而致介電層12之厚度 φ 不均。亦存在經圖案化間隔器材料層1 6 A ’之收縮導致在 介於圖案間之介電層1 2施加相反張力的問題，如圖6B所 示，使得位於圖案線之間的介電層1 2破裂。 雖然Norish類型I光聚合起始劑之內部固化性質優越 ，但其固化可能被氧所抑制，其可能阻礙在直接與氧接觸 之表面區域上的固化反應。是故，通常在使用透明膜180 諸如聚對苯二甲酸乙二酯覆蓋光敏性玻璃糊表面之情況下 進行曝光，以隔絕氧，如圖5所示。然而，即使該表面覆 φ 蓋聚對苯二甲酸乙二酯膜，但該膜仍薄，使得氧稍微穿透 該膜。是故，該圖案之表面部分可能在曝光之後仍保持未 固化狀態，因此被顯影溶液洗除，而破壞圖案表面之平坦 性。存在之問題爲當圖案於該種狀態下烘烤時，玻璃料成 份藉烘烤處理來熔融，以使表面稍爲平坦，但該表面仍保 持不均勻，使得圖案之厚度不均勻。 本發明係針對先前技術之問題來完成，有關一種圖案 準確度改善至足可適用於電漿顯示器所需之精細圖案化的 程度之光敏性無機糊料組成物、一種使用該組成物而用以 -9- 200535564 (6) 製造電漿顯示前板之薄板型未烘烤坯體及一種製造電漿顯 示前板之方法。 【發明內容】 進行徹底硏究以解決前述問題的結果，本發明者發現 在至少包含光聚合起始劑、光可聚合單體及無機粉末之光 敏性無機糊料組成物中，同時採用Norish類型I光聚合起 φ 始劑及拉氫型光聚合起始劑作爲光聚合起始劑，可得到可 完全適用於電漿顯示器所需之精細圖案化的優越圖案形狀 。基於此項發現，完成了本發明。 根據本發明光敏性無機糊料組成物之較佳實施例，所 使用之Norish類型I光聚合起始劑較佳係至少一種選自下 列者之化合物：安息香醚化合物、苄基縮酮化合物、^ _ 羥基乙醯苯化合物' α -胺基乙醯苯化合物、雙醯基膦氧 化物化合物、醯基膦氧化物化合物、苯基二羰基化合物及 φ 苯基醯基肟化合物。所使用之拉氫型聚合起始劑較佳係爲 至少一種選自下列者之化合物：芳族酮化合物、噻噸酮化 合物、蒽醌化合物及胺化合物。該光敏性無機糊料組成物 所含之每100重量份數光聚合起始劑總量含有Norish類 型Ϊ光聚合起始劑的較佳比例係爲1 0至9 9重量份數，而 含有拉氫光聚合起始劑之比例係爲1至90重量份數。 本發明用以製造電發顯示前板之薄板型未烘烤还體係 爲一未烘烤坯體，其中由本發明光敏性無機糊料組成物所 構成之間隔器材料層係形成於可移除之承載膜上。本發明 -10- 200535564 (7) 中， '、用以製造電漿顯示前板之薄板型未烘烤坯體〃係表 示在該可移除承載膜上形成有料層之薄板型材料，該等料 層係自該可移除承載膜脫離並轉移至玻璃基板上，而產生 電漿顯示前板。 本發明製造電漿前板之方法中，本發明光敏性無機糊 料組成物係用以形成間隔器材料層。該曝光處理及後續處 理可依習用方式進行。根據本發明製造電漿顯示前板方法 φ 之較佳實施例，該間隔器材料層中所含之無機粉末之軟化 點較佳係較未烘烤介電層中所含之無機粉末的軟化點高， 以較該未烘烤介電層中所含之無機粉末的軟化點高5 °C或 更多爲佳。 使用本發明光敏性無機糊料組成物所形成之光敏性無 機糊膜提供在曝光之後具有優越固化狀態之表面的谓案。 是故，可產生與先前技術不同之效果，可防止位於圖案表 面上之未固化光敏性無機糊料材料被顯影溶液所洗除，因 # 此防止經圖案化薄膜之厚度縮減，而產生具有均一厚度之 圖案。 藉著結合使用Norish類型I光聚合起始劑與拉氫型光 聚合起始劑’該圖案在曝光後之剖面可控制在接近矩形（ 如圖7A所示）或爲梯形，其中圖案之底部寬度Wbtm稍短 於頂部寬度Wt()p (如圖7B所示）。存在底部寬度Wbtm增 寬之問題’尤其是利用微影術製造電漿顯示前板之方法（ 其中間隔器層之形成易在曝光時受到底層所反射之光的影 響）’但此問題可由本發明解決。與該未烘烤介電層之接 -11 - 200535564 (8) 觸區可因而縮小，使得在圖案收縮時，防止介電層破裂或 變形，因而防止不均勻之厚度。 根據本發明用以製造電漿顯示前板之薄板型未烘烤坯 體，可於可移除承載膜上至少預先形成由本發明光敏性無 機糊料組成物所構成之間隔器材料層，此未烘烤还體在製 造時層積於基板上，以於該玻璃基板上形成表面光滑度優 越而具均勻厚度之間隔器層。 φ 本發明光敏性絕緣糊料組成物可作爲用以形成多層電 路及各種顯示器諸如電漿顯示器、電漿位址液晶顯示器、 場域發射型顯示器等之材料，且可有利地用於製造特別需 要高準確度之電漿顯示前板中之間隔器材料層。 根據本發明製造電漿顯示前板之方法，兩層（即由非 光敏性無機糊料組成物構成之未烘烤介電層及由本發明光 敏性無機糊料組成物構成之間隔器材料層）係形成於玻璃 基板上，之後，依習用方式進行曝光處理及後續處理，以 φ可改善圖案準確度，且可防止介電層在烘烤時變形及裂開 〇 本發明製造電漿顯示前板之方法中，該間隔器材料層 中所含之無機粉末的軟化點可設定高於未烘烤介電層中所 含之無機粉末的軟化點，以防止圖案之側壁在烘烤時塌陷 〇 本發明光敏性無機糊料組成物係爲至少含有無機粉末 、光聚合起始劑及光可聚合單體之組成物，其中使用 Norish類型I光聚合起始劑及拉氫型光聚合起始劑之組合 -12- 200535564 (9) 物作爲光聚合起始劑。 電漿顯示前板之習用製法中，Norish類型I光聚合起 始劑已單獨用爲光聚合起始劑，因此圖案表面上之固化性 質尙不足，而表面上未固化光敏性無機糊料材料被顯影溶 液洗除，因而產生經圖案化薄膜之厚度縮減的問題。然而 ，藉著使用Norish類型I光聚合起始劑及拉氫型光聚合起 始劑之組合物，圖案表面上之固化性質可改善，因而防止 φ 經圖案化薄膜之厚度縮減，而使經圖案化薄膜之厚度均勻 〇 使用與拉氫型光聚合起始劑結合之Norish類型I光聚 合起始劑，圖案之剖面可製成接近矩形或梯形，其中圖案 底部寬度 Wbtm稍小於頂部寬度WtC)p。是故，可防止介電 層破裂或變形，因而得到均勻之厚度。微影術之領域中， 較頂部寬度Wt()p小之底部寬度Wbtm通常被視爲不佳，因 爲圖案之安定性降低，但在光敏性無機糊膜中，無機粉末 φ 係藉烘烤處理熔融，使得底部寬度Wbtm大於烘烤前。是 故，若爲底部寬度Wbtm稍小於頂部寬度wt()p時，則底部 寬度wbtm於烘烤時變寬，使底部寬度wbtm增加至接近頂 部寬度W t。p，故在烘烤後，則無圖案安定性之問題。 本發明例示實施例係依下列順序詳細說明於下文。 (A )光敏性無機糊料組成物 (B )用以製造電漿顯示前板之薄板型未烘烤坯體 (C)製造電漿顯示前板之方法 -13- 200535564 (10) (A )光敏性無機糊料組成物 本發明光敏性無機糊料組成物係爲至少包含無機粉末 、光聚合起始劑及光可聚合單體之組成物，其中含有 Norish類型I光聚合起始劑及拉氫型光聚合起始劑作爲光 聚合起始劑。 本發明光敏性無機糊料組成物具有使用紫外線、激勵 雷射、X射線及電子射線（以下稱爲光線）進行曝光處理 φ 所需之透明性，其係爲可藉微影方式形成高準確圖案且可 有利地用以製造電漿顯示器的組成物。 (B )光聚合起始劑 本發明中’ Norish類型I光聚合起始劑及拉氫型光聚 合起始劑係一起用爲光聚合起始劑。 該Norish類型I光聚合起始劑係爲可在α碳位置裂解 以形成自由基之光聚合起始劑，如以下流程圖（1 )所示 # 。一方面’拉氫型光聚合起始劑係爲拉取氫予體（RH)之 氫以形成自由基之光聚合起始劑，如以下流程圖（2 )所 示0 〇 X—C —γ200535564 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a photosensitive inorganic paste composition, which uses lithography to produce a superior pattern shape, and related ~ used by using the composition The thin-plate-type unbaked body is made of a plasma display panel, and a method for manufacturing a plasma display front panel. φ [Previous technology] Plasma displays that use the electron emission phenomenon to emit images from many fine components themselves have superior characteristics, that is, they are large, thin, light, and flat displays that cannot be obtained by conventional displays, and their widths are limited. It is desired that the conventional plasma display mainly includes a linear structure member having a rib located in a vertical direction of the display. However, in recent years, a φ-shaped structural member having ribs not only in the vertical direction but also in the horizontal direction has been developed in an attempt to effectively guide the light self-emission part to the front of the plasma display. The pancake-shaped structure of this member can guide light to the front very effectively by preventing light from leaking from the adjacent member. A perspective view of an exploded essential part of a plasma display having a wafer-type member is shown in FIG. The plasma display has a front plate 1 on which bonding electrodes 1 1 each formed of a transparent electrode 1 10 and a bus electrode 1 12 are formed parallel to each other; and a back plate 2 on which a parallel plate is formed and Address electrode 2 1 intersected with the bonding electrode] 1. The front plate 1 and the back plate 2 are arranged to face each other and are integrated to constitute a display element. The front plate 1 has a transparent glass substrate 10 as a display 200535564 (2). The bonding electrode 11 is disposed inside the glass substrate 10, that is, on the side facing the back plate 2. A dielectric layer 12 is formed to cover the bonding electrode 11. The dielectric layer 12 has a patterned spacer layer 16. A protective film 19 made of MgO is formed on the spacer layer 16 and the dielectric layer 12. on. On the other hand, the combination board 2 has a substrate 20 'having address electrodes 21 arranged on the side of the substrate 20 facing the front plate 1. A dielectric layer 22 is formed to cover the address electrode 21, and a light emitting portion φ is formed on the dielectric layer 22 as described below. The light-emitting portion is composed of a plurality of members, and each member is located in a space where the bonding electrode 11 and the address electrode 21 intersect. Each member is delimited by a rib 24 formed on the dielectric layer 22 in the vertical and horizontal directions of the display. A fluorescent layer 26 is provided to cover the side walls of the ribs and the surface 'of the dielectric layer 22 of the ribs, i.e., the inner wall and the bottom of each member. In a plasma display, a predetermined voltage from an AC power source is applied to a bonding electrode on the front plate to form an electric field, and a discharge is caused in the component. This discharge causes the generation of ultraviolet light, and φ further causes the light emission of the fluorescent layer 26. Fig. 2 is a perspective view of the front panel 1 viewed from the side of the back panel of the plasma display having a wafer-shaped member. Fig. 3 is a sectional view of a plasma display having a wafer-type member. As shown in Fig. 2, a plasma display having a wafer-type structure has a large number of spacer layers 16 on the dielectric layer 12 so that they are arranged in the form of equally spaced lines. As shown in FIG. 3, the spacer layer 16 in the front panel 1 is in contact with the ribs 24 'and thus in the gap X in the top of each member surrounded by the ribs 24, and the rare gas can be introduced into each member through the gap X. A manufacturing method using screen printing is a known method for manufacturing a front plate. -6- 200535564 (3) The manufacturing method using screen printing includes forming a glass paste film on glass substrate 10, baking at 400 to 70 ° C to form dielectric layer 12, and then using screen printing to form the glass paste. The layers are laminated on the dielectric layer 12 according to a pattern, and then baked twice at 400 to 700 ° C to form the spacer layer 16. However, the manufacturing method using screen printing requires two baking steps. Therefore, the manufacturing cost is increased. This method also has a problem that the accuracy of the pattern position is poor. Φ The foregoing prior art is described in, for example, Patent Document 1 (Japanese Patent Laid-Open Application No. 2002- 1 50949) and Patent Document 2 (Japanese Patent Publication Application No. 2002-3 2 8467). As a method to solve the problems in the screen printing method, a novel method for manufacturing a plasma display front plate using lithography has been provided. The manufacturing method using lithography is with reference to the drawings 4A to 4 C. First, an unbaked dielectric layer 1 2 A composed of a non-photosensitive glass paste film and a photosensitive non-exposed non-exposed photosensitized glass paste film are formed on a glass substrate 10. Baking interval equipment φ Layer 16 A. The spacer material layer 16 A is irradiated with ultraviolet rays or the like through the photomask 3 (Fig. 4A). This layer is subsequently developed to give a resist pattern 16A, (Fig. 4B). The product formed Bake at 400 to 70 ° C to simultaneously form the dielectric layer 12 and the spacer layer 16 (FIG. 4C). The advantage of using the lithography method is that the dielectric layer 12 and the spacer 16 can be performed only by Single baking step and simultaneous baking. Therefore, the manufacturing cost can be reduced compared to the manufacturing method using screen printing. In the foregoing manufacturing method, a resin containing a glass frit, a photopolymerization initiator, a photopolymerizable monomer, and a binder resin is used. The photosensitive glass paste composition is used as a material of 7-200535564 (4) for forming the spacer material layer 16a. As the photopolymerization initiator used in this photosensitive glass paste composition, a so-called Norish is used Type I photopolymerization initiator, which is cleaved at the α-carbon position to generate free radicals. The Norish type I photopolymerization initiator is characterized by high curing speed and excellent internal curing properties. Norish type I with excellent internal curing properties is used. Photopolymerization initiator The curing of the glass paste film is sufficiently advanced to the bottom thereof, resulting in a high-stability pattern having a shape that is slightly trapezoidal in cross section. However, in recent years, the demand for finer patterns has been increasing, so the conventional photosensitive glass paste composition cannot be produced. Fully cope with the fine patterning problems required for plasma displays. For example, when the photosensitive glass paste film is exposed to form the pattern in FIG. 4A, the exposure light enters at a right angle to the surface of the photosensitive glass paste film. However, The exposure light is reflected by the glass frit contained in the photosensitive glass paste film, resulting in halo, so that the exposure light reaches a wider area. Therefore, the cross-section of the formed pattern # 16A 'becomes trapezoidal as shown in FIG. Therefore, when the finer patterning required by the plasma display causes the interval between the patterns to become narrower, the problem that the effect of this trapezoid becomes more and more apparently destroys the accuracy of the pattern. In particular, in the above-mentioned manufacturing method using lithography, the unbaked dielectric layer 1 2 A composed of a non-photosensitive glass paste film is disposed under the photosensitive glass paste film 16A as a bottom layer and exposed. Therefore, the effect of vignetting becomes obvious not only by the light reflected by the glass frit contained in the photosensitive glass paste film, but also by the glass frit contained in the unbaked dielectric layer 1 2 A as the bottom layer. The reflected light becomes apparent. Therefore, the tendency to make the width Wbtm at the bottom of the pattern wider than the width Wt () p of the top 200535564 (5) portion becomes more apparent. The patterned spacer material layer 16A 'and the unbaked dielectric layer 12A shrink slightly due to the subsequent baking process. When the contact area between the pattern and the unbaked dielectric layer 1 2 A (ie, the bottom area of the patterned spacer material layer 16 A ') is large, the dielectric layer 12 as the bottom layer is individually The patterned spacer material 16A 'shrinks and is pulled, as shown in FIG. 6A, so that the dielectric layer 12 in the patterned region is raised, and the thickness φ of the dielectric layer 12 is uneven. There is also a problem that the contraction of the patterned spacer material layer 16 A ′ causes the opposite tension to be applied to the dielectric layer 12 between the patterns, as shown in FIG. 6B, so that the dielectric layer 1 located between the pattern lines 2 cracked. Although Norish Type I photopolymerization initiators have excellent internal curing properties, their curing may be inhibited by oxygen, which may hinder the curing reaction on the surface area that is in direct contact with oxygen. For this reason, exposure is usually performed with a transparent film 180 such as polyethylene terephthalate covering the surface of the photosensitive glass paste to isolate oxygen, as shown in FIG. 5. However, even if the surface is covered with a φ-covered polyethylene terephthalate film, the film is still thin, so that oxygen penetrates the film slightly. Because of this, the surface portion of the pattern may remain uncured after exposure, so it is washed away by the developing solution, thereby destroying the flatness of the pattern surface. The problem is that when the pattern is baked in this state, the glass frit component is melted by the baking process to make the surface slightly flat, but the surface remains uneven, making the thickness of the pattern uneven. The present invention has been made in view of the problems of the prior art, and relates to a photosensitive inorganic paste composition having improved pattern accuracy to a level sufficient for fine patterning required for a plasma display, and a composition using the composition for -9- 200535564 (6) A thin plate type unbaked blank for manufacturing a plasma display front plate and a method for manufacturing a plasma display front plate. [Summary of the Invention] As a result of thorough research to solve the foregoing problems, the inventors have found that in a photosensitive inorganic paste composition containing at least a photopolymerization initiator, a photopolymerizable monomer, and an inorganic powder, a Norish type is also used at the same time I Photopolymerization initiator φ initiator and hydrogenated photopolymerization initiator can be used as photopolymerization initiators to obtain superior pattern shapes that can be completely applied to the fine patterning required for plasma displays. Based on this finding, the present invention has been completed. According to a preferred embodiment of the photosensitive inorganic paste composition of the present invention, the Norish type I photopolymerization initiator used is preferably at least one compound selected from the group consisting of a benzoin ether compound, a benzyl ketal compound, _Hydroxyacetophenone compound 'α-Aminoacetophenone compound, bisfluorenylphosphine oxide compound, fluorenylphosphine oxide compound, phenyldicarbonyl compound, and φphenylphosphonium oxime compound. The hydrogenated polymerization initiator used is preferably at least one compound selected from the group consisting of an aromatic ketone compound, a thioxanthone compound, an anthraquinone compound, and an amine compound. The photosensitive inorganic paste composition contains a Norish-type photopolymerization initiator per 100 parts by weight of the total photopolymerization initiator. The preferred ratio is 10 to 99 parts by weight, and The proportion of the hydrogen photopolymerization initiator is 1 to 90 parts by weight. The thin-plate type unbaked system for manufacturing an electric display front plate of the present invention is an unbaked green body, in which a spacer material layer composed of the photosensitive inorganic paste composition of the present invention is formed in a removable Carrier film. In the present invention -10- 200535564 (7), ', a thin-plate type unbaked green body used for manufacturing a plasma display front panel is a thin-plate type material having a layer formed on the removable carrier film, etc. The material layer is detached from the removable carrier film and transferred to the glass substrate, thereby generating a plasma display front plate. In the method for manufacturing a plasma front plate of the present invention, the photosensitive inorganic paste composition of the present invention is used to form a spacer material layer. This exposure processing and subsequent processing can be performed in a customary manner. According to a preferred embodiment of the method φ for manufacturing a plasma display front plate according to the present invention, the softening point of the inorganic powder contained in the spacer material layer is preferably softer than that of the inorganic powder contained in the unbaked dielectric layer. High, preferably 5 ° C or more higher than the softening point of the inorganic powder contained in the unbaked dielectric layer. The photosensitive inorganic paste film formed using the photosensitive inorganic paste composition of the present invention provides the premise that the surface has a superior curing state after exposure. Therefore, it can produce a different effect from the prior art, and can prevent the uncured photosensitive inorganic paste material located on the pattern surface from being washed away by the developing solution, so # prevents the thickness of the patterned film from being reduced, resulting in uniformity. Thickness pattern. By combining Norish type I photopolymerization initiator and hydrogenated photopolymerization initiator, the cross-section of the pattern after exposure can be controlled to be close to a rectangle (as shown in FIG. 7A) or trapezoidal, where the width of the bottom of the pattern is Wbtm is slightly shorter than the top width Wt () p (as shown in Figure 7B). There is a problem of widening the bottom width Wbtm 'especially a method for manufacturing a plasma display front plate by lithography (where the formation of a spacer layer is easily affected by light reflected from the bottom layer during exposure)' but this problem can be solved by the present invention solve. Contact with the unbaked dielectric layer -11-200535564 (8) The contact area can thus be reduced, so that when the pattern shrinks, the dielectric layer is prevented from cracking or deforming, thus preventing uneven thickness. According to the present invention, a thin-plate type unbaked blank used for manufacturing a plasma display front plate can be formed at least in advance on a removable carrier film with a spacer material layer composed of the photosensitive inorganic paste composition of the present invention. The baking body is laminated on the substrate during manufacturing so as to form a spacer layer with excellent surface smoothness and uniform thickness on the glass substrate. φ The photosensitive insulating paste composition of the present invention can be used as a material for forming a multilayer circuit and various displays such as a plasma display, a plasma-address liquid crystal display, a field emission display, and the like, and can be advantageously used for manufacturing a special need High-accuracy plasma display of the spacer material layer in the front panel. According to the method for manufacturing a plasma display front panel according to the present invention, two layers (that is, an unbaked dielectric layer composed of a non-photosensitive inorganic paste composition and a spacer material layer composed of the photosensitive inorganic paste composition) It is formed on a glass substrate. After that, exposure processing and subsequent processing are performed according to the conventional method. Using φ can improve the accuracy of the pattern, and can prevent the dielectric layer from deforming and cracking during baking. In the method, the softening point of the inorganic powder contained in the spacer material layer can be set higher than the softening point of the inorganic powder contained in the unbaked dielectric layer to prevent the sidewall of the pattern from collapsing during baking. The photosensitive inorganic paste composition of the present invention is a composition containing at least an inorganic powder, a photopolymerization initiator, and a photopolymerizable monomer. Among them, a Norish type I photopolymerization initiator and a hydrogenated photopolymerization initiator are used. Combination-12-200535564 (9) as a photopolymerization initiator. In the conventional manufacturing method of the plasma display front plate, the Norish type I photopolymerization initiator has been used alone as a photopolymerization initiator, so the curing properties on the pattern surface are insufficient, and the uncured photosensitive inorganic paste material on the surface is The developing solution is washed away, thereby causing a problem that the thickness of the patterned film is reduced. However, by using a composition of a Norish type I photopolymerization initiator and a hydrogenated type photopolymerization initiator, the curing properties on the pattern surface can be improved, thereby preventing the φ pattern thickness of the patterned film from shrinking and making the pattern The thickness of the thin film is uniform. Using a Norish type I photopolymerization initiator combined with a hydrogenated photopolymerization initiator, the cross section of the pattern can be made close to a rectangle or a trapezoid, where the bottom width Wbtm of the pattern is slightly smaller than the top width WtC) p . Therefore, it is possible to prevent the dielectric layer from being cracked or deformed, thereby obtaining a uniform thickness. In the field of lithography, the bottom width Wbtm, which is smaller than the top width Wt () p, is generally regarded as poor, because the stability of the pattern is reduced, but in the photosensitive inorganic paste film, the inorganic powder φ is processed by baking Melt so that the bottom width Wbtm is larger than before baking. Therefore, if the bottom width Wbtm is slightly smaller than the top width wt () p, the bottom width wbtm becomes wider during baking, so that the bottom width wbtm increases to near the top width Wt. p, so there is no problem of pattern stability after baking. The exemplary embodiments of the present invention are described in detail in the following order. (A) Photosensitive inorganic paste composition (B) Thin-plate type unbaked blank for manufacturing plasma display front plate (C) Method for manufacturing plasma display front plate-13- 200535564 (10) (A) Photosensitive inorganic paste composition The photosensitive inorganic paste composition of the present invention is a composition including at least an inorganic powder, a photopolymerization initiator, and a photopolymerizable monomer, and contains a Norish type I photopolymerization initiator and a drawing A hydrogen-type photopolymerization initiator is used as the photopolymerization initiator. The photosensitive inorganic paste composition of the present invention has the transparency required for exposure processing φ using ultraviolet rays, excited lasers, X-rays, and electron rays (hereinafter referred to as light rays), and is capable of forming highly accurate patterns by lithography. And it can be advantageously used to make a composition of a plasma display. (B) Photopolymerization initiator In the present invention, a 'Norish type I photopolymerization initiator and a hydrogenated type photopolymerization initiator are used together as a photopolymerization initiator. The Norish Type I photopolymerization initiator is a photopolymerization initiator that can be cleaved at the alpha carbon position to form a radical, as shown in the following flow chart (1) #. On the one hand, the hydrogenated photopolymerization initiator is a photopolymerization initiator that pulls hydrogen from a hydrogen donor (RH) to form a free radical, as shown in the following flow chart (2). 0 〇 X-C —γ

〇 II , X——C—Y + RH 0 (1) • (2)〇 II, X——C—Y + RH 0 (1) • (2)

II X—C· + ·ΥII X—C · + · Υ

OHOH

II

X—C —Y + · R 其中X係爲經取代或未經取代之芳族基團，其係爲包含至 -14- 200535564 (11) 少一個選自C、Η、〇、^^及s者之有機基團。 有些自由基光聚合起始劑在α碳之位置裂解以形成 Norish類型I之自由基（· γ)，之後拉取氫予體（rH) 之氫以形成拉氫型自由基（.r)。然而，在本發明中， 該等自由基光聚合起始劑係定義爲屬於Norish類型I光聚 合起始劑’只要其於α碳之位置裂解以形成自由基。因此 ’在本發明中’同時形成Norish類型I及拉氫型兩種自由 φ 基之光聚合起始劑係歸類爲Norish類型I光聚合起始劑。 (I) Norish類型丨光聚合起始劑 本發明所使用之Norish類型I光聚合起始劑較佳係爲 以下通式（1-1 )至（1-3 )所示之化合物：X—C —Y + · R Where X is a substituted or unsubstituted aromatic group, it is a group containing up to -14-200535564 (11) at least one selected from C, Η, 〇, ^^ and s Of the organic group. Some free radical photopolymerization initiators are cleaved at the alpha carbon site to form Norish type I radicals (· γ), and then pull hydrogen from the hydrogen precursor (rH) to form hydrogenated radicals (.r). However, in the present invention, the radical photopolymerization initiators are defined as belonging to the Norish type I photopolymerization initiator 'as long as it is cleaved at the position of α carbon to form a radical. Therefore, in the present invention, a photopolymerization initiator which simultaneously forms two free φ groups of Norish type I and hydrogen pulling type is classified as Norish type I photopolymerization initiator. (I) Norish type 丨 Photopolymerization initiator The Norish type I photopolymerization initiator used in the present invention is preferably a compound represented by the following general formulae (1-1) to (1-3):

其中Rio至Ri3各表示包含至少一個選自c、H、0、N S者之有機基團，當存有多個R1G時，其可彼此相同或 異’而Rn至R!3中之兩者可彼此鍵結以形成環狀結構 且nl係爲0至5之整數。 (R2〇)n2Among them, Rio to Ri3 each represent an organic group including at least one selected from c, H, 0, and NS. When there are multiple R1Gs, they may be the same or different from each other, and both of Rn to R! 3 may be They are bonded to each other to form a ring structure and nl is an integer of 0 to 5. (R2〇) n2

• · · (1-2) 其中r2G至r22各表示包含至少一個選自C、h、〇、N及 S者之有機基團，且當存有多個r20時，其可彼此相同或 -15- 200535564 (12) 相異，且n2係爲0至5之整數。 _ Ο X—R32 (R30)n3^^—一R31 · · · (I_3) 其中X係爲Ο或N，R3〇及R3]各表示包含至少一個選 C、H、0、N及S者之有機基團，且當存有多個r3Q時 其可彼此相同或相異，R32係表示包含至少一個選自C， 、0、N及S者之有機基團，且π3係爲0至5之整數。 該No rish類型I光聚合起始劑較佳可爲至少一種選 安息香醚化合物、苄基縮酮化合物、α -羥基乙醯苯化 物、α -胺基乙醯苯化合物、雙醯基膦氧化物化合物、 基膦氧化物化合物、苯基二羰基化合物及苯基醯基肟化 物，其中以苄基縮酮化合物、雙醯基膦氧化物化合物及 基膦氧化物較佳，而苄基縮酮化合物更佳。 下文中，說明通式（Ι·1)至（1_3)所示之Norish 型I光聚合起始劑之實例，但本發明所使用之Norish類 Ϊ光聚合起始劑不限於此。當然，此等化合物之類似物 可於本發明中作爲N 〇 r i s h類型I光聚合起始劑。 (1 )安息香醚化合物 0 oc4h9 白 Η 白 合 醯 合 醯 類 型 亦 II . -16- 200535564 (13) 安息香甲基醚 安息香乙基醚 安息香異丙基醚 (2 )苄基縮酮化合物(1-2) where r2G to r22 each represent at least one organic group selected from C, h, 〇, N, and S, and when there are multiple r20, they may be the same as each other or -15 -200535564 (12) are different and n2 is an integer from 0 to 5. _ 〇 X—R32 (R30) n3 ^^ —— R31 · · · (I_3) where X is 0 or N, R3〇 and R3] each means that it contains at least one of C, H, 0, N, and S. An organic group, and may be the same or different from each other when multiple r3Qs are present, R32 means that it contains at least one organic group selected from C, 0, N, and S, and π3 is 0 to 5 Integer. The No rish type I photopolymerization initiator may preferably be at least one selected benzoin ether compound, benzyl ketal compound, α-hydroxyacetophenone compound, α-aminoacetophenone compound, and bisfluorenylphosphine oxide. Compounds, phenylphosphine oxide compounds, phenyldicarbonyl compounds, and phenylphosphonium oxime compounds. Among them, benzyl ketal compounds, bisfluorenyl phosphine oxide compounds, and phenylphosphonium oxides are preferred, and benzyl ketal compounds Better. Hereinafter, examples of the Norish-type I photopolymerization initiator represented by the general formulae (1.1) to (1-3) are described, but the Norish-type fluorene photopolymerization initiator used in the present invention is not limited thereto. Of course, analogues of these compounds can be used in the present invention as Norish type I photopolymerization initiators. (1) Benzoyl ether compound 0 oc4h9 white Η white 合 醯 醯 型 type II also. -16- 200535564 (13) benzoin methyl ether benzoin ethyl ether benzoin isopropyl ether (2) benzyl ketal compound

(3 ) α -羥基乙醯苯化合物 C——C——C Η(3) α-Hydroxyacetophenone compound C——C——C Η

0 ch3 —C—C-OH — CH30 ch3 —C—C-OH — CH3

Cl2H25Cl2H25

o ch3II I C—C-OH I ch3 - 17- 200535564 (14) HO —C 一 HsC—h^C — Ο Η2 Ο Ο ?Η3 ιι I 0—C — OH I ch3 1-(4-異丙基苯基）-2-羥基-2-甲基丙烷-1-酮 1-(4-十二碳基苯基）-2-羥基-2-甲基丙烷-1-酮 (4 ) α ·胺基乙醯苯化合物o ch3II IC—C-OH I ch3-17- 200535564 (14) HO —C -HsC—h ^ C — Ο Η2 Ο Ο? Η3 ιι I 0—C — OH I ch3 1- (4-isopropylbenzene ) -2-hydroxy-2-methylpropane-1-one 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1-one (4) α · aminoethyl Toluene compounds

ch3sch3s

ch3ch3

(5 )雙醯基膦氧化物化合物(5) bisfluorenyl phosphine oxide compound

(6 )醯基膦氧化物化合物 -18- 200535564(6) fluorenylphosphine oxide compound -18- 200535564

〇 II —C—OCH3〇 II —C—OCH3

)苯基醯基肟化合物 〇) Phenylhydrazine compound

II Ο—C —OC2H5 Ο N /=\ II II ^\-c-c-ch3 (Π)拉氫型光聚合起始劑 本發明所使用之拉氫型光聚合起始劑較佳係爲以下通 式（II-1 )或（II-2 )所示之化合物：II Ο—C —OC2H5 Ο N / = \ II II ^ \-cc-ch3 (Π) hydrogenated photopolymerization initiator The hydrogenated photopolymerization initiator used in the present invention is preferably the following general formula Compound represented by (II-1) or (II-2):

(R4l)n41 • · · (II-1) 其中R4g及R41各表示包含至少一個選自C、H、0、N及 -19- 200535564 (16) S者之有機基團，當存有多個R4ο及Ru時，其可彼此相 同或相異，R4G及R41中之兩者可彼此鍵結以形成環狀結 構，且n4 0及n41各爲〇至5之整數。 • · · (II-2) R5〇sm /~\ ϊ r5/N<J-C-R52 _ 其中R5G及R51各表示烴基，且r52係爲包含至少一個選 自C、H、0、N及S者之有機基團。 該拉氫型光聚合起始劑可較佳地爲至少一種選自芳族 酮化合物、噻噸酮化合物、蒽醌化合物及胺化合物（具有 二烷基胺基之芳族化合物、烷基烷醇胺等）之化合物，更 佳爲噻噸酮化合物及具有二烷基胺基之芳族化合物，再更 佳爲噻噸酮化合物。 下文說明通式（II-1)或（II-2)所示之拉氫型光聚 φ 合起始劑的實例’但本發明所使用之拉氫型光聚合起始劑 不限於此。當然’此等化合物之類似物亦可作爲本發明拉 氫型光聚合起始劑。 (1 )芳族酮化合物 -20- 200535564 7(R4l) n41 • (II-1) where R4g and R41 each represent an organic group containing at least one selected from the group consisting of C, H, 0, N, and -19-200535564 (16) S, when a plurality of In the case of R4ο and Ru, they may be the same or different from each other, and both of R4G and R41 may be bonded to each other to form a ring structure, and n4 0 and n41 are each an integer of 0 to 5. (II-2) R5〇sm / ~ \ ϊ r5 / N < JC-R52 _ where R5G and R51 each represent a hydrocarbon group, and r52 is a group containing at least one member selected from C, H, 0, N and S Of organic groups. The hydrogenated photopolymerization initiator may preferably be at least one selected from the group consisting of an aromatic ketone compound, a thioxanthone compound, an anthraquinone compound, and an amine compound (an aromatic compound having a dialkylamino group, an alkylalkanol Compounds such as amines are more preferably thioxanthone compounds and aromatic compounds having a dialkylamino group, and even more preferably thioxanthone compounds. Examples of the hydrogenated type photopolymerization φ starter represented by the general formula (II-1) or (II-2) are described below, but the hydrogenated type photopolymerization starter used in the present invention is not limited thereto. Of course, the analogues of these compounds can also be used as the hydrogenation-type photopolymerization initiator of the present invention. (1) Aromatic ketone compound -20- 200535564 7

〇 •c—och3 OH〇 • c—och3 OH

噻噸酮 2 -甲基噻噸酮 2 -異丙基噻噸酮 2，4 -二甲基噻噸酮 2 -氯噻噸酮 1-氯-4-丙氧基噻噸酮 -21 - 200535564 (18) (3 )蒽醌化合物Thioxanthone 2-methylthioxanthone 2-isopropylthioxanthone 2,4-dimethylthioxanthone 2-chlorothioxanthone 1-chloro-4-propoxythioxanthone-21-200535564 (18) (3) Anthraquinone compound

(4 )胺化合物 (i )具有二烷基胺基之芳族化合(4) amine compound (i) an aromatic compound having a dialkylamino group

4，4-雙（二甲基胺基）-二苯基甲酮 戊基-4-二甲基胺基苄酸酯 N-丁氧乙基-4-二甲基胺基苄酸酯 苄酸2-(二甲基胺基）乙酯 4-二甲基胺基苄酸 4-二甲基胺基苄酸甲酯 4-二甲基胺基苄酸乙酯 4-二甲基胺基苄酸丁酯 4-二甲基胺基苄酸2-乙基己酯 4-二甲基胺基苄酸2-異戊酯 4-二甲基胺基苄酸戊酯 物 I c2h5 (Michler 氏酮） -22- 200535564 (19) (i i )烷基烷醇胺 單乙醇胺 二乙醇胺 三乙醇胺 N -甲基乙醇胺 N-甲基二乙醇胺 0 2-二乙基乙醇胺 三異丙醇胺 (b)光可聚合單體 光可聚合單體可爲已知之光可聚合單體且不特別限制 ，其實例可包括丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸環 己酯、甲基丙烯酸環己酯、丙烯酸苯氧基乙酯、甲基丙烯 酸苯氧基乙酯、苯氧基聚乙二醇丙烯酸酯、苯氧基聚乙二 # 醇甲基丙烯酸酯、苯乙烯、壬基苯氧基聚乙二醇單丙嫌酸 酯、壬基苯氧基聚乙二醇單甲基丙烯酸酯、壬基苯氧基聚 丙二醇單丙烯酸酯、壬基苯氧基聚丙二醇單甲基丙烯酸酯 、丙烯酸2-羥基-3-苯氧基丙酯、苯二甲酸2-丙嫌醯氧乙 酯、苯二甲酸2 -丙烯醯氧乙基-2·羥基乙酯、苯二甲酸2-甲基丙烯醯氧乙基-2-羥基丙酯、丙烯酸甲酯、丙烯酸乙酯 、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸正丙酯、甲 基丙烯酸正丙酯、丙烯酸2 -羥基乙酯、甲基丙烯酸2 -羥基 乙酯、丙烯酸2-羥基丙酯、甲基丙烯酸2_羥基丙酯、丙烯 -23- 200535564 (20) 酸3-羥基丙酯、甲基丙烯酸3_羥基丙酯、乙二醇單丙烯酸 酯、乙二醇單甲基丙烯酸酯、甘油丙烯酸酯、甘油甲基丙 烯酸酯、二（異戊四醇）單丙烯酸酯、二（異戊四醇）單 甲基丙烯酸酯、丙烯酸二甲基胺基乙酯 '甲基丙烯酸二甲 基胺基乙酯、丙烯酸四氫糠酯、甲基丙烯酸四氫糠酯、經 苯二甲酸修飾之單丙烯酸酯、乙二醇二丙烯酸酯、乙二醇 二甲基丙烯酸酯、三（乙二醇）二丙烯酸酯、三（乙二醇 •)二（甲基丙烯酸）酯、三羥甲基丙烷三丙烯酸酯、三羥 甲基丙烷三（甲基丙烯酸）酯、三羥甲基乙烷三丙烯酸酯 、三羥甲基乙酯三（甲基丙烯酸）酯、異戊四醇二丙烯酸 酯、異戊四醇二（甲基丙烯酸）酯、異戊四醇三丙烯酸酯 、異戊四醇三（甲基丙烯酸）酯、異戊四醇四丙烯酸酯、 異戊四醇四（甲基丙烯酸）酯、二（異戊四醇）四丙烯酸 酯、二（異戊四醇）四（甲基丙烯酸）酯、二（異戊四醇 )五丙烯酸酯、二（異戊四醇）五（甲基丙烯酸）酯、二 # (異戊四醇）六丙烯酸酯、二（異戊四醇）六（甲基丙嫌 酸）酯、甘油丙烯酸酯、甘油甲基丙烯酸酯、卡朵環氧二 丙嫌酸酯（cardoepoxy diacry late )及所說明之化合物中 (甲基）丙烯酸個別被反丁烯二酸酯、衣康酸酯及順丁燃 二酸酯所置換之反丁烯二酸酯、衣康酸酯及順丁；1¾二酸酯 (c )無機粉末 本發明光敏性無機糊料組成物中所含之無機粉$ + f寺 -24- 200535564 (21) 別限制，只要其滿足曝光用之光源所需之透明性，其實例 可包括玻璃、陶瓷（堇青石等）、金屬等。詳言之，玻璃 粉末諸如基於 PbO-Si〇2、Pb0-B203-Si02、Zn0-Si02、 Zn0-B203 -Si02、BiO-Si〇2、Bi0-B203 -Si02 等爲主之硼矽 酸鹽鉛玻璃、硼矽酸鹽鋅玻璃、硼矽酸鹽鉍玻璃，Na、K 、Mg、Ca、Ba、Ti、Zr、Α1等之氧化物，諸如氧化鈷、 氧化物鐵、氧化鉻、氧化鎳、氧化銅、氧化錳、氧化銨、 φ 氧化釩、氧化鈽、提帕克（tipaque )黃、氧化鎘、氧化釕 、二氧化矽、氧化鎂、尖晶石等，螢光粉末諸如ZnO : Zn ’ Ζη3(Ρ04)2 : Μη ’ Y 2 S i Ο 5 : C e ， C a W Ο 4 : P b ，4,4-bis (dimethylamino) -diphenylmethylketopentyl-4-dimethylaminobenzoate N-butoxyethyl-4-dimethylaminobenzate benzate 2- (dimethylamino) ethyl ester 4-dimethylaminobenzyl acid 4-dimethylaminobenzyl methyl ester 4-dimethylaminobenzyl ethyl ester 4-dimethylaminobenzyl Butyl 4-dimethylaminobenzyl 2-ethylhexyl 4-dimethylaminobenzyl 2-isoamyl 4-dimethylaminobenzyl amyl ester I c2h5 (Michler's ketone ) -22- 200535564 (19) (ii) alkylalkanolamine monoethanolamine diethanolamine triethanolamine N-methylethanolamine N-methyldiethanolamine 0 2-diethylethanolamine triisopropanolamine (b) The polymerizable monomer The photopolymerizable monomer may be a known photopolymerizable monomer and is not particularly limited, and examples thereof may include benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzene acrylate Ethoxyethyl ester, phenoxyethyl methacrylate, phenoxy polyethylene glycol acrylate, phenoxy polyethylene glycol # alcohol methacrylate, styrene, nonylphenoxy polyethylene glycol mono Propionate, nonylphenoxy polyethylene glycol mono Acrylate, nonylphenoxy polypropylene glycol monoacrylate, nonylphenoxy polypropylene glycol monomethacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-propanoic acid phthalate Ethyl ester, 2-acrylic acid ethyl-2-hydroxyethyl phthalate, 2-methacrylic acid ethyl-2-hydroxypropyl phthalate, methyl acrylate, ethyl acrylate, methacrylic acid Methyl ester, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy methacrylate Propyl ester, propylene-23- 200535564 (20) 3-hydroxypropyl acid, 3-hydroxypropyl methacrylate, ethylene glycol monoacrylate, ethylene glycol monomethacrylate, glyceryl acrylate, glyceryl methyl Acrylate, di (isopentaerythritol) monoacrylate, bis (isopentaerythritol) monomethacrylate, dimethylaminoethyl acrylate 'dimethylaminoethyl methacrylate, tetrahydroacrylic acid Furfuryl ester, tetrahydrofurfuryl methacrylate, monoacrylate modified with phthalic acid, ethyl Alcohol diacrylate, ethylene glycol dimethacrylate, tris (ethylene glycol) diacrylate, tris (ethylene glycol) di (methacrylate), trimethylolpropane triacrylate, trishydroxy Methylpropane tri (methacrylate), trimethylolethane triacrylate, trimethylol ethyl tri (methacrylate), isopentaerythritol diacrylate, isopentaerythritol di (methyl) Acrylic acid) ester, isopentaerythritol triacrylate, isopentaerythritol tri (methacrylate), isopentaerythritol tetraacrylate, isopentaerythritol tetra (methacrylate), di (isoprene Alcohol) tetraacrylate, di (isopentaerythritol) tetra (methacrylate), di (isopentaerythritol) pentaacrylate, di (isopentaerythritol) penta (methacrylate), two # ( Isopentaerythritol) hexaacrylate, bis (isopentaerythritol) hexa (methylpropionic acid) ester, glyceryl acrylate, glycerol methacrylate, cardoepoxy diacry late And the compounds described (meth) acrylic acid are individually fumarate, itaconic acid and Fumaric acid esters, itaconic acid esters, and maleic acid substituted by succinic acid diacid; 1¾ diacid (c) inorganic powder The inorganic powder contained in the photosensitive inorganic paste composition of the present invention $ + f Temple-24- 200535564 (21) Do not restrict, as long as it meets the transparency required for the light source for exposure, examples can include glass, ceramics (cordierite, etc.), metals, and the like. Specifically, glass powders such as lead borosilicate based on PbO-Si〇2, Pb0-B203-Si02, Zn0-Si02, Zn0-B203-Si02, BiO-Si〇2, Bi0-B203-Si02, etc. Glass, zinc borosilicate glass, bismuth borosilicate glass, oxides of Na, K, Mg, Ca, Ba, Ti, Zr, A1, etc., such as cobalt oxide, iron oxide, chromium oxide, nickel oxide, Copper oxide, manganese oxide, ammonium oxide, φ vanadium oxide, hafnium oxide, tipaque yellow, cadmium oxide, ruthenium oxide, silicon dioxide, magnesium oxide, spinel, etc., fluorescent powder such as ZnO: Zn 'Znη3 (P04) 2: Mn 'Y 2 S i Ο 5: C e, C a W Ο 4: P b,

BaMgAl14023 : Eu，ZnS : (Ag，Cd)，Y203 : Eu，Y2Si05 :Eu，Y3A15012 : Eu，YB03 : Eu，（Y，Gd)B03 : Eu， G d B O 3 ' Eu，ScB〇3 : Eu，L11BO3 : Eu，Z n 2 S i 0 4 · Mn， BaAl12〇i9 : Mn，SrAl13019 ·· Mn，CaAli2019 : Mn，YB03 :Tb，BaMgAl]4〇23 : Mn，LuB03 : Tb，GdBO : Tb， φ ScB03Tb，Sr6Si 3 03 Cl4 : Eu，ZnS : (Cu，Al)，ZnS : Ag， Y 2 〇 2 S : E u，Z n S : Z n，（ Y，C d) B O 3 : E u，B a M g A11 2 〇 2 3 : Ευ等，及金屬粉末諸如鐵、鎳、鈀、鎢、銅、鋁、銀、 金、鉑等。尤其，玻璃、陶瓷等因爲優越之透明性而較佳 。玻璃粉末（玻璃料）特別可用於產生最重要之效果。當 無機粉末含有氧化矽、氧化鋁或氧化鈦時，其變成不透明 而降低透光度，因此期望該無機粉末可不含該種成份。 無機粉末之粒徑視待形成之圖案的形狀而定，但以使 用平均粒徑爲0.1至1 0微米之無機粉末爲佳，而〇. 5至8 -25- 200535564 (22) 微米更佳。大於1 0微米之平均粒徑因爲在形成高準確度 Η案時形成不均勻之表面而不佳，而小於〇.1微米之平均 粒徑則因爲在烘烤時形成細孔導致絕緣不足及不充分之分 散性而較不佳。該無機粉末可爲球形、方塊、薄片及樹枝 形式，可使用此等形式中之一或其中二或多種之組合。 該無機粉末除了黑色外可另含有發射例如紅光、藍光 及綠光之無機顏料。含有該等顏料之光敏性絕緣糊料組成 Φ 物可用以形成各種顏色之圖案，適於製備例如電漿顯示面 板中之濾色。此外，無機粉末可爲物性相異之細粒的混合 物。尤其，可使用熱軟化點相異之玻璃粉末及陶瓷粉末來 抑制烘烤期間之收縮。該無機粉末可調配以視分隔壁等之 性質來改變形狀及物理數値等的組合。 如前文所述，無機粉末具有1至10微米之平均粒徑 ，即1 0微米或較小。因此，爲了防止其二次聚集且改善 分散性’其表面可預先以矽烷偶合劑、以鈦酸鹽爲主之偶 • 合劑、以鋁爲主之偶合劑、界面活性劑等處理，處理程度 係不破壞該無機粉末之性質。第一處理方法中，處理劑可 溶解於有機溶劑或水中，之後添加無機粉末並攪拌，可飽 除該溶劑’之後於約5 0至2 0 0 °c熱處理2小時或更久。該 處理劑可在光敏性組成物轉化成糊料時添加。 (d )黏合劑樹脂 通常，可添加黏合劑樹脂於光敏性無機糊料組成物中 ’以改善塗覆性質及膜形成性。本發明中，該黏合劑樹脂 -26- 200535564 (23) 可爲已知之黏合劑樹脂，且不特別限制，可使用丙烯酸系 樹脂、纖維素衍生物、聚乙烯醇、聚乙烯基丁醛、聚乙二 醇、胺基甲酸乙酯樹脂及三聚氰胺樹脂。較佳係含有丙烯 酸系樹脂，尤其是具有羥基之丙烯酸系樹脂，以形成具有 改良之抗顯影性而準確性優越之影像。 本發明光敏性無機糊料組成物中，具有羥基之丙烯酸 系樹脂及水溶性纖維素衍生物以結合使用爲佳，因爲可改 φ 善活性射線諸如紫外線、激勵雷射、X射線、電子射線等 之透光度，以形成具有優越之準確度的圖案。 具羥基之丙烯酸系樹脂可包括藉著含羥基之單體（作 爲主要之可共聚單體）及視需要使用之另一種可與之共聚 之單體進行聚合而製得的共聚物。該含羥基單體可較佳地 爲將氧化烯加成於丙烯酸或甲基丙烯酸之氧化烯加合物， 尤其是氧化乙烯、氧化丙烯或氧化丁烯之加合物.，或此等 加合物之混合物，其實例可包括丙烯酸羥基甲酯、甲基丙 Φ 烯酸羥基甲酯、丙烯酸2-羥基乙酯、甲基丙烯酸2-羥基乙 酯、丙烯酸2 -羥基丙酯、甲基丙烯酸2 -羥基丙酯、丙烯酸 3-羥基丙酯、甲基丙烯酸3-羥基丙酯、丙烯酸2-羥基丁酯 、甲基丙烯酸2-羥基丁酯、丙烯酸3-羥基丁酯、甲基丙烯 酸3-羥基丁酯、丙烯酸4-羥基丁酯、甲基丙烯酸4_羥基 丁酯等，及經環氧基化酯化合物，諸如丙烯酸或甲基丙烯 酸與C 1至C 1 0二醇之單酯、甘油丙烯酸酯、甘油甲基丙 烯酸酯、二（異戊四醇）單丙烯酸酯、二（異戊四醇）單 (甲基丙烯酸）酯、經ε -己內酯修飾之丙烯酸羥乙酯、 -27- 200535564 (24) 經ε -己內酯修飾之甲基丙烯酸羥乙酯、丙烯酸 苯氧基丙酯等。 其他可與含羥基單體共聚之單體的較佳實例 如α，/3 -不飽和羧酸，諸如丙烯酸、甲基丙烯酸 、檸康酸、衣康酸、順丁烯二酸、反丁烯二酸等 或半酯；a，yS ·不飽和羧酸酯，諸如丙烯酸甲酯 乙酯、丙烯酸正丙酯、丙烯酸異丙酯、丙烯酸正 φ 烯酸異丁酯、丙烯酸第二丁酯、丙烯酸環己酯、 乙基己酯、丙烯酸硬脂酯、甲基丙烯酸甲酯、甲 乙酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、 酸第二丙酯、甲基丙烯酸正丁酯、甲基丙烯酸異 基丙烯酸第二丁酯、甲基丙嫌酸環己酯、甲基丙; 基己酯、甲基丙烯酸硬脂酯、丙烯酸2,2,2-三氟 基丙烯酸2,2,2-三氟甲酯等·，苯乙烯及苯乙烯衍 如α -甲基苯乙烯、對-乙烯基甲苯等。此外，亦 Φ 烯腈、甲基丙烯腈、丙烯醯胺、甲基丙烯醯胺、 酯、丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯 可單獨使用或其中二或多種混合使用。 所使用之水溶性纖維素衍生物可爲已知者， 限制，其實例可包括羧甲基纖維素、羥甲基纖維 基纖維素、經乙基甲基纖維素、羥丙基纖維素、 乙基纖維素、羧甲基乙基纖維素、羥丙基甲基纖 此等可單獨或其中二或多種混合使用。 2-羥基-3- 可包括例 、衣康酸 ，及其酐 、丙烯酸 丁酯、丙 写烯酸2-基丙烯酸 甲基丙燒 丁酯、甲 希酸2-乙 甲酯、甲 生物，諸 可使用丙 乙酸乙烯 等。此等 且不特別 素、羥乙 乙基羥基 維素等。 -28- 200535564 (25) (e )各成份之調配比例 本發明光敏性無機糊料組成物中，Norish類型 合起始劑與抗氫型光聚合起始劑之比例可如下。該 類型I光聚合起始劑之比例可介於1至90重量份 內，而該拉氫型光聚合起始劑之比例可爲10至99 數。該Norish類型I光聚合起始劑之比例較佳可赁 50重量份數範圍，而該拉氫型光聚合起始劑之比 • 50至90重量份數。該Norish類型I光聚合起始劑 更佳可爲20至40重量份數範圍，而該拉氫型光聚 劑之比例可爲6 0至8 0重量份數，所有比例皆基於 量份數之兩成份總和。 尤其當本發明光敏性無機糊料組成物在電漿顯 中作爲間隔器材料時，該拉氫型光聚合起始劑於光 機糊料組成物中光聚合起始劑中的比例以決定爲相 爲佳。詳言之，該Norish類型I光聚合起始劑之比 φ 10至90重量份數，而該拉氫型光聚合起始劑之比 10至90重量份數。該Norish類型I光聚合起始劑 車父佳可爲20至50重量份數’而該拉氬型光聚合起 比例可爲50至80重量份數。該Norish類型I光聚 劑之比例更佳可爲3 0至40重量份數，而該拉氫型 起始劑之比例可爲6 0至7 0重量份數，所有比例皆 光敏性無機糊料組成物中1 00重量份數光聚合起始 〇 製造電漿顯示前板時，由非光敏性無機糊料層 I光聚 Norish 數範圍 重量份 ;10至 例可爲 之比例 合起始 1 0 0重 示前板 敏性無 對高値 例可爲 例可爲 之比例 始劑之 合起始 光聚合 基於該 劑總和 所構成 -29- 200535564 (26) 之未烘烤介電層1 2 A係配置爲位在光敏性無機糊膜1 下方之底層並曝光。是故，暈影之影響不僅因爲光敏性 機糊膜中所含之無機粉末所反射之光而變得明顯，亦因 層未烘烤介電層12A中所含之無機粉末所反射之光而變 明顯，因此在曝光後有增寬圖案之底部寬度Wbtm的傾 。然而，當該Norish類型I光聚合起始劑相對於該拉氫 光聚合起始劑之調配比例設定於前述範圍內時，圖案於 φ 光後之剖面可變成接近矩形或梯形，其中圖案之底部寬 Wbtm稍小於頂部寬度Wt()p，而防止在烘烤期間因爲圖 收縮而導致介電層變形及破裂。 本發明光敏性無機糊料組成物中，水溶性纖維素衍 物與具有羥基之丙烯酸系樹脂的比例可如下。基於100 量份數兩成份總和，水溶性纖維素衍生物之比例可介於 至90重量份數範圍內，而具有羥基之丙烯酸系樹脂之 例可爲5 0至1 0重量份數。水溶性纖維素衍生物之比例 φ 佳可爲60至80重量份數範圍內，而具有羥基之丙烯酸 樹脂之比例可爲40至20重量份數。水溶性纖維素衍生 之比例更佳可爲60至70重量份數範圍內，而具有羥基 丙烯酸系樹脂之比例可爲40至3 0重量份數。 基於1 〇〇重量份數水溶性纖維素衍生物與光可聚合 體總和，該光聚合起始劑可使用範圍較佳爲0.1至10 量份數，更佳爲0.2至5重量份數。當該光聚合起始劑 比例低於0.1重量份數時，固化性質可能降低。當光聚 起始劑之比例高於1 〇重量份數時，底部可能因爲起始 6 A Μ j \ \\ 底 得 向 型 曝 度 案 生 重 50 比: 較 系 物 之 單 重 之 合 劑 -30- 200535564 (27) 之吸收而發生固化不充分之情況。 有機成份諸如黏合劑樹脂（諸如水溶性纖維素衍生物 及丙儲酸系樹脂、光聚合起始劑等）相對於無機成份諸如 玻璃料及其他無機粉末之比例可如下。基於〗〇 〇重量份數 光敏性無機糊料組成物總和，有機成份之比例可爲〗〇至 4〇重量份數，而無機成份之比例可爲9〇至6〇重量份數。 有機成份之比例較佳可爲1 5至3 5重量份數，而無機成份 Φ 之比例可爲8 5至6 5重量份數。有機成份之比例更佳可爲 20至30重量份數，而無機成份之比例可爲80至70重量 份數。 形成間隔器材料層時，若需要，則可添加溶劑，以將 本發明光敏性無機糊料組成物之黏度保持於適當之範圍內 〇 該光敏性無機糊料組成物中所含之溶劑不特別限制， 只要其足以溶解有機成份，可使該光敏性無機糊料組成物 # 具有適當之黏度，且可輕易蒸發並藉乾燥移除。該溶劑以 沸點爲1 0 0至2 0 0 °c之酮、醇及酯尤佳。 該等溶劑之實例可包括酮類，諸如二乙基酮、甲基丁 基酮、二丙基酮、環己酮等；醇類，諸如正戊醇、4 -甲基-2 -戊醇、環己醇、雙丙酮醇等；醚醇類，諸如乙二醇單甲 基醚、乙二醇單乙基醚、乙二醇單丁基醚、丙二醇單甲基 醚、丙二醇單乙基醚、二（乙二醇）單甲基醚、二（乙二 醇）單乙基醚、二（乙二醇）二甲基醚、二（乙二醇）二 乙基醚等；飽和烷基脂族單羧酸酯，諸如乙酸正丁酯、乙 -31 - 200535564 (28) 酸戊酯等；乳酸酯，諸如乳酸乙酯、乳酸正丁酯等；及以 醚爲主之酯類，諸如甲基溶纖素乙酸酯、乙基溶纖素乙酸 酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、乙 基-3-乙氧基丙酸酯、乙酸2-甲氧基丁酯、乙酸3-甲氧基 丁酯、乙酸4-甲氧基丁酯、乙酸2-甲基-3-甲氧基丁酯、 乙酸3_甲基-3-甲氧基丁酯、乙酸3-乙基-3-甲氧基丁酯、 乙酸2-乙氧基丁酯、乙酸4-乙氧基丁酯、乙酸4-丙氧基 φ 丁酯、乙酸2-甲氧基戊酯等，且此等可單獨或其中二或多 種混合使用。 基於1 00重量份數無機成份及有機成份總和，溶劑之 含量較佳可爲300重量份數或較低，更佳爲10至70重量 份數，最佳爲25至35重量份數。 除了前述者外，若需要可添加附加成份，諸如紫外線 吸收劑、敏化劑、聚合抑制劑、增塑劑、增稠劑、有機溶 劑、分散劑、消泡劑及有機或無機懸浮劑。 φ 可添加聚合抑制劑以改善儲存期間之熱安定性，其詳 例可包括氫醌、氫醌單酯、N-亞硝基二苯基胺、吩鸣畊、 對-第三丁基兒查酚、N-苯基萘基胺、2,6-二-第三丁基-對-甲基酚、氯醌、焦掊酚等。 用以改善基板之塑性的增塑劑可包括苯二甲酸酯尤其 是苯二甲酸二丁酯（DBP )、苯二甲酸二辛酯（DOP )、 聚乙二醇、甘油、酒石酸二酯尤其是酒石酸二乙酯、酒石 酸二丁酯等，及檸檬酸酯，尤其是檸檬酸三乙酯、檸檬酸 三丁酯等。 -32- 200535564 (29) 消泡劑之特例可包括基於烷二醇之消泡劑，諸如聚乙 二醇（分子量4 0 0至8 0 0 )、聚矽氧及高級醇，藉以減少 糊料或薄膜中之氣泡且可減少烘烤後之孔隙。 (B )用以製造電漿顯示前板之薄板型未烘烤坯體 本發明用以製造電漿顯示前板之薄板型未烘烤坯體係 爲其中至少將由本發明光敏性無機糊料組成物之塗膜所構 Φ 成之間隔器材料層形成於可移除承載膜上之未烘烤坯體。 認爲本發明薄板型未烘烤坯體主要可爲僅由間隔器材 料層構成之單層結構、由間隔器材料層及未烘烤介電層或 可燃性中間層所構成之雙層結構、或由間隔器材料層、未 烘烤之介電層及可燃性之中間層所構成之三層結構的形式 ^此等單至三層結構之兩表面皆可藉由可輕易剝除之可移 除承載膜加以保護，使得該未烘烤坯體可輕易.儲存、輸送 及操作。 • 本發明薄板型未烘烤坯體在製造後可在有效使用期間 內儲存預定週期，且可在製造電漿顯示前板時立即使用， 以增加電漿顯示前板之製造效率。 下文中，詳細說明提供本發明薄板型未烘烤坯體的詳 例。 其一係爲在可移除承載膜上形成本發明光敏性無機糊 料組成物之塗膜的薄板型未烘烤坯體。藉著將以溶劑稀釋 至適於施加之濃度的本發明光敏性無機糊料組成物施加於 可剝離承載膜上，形成間隔器材料層。該間隔器材料層隨 -33- 200535564 (30) 後覆上作爲保護層之保護膜。 另一實例係爲具有間隔器材料層及未烘烤之介電坯體 之薄板型未烘烤坯體。由本發明光敏性無機糊料組成物所 構成之間隔器材料層係形成於可剝離承載膜上。隨之將由 非光敏性無機糊料組成物構成之未烘烤介電層形成於間隔 器材料層上，且覆蓋作爲保護層之保護膜。 再另一實例爲間隔器材料層上形成有可燃性中間層之 φ 薄板型未烘烤坯體。由本發明光敏性無機糊料組成物之塗 膜構成之間隔器材料層係形成於可剝離承載膜上。水溶性 或水潤脹性可燃性中間層係形成於該間隔器材料層上並覆 以作爲保護層之保護膜。 另一實例係爲間隔器材料層上具有可燃性中間層及未 烘烤之介電層的薄板型未烘烤坯體。圖18A中，由本發明 光敏性無機糊料組成物之塗膜構成之間隔器材料層1 6 A形 成於可剝離承載膜1 8 0上。在間隔器材料層1 6 A上形成水 φ 溶性或水潤脹性可燃性中間層1 4，上面形成由非光敏性無 機糊膜所構成之未烘烤介電層12A。該未烘烤介電層12A 係覆以作爲保護層之保護膜1 82。 此等實例中，使用其中本發明光敏性無機糊料組成物 之塗膜係形成於可移除承載膜上並覆蓋保護膜之薄板型未 烘烤坯體最佳。 下文描述構成本發明薄板型未烘烤坯體之個別層，之 後詳細描述本發明製造薄板型未烘烤坯體的方法。 -34- 200535564 (31) (a )間隔器材料層 間隔器材料層1 6 A係爲藉微影術使彼者進行圖案化且 之後移除有機材料，並同時於烘烤步驟中烘烤該無機粉末 ，而形成間隔器層1 6 A之層。本發明中，間隔器材料層 1 6A係使用本發明光敏性無機糊料組成物製得。 本發明中，Norish類型I光聚合起始劑及拉氫型光聚 合起始劑係結合使用，使得形成之圖案於曝光後之剖面係 φ 接近矩形或梯形，其中圖案之底部寬度Wbtm可稍小於頂 部寬度Wt〇p。經圖案化間隔器材料層丨6A可藉後續烘烤處 理而收縮。然而，藉著稍微縮小圖案之底部寬度Wbtm，可 防止在圖案收縮時變形或破裂。 當經圖案化之間:倡器材料層中所含玻璃料在烘烤處理 (描述於下文）中熔融時，圖案之側壁可能塌陷。當圖案 係爲其中圖案之底部寬度Wbtm稍小於頂部寬度WtC)p之梯 形時’底部寬度Wbtm較佳係藉著故意以烘烤處理使之塌 φ 陷而有某一程度之增加，以改善圖案之安定性。 一方面’當形成之圖案的剖面係接近矩形時，較佳係 甚至在烘烤處理後仍保持此矩形，因此較佳係防止圖案之 側壁在烘烤處理期間塌陷。爲防止圖案側壁在烘烤期間塌 陷’間隔器材料層中所含之玻璃料的軟化點較佳係設定於 高於未烘烤介電層中所含之玻璃料的軟化點。尤其，可藉 著將間隔器材料層中所含之玻璃料之軟化點調整設定成較 未烘烤介電層中所含之玻璃料的軟化點高至少5 °C (以至 少7 °C爲佳’至少1 〇 °c更佳），來使圖案側壁於烘烤處理 -35- 200535564 (32) 期間之塌陷達到可忽略程度。 藉著將本發明光敏性無機糊料組成物之塗膜乾燥所得 之間隔器材料層的厚度可爲10至50微米，以15至40微 米爲佳。 (b)未烘烤之介電層 未烘烤之介電層1 2 A係由藉著將非光敏性無機糊料組 φ 成物所形成之塗膜乾燥所製備之無機糊膜構成。未烘烤之 介電層12A係爲在烘烤步驟爲介電層12之層，在該烘烤 步驟中移除有機材料且同時烘烤該無機粉末。用以形成未 烘烤介電層1 2 A之無機糊料組成物含有無機粉末及黏合劑 樹脂爲主成份％。 至於用以形成未烘烤介電層之非光敏性無機糊料組成 物中所含之無機粉末，可使用如同（A )項光敏性無機糊 料組成物中所述之無機粉末。 φ 非光敏性無機糊料組成物中所含之黏合劑樹脂可爲已 知之黏合劑樹脂且不特別限制，可使用丙烯酸系樹脂、纖 維素衍生物、聚乙烯醇、聚乙烯基丁醛、聚乙二醇、聚酯 樹脂、胺基甲酸乙酯樹脂等。較佳係含有丙燒酸系樹脂， 尤其是具有羥基之丙烯酸系樹脂，以對玻璃基板具有優越 之熱黏著性。至於具有羥基之丙烯酸系樹脂，可使用如同 (A )項光敏性無機糊料組成物所述之丙烯酸系樹脂。 無機成份整體（即玻璃料及無機粒子）與有機成份諸 如黏合劑樹脂等之比例可如下。基於總量〗00重量份數之 -36- 200535564 (33) 無機成份及有機成份，有機成份之比例係爲1 0至40重量 份數，而無機粉末之比例係爲9 0至6 0重量份數。有機成 份之比例較佳係爲1 5至3 5重量份數’而無機粉末之比例 係爲85至65重量份數。有機成份之比例更佳係爲20至 30重量份數，而無機粉末之比例係爲80至70重量份數。 超過前述範圍之量較爲不利，因爲有機成份之比例低於1 〇 重量份數時，無法形成薄膜，而當有機成份高於40重量 φ 份數時，在烘烤後可能發生明顯收縮。 形成未烘烤之介電層時，若需要則可添加溶劑，以使 非光敏性無機糊料組成物之黏度保持於適當之範圍內。至 於非光敏性無機糊料組成物中所含之溶劑，可使用如同（ A )項光，敏性無機糊料組成物中所述之溶劑。爲了使非光 敏性無機糊料組成物之黏度保持於適當之範圍內，以1 00 重量份數之無機成份及有機成份總量計，溶劑之含量較佳 係爲300重量份數或較低，溶劑量係達到3000 csp或更高 φ 之黏度更佳，而5〇〇〇cps或更高最佳。 該非光敏性無機糊料組成物可含有各種添加劑，諸如 增塑劑、分散劑、膠黏劑、表面張力調節劑、安定劑及消 泡劑作爲在無機粉末、黏合劑樹脂及溶劑之外的選擇性成 份。 該未烘烤介電層可藉著形成非光敏性無機糊料組成物 之塗膜且隨之乾燥該塗膜以移除溶劑而形成。 未烘烤之介電層在乾燥後之厚度可爲10至；[〇〇微米 ，以25至70微米爲佳。 -37- 200535564 (34) (c )可燃性中間層 可燃性中間層1 4係爲水溶性或水潤脹性層，其藉著 水洗來溶解或潤賬，以抬高並移除殘留在已藉顯影劑進行 移除處理之部位上之間隔器材料層。該可燃性中間層1 4 係爲可選擇性提供於該間隔器材料層1 6 A上之層。 在製造電漿顯示前板時，此可燃性中間層係位於未烘 | 烤介電層與間隔器材料層之間，如下文中製造方法所詳述 。當此層積狀態中之間隔器材料層係圖案化光照射並顯影 以將間隔器材料層圖案化時，間隔器材料之殘留物可能殘 留於介於圖案凸起物之間的可燃性中間層的經曝光表面上 。殘留於圖案凸起物之間的間隔器材料殘留物因烘烤處理 而熔融，介電層原應爲均勻平滑表面之經曝光表面因此被 破壞，而形成不均勻之表面。爲解決此問題，在未烘烤介 電層與間隔器材料層之間配置可燃性中間層，使得間隔器 φ 材料之殘留物形成於可燃性中間層之表面上，當可燃性中 間層係水溶性時，曝光區中之間隔自材料殘留物與可燃性 中間層一起被顯影溶液（水或水溶液）洗除。當可燃性中 間層係水潤脹性時，該中間層被顯影溶液潤脹，使位於表 面上之間隔器材料殘留物升高，而可輕易使用顯影溶液洗 除殘留物。 在完成其工作之後，使間隔器材料殘留物可被顯影溶 液移除之可燃性中間層藉著未烘烤介電層及未烘烤間隔器 材料層之烘烤處理完全燃燒。結果，在玻璃基板上形成具 -38- 200535564 (35) 有如同先前技術之結構及尺寸的介電層及間隔器層而成爲 前板。形成之本發明前板與先前技術前板之間的差異在於 介於間隔器層與其相鄰間隔器層之間的介電層之曝光表面 在先前技術係不均勻者，而本發明所製之前板中的曝光表 面係平滑。此係特別可藉著在未烘烤介電層與間隔器材料 層之間提供水溶性或水可潤脹性可燃性中間層而獲得之重 要效果。 φ 只要可燃性中間層1 4係爲水溶性或水可潤脹性且藉 著在400至70 0 °C烘烤而分解並燃盡，則中間層不特別限 制，但較佳係由至少一種水溶性樹脂及水可潤脹性樹脂構 成。該可燃性中間層較佳係使用含有溶劑及至少一種水溶 性樹脂及水可潤脹性樹脂之可燃性中間層組成物形成。 至於水溶性樹脂，可較佳地使用聚乙烯醇、聚乙烯醇 衍生物、水溶性纖維素等。至於水可潤脹性樹脂，可使用 水溶性樹脂之部分交聯產物。此等可單獨或其中二或多種 φ 混合使用。 聚乙烯醇衍生物之特別可包括例如經矽烷醇修飾之聚 乙稀醇、經陽離子修飾之聚乙燃醇、含氯硫基之聚乙嫌醇 、丁醛樹脂等。 水溶性纖維素之特別可包括例如羧甲基纖維素、羥甲 基纖維素、羥乙基纖維素、羥乙基甲基纖維素、羥丙基纖 維素、乙基羥基乙基纖維素、羧甲基乙基纖維素、羥丙基 甲基纖維素等。 其中，就水溶性、熱降解性及耐溶劑性（耐介電層中 -39- 200535564 (36) 之溶劑）而言，以聚乙烯醇及羥甲基纖維素爲佳。 用以形成可燃性中間層之溶劑不特別限制，只要其足 以溶解該水溶性樹脂或水可潤脹性樹脂、可使黏度適於塗 覆且可藉乾燥蒸發並移除，可使用水及有機溶劑諸如丙醇 等。 可燃性中間層可藉著使用溶劑將水溶性樹脂或水可潤 脹性樹脂稀釋至適於塗覆之濃度，形成組成物之塗膜，並 φ 藉乾燥移除溶劑而形成。 用以形成可燃性中間層之可燃性中間層組成物中的水 溶性樹脂或水可潤脹性樹脂之比例較佳係50重量％或較低 ，更佳係3 0重量％或較低，最佳係〇 · 1至2 0重量％。 可燃性，中間層之厚度較佳係爲20微米或較薄，更佳 爲10微米或較薄，而5微米或更薄又更佳。該可燃性中 間層太薄較不佳，因爲該光敏性未曝光未烘烤間隔器材料 層之圖案亦可能在稍後顯影步驟中洗除。該可燃性中間層 φ 之最佳厚度係爲0.1至3微米。 (d )製造薄板型未烘烤坯體之方法 至於本發明薄板型未烘烤坯體中所使用之承載膜1 8 0 ’可使用可使上面所形成之各層輕易脫離並將未烘烤之層 轉移至玻璃基板上之可移除薄膜，而無特別限制。其實例 可包括由合成樹脂膜諸如聚對苯二甲酸乙二酯、聚乙烯、 聚丙烯、聚碳酸酯、聚氯乙烯等所構成之厚度15至125 微米的可撓性薄膜。該承載膜較佳係進行脫離處理，以利 -40- 200535564 (37) 於轉移。 爲於承載膜上形成間隔器材料層1 6 A、可燃性中間層 1 4及未烘烤之介電層1 2 A，可製備用以形成各層之組成物 ，之後藉施加器、桿塗器、線桿塗器、狹縫型塗覆器、幕 流式塗覆器等施加於該承載膜1 8 0上。尤其，以輥塗器爲 佳，因爲可有效地形成具有優越之均勻厚度的厚膜。塗膜 乾燥後，乾燥之塗膜可塗覆以另一組成物作爲後續層，以 φ 層積各層，而製備本發明薄板型未烘烤坯體。 保護膜182較佳係黏著於與承載膜180相反之表面上 ，以於使用前穩定地保護該光敏性糊料組成物層等。該保 護膜較佳係爲厚度約1 5至1 2 5微米之聚對苯二甲酸乙二 酯膜、聚丙烯膜或聚乙烯膜，上層塗覆有聚矽氧或經烘烤 (C)製造電漿顯示前板之方法 本發明製造電漿顯示前板之方法係包含依此順序將未 烘烤之介電層及間隔器材料層層積於玻璃基板已形成電極 之表面上，之後使用圖案化光照射該間隔器材料層，顯影 以使該間隔器材料層圖案化，同時使位於矽膠基板上之未 烘烤介電層及經圖案化間隔材料層進行烘烤處理，以同時 於玻璃基板上形成介電層及間隔器層。 本發明中，水溶性或水潤勝性可燃性中間層可視情況 配置於未烘烤介電層與間隔器材料層之間。可使用水溶液 或顯影液體溶解或潤脹以產生間隔器層且可藉烘烤處理燃 «41 - 200535564 (38) 盡之材料層較佳係層積於未烘烤介電層及其上形成之間隔 器材料層之間而成爲中間層。後續曝光處理及後續處理可 依習用方式進行，以在烘烤處理之前移除殘留於圖案間凹 陷部分中的間隔器材料殘留物，且中間層藉烘烤處理燃盡 消失，烘烤後之積層體結構成爲與先前技術相同。 (a )玻璃基板上各層之形成 將未烘烤之介電層及間隔器材料層層積於玻璃基板上 之方法不特別限制，各層可使用已知方式諸如例如塗覆方 法、網版印刷方法等層積。然而，就表面光滑性優越之具 有均勻厚度的料層形成性觀點而言，使用前述本發明薄度 狀未烘烤坯體形成個別層之方法最佳。 詳細描述使用本發明薄板型未烘烤坯體製造電漿顯示 前板之方法的實例。首先，製備具有依此順序層積之承載 膜、間隔器材料層及保護層的薄板型未烘烤坯體。 個別地將未烘烤之介電層形成於玻璃基板已形成有電 極之表面上。形成未烘烤介電層之方法不特別限制，但較 佳係將非光敏性無機糊料組成物施加於承載膜上並乾燥以 形成未烘烤之介電層，若需要，則藉塗覆及乾燥形成可燃 性中間層，之後層積於玻璃基板上，使得未烘烤之介電層 與玻璃基板已形成電極之表面接觸，而未烘烤之介電層藉 著將經加熱之輥移至承載膜而轉移至玻璃基板上。 之後，自薄板型未烘烤坯體移除保護膜，將剝離之間 隔器材料層黏附於未烘烤之介電層。熱輥隨後移至承載膜 -42- 200535564 (39) 上，以將間隔器材料層熱壓於未烘烤介電層之表面上。 熱壓較佳可在1至5公斤/厘米2範圍內之輥壓及〇」 至10.0米/分鐘之行進速度下進行，而玻璃基板之表面 溫度係於8 0至1 4 0 °C下加熱。玻璃基板可經預熱，預熱溫 度選擇例如介於4 0至1 2 0 °C範圍內。 之後’說明使用下述薄板型未烘烤坯體製造電漿顯示 前板之另一實例。首先，製備依序層積承載膜、間隔器材 φ 料層、未烘烤之介電層及保護膜之薄板型未烘烤坯體。自 該薄板型未烘考坯體移除保護膜後，未烘烤介電層黏附於 玻璃基板已備有電極之表面上，熱輥於承載膜上移除，以 將未烘烤之介電層及間隔器材料層熱壓至該玻璃基板上。 說明使用下述薄板型未烘烤坯體製造電漿顯示前板之 另一實例。首先，製備依序層積有承載膜、間隔器材料層 、可燃性中間層及保護膜之薄板型未烘烤坯體。個別地將 未烘烤之介電層形成於玻璃基板已形成電極之表面上。自 φ 薄板型未烘烤坯體移除保護層以暴露出可燃性中間層，所 暴露之可燃性中間層係黏附於形成在玻璃基板已備有電極 之表面上的未烘烤介電層，隨後熱輥於承載膜上移動，以 將可燃性中間層及間隔器材料層熱壓於玻璃基板之表面上 〇 參照圖8A及圖8B詳述使用下述薄板型未烘烤坯體製 造電漿顯示前板之另一實例。首先，製備依序層積有承載 膜1 8 0、間隔器材料層〗6 A、可燃性中間層1 4、未烘烤之 介電層1 2 A及保護膜1 8 2之薄板型未烘烤坯體（圖8 A ) -43- 200535564 (40) 。自薄板型未烘烤坯體移除保護層1 82以暴露出未烘烤之 介電層12A，所暴露之未烘烤介電層12A黏附於玻璃基板 1 〇已備有電極之表面，熱輥4 0於承載膜1 8 0上移除，以 將未烘烤之介電層1 2 A、可燃性中間層1 4及間隔器材料 層16A熱壓於玻璃基板之表面（圖8B)。 (b )曝光/顯影處理 φ 曝光處理及後續處理可依習用方式進行。曝光/顯影 處理係參照圖4a至4c詳述。根據前述方法，未烘烤之介 電層1 2a及間隔器材料層1 6a係形成於玻璃基板上，之後 將光罩3放置於間隔器材料層1 6a上，其隨後曝光，以使 圖案部分中之間隔器材料層固化（圖4A )。 本發明中，Norish類型I光聚合起始劑及拉氫型光聚 合起始劑係同時使用，因此可防止被氧所抑制之影響。是 故，即使間隔器材料層1 6 A之表面未覆以透明膜，仍可進 φ 行表面之固化。然而，當粉塵等因靜電黏附於間隔器材料 層1 6 A之表面時，可能破壞品質。因此，若使用透明膜作 爲本發明薄板型未烘烤坯體中之承載膜〗8 〇，則較佳係在 該等料層層積於玻璃基板上後該承載膜1 8 0保持黏附於間 隔器層1 6 A上時進行曝光，在曝光後，可隨之移除承載膜 180° 至於曝光時所使用之輻射照射裝置，可採用一般使用 於微影術之紫外線照射裝置及用於製造半導體及液晶顯示 器之曝光裝置。 -44- 200535564 (41) 之後，藉顯影移除光敏性未曝光未烘烤間隔器 之未固化部分1 6 A，使得抗蝕劑圖案丨6 A，顯現（ 4B )。 顯影處理中，可使用通用型鹼顯影溶液或水。 影溶液中之鹼成份可包括鹼金屬諸如鋰、鈉、鉀等 化物、碳酸鹽、碳酸氫鹽、磷酸鹽及焦磷酸鹽，一 如苄基胺、丁基胺等，二級胺諸如二甲基胺、二苄 φ 二乙醇胺等，三級胺諸如三甲基胺、三乙基胺、三 等，環胺諸如嗎啉、哌畊、吡啶等，多胺諸如乙二 亞甲基二胺等，氫氧化銨諸如氫氧化四甲基銨、氫 乙基胺、氫氧化三甲基苄基銨、氫氧化三甲基苯基 .、等，，氫氧化三甲基銃、氫氧化銃諸如氫氧化三甲基 氧化二乙基甲基銃、氫氧化二甲基苄基銃等，膽鹼 酸鹽之緩衝劑，其中若考慮鹼成份對玻璃料所造成 ，則以水爲佳。 φ 使用與拉氫型光聚合起始劑結合使用之Norish 光聚合起始劑形成之圖案的剖面可製成接近矩形 7A所示，或梯形，其中圖案之底部寬度Wbtm稍小 寬度WtC)p，如圖7B所示。是故’可防止該介電層 處理期間變形或破裂。 (c )烘烤 上層形成有圖案之積層體可加以烘烤，以使未 介電層1 2 A及光敏性未曝光未烘烤間隔器材料層 材料層 參照圖 該鹼顯 之氫氧 級胺諸 基胺、 乙醇胺 胺、六 氧化四 苄基銨 疏、氫 ，含矽 之損壞 類型I ，如圖 於頂部 在烘烤 烘烤之 16A’ 中 -45- 200535564 (42) 所含之玻璃料被烘烤，將該等層個別轉化成介電層1 2及 間隔器層1 6。因而製得包含位於介電層1 2上經圖案化之 間隔器層1 6的本發明電漿顯示前板（參照圖4C )。 此烘烤中所使用之溫度可爲該光敏性無機糊料組成物 中有機材料因燃燒而消失且無機粉末被烘烤之溫度，可選 擇在400至700 °C烘烤10至90分鐘。 當間隔材料層中所含之無機粉末的軟化點調成高於未 φ 烘烤介電層中所含無機粉末之軟化點，以防止該圖案之側 壁在烘烤處理期間塌陷時’該烘烤溫度較佳可調成不高於 間隔器材料層中所含之無機粉末的軟化點τ 1 (艺）且不低 於未烘烤介電層中所含之無機粉末的軟化點T2 ( °c )( τ2 < τ !)。尤其’稍低於間隔器材料層中所含之無機粉末 的軟化點T !的烘烤溫度爲佳。該烘烤溫度較佳可爲τ 2。〇 或較局及T】°c或較低’更佳（Ti-5) °C或較高及TVC或較 低’更佳爲（Ti-7) C或較局及或較低，尤其是約（ _ Trio)。(：。 依此方式製造電漿滅7K則板（具有形成於介電層上之 經圖案化間隔器層’而該介電層係形成於上層具有電極之 玻璃基板上）後，未覆蓋之介電層及間隔器層較佳可覆以 保護層1 9，諸如M g 0等。 【實施方式】 爹照以下貫施例更δ羊細地描述本發明。然而，本發明 不受限於此。 -46- 200535564 (43) <實驗例l> (光敏性無機糊料組成物之製備） 就水溶性纖維素衍生物而言，2 2重量份數羥丙基纖維 素、1 4重量份數作爲具有羥基之丙烯酸系樹脂的苯乙烯/ 甲基丙烯酸羥乙酯= 5 5/45 (重量％ )共聚物（Mw = 40000 ) 、60重量份數作爲光可聚合單體之苯二甲酸2-甲基丙烯 φ 醯氧乙基-2·羥基丙酯（商標：η〇·ΜΡΡ，Kyoeisha Chemical Co.，Ltd·製造）、〇 . 9 重量份數 2，2 - 一> 甲氧基-2 -苯基乙醯基苯（商標·· IR-651，Norish類型I，Chiba-Geigy製造）及1·8重量份數作爲光聚合起始劑之2,4-二 乙基噻噸酮（·商標·· DETX-S，拉氫型，Nippon Kayaku Co ·，Ltd·製造）、3.9重量份數作爲增塑劑之酒石酸丁酯 、〇 · 1重量份數作爲紫外線吸收劑之偶氮基染料（商標： Dye SS，Daito Chemix Corporation 製造）及 100 重量份 φ 數作爲溶劑之3-甲氧基-3-甲基丁醇藉混合器混合3小時 ，以製備有機成份溶液。之後，捏和4 0重量份數此有機 成份溶液（固體含量50% )與80重量份數作爲無機成份 之軟化點爲5 8 1°C的玻璃料，以製備光敏性無機糊料組成 物。 <實驗例2> (非光敏性無機糊料組成物之製備） 4 5重量份數作爲具有羥基之丙烯酸系樹脂的甲基丙烯 -47- 200535564 (44) 酸異丁酯/甲基丙烯酸羥基乙酯= 60/40 Mw = 7 0 000 )、5重量份數作爲增塑劑5 5 〇重量份數作爲溶劑之3 -甲氧基-3 ·甲 水浴之攪拌機中於8 0 °C下攪拌2小時， 液。之後，40重量份數此有機成份溶泌 與80重量份數軟化點爲5 74它之玻璃和 敏性無機糊料組成物。 <實驗例3〉 (用以形成可燃性中間層之組成物 4重量份數聚乙烯醇（商標：PVA· Ltd.製造）及作爲溶劑之53重量份數7」 丙醇藉混合器混合1 2小時，以製備防渗 <實施例1 > 實驗例2之非光敏性無機糊料組成 =甲酸乙二酯製得之承載膜上，使得形 之厚度係爲60微米，而於上層形成塗 100 °C層積溫度、2.5公斤/厘米2層積| 層積速度下層積於在80艺下預熱之玻璃 之介電層。 M $所製備之光敏性無機糊料組成 g # m層上，使得薄膜於乾燥後之厚度 @ Μ @試驗方形圖案罩幕曝照來自超高 (重量％)共聚物（ :苯二甲酸二丁酯及 i基丁醇係於裝置有 以製備有機成份溶 [(固體含量5 0 % ) 捏和，以製備非光 的製備） -23 5，Kuraray Co” <與43重量份數異 ^透層組成物。 物施加於由聚對苯 成之塗膜於乾燥後 膜。此塗膜隨之於 g力及1·〇米/分鐘 上，以形成未烘烤 物隨之施加於未烘 係爲4 0微米，之 壓汞燈之400毫焦 -48- 200535564 (45) 耳/厘米2的紫外線。之後，使用液溫爲30°C之水於3.0公 斤/厘米2之噴射壓力下噴霧顯影3 0秒，以形成圖案。評 估形成之圖案的黏著性，發現殘留之最小線寬爲60微米 ，最小形成間隔爲60微米。形成之圖案的剖面係爲梯形 ，其中底部寬度Wbtm係小於頂部寬度Wt()p，且 Wt()p : wbtm 係爲 1 ·· 0.9。 爲評估圖案於烘烤後之形穩性，根據前述方法形成罩 φ 幕線寬爲200微米之圖案，進行烘烤處理，其中試樣係於 10°c/分鐘之漸增溫度下加熱，之後保持5 8 0°c歷經30分 鐘。結果，保持良好之經烘烤圖案。圖案於烘烤後之剖面 係爲矩形，其中Wtcp : Wbtm係爲1 : 1。 <實施例2> 實驗例2之非光敏性無機糊料組成物藉唇塗器施加於 由可移除聚對苯二甲酸乙二酯構成之承載膜（商標： Pur ex A24，T e i j i n D u Ρ ο n t F i 1 m s J ap an L i m i t e d 製造）上 ，形成之塗膜於i〇〇°c乾燥6分鐘，以完全移除溶劑，以 於承載膜上形成厚度60微米之未烘烤介電層。 實驗例3之可燃性中間層形成用組成物隨之藉唇塗器 施加於形成在承載膜上之未烘烤介電層上’塗膜於1 0 0 °C 下乾燥6分鐘，以完全移除溶劑’而於未烘烤之介電層上 形成厚度〇 · 5微米之可燃性中間層。 實驗例1之光敏性無機糊料組成物藉唇塗器施加於形 成在承載膜上之可燃性中間層上，塗膜於1 〇〇°c下乾燥6 -49- 200535564 (46) 分鐘，以完全移除溶劑，而形成厚度40微米之光敏性未 曝光未烘烤間隔器材料層。之後，將由可移除聚對苯二甲 酸乙二酯（商標：Purex A53，Teijin DuPont Film 製造） 構成之保護膜堆疊於光敏性未曝光未烘烤間隔器材料層上 ，以製得具有5層結構之水顯影性光敏性薄膜。 剝除係爲前文製備之水顯影性光敏性薄膜之承載膜的 可移除聚對苯二甲酸乙二酯（商標：Purex A24，Teijin ^ DuPont Films Japan Limited製造），而光敏性薄膜藉熱輥 層積機於1 5 (TC下層積於上層形成有匯流排電極而已預先 於80 °C加熱之玻璃基板上。空氣壓力係爲3公斤/厘米2， 層積速度係爲1.0米/分鐘。 該光敏性膜層經由試驗方形圖案罩幕曝照來自超高壓 汞燈而曝照量爲3 00毫焦耳/厘米2的紫外線。移馀聚對苯 二甲酸乙二酯保護膜後，使用液溫爲3 (TC之水於3公斤/ 厘米2之噴射壓力下噴霧顯影3 0秒，以形成圖案。評估 φ 形成之圖案的黏著性及圖案形狀，發現殘留之最小線寬爲 60微米，最小形成間隔爲60微米，其係良好圖案形狀。 形成之圖案的剖面係爲梯形，其中底部寬度Wbtm係小於 頂部寬度 WtQp，且 WtC)p ·· Wbtm 係爲 1 : 0.9。 爲評估圖案於烘烤後之形穩性，根據前述方法形成罩 幕線寬爲200微米之圖案，進行烘烤處理，其中試樣係於 1 〇°C /分鐘之漸增溫度下加熱，之後保持5 8 0°C歷經30分 鐘。結果，保持良好之經烘烤圖案。圖案於烘烤後之剖面 係爲矩形，其中Wt()p : Wbtm係爲1 : 1。 -50- 200535564 (47) <實施例3> 實驗例3之可燃性中間層形成用組成物施加於由聚對 苯二甲酸乙二酯製得之承載膜上，使得塗膜於乾燥後之厚 度係爲0.5微米，之後於100°C下乾燥此塗膜6分鐘以移 除溶劑，而形成可燃性中間層。之後，於其上層施加實驗 例2之非光敏性無機糊料組成物並乾燥以形成塗膜，使得 φ 塗膜於乾燥後之厚度係爲60微米。塗膜之表面黏附於經 預熱之玻璃上，層積係於8(TC下在100 °C層積溫度、2.5 公斤/厘米2之層積壓力及1.0米/分鐘之層積速度下進行 ，以形成上層形成有可燃性中間層之未烘烤介電層。之後 移除承載膜。 前文所製備之光敏性無機糊料組成物隨後施加於未烘 烤之介電層上，使得形成之塗膜於乾燥後之厚度係爲40 微米，經由試驗方形圖案罩幕曝照來自超高壓汞燈而曝照 φ 量爲400毫焦耳/厘米2的紫外線。之後，使用液溫爲30 t之水於3.0公斤/厘米2之噴射壓力下噴霧顯影3 0秒， 以形成圖案。評估形成之圖案的黏著性，發現殘留之最小 線寬爲60微米，最小形成間隔爲60微米。形成之圖案的 剖面係爲梯形，其中底部寬度Wbtm係小於頂部寬度WtC)p ，且 WtC)p : Wbtm 係爲 1 : 0.9。 爲評估圖案於烘烤後之形穩性，根據前述方法形成罩 幕線寬爲200微米之圖案，進行烘烤處理，其中試樣係於 10 °C/分鐘之漸增溫度下加熱，之後保持5 8 0 °C歷經30分 200535564 (48) 鐘。結果，保持良好之經烘烤圖案。圖案於烘烤後之剖面 係爲矩形’其中W t。p · W b t 111係爲1 · 1。 <對照例1> 依如同實施例1之方式製備光敏性無機糊料組成物及 絕緣薄板組成物，不同處係單獨使用0.9重量份數Norish 類型I光聚合起始劑2,2-二甲氧基-2-苯基乙醯基苯（商標 • : IR-65 1，Ciba-Geigy製造）作爲光敏性無機糊料組成物 中之光聚合起始劑，而依如同前述方式評估黏著性。結果 ，殘留之最小線寬爲60微米，唯最小形成間隔爲1〇〇微 米。形成之圖案的剖面係爲梯形，其中底部寬度wbtm係 大於頂部寬度Wt〇p’且Wt()p: Wbtm係爲0.6: 1。 <對照例2> 依如同前述實施例之方式製備光敏性無機糊料組成物 # 及絕緣薄板組成物’不同處係單獨使用1 · 8重量份數拉氫 型 2,4-二甲基噻噸酮（商標：DETX-S，Nippon Kayaku Co.，Ltd.製造）作爲光敏性無機糊料組成物中之光聚合起 始劑’而依如同前述方式進行噴霧顯影3 〇秒。結果，圖 案被洗除且無法固化。 工業應用 如前文所述’本發明光敏性無機糊料組成物可藉著結 合Norish類型I光聚合起始劑與拉氫型光聚合起始劑來產 -52- 200535564 (49) 生良好之圖案形狀，且因此可較佳地用爲形成多層電路及 各種顯示器諸如電漿顯示器、電漿位址液晶顯示器等之材 料’尤其是用於製造需要高準確度之電漿顯示前板中的間 隔器材料層。 【圖式簡單說明】 圖1係爲具有薄餅型結構構件之電發顯示器的分解圖 圖2係爲電漿顯示前板之背側的透視圖。 圖3係爲具有薄餅型結構構件之電漿顯示器的剖面圖 〇 圖4 A係爲利用微影術製造電漿顯示前板之步驟（曝 光步驟）的說明。 圖4 B係爲利用微影術製造電漿顯示前板之步驟（顯 影步驟）的說明。 φ 圖4 C係爲利用微影術製造電漿顯示前板之步驟（烘 烤步驟）的說明。 圖5係爲顯影後之圖案的剖面圖，其係藉先前技術製 造電漿顯示前板之方法製得。 圖6 A係爲烘烤後之圖案的剖面圖，其係藉先前技術 製造電漿顯示前板之方法製得。 圖6B係爲另一圖案在烘烤後之剖面圖，其係藉先前 技術製造電漿顯示前板之方法製得。 圖7 A係爲顯影後之圖案的剖面圖，其係藉本發明製 -53- 200535564 (50) 造電漿顯不前板之方法製得。 藉本發 型經烘 型經烘 :8B中 182 ) 圖7 B係爲另一圖案在顯影後之剖面圖，其係 明製造電漿顯示前板之方法製得。 圖8 A係爲使用製造電漿顯示前板所用之薄板 烤坯體來製造電漿顯示前板的方法之說明。 圖8B係爲使用製造電漿顯示前板所用之薄板 烤坯體來製造電漿顯示前板的方法之說明。圖8 A J ’編號1 8係表示可移除之膜（承載膜1 8 〇或保護腹 【主要元件符號說明】 1 刖 板 2 背 板 3 光 罩 10 透 明 玻 璃 基 板 11 結 合 電 極 12 介 電 層 1 2 A 未 烘 烤 介 電 層 16 間 隔 器 層 1 6A 間 隔 器 材 料 層 1 6A’ 抗 蝕 劑 圖 案 19 保 護 膜 20 基 板 2 1 位 址 電 極 -54- 200535564 (51) 22 介 電 層 24 肋 條 26 火火 光 層 110 透 明 電 極 112 匯 流 排 電極BaMgAl14023: Eu, ZnS: (Ag, Cd), Y203: Eu, Y2Si05: Eu, Y3A15012: Eu, YB03: Eu, (Y, Gd) B03: Eu, G d BO 3 'Eu, ScB〇3: Eu, L11BO3: Eu, Z n 2 S i 0 4 · Mn, BaAl12〇i9: Mn, SrAl13019 · · Mn, CaAli2019: Mn, YB03: Tb, BaMgAl] 4〇23: Mn, LuB03: Tb, GdBO: Tb, φ ScB03Tb, Sr6Si 3 03 Cl4: Eu, ZnS: (Cu, Al), ZnS: Ag, Y 2 〇2 S: E u, Z n S: Z n, (Y, C d) BO 3: E u, B a M g A11 2 0 2 3: Ευ and the like, and metal powders such as iron, nickel, palladium, tungsten, copper, aluminum, silver, gold, platinum and the like. In particular, glass, ceramics, etc. are preferred because of superior transparency. Glass powder (glass frit) is particularly useful for producing the most important effects. When the inorganic powder contains silicon oxide, aluminum oxide or titanium oxide, it becomes opaque and decreases the light transmittance, and therefore it is desirable that the inorganic powder may not contain such an ingredient. The particle size of the inorganic powder depends on the shape of the pattern to be formed, but the average particle size used is 0. 1 to 10 microns of inorganic powder is preferred, and 0.  5 to 8 -25- 200535564 (22) micron is better. An average particle size of more than 10 microns is not good because it forms an uneven surface when forming a high-accuracy solution, but is less than 0. The average particle size of 1 micron is inferior because of insufficient insulation and insufficient dispersion due to the formation of pores during baking. The inorganic powder may be in the form of spheres, cubes, flakes, and branches, and one of these forms or a combination of two or more of them may be used. The inorganic powder may contain, in addition to black, an inorganic pigment that emits, for example, red light, blue light, and green light. The composition of the photosensitive insulating paste containing these pigments can be used to form patterns of various colors, and is suitable for preparing, for example, a color filter in a plasma display panel. The inorganic powder may be a mixture of fine particles having different physical properties. In particular, glass powders and ceramic powders having different thermal softening points can be used to suppress shrinkage during baking. This inorganic powder can be combined with a combination of changing the shape and physical number depending on the properties of the partition wall and the like. As mentioned earlier, the inorganic powder has an average particle diameter of 1 to 10 microns, that is, 10 microns or less. Therefore, in order to prevent secondary aggregation and improve dispersibility, its surface can be treated with a silane coupling agent, a titanate-based coupler, an aluminum-based coupler, and a surfactant in advance. Does not destroy the properties of the inorganic powder. In the first treatment method, the treatment agent may be dissolved in an organic solvent or water, and then an inorganic powder is added and stirred. After the solvent is saturated, the heat treatment may be performed at about 50 to 200 ° C for 2 hours or more. This treatment agent can be added when the photosensitive composition is converted into a paste. (d) Binder resin In general, a binder resin can be added to the photosensitive inorganic paste composition to improve coating properties and film forming properties. In the present invention, the binder resin-26-200535564 (23) may be a known binder resin, and is not particularly limited. Acrylic resins, cellulose derivatives, polyvinyl alcohol, polyvinyl butyral, poly Ethylene glycol, urethane resin and melamine resin. It is preferable to contain an acrylic resin, especially an acrylic resin having a hydroxyl group, to form an image having improved development resistance and excellent accuracy. In the photosensitive inorganic paste composition of the present invention, an acrylic resin having a hydroxyl group and a water-soluble cellulose derivative are preferably used in combination, because φ can be changed, such as ultraviolet rays, excitation lasers, X-rays, electron rays, and the like. Transmittance to form a pattern with superior accuracy. The acrylic resin having a hydroxyl group may include a copolymer prepared by polymerizing a hydroxyl-containing monomer (as a main copolymerizable monomer) and, if necessary, another copolymerizable monomer. The hydroxyl-containing monomer may preferably be an alkylene oxide adduct of an alkylene oxide added to acrylic acid or methacrylic acid, especially an adduct of ethylene oxide, propylene oxide, or butylene oxide. , Or a mixture of these adducts, examples of which may include hydroxymethyl acrylate, methacrylic hydroxy methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate Ester, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and the like, and epoxy-based ester compounds such as acrylic acid or methacrylic acid with C 1 to C 1 0 glycol Monoester, glyceryl acrylate, glycerol methacrylate, bis (isopentaerythritol) monoacrylate, bis (isopentaerythritol) mono (methacrylate), ε-caprolactone modified acrylic hydroxyl Ethyl esters, -27- 200535564 (24) Hydroxyethyl methacrylate, phenoxypropyl acrylate, etc. modified with ε-caprolactone. Preferred examples of other monomers copolymerizable with hydroxyl-containing monomers are α, / 3-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, citraconic acid, itaconic acid, maleic acid, fumaric acid Diacids, etc. or half esters; a, yS unsaturated carboxylic acid esters, such as methyl ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-isobutyl acrylate, second butyl acrylate, acrylic acid Cyclohexyl, ethylhexyl, stearyl acrylate, methyl methacrylate, methyl ethyl ester, n-propyl methacrylate, isopropyl methacrylate, second propyl acid, n-butyl methacrylate , Second butyl methacrylate, cyclohexyl methacrylate, methyl propylene; methylhexyl ester, stearyl methacrylate, acrylic acid 2,2,2-trifluoroacrylic acid 2,2 , 2-trifluoromethyl, etc., styrene and styrene derivatives such as α-methylstyrene, p-vinyltoluene and the like. In addition, methacrylonitrile, methacrylonitrile, acrylamide, methacrylamide, esters, glycidyl acrylate, glycidyl methacrylate can be used alone or in combination of two or more of them. The water-soluble cellulose derivative to be used may be known and limited, and examples thereof may include carboxymethyl cellulose, methylol cellulose based cellulose, ethyl methyl cellulose, hydroxypropyl cellulose, ethyl acetate Cellulose, carboxymethylethylcellulose, hydroxypropylmethylcellulose, etc. may be used alone or in combination of two or more thereof. Examples of 2-hydroxy-3- include itaconic acid, itaconic acid, and its anhydride, butyl acrylate, 2-propenoic acid methyl butyl acrylate, 2-ethyl methyl hexanoate, and formazan. Propylene acetate and the like can be used. These are not particularly vegetarian, hydroxyethyl ethyl hydroxyvitamin, and the like. -28- 200535564 (25) (e) Formulation ratio of each component In the photosensitive inorganic paste composition of the present invention, the ratio of the Norish type composite initiator and the hydrogen-resistant type photopolymerization initiator can be as follows. The proportion of the type I photopolymerization initiator may be in the range of 1 to 90 parts by weight, and the proportion of the hydrogenated type photopolymerization initiator may be in the range of 10 to 99. The ratio of the Norish type I photopolymerization initiator is preferably in the range of 50 parts by weight, and the ratio of the hydrogenated photopolymerization initiator is 50 to 90 parts by weight. The Norish type I photopolymerization initiator may be more preferably in the range of 20 to 40 parts by weight, and the proportion of the hydrogenated photopolymerization agent may be 60 to 80 parts by weight. All ratios are based on the parts by weight. The sum of two ingredients. Especially when the photosensitive inorganic paste composition of the present invention is used as a spacer material in a plasma display, the ratio of the hydrogenated photopolymerization initiator to the photopolymerization initiator in the photomechanical paste composition is determined as The phase is better. In detail, the ratio of the Norish type I photopolymerization initiator φ is 10 to 90 parts by weight, and the ratio of the hydrogenated photopolymerization initiator is 10 to 90 parts by weight. The Norish type I photopolymerization initiator Chevroja may be 20 to 50 parts by weight ' and the argon type photopolymerization may be 50 to 80 parts by weight. The proportion of the Norish type I photopolymerizing agent may be more preferably 30 to 40 parts by weight, and the proportion of the hydrogenated initiator may be 60 to 70 parts by weight. All ratios are photosensitive inorganic pastes. In the composition, 100 parts by weight of photopolymerization is initiated. When a plasma display front plate is manufactured, a non-photosensitive inorganic paste layer I is used to photopolymerize a Norish number in a range of parts by weight. 0 Re-display the sensitivity of the front plate is not high. Examples can be taken as examples. Proportion of the initiator. Photopolymerization based on the sum of the agents. Unbaked dielectric layer -29- 200535564 (26) 1 2 A series The bottom layer is disposed under the photosensitive inorganic paste film 1 and exposed. Because of this, the effect of vignetting becomes apparent not only by the light reflected by the inorganic powder contained in the photosensitive organic paste film, but also by the light reflected by the inorganic powder contained in the unbaked dielectric layer 12A. It becomes obvious, so there is an inclination to widen the bottom width Wbtm of the pattern after exposure. However, when the blending ratio of the Norish type I photopolymerization initiator to the hydrogenated photopolymerization initiator is set within the foregoing range, the cross section of the pattern after φ light can become close to a rectangle or trapezoid, where the bottom of the pattern is The width Wbtm is slightly smaller than the top width Wt () p, and prevents the dielectric layer from deforming and cracking due to contraction of the pattern during baking. In the photosensitive inorganic paste composition of the present invention, the ratio of the water-soluble cellulose derivative to the acrylic resin having a hydroxyl group can be as follows. The proportion of the water-soluble cellulose derivative may be in the range of up to 90 parts by weight based on 100 parts by weight of the two components, and the example of the acrylic resin having a hydroxyl group may be 50 to 10 parts by weight. The ratio of the water-soluble cellulose derivative φ may be in the range of 60 to 80 parts by weight, and the ratio of the acrylic resin having a hydroxyl group may be 40 to 20 parts by weight. The proportion of the water-soluble cellulose derivative is more preferably in the range of 60 to 70 parts by weight, and the proportion of the acrylic resin having a hydroxyl group may be 40 to 30 parts by weight. Based on the sum of 100 parts by weight of the water-soluble cellulose derivative and the photopolymerizable polymer, the usable range of the photopolymerization initiator is preferably 0.1. 1 to 10 servings, more preferably 0. 2 to 5 parts by weight. When the proportion of the photopolymerization initiator is lower than 0. At 1 part by weight, curing properties may be reduced. When the proportion of the photopolymerization initiator is higher than 10 parts by weight, the bottom may have a weight of 50 due to the initial 6 A Μ j \ \\ bottom exposure. The ratio is more than the single weight mixture of the system- 30- 200535564 (27) absorption may cause insufficient curing. The ratio of organic components such as binder resins (such as water-soluble cellulose derivatives and acrylic acid-based resins, photopolymerization initiators, etc.) to inorganic components such as glass frit and other inorganic powders can be as follows. Based on the total weight of the photosensitive inorganic paste composition, the proportion of the organic component may be in the range of 0 to 40 parts by weight, and the proportion of the inorganic component may be in the range of 90 to 60 parts by weight. The proportion of the organic component may be preferably 15 to 35 parts by weight, and the proportion of the inorganic component Φ may be 85 to 65 parts by weight. The proportion of the organic component is more preferably 20 to 30 parts by weight, and the proportion of the inorganic component is 80 to 70 parts by weight. When forming the spacer material layer, if necessary, a solvent may be added to keep the viscosity of the photosensitive inorganic paste composition of the present invention within an appropriate range. The solvent contained in the photosensitive inorganic paste composition is not particularly Limitation, as long as it is sufficient to dissolve the organic components, the photosensitive inorganic paste composition # can have an appropriate viscosity, and can be easily evaporated and removed by drying. The solvents are particularly preferably ketones, alcohols and esters having a boiling point of 100 to 200 ° C. Examples of such solvents may include ketones such as diethyl ketone, methylbutyl ketone, dipropyl ketone, cyclohexanone, and the like; alcohols such as n-pentanol, 4-methyl-2-pentanol, Cyclohexanol, diacetone alcohol, etc .; ether alcohols, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Di (ethylene glycol) monomethyl ether, bis (ethylene glycol) monoethyl ether, bis (ethylene glycol) dimethyl ether, bis (ethylene glycol) diethyl ether, etc .; saturated alkyl aliphatic Monocarboxylic acid esters, such as n-butyl acetate, ethyl-31-200535564 (28) amyl esters, etc .; Lactates, such as ethyl lactate, n-butyl lactate, etc .; and ether-based esters, such as methyl formate Base cellolysin acetate, ethyl cellolysin acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, acetic acid 2- Methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate Ester, 3-ethyl-3-methoxybutyl acetate, 2-ethyl acetate Butyl acetate, butyl 4-ethoxy, propoxy, φ acetic acid 4-butyl, 2-methoxyethyl acetate, amyl acetate and the like, and these may be used alone or in a mixture wherein two or more. The content of the solvent may be preferably 300 parts by weight or less, more preferably 10 to 70 parts by weight, and most preferably 25 to 35 parts by weight based on 100 parts by weight of the inorganic and organic components. In addition to the foregoing, additional ingredients such as ultraviolet absorbers, sensitizers, polymerization inhibitors, plasticizers, thickeners, organic solvents, dispersants, defoamers, and organic or inorganic suspending agents may be added if necessary. φ Polymerization inhibitors can be added to improve thermal stability during storage. Specific examples can include hydroquinone, hydroquinone monoester, N-nitrosodiphenylamine, phenoxamine, p-tert-butylbenzene Phenol, N-phenylnaphthylamine, 2,6-di-third-butyl-p-methylphenol, chloroquinone, pyrogallol, and the like. Plasticizers used to improve the plasticity of the substrate may include phthalates, especially dibutyl phthalate (DBP), dioctyl phthalate (DOP), polyethylene glycol, glycerol, tartaric acid diester, etc. Diethyl tartrate, dibutyl tartrate, etc., and citrates, especially triethyl citrate, tributyl citrate, and the like. -32- 200535564 (29) Specific examples of defoamers may include alkanediol-based defoamers such as polyethylene glycol (molecular weight 400 to 800), polysiloxane and higher alcohols to reduce paste Or bubbles in the film and can reduce the porosity after baking. (B) Thin-plate type unbaked blank for manufacturing plasma display front plate The thin-plate type unbaked blank system for manufacturing plasma display front plate according to the present invention includes at least the photosensitive inorganic paste composition of the present invention. The spacer material layer formed by the coating film is formed on the unbaked green body on the removable carrier film. It is considered that the thin-plate unbaked body of the present invention can be mainly a single-layer structure consisting of only a spacer material layer, a double-layer structure consisting of a spacer material layer and an unbaked dielectric layer or a flammable intermediate layer, Or a three-layer structure consisting of a spacer material layer, an unbaked dielectric layer, and a flammable intermediate layer ^ Both surfaces of these single-to-three-layer structures can be easily removed by removable In addition to the carrier film to protect, so that the unbaked body can be easily. Storage, transportation and handling. • The thin-plate unbaked green body of the present invention can be stored for a predetermined period of time during the effective use period after manufacturing, and can be used immediately when manufacturing a plasma display front panel to increase the manufacturing efficiency of the plasma display front panel. Hereinafter, a detailed example of providing a thin-plate type unbaked body of the present invention will be described in detail. One of them is a thin-plate type unbaked green body that forms a coating film of the photosensitive inorganic paste composition of the present invention on a removable carrier film. The spacer material layer is formed by applying the photosensitive inorganic paste composition of the present invention diluted with a solvent to a concentration suitable for application to a peelable carrier film. The spacer material layer is covered with a protective film as a protective layer after -33- 200535564 (30). Another example is a thin plate type unbaked body having a layer of spacer material and an unbaked dielectric body. A spacer material layer composed of the photosensitive inorganic paste composition of the present invention is formed on a peelable carrier film. Subsequently, an unbaked dielectric layer composed of a non-photosensitive inorganic paste composition is formed on the spacer material layer, and is covered with a protective film as a protective layer. Yet another example is a φ thin-plate type unbaked green body having a flammable intermediate layer formed on a spacer material layer. A spacer material layer composed of a coating film of the photosensitive inorganic paste composition of the present invention is formed on a peelable carrier film. A water-soluble or water-swellable flammable intermediate layer is formed on the spacer material layer and covered with a protective film as a protective layer. Another example is a thin plate type unbaked green body with a flammable intermediate layer and an unbaked dielectric layer on the spacer material layer. In Fig. 18A, a spacer material layer 16 A composed of a coating film of a photosensitive inorganic paste composition of the present invention is formed on a peelable carrier film 180. A water-soluble or water-swellable flammable intermediate layer 14 is formed on the spacer material layer 16 A, and an unbaked dielectric layer 12A composed of a non-photosensitive inorganic paste film is formed thereon. The unbaked dielectric layer 12A is covered with a protective film 182 as a protective layer. Among these examples, a thin-plate type unbaked body in which a coating film of the photosensitive inorganic paste composition of the present invention is formed on a removable carrier film and covered with a protective film is most preferably used. The individual layers constituting the thin-plate type unbaked green body of the present invention are described below, and the method of manufacturing the thin-plate type unbaked green body of the present invention is described in detail later. -34- 200535564 (31) (a) Spacer material layer Spacer material layer 16 A is used to pattern one by lithography and then remove the organic material, and bake the same in the baking step at the same time The inorganic powder forms a layer of 16 A of spacer layers. In the present invention, the spacer material layer 16A is prepared by using the photosensitive inorganic paste composition of the present invention. In the present invention, the Norish type I photopolymerization initiator and the hydrogenated photopolymerization initiator are used in combination, so that the profile φ of the pattern after exposure is close to a rectangle or a trapezoid, and the bottom width Wbtm of the pattern may be slightly smaller than Top width WtOp. The patterned spacer material layer 6A can be shrunk by subsequent baking treatment. However, by slightly reducing the bottom width Wbtm of the pattern, it is possible to prevent the pattern from being deformed or broken when the pattern shrinks. When patterned between: the frit contained in the material layer of the promoter is melted during the baking process (described below), the sidewall of the pattern may collapse. When the pattern is a trapezoid in which the bottom width Wbtm of the pattern is slightly smaller than the top width WtC) p, the 'bottom width Wbtm is preferably increased to a certain extent by deliberately baking it by a baking process to improve the pattern Stability. On the one hand, when the cross-section of the formed pattern is close to a rectangle, it is preferable to maintain the rectangle even after the baking process, so it is preferable to prevent the sidewall of the pattern from collapsing during the baking process. To prevent the sidewall of the pattern from collapsing during baking, the softening point of the glass frit contained in the spacer material layer is preferably set higher than the softening point of the glass frit contained in the unbaked dielectric layer. In particular, the softening point of the glass frit contained in the spacer material layer can be adjusted to be at least 5 ° C higher than the softening point of the glass frit contained in the unbaked dielectric layer (at least 7 ° C as (Better at least 10 ° c), to make the pattern sidewall collapse during the baking process -35- 200535564 (32) to a negligible degree. The thickness of the spacer material layer obtained by drying the coating film of the photosensitive inorganic paste composition of the present invention may be 10 to 50 m, and preferably 15 to 40 m. (b) Unbaked dielectric layer The unbaked dielectric layer 1 2 A is an inorganic paste film prepared by drying a coating film formed of a non-photosensitive inorganic paste group φ. The unbaked dielectric layer 12A is a layer that is the dielectric layer 12 in the baking step, in which the organic material is removed and the inorganic powder is baked at the same time. The inorganic paste composition for forming the unbaked dielectric layer 1 2 A contains inorganic powder and a binder resin as a main component%. As the inorganic powder contained in the non-photosensitive inorganic paste composition for forming the unbaked dielectric layer, the inorganic powder as described in the photosensitive inorganic paste composition of the item (A) can be used. φ The binder resin contained in the non-photosensitive inorganic paste composition may be a known binder resin and is not particularly limited. Acrylic resin, cellulose derivative, polyvinyl alcohol, polyvinyl butyral, poly Glycol, polyester resin, urethane resin, etc. It is preferable to contain a propionic acid-based resin, especially an acrylic resin having a hydroxyl group, in order to have excellent thermal adhesion to a glass substrate. As for the acrylic resin having a hydroxyl group, an acrylic resin as described in the photosensitive inorganic paste composition of (A) can be used. The ratio of the entire inorganic component (that is, the glass frit and the inorganic particles) to the organic component such as the binder resin can be as follows. Based on the total amount of -36- 200535564 (33) inorganic components and organic components, the proportion of organic components is 10 to 40 parts by weight, and the proportion of inorganic powder is 90 to 60 parts by weight number. The proportion of the organic component is preferably 15 to 35 parts by weight 'and the proportion of the inorganic powder is 85 to 65 parts by weight. The proportion of the organic component is more preferably 20 to 30 parts by weight, and the proportion of the inorganic powder is 80 to 70 parts by weight. An amount exceeding the foregoing range is disadvantageous, because when the proportion of the organic component is less than 10 parts by weight, a thin film cannot be formed, and when the organic component is more than 40 parts by weight, the shrinkage may occur significantly after baking. When the unbaked dielectric layer is formed, a solvent may be added if necessary to keep the viscosity of the non-photosensitive inorganic paste composition within an appropriate range. As for the solvent contained in the non-photosensitive inorganic paste composition, the solvent described in (A) Light, sensitive inorganic paste composition can be used. In order to keep the viscosity of the non-photosensitive inorganic paste composition within an appropriate range, the content of the solvent is preferably 300 parts by weight or less based on 100 parts by weight of the inorganic and organic components. The amount of solvent is better for viscosities up to 3000 csp or more φ, and more preferably 5000 cps or more. The non-photosensitive inorganic paste composition may contain various additives such as a plasticizer, a dispersant, an adhesive, a surface tension modifier, a stabilizer, and a defoaming agent as alternatives to the inorganic powder, the binder resin, and the solvent Sexual ingredients. The unbaked dielectric layer can be formed by forming a coating film of a non-photosensitive inorganic paste composition and then drying the coating film to remove the solvent. The thickness of the unbaked dielectric layer after drying may be 10 to 100 μm, preferably 25 to 70 μm. -37- 200535564 (34) (c) Flammable intermediate layer The flammable intermediate layer 14 is a water-soluble or water-swellable layer, which is dissolved or moisturized by washing to raise and remove the remaining The spacer material layer on the part where the developer is removed. The flammable intermediate layer 14 is a layer that can be selectively provided on the spacer material layer 16A. When manufacturing the plasma display front plate, this flammable intermediate layer is located between the unbaked | baked dielectric layer and the spacer material layer, as described in detail in the manufacturing method below. When the spacer material layer in this laminated state is irradiated with patterned light and developed to pattern the spacer material layer, residues of the spacer material may remain in a flammable intermediate layer between the pattern protrusions On the exposed surface. The residue of the spacer material remaining between the pattern protrusions is melted due to the baking treatment, and the exposed surface of the dielectric layer, which should have been a uniform and smooth surface, is destroyed, thereby forming an uneven surface. In order to solve this problem, a flammable intermediate layer is disposed between the unbaked dielectric layer and the spacer material layer, so that the residue of the spacer φ material is formed on the surface of the flammable intermediate layer. In the case of exposure, the interval in the exposure area is washed away by the developing solution (water or aqueous solution) together with the material residue and the flammable intermediate layer. When the flammable intermediate layer is water-swellable, the intermediate layer is swelled by the developing solution, which raises the residue of the spacer material on the surface, and the residue can be easily washed away with the developing solution. After completing its work, the flammable intermediate layer that allows the residue of the spacer material to be removed by the developing solution is completely burned by the baking treatment of the unbaked dielectric layer and the unbaked spacer material layer. As a result, a dielectric layer and a spacer layer having a structure and dimensions similar to those of the prior art were formed on the glass substrate to form a front plate. The difference between the formed front plate of the present invention and the prior art is that the exposed surface of the dielectric layer between the spacer layer and its adjacent spacer layer is not uniform in the prior art, and before the invention The exposed surface in the plate is smooth. This is an important effect obtained particularly by providing a water-soluble or water-swellable flammable intermediate layer between the unbaked dielectric layer and the spacer material layer. φ As long as the flammable intermediate layer 14 is water-soluble or water-swellable and is decomposed and burned out by baking at 400 to 70 0 ° C, the intermediate layer is not particularly limited, but it is preferably composed of at least one It consists of water-soluble resin and water-swellable resin. The flammable intermediate layer is preferably formed using a flammable intermediate layer composition containing a solvent and at least one water-soluble resin and a water-swellable resin. As for the water-soluble resin, polyvinyl alcohol, a polyvinyl alcohol derivative, water-soluble cellulose, and the like can be preferably used. As for the water-swellable resin, a partially cross-linked product of a water-soluble resin can be used. These can be used singly or in combination of two or more of them. Polyvinyl alcohol derivatives may include, in particular, polyvinyl alcohol modified with silanol, polyethylene glycol modified with cation, polyethylene glycol containing chlorothio group, butyraldehyde resin, and the like. Particularly, water-soluble cellulose may include, for example, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, carboxyl cellulose Methyl ethyl cellulose, hydroxypropyl methyl cellulose, and the like. Among them, polyvinyl alcohol and hydroxymethyl cellulose are preferred in terms of water solubility, thermal degradation, and solvent resistance (a solvent in the dielectric layer -39- 200535564 (36)). The solvent used to form the flammable intermediate layer is not particularly limited, as long as it is sufficient to dissolve the water-soluble resin or water-swellable resin, can make the viscosity suitable for coating, and can be evaporated and removed by drying. Water and organic can be used Solvents such as propanol. The flammable intermediate layer can be formed by diluting a water-soluble resin or a water-swellable resin to a concentration suitable for coating by using a solvent to form a coating film of the composition, and φ is formed by removing the solvent by drying. The proportion of the water-soluble resin or water-swellable resin in the flammable intermediate layer composition used to form the flammable intermediate layer is preferably 50% by weight or less, more preferably 30% by weight or less, and most preferably The preferred range is 0.1 to 20% by weight. For flammability, the thickness of the intermediate layer is preferably 20 micrometers or less, more preferably 10 micrometers or less, and 5 micrometers or less. The flammable interlayer is too thin to be less desirable because the pattern of the photosensitive unexposed unbaked spacer material layer may also be removed in a later development step. The optimal thickness of the flammable intermediate layer φ is 0. 1 to 3 microns. (d) Method for manufacturing thin-plate type unbaked green body As for the carrier film 1 80 'used in the thin-plate type unbaked green body of the present invention, the layers formed above can be easily detached and unbaked. The layer is transferred to a removable film on a glass substrate without particular limitation. Examples thereof may include a flexible film having a thickness of 15 to 125 m composed of a synthetic resin film such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, polyvinyl chloride, and the like. The carrier film is preferably subjected to a detachment treatment in order to facilitate the transfer of -40-200535564 (37). In order to form a spacer material layer 16 A, a flammable intermediate layer 14 and an unbaked dielectric layer 1 2 A on the carrier film, a composition for forming each layer can be prepared, and then an applicator or a rod coater is used. , Wire rod applicator, slot type applicator, curtain flow applicator, etc. are applied to the carrier film 180. In particular, a roll coater is preferable because a thick film having an excellent uniform thickness can be effectively formed. After the coating film is dried, the dried coating film can be coated with another composition as a subsequent layer, and the layers are laminated with φ to prepare the thin-plate type unbaked green body of the present invention. The protective film 182 is preferably adhered to the surface opposite to the carrier film 180 to stably protect the photosensitive paste composition layer and the like before use. The protective film is preferably a polyethylene terephthalate film, a polypropylene film, or a polyethylene film having a thickness of about 15 to 125 micrometers. The upper layer is coated with polysiloxane or manufactured by baking (C). Plasma display front plate method The method for manufacturing a plasma display front plate of the present invention includes laminating an unbaked dielectric layer and a spacer material layer on the surface of an electrode on a glass substrate in this order, and then using a pattern The spacer material layer is irradiated with the light, and development is performed to pattern the spacer material layer. At the same time, the unbaked dielectric layer and the patterned spacer material layer on the silicon substrate are subjected to a baking treatment so as to be simultaneously applied to the glass substrate A dielectric layer and a spacer layer are formed thereon. In the present invention, the water-soluble or water-resistant flammable intermediate layer may be disposed between the unbaked dielectric layer and the spacer material layer as appropriate. Aqueous solution or developing liquid can be used to dissolve or swell to produce the spacer layer and can be burned by baking treatment. «41-200535564 (38) The material layer made up is preferably laminated on the unbaked dielectric layer and the layer formed on it. The spacer material layer becomes an intermediate layer. Subsequent exposure processing and subsequent processing can be performed in a customary manner to remove the spacer material residues remaining in the recessed portions between the patterns before the baking process, and the intermediate layer is burned out by the baking process, and the layer after baking is stacked The body structure becomes the same as the prior art. (a) Formation of each layer on the glass substrate The method of laminating an unbaked dielectric layer and a spacer material layer on the glass substrate is not particularly limited, and each layer can be used in a known manner such as, for example, a coating method, a screen printing method Is stratified. However, from the standpoint of forming a layer having a uniform thickness and having excellent surface smoothness, the method for forming individual layers using the aforementioned thin unbaked green body of the present invention is the best. An example of a method for manufacturing a plasma display front plate using the thin-plate type unbaked body of the present invention will be described in detail. First, a thin-plate-type unbaked green body having a carrier film, a spacer material layer, and a protective layer laminated in this order is prepared. Unbaked dielectric layers are individually formed on the surface of the glass substrate on which the electrodes have been formed. The method of forming the unbaked dielectric layer is not particularly limited, but it is preferred to apply a non-photosensitive inorganic paste composition on a carrier film and dry to form an unbaked dielectric layer, and if necessary, by coating And dried to form a flammable intermediate layer, and then laminated on the glass substrate, so that the unbaked dielectric layer is in contact with the surface of the glass substrate on which the electrodes have been formed, and the unbaked dielectric layer is moved by the heated roller It is transferred to the glass substrate by the carrier film. After that, the protective film is removed from the thin-plate type unbaked body, and the peeled spacer material layer is adhered to the unbaked dielectric layer. The heat roller is then moved onto the carrier film -42- 200535564 (39) to heat press the spacer material layer onto the surface of the unbaked dielectric layer. The hot pressing may preferably be a rolling pressure in the range of 1 to 5 kg / cm2 and 0 '' to 10. It is performed at a traveling speed of 0 m / min, and the surface temperature of the glass substrate is heated at 80 to 140 ° C. The glass substrate can be preheated, and the preheating temperature is selected, for example, in the range of 40 to 120 ° C. Hereinafter, another example of manufacturing a plasma display front plate using the following thin-plate type unbaked body will be described. First, a thin-plate type unbaked green body in which a carrier film, a spacer material layer, an unbaked dielectric layer, and a protective film are sequentially laminated is prepared. After removing the protective film from the thin plate unbaked green body, the unbaked dielectric layer is adhered to the surface of the glass substrate that is already provided with electrodes, and the heat roller is removed on the carrier film to remove the unbaked dielectric. The layer and the spacer material layer are hot pressed onto the glass substrate. A description will be given of another example of manufacturing a plasma display front plate using the following thin plate type unbaked body. First, a thin-plate type unbaked green body in which a carrier film, a spacer material layer, a flammable intermediate layer, and a protective film are sequentially laminated is prepared. An unbaked dielectric layer is individually formed on the surface of the glass substrate on which the electrodes have been formed. Remove the protective layer from the φ thin plate type unbaked body to expose the flammable intermediate layer. The exposed flammable intermediate layer is adhered to the unbaked dielectric layer formed on the surface of the glass substrate that has been prepared with electrodes. The heat roller is then moved on the carrier film to heat press the flammable intermediate layer and the spacer material layer on the surface of the glass substrate. Referring to FIG. 8A and FIG. 8B, the plasma is manufactured using the following thin plate type unbaked green body Show another example of the front panel. First, a thin plate-type unbaked layer having a carrier film 1 80, a spacer material layer 6 A, a flammable intermediate layer 1 4, an unbaked dielectric layer 1 2 A, and a protective film 1 8 2 is sequentially laminated. Baked green body (Figure 8A) -43- 200535564 (40). The protective layer 182 is removed from the thin-plate type unbaked green body to expose the unbaked dielectric layer 12A. The exposed unbaked dielectric layer 12A is adhered to the glass substrate 10, and the surface of the electrode is prepared. The roller 40 is removed from the carrier film 180 to heat press the unbaked dielectric layer 12 A, the flammable intermediate layer 14 and the spacer material layer 16A on the surface of the glass substrate (FIG. 8B). (b) Exposure / development processing φ Exposure processing and subsequent processing can be performed according to customary methods. The exposure / development process is described in detail with reference to Figs. 4a to 4c. According to the aforementioned method, the unbaked dielectric layer 12a and the spacer material layer 16a are formed on the glass substrate, and then the photomask 3 is placed on the spacer material layer 16a, which is then exposed to make the pattern portion The layer of spacer material is cured (Figure 4A). In the present invention, since the Norish type I photopolymerization initiator and the hydrogenated type photopolymerization initiator are used simultaneously, the effect of being suppressed by oxygen can be prevented. Therefore, even if the surface of the spacer material layer 16 A is not covered with a transparent film, the surface can still be cured. However, when dust or the like adheres to the surface of the spacer material layer 16 A due to static electricity, the quality may be deteriorated. Therefore, if a transparent film is used as the carrier film in the thin-plate unbaked green body of the present invention, it is preferable that the carrier film 1 80 remains adhered to the space after the layers are laminated on the glass substrate. Exposure is performed on the device layer 16 A. After exposure, the carrier film can be removed by 180 °. As for the radiation irradiation device used in the exposure, an ultraviolet irradiation device generally used in lithography and semiconductor manufacturing can be used. And liquid crystal display exposure device. -44- 200535564 (41) After that, the uncured portion 16 A of the photosensitive unexposed unbaked spacer is removed by development, so that the resist pattern 丨 6 A appears (4B). In the development process, a general-purpose alkali developing solution or water can be used. The alkali component in the shadow solution may include alkali metals such as lithium, sodium, potassium and the like, carbonates, bicarbonates, phosphates and pyrophosphates, such as benzylamine, butylamine, etc., and secondary amines such as dimethylamine. Diamine, dibenzyl φ diethanolamine, etc., tertiary amines such as trimethylamine, triethylamine, tertiary, cyclic amines such as morpholine, piperine, pyridine, etc., polyamines such as ethylene dimethylene diamine, etc. Ammonium hydroxide such as tetramethylammonium hydroxide, hydroethylamine, trimethylbenzyl ammonium hydroxide, trimethylphenyl hydroxide. , Etc., trimethylphosphonium hydroxide, phosphonium hydroxide such as trimethyloxydiethylmethylphosphonium hydroxide, dimethylbenzylphosphonium hydroxide, etc., a buffering agent for choline salts The composition of the glass frit is preferably water. φ The cross-section of the pattern formed by the Norish photopolymerization initiator used in combination with the hydrogenated photopolymerization initiator can be made close to rectangular 7A, or trapezoidal, where the bottom width of the pattern Wbtm is slightly smaller than the width WtC) p, As shown in Figure 7B. That's why it prevents deformation or cracking of the dielectric layer during processing. (c) Baking the laminated body with the pattern formed on the upper layer can be baked to make the non-dielectric layer 12 A and the photosensitive unexposed unbaked spacer material layer material layer. Allylamine, ethanolamine, tetrabenzyl ammonium hexaoxide, hydrogen, silicon-containing damage type I, as shown on the top at 16A 'in baking baking -45- 200535564 (42) The glass frit contained These layers are individually baked into a dielectric layer 12 and a spacer layer 16. Thus, a plasma display front plate including the patterned spacer layer 16 on the dielectric layer 12 was prepared (refer to FIG. 4C). The temperature used in this baking may be a temperature at which the organic material in the photosensitive inorganic paste composition disappears due to combustion and the inorganic powder is baked, and may be baked at 400 to 700 ° C for 10 to 90 minutes. When the softening point of the inorganic powder contained in the spacer material layer is adjusted to be higher than the softening point of the inorganic powder contained in the non-φ baked dielectric layer to prevent the sidewall of the pattern from collapsing during the baking process, the baking The temperature is preferably adjusted to be not higher than the softening point τ 1 (art) of the inorganic powder contained in the spacer material layer and not lower than the softening point T2 (° c) of the inorganic powder contained in the unbaked dielectric layer. ) (τ2 < τ!). In particular, the baking temperature is preferably slightly lower than the softening point T! Of the inorganic powder contained in the spacer material layer. The baking temperature may preferably be τ 2. 〇 or better and T] ° c or lower 'better (Ti-5) ° C or higher and TVC or lower' better (Ti-7) C or more than round and lower, especially About (_ Trio). (:. After the plasma 7K board is manufactured in this way (with a patterned spacer layer formed on a dielectric layer 'and the dielectric layer is formed on a glass substrate with electrodes on the upper layer), it is not covered. The dielectric layer and the spacer layer may preferably be covered with a protective layer 19, such as M g 0, etc. [Embodiment] The present invention will be described in more detail in accordance with the following embodiments. However, the present invention is not limited to this. This. -46- 200535564 (43) < Experimental Example 1 > (Preparation of Photosensitive Inorganic Paste Composition) As for a water-soluble cellulose derivative, 22 parts by weight of hydroxypropyl cellulose and 14 parts by weight as an acrylic resin having a hydroxyl group Styrene / hydroxyethyl methacrylate = 5 5/45 (wt%) copolymer (Mw = 40,000), 60 parts by weight of 2-methacrylic acid phthalic acid φ 醯 ethoxyethyl as photopolymerizable monomer 2-Hydroxypropyl ester (trademark: η〇MPP, manufactured by Kyoeisha Chemical Co., Ltd.), 0.9 parts by weight 2,2-mono > methoxy-2 -phenylethylfluorenylbenzene (Trademark ·· IR-651, Norish Type I, manufactured by Chiba-Geigy) and 1.8 parts by weight of 2,4-diethylthioxanthone as a photopolymerization initiator (· Trademark ·· DETX-S, Pull hydrogen type, manufactured by Nippon Kayaku Co., Ltd.), 3.9 parts by weight of butyl tartrate as a plasticizer, and 0.1 parts by weight of azo-based dyes as a UV absorber (trademark: Dye SS, Daito Chemix Corporation) and 3-methoxy-3-methylbutanol with 100 parts by weight of φ as a solvent were mixed by a mixer for 3 hours to prepare an organic Parts solution. Thereafter, 40 parts by weight of the organic component solution (50% solids content) and 80 parts by weight of the glass frit having a softening point of 5 8 ° C as an inorganic component were kneaded to prepare a photosensitive inorganic paste composition. < Experimental example 2 > (Preparation of non-photosensitive inorganic paste composition) 4 5 parts by weight of methacrylic acid as acrylic resin having a hydroxyl group-47- 200535564 (44) isobutyl acid acid / methacrylic acid hydroxyl group Ethyl ester = 60/40 Mw = 7 0 000), 5 parts by weight as a plasticizer, 5 5 parts by weight as a solvent, 3-methoxy-3-methyl water bath, stir at 80 ° C 2 hours, liquid. Thereafter, 40 parts by weight of the organic component was dissolved and 80 parts by weight of the glass and the sensitive inorganic paste composition having a softening point of 5 to 74. < Experimental example 3> (4 parts by weight of a composition for forming a flammable intermediate layer, polyvinyl alcohol (trademark: manufactured by PVA · Ltd.), and 53 parts by weight as a solvent 7 "Propanol was mixed by a mixer 1 2 hours to prepare impermeable < Example 1 > Composition of non-photosensitive inorganic paste of Experimental Example 2 on a carrier film made of ethylene formate, so that the thickness of the shape is 60 micrometers, and the upper layer is formed with a coating temperature of 100 ° C , 2.5 kg / cm2 Lamination | Layering at a lamination speed on the dielectric layer of glass preheated at 80 ° C. M $ The prepared photosensitive inorganic paste is composed on the g # m layer, so that the thickness of the film after drying @ Μ @ experimental square pattern mask exposure from the ultra-high (wt%) copolymer (: dibutyl phthalate) Esters and i-butanol are prepared in a device to dissolve organic ingredients [(solid content 50%) kneading to prepare non-light preparation) -23 5, Kuraray Co " < Different layer composition from 43 parts by weight. The product is applied to a coating film made of polyparaphenylene and the film is dried. This coating film was then applied to g force and 1.0 m / min to form an unbaked product. Then applied to the unbaked system at 40 micrometers, 400 millijoules of pressure mercury lamp -48- 200535564 (45) Ear / cm2 of ultraviolet light. Thereafter, spray development was performed using water having a liquid temperature of 30 ° C at a spray pressure of 3.0 kg / cm2 for 30 seconds to form a pattern. The adhesion of the formed pattern was evaluated, and it was found that the minimum remaining line width was 60 μm and the minimum formation interval was 60 μm. The cross-section of the formed pattern is trapezoidal, where the bottom width Wbtm is smaller than the top width Wt () p, and Wt () p: wbtm is 1 ·· 0.9. In order to evaluate the shape stability of the pattern after baking, a pattern with a cover φ curtain line width of 200 μm was formed according to the aforementioned method, and the baking process was performed. The sample was heated at an increasing temperature of 10 ° c / minute, and then Hold at 580 ° C for 30 minutes. As a result, a good baked pattern is maintained. The cross section of the pattern after baking is rectangular, where Wtcp: Wbtm is 1: 1. < Example 2 > The non-photosensitive inorganic paste composition of Experimental Example 2 was applied to a carrier film made of removable polyethylene terephthalate (trademark: Pur ex A24, Teijin D) by a lip applicator. u Ρ ο nt F i 1 ms (manufactured by J ap an Limited), the formed coating film was dried at OO ° C for 6 minutes to completely remove the solvent to form an unbaked thickness of 60 μm on the carrier film Dielectric layer. The flammable intermediate layer-forming composition of Experimental Example 3 was then applied to the unbaked dielectric layer formed on the carrier film by a lip applicator. The coating film was dried at 100 ° C for 6 minutes to completely transfer Remove the solvent 'to form a flammable intermediate layer with a thickness of 0.5 micron on the unbaked dielectric layer. The photosensitive inorganic paste composition of Experimental Example 1 was applied to a flammable intermediate layer formed on a carrier film by a lip applicator, and the coating film was dried at 100 ° C for 6 -49- 200535564 (46) minutes. The solvent was completely removed to form a layer of photosensitive unexposed unbaked spacer material with a thickness of 40 microns. After that, a protective film made of removable polyethylene terephthalate (trademark: Purex A53, manufactured by Teijin DuPont Film) was stacked on the photosensitive unexposed unbaked spacer material layer to obtain 5 layers. Structure water-developing photosensitive film. The peeling is a removable polyethylene terephthalate (trademark: Purex A24, manufactured by Teijin ^ DuPont Films Japan Limited), which is the carrier film of the water-developing photosensitive film prepared above, and the photosensitive film is borrowed from a heat roller The laminator was laminated on a 15 ° C on a glass substrate with bus electrodes formed on the upper layer and heated at 80 ° C in advance. The air pressure was 3 kg / cm2, and the lamination speed was 1.0 m / min. The The photosensitive film was exposed to ultraviolet light from an ultra-high pressure mercury lamp through an experimental square pattern mask with an exposure amount of 300 mJ / cm2. After removing the polyethylene terephthalate protective film, the liquid temperature was 3 (TC water was spray-developed under a spray pressure of 3 kg / cm2 for 30 seconds to form a pattern. The adhesion of the pattern formed by φ and the shape of the pattern were evaluated, and the minimum remaining line width was 60 microns, and the minimum formation interval was found. It is 60 microns, which is a good pattern shape. The cross-section of the pattern is trapezoidal, where the bottom width Wbtm is smaller than the top width WtQp, and WtC) p ·· Wbtm is 1: 0.9. To evaluate the pattern after baking, Dimensional stability The method described above forms a pattern with a line width of 200 micrometers and performs a baking treatment, in which the sample is heated at an increasing temperature of 10 ° C / minute, and then maintained at 580 ° C for 30 minutes. As a result, the Good baked pattern. The cross section of the pattern after baking is rectangular, where Wt () p: Wbtm is 1: 1. -50- 200535564 (47) < Example 3 > The composition for forming a flammable intermediate layer of Experimental Example 3 was applied to a carrier film made of polyethylene terephthalate so that the thickness of the coating film after drying was 0.5 μm, and thereafter This coating film was dried at 100 ° C for 6 minutes to remove the solvent and form a flammable intermediate layer. Thereafter, the non-photosensitive inorganic paste composition of Experimental Example 2 was applied on the upper layer and dried to form a coating film, so that the thickness of the φ coating film after drying was 60 m. The surface of the coating film is adhered to the preheated glass, and the lamination is performed at 8 ° C at a lamination temperature of 100 ° C, a lamination pressure of 2.5 kg / cm2, and a lamination speed of 1.0 m / min. An unbaked dielectric layer having a flammable intermediate layer formed thereon is formed. Then, the carrier film is removed. The photosensitive inorganic paste composition prepared above is then applied to the unbaked dielectric layer so that the formed coating is The thickness of the film after drying was 40 micrometers, and it was exposed to ultra-high pressure mercury lamps through a test square pattern mask to expose ultraviolet light with a quantity of φ 400 mJ / cm2. Then, water with a liquid temperature of 30 t was used. The pattern was spray-developed for 30 seconds at a spray pressure of 3.0 kg / cm2 to form a pattern. The adhesion of the formed pattern was evaluated, and the minimum remaining line width was 60 microns and the minimum formation interval was 60 microns. The profile of the formed pattern was It is trapezoidal, where the bottom width Wbtm is smaller than the top width WtC) p, and WtC) p: Wbtm is 1: 0.9. In order to evaluate the shape stability of the pattern after baking, a pattern with a mask line width of 200 μm was formed according to the aforementioned method, and the baking process was performed. The sample was heated at an increasing temperature of 10 ° C / min, and then maintained 5 8 0 ° C after 30 minutes 200535564 (48) minutes. As a result, a good baked pattern is maintained. The cross section of the pattern after baking is rectangular ' where Wt. p · W b t 111 is 1 · 1. < Comparative Example 1 > A photosensitive inorganic paste composition and an insulating sheet composition were prepared in the same manner as in Example 1, except that 0.9 parts by weight of Norish type I photopolymerization initiator 2,2-dimethylamine was used alone in different places. Oxy-2-phenylethenylbenzene (trademark •: IR-65 1, manufactured by Ciba-Geigy) was used as a photopolymerization initiator in a photosensitive inorganic paste composition, and the adhesion was evaluated in the same manner as described above. As a result, the minimum line width of the residue was 60 micrometers, but the minimum formation interval was 100 micrometers. The cross-section of the formed pattern is trapezoidal, where the bottom width wbtm is greater than the top width Wt〇p 'and Wt () p: Wbtm is 0.6: 1. < Comparative Example 2 > A photosensitive inorganic paste composition # and an insulating sheet composition were prepared in the same manner as in the previous example. The difference was that 1.8 parts by weight of a hydrogenated 2,4-dimethylthio compound was used alone. Ton ketone (trademark: DETX-S, manufactured by Nippon Kayaku Co., Ltd.) was used as a photopolymerization initiator in the photosensitive inorganic paste composition, and spray-developed for 30 seconds as described above. As a result, the pattern is washed away and cannot be cured. Industrial application is as described above. 'The photosensitive inorganic paste composition of the present invention can be produced by combining a Norish type I photopolymerization initiator and a hydrogenated photopolymerization initiator. -52- 200535564 (49) Good pattern Shape, and therefore can be preferably used as a material for forming multilayer circuits and various displays such as plasma displays, plasma address liquid crystal displays, etc., especially for use in manufacturing spacers in plasma display front panels that require high accuracy Material layer. [Brief description of the drawings] Fig. 1 is an exploded view of an electric hair display with a wafer-shaped structural member. Fig. 2 is a perspective view of a back side of a plasma display front plate. Fig. 3 is a cross-sectional view of a plasma display having a wafer-shaped structural member. Fig. 4 A is an explanation of a step (exposure step) of manufacturing a plasma display front panel by lithography. Fig. 4B is an explanation of the steps (developing steps) for manufacturing a plasma display front panel by lithography. φ Figure 4 C is an illustration of the steps (baking step) for manufacturing a plasma display front panel by lithography. Fig. 5 is a cross-sectional view of a pattern after development, which is made by a method for manufacturing a plasma display front plate by the prior art. Fig. 6A is a cross-sectional view of a pattern after baking, which is made by a method of manufacturing a plasma display front plate by the prior art. Fig. 6B is a cross-sectional view of another pattern after baking, which is made by a method of manufacturing a plasma display front plate by the prior art. Figure 7A is a cross-sectional view of the pattern after development, which is made by the method of the present invention -53- 200535564 (50) Plasma display front plate. Borrowed by this type of hair-type baking type: 182 in 8B) Figure 7B is a cross-sectional view of another pattern after development, which is prepared by the method of manufacturing a plasma display front plate. Fig. 8A is an illustration of a method for manufacturing a plasma display front plate using a thin plate baked body for manufacturing a plasma display front plate. Fig. 8B is an illustration of a method for manufacturing a plasma display front plate using a thin plate baked body for manufacturing a plasma display front plate. Figure 8 AJ 'No. 1 8 indicates a removable film (bearing film 1 8 〇 or protective belly [Description of main component symbols] 1 fascia 2 back plate 3 photomask 10 transparent glass substrate 11 bonding electrode 12 dielectric layer 1 2 A unbaked dielectric layer 16 spacer layer 1 6A spacer material layer 1 6A 'resist pattern 19 protective film 20 substrate 2 1 address electrode-54- 200535564 (51) 22 dielectric layer 24 rib 26 fire Flare layer 110 Transparent electrode 112 Bus electrode

Claims (1)

200535564 ⑴ 十、申請專利範圍 1 · 一種光敏性無機糊料組成物，其包含光聚合起始 劑、光可聚合單體及無機粉末，其中 該光聚合起始劑係同時含有Norish類型I光聚合起始 劑及拉氫型光聚合起始劑兩者。 2 ·如申g靑專利範圍第1項之光敏性無機糊料組成物 ，其中該Norish類型I光聚合起始劑係爲選自安息香醚化 φ 合物、苄基縮酮化合物、α -羥基乙醯苯化合物、α _胺基 乙醯苯化合物、雙醯基膦氧化物化合物、醯基膦氧化物化 合物、苯基二羰基化合物、苯基醯基肟化合物及其混合物 中之化合物。 3 ·如申請專利範圍第1項之光敏性無機糊料組成物 ，其中該拉氫型聚合起始劑係爲選自芳族酮化合物、@ _ 酮化合物、蒽醌化合物、具有二烷基胺基之芳族化合物、 烷基烷醇胺及其混合物之化合物。 φ 4 ·如申請專利範圍第1項之光敏性無機糊料組成物 ，其中該Ν 〇 r i s h類型I光聚合起始劑係爲苄基縮酮化合物 ，而該拉氫型光聚合起始劑係爲噻噸酮化合物。 5 ·如申請專利範圍第1項之光敏性無機糊料組成物 ，其中相對於該光敏性無機糊料組成物中1 0〇重量份數之 該Ν 〇 r i s h類型I光聚合起始劑與該拉氣型光聚合起始劑總 量，該Norish類型I光聚合起始劑之含量係爲1 〇至99重 量份數，而該拉氫型光聚合起始劑之含量係爲90至丨重 量份數。 -56 - 200535564 (2) 6 · —種用於製造電漿顯示前板之薄板型未烘烤坯體 ’該前板係包含表面上形成有多個電極之玻璃基板、形成 於該基板上之介電層及多層形成於該介電層上而具有均勻 厚度的間隔器層，該未烘烤坯體係包含： 可移除之承載膜及配置於其上層之光敏性未曝光未烘 烤間隔器材料層，該間隔器材料層係含有光聚合起始劑、 光可聚合單體及無機粉末，其中該光聚合起始劑係同時含 鲁 有Norish類型1光聚合起始劑及拉氫型光聚合起始劑兩者 〇 7 ·如申請專利範圍第6項之用以製造電漿顯示前板 的薄板型未烘烤坯體’其進一步包含配置於該間隔器材料 層上之未烘烤介電層，而該未烘烤介電層係含有無機粉末 及黏合劑樹脂。 8 ·如申g靑專利範圍第7項之用以製造電漿顯示前板 的薄板型未烘烤坯體，其中該間隔器材料層中所含之無丰幾 φ 粉末的軟化點係高於該未烘烤介電層中所含之無機粉$白勺 軟化點。 9 ·如申請專利範圍第8項之用以製造電漿顯示前板 的薄板型未烘烤坯體，其中該間隔器材料層中所含之無機 粉末的軟化點係較該未烘烤介電層中所含之無機粉$自勺車欠 化點高出至少5 °C。 1 0 .如申請專利範圍第6項之用以製造電漿顯示前板 的薄板型未烘烤坯體，其係包含位於該間隔器材料層上之 水溶性或水可潤脹性可燃性中間層。 -57- 200535564 (3) 1 1 · 一種製造電漿顯示前板之方法，該前板係包含表 面上形成有多個電極之玻璃基板、形成於該基板上之介電 層及多層形成於該介電層上而具有均勻厚度的間隔器層， 該方法係包含： (a )依序於具有該電極之該玻璃基板的表面上形成 未烘烤之介電層及光敏性未曝光未烘烤間隔器材料層，其 中該未烘烤介電層係含有無機粉末及黏合劑樹脂，且其中 φ 該光敏性未曝光未烘烤間隔器材料層係含有光聚合起始劑 、光可聚合單體及無機粉末’該光聚合起始劑係同時含有 Norish類型I光聚合起始劑及拉氫型光聚合起始劑兩者， (b )使用圖案化光照射該間隔器材料層並顯影，以 將該間隔器材料層圖案化，及· (c )同時烘烤位於該玻璃基板上之未烘烤介電層及 經圖案化之間隔器材料層，以同時於該玻璃基板上形成該 介電層及該間隔器層。 § 1 2 ·如申請專利範圍第1 1項之製造電漿顯示前板之 方法，其中該間隔器材料層中所含之無機粉末的軟化點係 較該未烘烤介電層中所含之無機粉末的軟化點高出至少5 °C。 1 3 ·如申請專利範圍第1 2項之製造電漿顯示前板之 方法，其中在步驟（c )中，烘烤溫度係爲不低於該未烘 烤介電層中所含之無機粉末的軟化點且不高於該間隔器材 料層所含之無機粉末的軟化點之溫度。 1 4 ·如申請專利範圍第1 1項之製造電漿顯示前板之 -58- 200535564 (4) 方法，其中在步驟（a )中，該未烘烤介電層係形成於該 玻璃基板上，之後於其上層積如申請專利範圍第6項之用 以製造電漿顯示前板之薄板型未烘烤坯體，使得該間隔器 材料層位於該未烘烤介電層上。 1 5 ·如申請專利範圍第1 1項之製造電漿顯示前板之 方法，其中在步驟（a )中，層積如申請專利範圍第7項 之用以製造電漿顯示前板之薄板型未烘烤坯體，使得該未 • 烘烤介電層係位於該玻璃基板上。200535564 十 X. Patent application scope 1 · A photosensitive inorganic paste composition comprising a photopolymerization initiator, a photopolymerizable monomer, and an inorganic powder, wherein the photopolymerization initiator contains both Norish type I photopolymerization Both initiators and hydrogenated photopolymerization initiators. 2. The photosensitive inorganic paste composition according to item 1 of the patent application, wherein the Norish type I photopolymerization initiator is selected from the group consisting of benzoin etherified φ compound, benzyl ketal compound, and α-hydroxyl group. Acetylbenzene compounds, α-aminoethynylbenzene compounds, bisfluorenylphosphine oxide compounds, fluorenylphosphine oxide compounds, phenyldicarbonyl compounds, phenylfluorenyloxime compounds, and mixtures thereof. 3. The photosensitive inorganic paste composition according to item 1 of the application, wherein the hydrogenated polymerization initiator is selected from the group consisting of aromatic ketone compounds, @ _ ketone compounds, anthraquinone compounds, and dialkylamines. Based aromatic compounds, alkylalkanolamines, and mixtures thereof. φ 4 · The photosensitive inorganic paste composition according to item 1 of the scope of the patent application, wherein the NOR type I photopolymerization initiator is a benzyl ketal compound, and the hydrogenated type photopolymerization initiator is It is a thioxanthone compound. 5. The photosensitive inorganic paste composition according to item 1 of the scope of the patent application, wherein the NR type I photopolymerization initiator and the photopolymerization initiator with respect to 100 parts by weight of the photosensitive inorganic paste composition The total amount of the gas-drawing type photopolymerization initiator. The content of the Norish type I photopolymerization initiator is 10 to 99 parts by weight, and the content of the gas-drawing type photopolymerization initiator is 90 to 丨 by weight. Number of copies. -56-200535564 (2) 6 · —A thin-plate type unbaked blank for manufacturing a plasma display front plate 'The front plate includes a glass substrate with a plurality of electrodes formed on the surface, and a glass substrate formed on the substrate. A dielectric layer and a plurality of spacer layers having a uniform thickness are formed on the dielectric layer. The unbaked blank system includes: a removable carrier film and a photosensitive unexposed unbaked spacer disposed on the upper layer. Material layer, the spacer material layer contains a photopolymerization initiator, a photopolymerizable monomer, and an inorganic powder, wherein the photopolymerization initiator system contains both a Norish type 1 photopolymerization initiator and a hydrogen-type photopolymerization initiator. Both of polymerization initiators.7. As the thin-plate type unbaked green body used to manufacture the plasma display front plate according to item 6 of the patent application scope, it further includes an unbaked medium disposed on the spacer material layer. An electrical layer, and the unbaked dielectric layer contains an inorganic powder and a binder resin. 8. The thin-plate type unbaked green body used to manufacture the plasma display front plate as described in item 7 of the patent scope, wherein the softening point of the non-abundant φ powder contained in the spacer material layer is higher than The softening point of the inorganic powder contained in the unbaked dielectric layer. 9 · If the thin-plate type unbaked green body for manufacturing a plasma display front plate is applied for item 8 of the scope of patent application, the softening point of the inorganic powder contained in the spacer material layer is higher than that of the unbaked dielectric. The inorganic powder contained in the layer is at least 5 ° C higher than the scouring point of the scoop. 10. The thin-plate type unbaked green body for manufacturing a plasma display front plate according to item 6 of the scope of patent application, which includes a water-soluble or water-swellable flammable intermediate layer on the spacer material layer. Floor. -57- 200535564 (3) 1 1 · A method for manufacturing a plasma display front plate, the front plate comprising a glass substrate having a plurality of electrodes formed on a surface, a dielectric layer formed on the substrate, and a plurality of layers formed on the substrate A spacer layer having a uniform thickness on a dielectric layer, the method includes: (a) sequentially forming an unbaked dielectric layer and a photosensitive unexposed unbaked layer on a surface of the glass substrate having the electrode; Spacer material layer, wherein the unbaked dielectric layer contains an inorganic powder and a binder resin, and wherein φ the photosensitive unexposed unbaked spacer material layer contains a photopolymerization initiator and a photopolymerizable monomer And inorganic powder 'The photopolymerization initiator system contains both Norish type I photopolymerization initiator and hydrogenated photopolymerization initiator. (B) The patterned light is irradiated on the spacer material layer and developed to Patterning the spacer material layer, and (c) simultaneously baking the unbaked dielectric layer and the patterned spacer material layer on the glass substrate to simultaneously form the dielectric on the glass substrate Layer and the spacer layer. § 12 · The method for manufacturing a plasma display front plate according to item 11 of the patent application scope, wherein the softening point of the inorganic powder contained in the spacer material layer is higher than that in the unbaked dielectric layer. The softening point of the inorganic powder is at least 5 ° C higher. 1 3 · The method for manufacturing a plasma display front plate according to item 12 of the patent application scope, wherein in step (c), the baking temperature is not lower than the inorganic powder contained in the unbaked dielectric layer The softening point is not higher than the softening point of the inorganic powder contained in the spacer material layer. 1 4-The method of manufacturing a plasma display front panel according to item 11 of the patent application -58- 200535564 (4) method, wherein in step (a), the unbaked dielectric layer is formed on the glass substrate Then, a thin plate-type unbaked green body for manufacturing a plasma display front plate is laminated on the upper layer, such that the spacer material layer is located on the unbaked dielectric layer. 15 · The method for manufacturing a plasma display front panel according to item 11 of the patent application scope, wherein in step (a), the thin plate type for manufacturing a plasma display front panel as described in item 7 of the patent application scope is laminated The green body is not baked so that the unbaked dielectric layer is located on the glass substrate. -59--59-
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