1311688 (1) 九、發明說明 【發明所屬之技術領域】 本發明係關於光敏性絕緣糊料組成物及使用彼之光敏 性薄膜。更特定言之’本發明係關於一種縱使在厚膜層中 仍具有高光敏性並足以確保高精密度圖形形成的光敏性絕 緣糊料組成物，彼含有無機粉末及具高度抗顯影劑特性之 有機組份。同時本發明也係關於使用此一光敏性絕緣糊料 組成物之光敏性薄膜。 【先前技術】 傳統上，如絲網印刷術及光刻術之技術已可用於厚膜 多層電路及各種顯示板之構件的製造上。在絲網印刷術中 ’所需之圖形係利用一含有無機粒子之光可熟化絕緣糊料 而在基材上絲網印刷。在光刻術中，塗布於基材上之光可 熟化絕緣糊料組成物係透過光罩使用激活光線，如UV光 照射以便在該基材上顯影出所要之圖形。 在各種形式之顯示板中，電漿顯示板（本文以下稱之 爲P D P S ”）具有相對簡單的構造，因此適用於大型顯示器 。P D P s係一發射裝置，不但可顯示高品質影像，還可顯 示高品質的彩色圖像。由於這些有利的特徵，P D P s已吸 引眾多的注意，也已努力進行了各種提案以便開發可顯現 更出色之圖像的更大型電漿顯示器。 PDP包含兩個對立基材’在此之間有眾多的顯示單元 格被絕緣性屏蔽肋材界定住。每一單元格充當爲像素並含 有一螢光物質，其一旦經由電漿發射之UV輻射曝光後就 -5- (2) 1311688 會發出光。需要產生電漿之電極、電阻器、介電質、及其 他組件係放在基材上或放在單元格內。爲了構成一高精密 度PDP，其組件，包括屏蔽肋材、電極、電阻器、介電質 、螢光物質、彩色濾光器、及黑色矩陣需精密地建構起來 (這些組件在本文以下將總稱爲”屏蔽肋材或其類似物·'） 。最後，形成屏蔽肋材或其類似物之圖形也就可精密地形 成。 在習知之絲網印刷技巧中，由糊料組成物構成之預定 圖形係印刷在另一圖形的上面以形成多層圖形。而爲了精 確地對準這些圖形以便形成高精密度屏蔽是很困難的。光 刻技巧也具有缺點：欲形成屏蔽肋材之薄膜物質在厚膜層 中的光敏性將易於隨著深度而減低。此舉也使形成高精密 度圖形變得困難。再者，光刻術需要昂貴的溶劑，如三氯 乙烷，作爲顯影劑。此舉將增加製造成本。這些有機溶劑 也會引起環境污染，並對人體健康有害。 爲了解決這些與利用有機溶劑之顯影過程有關的問題 ，業已提出一可在水溶液中顯影的光可熟化絕緣糊料組成 物。此組成物含有水溶性纖維素如甲基纖維素、光聚合單 體、光聚合引發劑、及無機粉末（舉例之，可參閱專利文 獻1 (日本專利特許公開申請案第Sho 63 — 26523 8案號） )。然而，此一組成物並沒有充足的抗顯影劑特性。因此 ，目前所提出一光敏性絕緣糊料組成物不但可解決此一問 題，還可解決絲網印刷術中無法準確地形成屏蔽肋材之問 題（其是因影像區域溶解及影像區域未對準所引起）。此 組成物含有水溶性纖維素衍生物、光聚合單體、含羥基丙 -6- (3) 1311688 烯酸系樹脂、光聚合引發劑、及無機粉末（舉例之，可參 閱專利文獻2 (日本專利特許公開申請案第2002 — 328470 案號））。 【發明內容】 然而，專利文獻2所揭示之光敏性絕緣糊料組成物若 含有50重量份或更多量之含羥基疏水性丙烯酸系樹脂（ 以水溶性纖維素衍生物及含羥基疏水性丙烯酸系樹脂之組 合量（=100重量份）計）時，在顯影過程期間會生成殘 留物。此丙烯酸系樹脂乃加入使該組成物更具有抗顯影劑 特性。而此殘留物將干擾顯影過程。 鑒於目前之技術狀態，本發明人在尋求解決前述問題 時已有顯著成果。此一努力終於導致如下發現，只要該含 羥基丙烯酸系樹脂具有不超過2 00 00的分子量，縱使該組 成物含有90至50重量份的含羥基丙烯酸系樹脂（以水溶 性纖維素衍生物及含羥基丙烯酸系樹脂之組合量（=1 00 重量份）計），也不會阻礙顯影過程，同時該組成物之抗 顯影劑特性也可藉由將含羥基丙烯酸系樹脂之量調整至50 重量份或更大量（以水溶性纖維素衍生物及含羥基丙烯酸 系樹脂之組合量（=1 〇〇重量份）計）而增進。本發明係 以此一發現爲基礎。 因此，本發明之目標係提供一種光敏性絕緣糊料組成 物，彼縱使含有相當量疏水性樹脂組份但仍可於鹼性顯影 劑或水中顯影，並可形成厚膜但仍具高光敏性膜層的薄膜 物質，因而可適用於高精密度圖形。本發明之另一目標係 (4) 1311688 提供一種利用此光敏性絕緣糊料組成物之光敏性薄膜。 如本發明之光敏性絕緣糊料組成物含有有機組份及無 機粉末。該有機組份含有（A )水溶性纖維素衍生物、（B )具有分子量爲20000或更低之含羥基丙烯酸系樹脂、（ C)光聚合單體、及（D)光聚合引發劑。較佳地，該光敏 性絕緣糊料組成物各別含有10至50重量份及90至50重 量份之組份（A )及組份（B )(以該有機組份中之組份（ A )和組份（B )之組合量（=1 00重量份）計）。 較佳地，該用於本發明之光敏性絕緣糊料組成物的無 機粉末係玻璃粉，且該組成物各別含有1 〇至5 0重量份及 90至50重量份之組份（A )及組份（C )(以該有機組份 中之組份（A )和組份（C )之組合量（=100重量份）計 )° 較佳地，本發明之光敏性絕緣糊料組成物各別含有5 至35重量份及95至65重量份之有機組份及無機粉末（ 以有機組份和無機粉末之組合量（=1 〇〇重量份）計）。 本發明之光敏性薄膜，其特徵爲上述之光敏性絕緣糊 料組成物的塗層係在一支撐膜形成。 當本發明之光敏性絕緣糊料組成物用於水中或鹼性顯 影劑中以便使高精密度圖形顯影時可展現優異性能：該組 成物可用來形成厚膜但仍具高光敏性高精密度之絕緣體圖I 形。據此，本發明之光敏性絕緣糊料組成物能以低成本製 造高精密度之PDPs，所以具有顯著的工業價値。 【實施方式】1311688 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a photosensitive insulating paste composition and a photosensitive film using the same. More specifically, the present invention relates to a photosensitive insulating paste composition which is highly photosensitive in a thick film layer and which is sufficient to ensure high-precision pattern formation, which contains an inorganic powder and is highly resistant to developer. Organic ingredients. Also, the present invention relates to a photosensitive film using the photosensitive insulating paste composition. [Prior Art] Conventionally, techniques such as screen printing and lithography have been used for the manufacture of thick film multilayer circuits and members of various display panels. In screen printing, the desired pattern is screen printed on a substrate using a light containing inorganic particles that can be cured by an insulating paste. In lithography, the photo-curable insulating paste composition applied to the substrate is irradiated with activating light, such as UV light, through a reticle to develop a desired pattern on the substrate. Among various types of display panels, the plasma display panel (hereinafter referred to as PDPS) has a relatively simple structure and is therefore suitable for large displays. The PDP s is a launcher that not only displays high quality images but also displays High-quality color images. Due to these advantageous features, PDPs have attracted a lot of attention, and various proposals have been made to develop larger plasma displays that can display better images. PDP consists of two opposing bases. The material 'between there are numerous display cells defined by insulating shielding ribs. Each cell acts as a pixel and contains a fluorescent substance that is exposed to UV radiation emitted by the plasma -5- (2) 1311688 emits light. Electrodes, resistors, dielectrics, and other components that require plasma are placed on the substrate or placed in cells. To form a high-precision PDP, its components include Shielding ribs, electrodes, resistors, dielectrics, phosphors, color filters, and black matrices need to be carefully constructed (these components will be collectively referred to below as "screens") · Ribs or the like '). Finally, the pattern forming the shield rib or the like can be precisely formed. In the conventional screen printing technique, a predetermined pattern composed of a paste composition is printed on top of another pattern to form a multi-layer pattern. It is difficult to accurately align these patterns to form a high-precision shield. The lithographic technique also has the disadvantage that the photosensitivity of the film material to form the shielding ribs in the thick film layer will tend to decrease with depth. This also makes it difficult to form high-precision graphics. Further, photolithography requires an expensive solvent such as trichloroethane as a developer. This will increase manufacturing costs. These organic solvents also cause environmental pollution and are harmful to human health. In order to solve these problems associated with the development process using an organic solvent, a photocurable insulating paste composition which can be developed in an aqueous solution has been proposed. The composition contains a water-soluble cellulose such as methyl cellulose, a photopolymerizable monomer, a photopolymerization initiator, and an inorganic powder (for example, see Patent Document 1 (Japanese Patent Application Laid-Open No. Sho 63-26523 8) number) ). However, this composition does not have sufficient anti-developer properties. Therefore, a photosensitive insulating paste composition has been proposed not only to solve this problem, but also to solve the problem that the shielding rib cannot be accurately formed in screen printing (which is due to image area dissolution and image area misalignment). cause). This composition contains a water-soluble cellulose derivative, a photopolymerizable monomer, a hydroxypropyl-6-(3) 1311688 olefinic resin, a photopolymerization initiator, and an inorganic powder (for example, see Patent Document 2 (Japan) Patent Licensing Application No. 2002 — 328470 Case No.)). SUMMARY OF THE INVENTION However, the photosensitive insulating paste composition disclosed in Patent Document 2 contains 50 parts by weight or more of a hydroxyl group-containing hydrophobic acrylic resin (a water-soluble cellulose derivative and a hydroxyl group-containing hydrophobic acrylic acid). When the combined amount of the resin (= 100 parts by weight) is calculated, a residue is generated during the development process. This acrylic resin is added to make the composition more resistant to developer. This residue will interfere with the development process. In view of the current state of the art, the inventors have made significant achievements in seeking to solve the aforementioned problems. This effort has finally led to the discovery that the hydroxyl group-containing acrylic resin has a molecular weight of not more than 200 00, even if the composition contains 90 to 50 parts by weight of a hydroxyl group-containing acrylic resin (as a water-soluble cellulose derivative and The combined amount of the hydroxy acrylic resin (1 = 100 parts by weight) does not hinder the development process, and the anti-developer property of the composition can also be adjusted to 50 parts by weight of the hydroxyl group-containing acrylic resin. The amount is more or more (based on the combined amount of the water-soluble cellulose derivative and the hydroxyl group-containing acrylic resin (= 1 part by weight)). The present invention is based on this discovery. Accordingly, it is an object of the present invention to provide a photosensitive insulating paste composition which, while containing a relatively large amount of a hydrophobic resin component, can be developed in an alkaline developer or water, and can form a thick film but still has high photosensitivity. The film material of the film layer is thus suitable for high-precision graphics. Another object of the invention is (4) 1311688 which provides a photosensitive film utilizing the photosensitive insulating paste composition. The photosensitive insulating paste composition of the present invention contains an organic component and an inorganic powder. The organic component contains (A) a water-soluble cellulose derivative, (B) a hydroxyl group-containing acrylic resin having a molecular weight of 20,000 or less, (C) a photopolymerizable monomer, and (D) a photopolymerization initiator. Preferably, the photosensitive insulating paste composition separately contains 10 to 50 parts by weight and 90 to 50 parts by weight of the component (A) and the component (B) (in the component of the organic component (A) And the combined amount of component (B) (=1 00 parts by weight). Preferably, the inorganic powder-based glass powder used in the photosensitive insulating paste composition of the present invention, and the composition each contains 1 〇 to 50 parts by weight and 90 to 50 parts by weight of the component (A) And component (C) (in combination of component (A) and component (C) in the organic component (= 100 parts by weight)) preferably, the photosensitive insulating paste composition of the present invention Each of the materials contains 5 to 35 parts by weight and 95 to 65 parts by weight of the organic component and the inorganic powder (based on the combined amount of the organic component and the inorganic powder (= 1 part by weight)). The photosensitive film of the present invention is characterized in that the coating of the photosensitive insulating paste composition described above is formed on a support film. When the photosensitive insulating paste composition of the present invention is used in water or an alkaline developer to develop a high-precision pattern, it exhibits excellent properties: the composition can be used to form a thick film but still has high photosensitivity and high precision. Insulator Figure I shape. Accordingly, the photosensitive insulating paste composition of the present invention can produce high-precision PDPs at low cost, and thus has a remarkable industrial price. [Embodiment]
-8- (5) 1311688 本發明之範例式具體實施例將說明如下。 本發明之光敏性絕緣糊料組成物含有有機組份及無機 粉未。該有機組份含有（A )水溶性纖維素衍生物、（B ) 具有分子量爲20000或更低之含羥基丙烯酸系樹脂、（C )光聚合單體、及（D)光聚合引發劑。 本發明之光敏性絕緣糊料組成物含有水溶性纖維素衍 生物以作用爲黏合劑樹脂，因此可展現了較高的UV -光 、激元雷射、X_射線、電子光束及其他激活光線之透射 率’並且呈現比習知之以丙烯酸系樹脂爲基礎的光敏性絕 緣糊料組成物還高的抗顯影劑特性。基於此，本發明之組 成物能形成高度精確的圖形。 本發明之光敏性絕緣糊料組成物使用了具有分子量爲 2 0 000或更低之含羥基丙烯酸系樹脂充當爲組份（B)， 所以縱使彼含有50重量份或更多量之組份（B )(以水溶 性纖維素衍生物及含羥基丙烯酸系樹脂之組合量（=1 〇〇 重量份，本文以下將稱爲"樹脂總量”）計），也不會干擾 顯影過程。同時，該糊料組成物可藉由將組份（B)之量 調整至5 0重量份或更大量（以樹脂總量（=i 00重量份） 計）而展現出增進之可顯影性。 充當爲組份（A )之水溶性纖維素衍生物可爲任一已 知的水溶性纖維素衍生物’包括有羧甲基纖維素、羥乙基 纖維素、羥乙基甲基纖維素、羥丙基纖維素、乙基羥乙基 纖維素、羧甲基乙基纖維素、及羥丙基甲基纖維素。這些 纖維素衍生物可各別使用或以二或多個衍生物之混合物使 用。 -9- (6) 1311688 充當爲組份（B)之含羥基丙烯酸系樹脂典型地具有 分子量爲20000或更低’而以5000至15000爲較佳， 8000至12000更佳。若組份（B)之分子量超過20000且 含羥基丙烯酸系樹脂之量係50重量份或更大量（以水溶 性纖維素衍生物及含羥基丙烯酸系樹脂之組合量（=1 〇 〇 重量份）計），則組成物之可顯影性將減低並會生成不想 要的殘留物。 含羥基丙烯酸系樹脂係藉使一充當爲主要之共聚單體 的含羥基單體聚合而製得的共聚物。若需要時，也可使用 其他可與此含羥基單體共聚之單體。 此含羥基單體之較佳實例係丙烯酸或甲基丙烯酸與一 具有1至2〇個碳原子之一元醇反應中所生成的單醋，包 括有羥甲基丙烯酸酯、羥甲基甲基丙烯酸酯、2 -羥乙基 丙烯酸酯、2-羥乙基甲基丙烯酸酯、2 -羥丙基丙烯酸酯 、2-羥丙基甲基丙烯酸酯、3 -羥丙基丙烯酸酯、3 —羥 丙基甲基丙烯酸_醋、2—羥丁基丙烯酸酯、2 -羥丁基甲基 丙烯酸酯、3 -羥丁基丙烯酸酯、3 -羥丁基甲基丙烯酸酯 、4一羥丁基丙烯酸酯、及4 —羥丁基甲基丙烯酸酯。 其他含羥基單體之較佳實例包括丙烯酸或甲基丙烯酸 與一具有1至10個碳原子之乙二醇反應中所生成的單酯 ，以及環氧酯化合物，彼等包括有丙烯酸甘油酯、甲基丙 烯酸甘油酯、二季戊四醇一丙烯酸酯、二季戊四醇一甲基 丙烯酸酯、ε -己內酯-改質之丙烯酸羥乙酯、ε -己內 酯一改質之甲基丙烯酸羥乙酯、以及2 -羥基一 3 -苯氧基 丙基丙烯酸酯。 -10- (7) 1311688 其他可與含羥基單體共聚之單體較佳實例包括α , ^ -不飽和羧酸’如丙烯酸、甲基丙烯酸、衣康酸、檸康酸 、馬來酸、及富馬酸、及彼之酐類和半酯化產品；α，冷 -不飽和羧酸酯’丙烯酸甲酯、丙烯酸乙酯、丙烯酸正— 丙酯、丙烯酸異一丙酯、丙烯酸正- 丁酯、丙烯酸異—丁 酯、丙烯酸第二-丁酯、丙烯酸環己酯、丙烯酸2 -乙基 己酯、丙烯酸十八烷酯、甲基丙烯酸甲酯、甲基丙烯酸乙 酯、甲基丙烯酸正一丙酯 '甲基丙烯酸異一丙酯、甲基丙 烯酸第二一丙酯、甲基丙烯酸正-丁酯、甲基丙烯酸異一 丁酯、甲基丙烯酸第二一丁酯、甲基丙烯酸環己酯、甲基 丙烯酸2 -乙基己酯、甲基丙烯酸十八烷酯、丙烯酸酯 2,2,2—三氟甲酯、及甲基丙烯酸酯2,2,2 —三氟甲酯；以 及苯乙烯類，如苯乙烯、α —甲基苯乙烯、及對-乙烯基 甲苯。其他實例包括丙烯腈、甲基丙烯腈、丙烯醯胺、甲 基丙烯醯胺、醋酸乙烯酯、丙烯酸縮水甘油酯、及甲基丙 烯酸縮水甘油酯。這些化合物可各別使用或以二或多個化 合物之混合物使用。 本發明之光敏性絕緣糊料組成物較佳地含有50至90 重量份之含羥基丙烯酸系樹脂，而以60至80重量份爲更 佳，65至75重量份又更佳，以樹脂之總量（=1〇〇重量份 )計。 若含羥基丙烯酸系樹脂之量沒有落在特定範圍時，則 在所得之圖形中就無法達成所需的精確性：含羥基丙烯酸 系樹脂之量小於5 0重量份時會減低抗顯影劑特性，然而 該樹脂之量若大於90重量份，將易於導致變低之可顯影 -11 - (8) 1311688 性並在顯影過程期間會生成不想要的殘留物。舉例之’若 光聚合單體的量少於50重量份會引起不充份的光聚合反 應，進而依次地導致顯影期間圖像區域溶解，因而使圖像 成形失敗。對照下，光聚合單體的量若大於90重量份時 ，則會減低精細圖像的解析度。 充當爲組份（C)之光聚合單體可爲任一已知的光聚 合單體，其可包括，但不受限於，二丙烯酸乙二醇酯、二 甲基丙烯酸乙二醇酯、二丙烯酸三乙二醇酯、二甲基丙烯 酸三乙二醇酯、三丙烯酸三羥甲基丙烷酯、三甲基丙烯酸 三羥甲基丙烷酯、三丙烯酸三羥甲基乙烷酯、三甲基丙烯 酸三羥甲基乙烷酯、二丙烯酸季戊四醇酯、二甲基丙烯酸 季戊四醇酯、三丙烯酸季戊四醇酯、三甲基丙烯酸季戊四 醇酯、四丙烯酸季戊四醇酯、四甲基丙烯酸季戊四醇酯、 四丙烯酸二季戊四醇酯、四甲基丙烯酸二季戊四醇酯、五 丙烯酸二季戊四醇酯、五甲基丙烯酸二季戊四醇酯、六丙 烯酸二季戊四醇酯、六甲基丙烯酸二季戊四醇酯、丙烯酸 甘油酯、甲基丙烯酸甘油酯、及軸節形式（Cardo— type) 環氧基二丙烯酸酯，以及那些可各別地以富馬酸酯、衣康 酸酯和馬來酸酯置換上述所列之化合物的（甲基）丙烯酸 酯而獲得的富馬酸酯類、衣康酸酯類及和馬來酸酯類。 充當爲組份（D)之光聚合引發劑可爲任一通用之光 聚合引發劑，其包括，二苯甲酮類、苯偶姻類、苯偶姻烷 基醚類、苯乙酮類' 胺基苯乙酮類、苯甲基類、苯甲基烷 基縮酮、蒽醌、縮酮類、及噻噸酮類。特定之實例包括 2，4 —雙—二氯甲基一 6— (3 —溴基一 4 一甲氧基）苯基~s -12- (9) 1311688 —三嗪、2,4_雙一三氯甲基一 6— (2—溴基_4 一甲氧基 )苯基_s—三嗪、2,4_雙一三氯甲基一 6_ (3—溴基—4 一甲氧基）苯乙烯基苯基一 s—三嗪、2,4 -雙一三氯甲基 一 6— (2 -溴基一 4 -甲氧基）苯乙烯基苯基一s —三嗪、 2，4,6—三甲基苯甲醯二苯基膦化氧、1 一 [4- (2_羥乙氧 基）苯基]一2_經基_2-甲基_1_丙院—1一酮、2,4 — 二乙基噻噸酮、2,4 —二甲基噻噸酮、2—氯基噻噸酮、1 一氯基一 4 —丙氧基噻噸酮、3,3 —二甲基_4 一甲氧基二 苯甲酮、二苯甲酮、1_ (4_異丙基苯基）一2—羥基_2 一甲基丙烷一 1_酮、1_ (4 一十二烷基苯基）一 2 —羥基 —2—甲基丙烷一1—酮、4一苯甲醯基_4’_甲基二甲基 硫化物、4一二甲胺基苯甲酸酯、4 —二甲胺基苯甲酸甲酯 、4_二甲胺基苯甲酸乙酯、4一二甲胺基苯甲酸丁酯、4 一二甲胺基苯甲酸2_乙基己酯、4_二甲胺基苯甲酸2_ 異戊酯、2,2 -二乙氧基苯乙酮、苄基二甲基縮酮、苄基 —甲氧基乙基乙縮醛、1 一苯基一 1，2 —丙二酮一 2 — (鄰一乙氧基羧基）肟、鄰一苯甲醯苯甲酸甲酯、雙（4 一二甲胺基苯基）酮、4,4’ 一雙二乙胺基二苯甲酮、苯甲 基、苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙 基醚、苯偶姻正- 丁基醚、苯偶姻異丁基醚、對-二甲胺 基苯乙酮、對-第三一丁基三氯基苯乙酮、對-第三-丁 基二氯基苯乙酮、噻噸酮、2-甲基噻噸酮、2-異丙基噻 噸酮、二苯並環庚酮、-二氯基一 4 —苯氧基苯乙酮 、戊基—4 一二甲胺基苯甲酸酯、及2- （鄰一氯苯基）一 4,5 —二苯基咪唑基二聚物。這些化合物可各別使用或以 -13- (10) 1311688 二或多個化合物之混合物使用。 光聚合引發劑的使用量較佳地係在〇. 1至1 範圍內，而以〇. 2至5重量份更佳，以水溶性纖 物及光聚合單體之組合量（=100重量份）計。 發劑的量若小於0. 1重量份將導致變低的熟化性 ，若光聚合引發劑含有大於1 0重量份時，則會 達底部之前就吸收光，進而使之不充份熟化。 除了（ A )到（D )，本發明之光敏性絕緣 物還可含有光學添加劑，如UV吸收劑、敏化劑 輔導劑、聚合抑制劑、增塑劑、增稠劑、有機溶 劑、防泡劑、無機或有機懸浮劑。 敏化劑係基於增加敏化性而添加。敏化劑之 包括2,4 —二乙基噻噸酮、異丙基噻噸酮、2，3-二乙胺基苯叉）環戊酮、2,6—雙（4 一二甲胺基 己酮、2,6 —雙（4 —二甲胺基苯叉）-4—甲基 米勒氏（Michler’s)酮、4,4 一雙（二乙胺基） 、4，4~雙（二甲胺基）一查耳酮、4,4 一雙（二 '查耳酮、對-二甲胺基亞肉桂基茚滿酮、對— 节叉節滿酮、2— （對一二甲胺基苯基乙烯撐） 哩、1，3~雙（4~二甲胺基苯叉）丙酮、1，3_羰 4~二乙胺基苯叉）丙酮、3,3 —羰基一雙（7 -香旦素）、N_苯基—N—乙基乙醇胺、N —苯基 N—甲苯基二乙醇胺、N—苯基乙醇胺、二甲胺 異戊酯、二乙胺基苯甲酸異戊酯、3 一苯基一 5 一 嚷四哩、及丨一苯基_5_乙氧羰基噻四唑。這些 〇重量份 維素衍生 光聚合引 能，然而 在光線到 糊料組成 、敏化劑 劑、分散 特定實例 -雙（4- 苯叉）環 環己酮、 一苯甲酮 乙胺基） 二甲胺基 -異萘噻 基一雙（ 二乙胺基 乙醇胺、 基苯甲酸 苯甲醯基 敏化劑可 -14- (11) 1311688 各別使用或以二或多個之混合物使用。 聚合抑制劑係爲了增加儲存時之熱安定性而添加。聚 合抑制劑之特定實例包括氫醌、氫醌一酯、N -亞硝基二 苯胺、吩噻嗪、對一第三一 丁基兒茶酚、N-苯基萘胺、 2，6~二—第三一丁基—對_甲基酚、氯醌、及連苯三酚 增塑劑係爲了增進基材的一致性而添加。增塑劑之特 定實例包括鄰苯二甲酸酯類，如鄰苯二甲酸二丁酯（DBP )、鄰苯二甲酸二辛酯（DOP)、及鄰苯二甲酸二己酯（ D0P )、以及聚乙二醇、甘油、及酒石酸二丁酯。 防泡劑係爲防止在糊料或薄膜中形成氣泡，否則在烘 烤後會使微孔形成。防泡劑之特定實例包括那些以烷撐二 醇爲基礎者，如聚乙二醇（分子量=400至800)、矽酮類 、或闻碳醇類。 用於本發明之光敏性絕緣糊料組成物的無機粉末可爲 對所用光源呈透明狀之無機粉末。彼之實例包括玻璃、陶 瓷（如堇青石）、及金屬粉末。更特定之實例係由硼矽酸 錯玻璃、硼硅酸鋅玻璃、及硼硅酸鉍玻璃所組成之粉末， 例如 Pb0-Si02 玻璃、PbO — B203-Si02 玻璃、ZnO — Si〇2 玻璃、Zn〇— B203-Si02 玻璃、BiO— Si02 玻璃、及 Bi〇 — B2O3 - Si〇2 玻璃，Na、K、Mg、Ca、Ba、Ti、Zr、 及之氧化物所組成之粉末’例如氧化鈷、氧化鐵、氧 化鉻、氧化鎳、氧化銅、氧化鎂、氧化鈸、氧化釩 '氧化 鈽、二氧化鈦黃、氧化鎘、氧化釕、二氧化矽、氧化鎂、 及尖晶石；螢光物質組成的粉末，例如ZnO ·· Zn、Zn3 ( (β) -15- (12) !311688 P〇4 ) 2 : Mn ' Y2Si〇5 • C e、 CaWO 4 · Pb、BaMgA11 4 〇 2 3 : Eu 、 ZnS : ( Ag ， C u )、 Y2O3 Eu 、 Y2Si05 ： E u、 Y3AI5O12 : Eu ' YBO3 :E XI、 (Y， Cd ) B O3 : E11、 GdB03 :Eu 、 S cB 03 ： Eu 、LuB〇3 : Ευ i ' Z112 S i 0 4 : Μ n 、 BaAli2〇i9 : Mn ' SrAl 13 〇 19 : Mn、 Ci aAl)2〇i9 · Mn、 YBO3 :Tb、 BaMgAl"〇23 : Mn、 LuBO 3 :Tb 、 GdBO ： Tb、-8- (5) 1311688 An exemplary embodiment of the present invention will be described below. The photosensitive insulating paste composition of the present invention contains an organic component and an inorganic powder. The organic component contains (A) a water-soluble cellulose derivative, (B) a hydroxyl group-containing acrylic resin having a molecular weight of 20,000 or less, (C) a photopolymerizable monomer, and (D) a photopolymerization initiator. The photosensitive insulating paste composition of the present invention contains a water-soluble cellulose derivative to function as a binder resin, thereby exhibiting high UV-light, excimer laser, X-ray, electron beam and other activating light. The transmittance 'and exhibits higher anti-developer properties than the conventional acrylic resin-based photosensitive insulating paste composition. Based on this, the composition of the present invention can form a highly accurate pattern. The photosensitive insulating paste composition of the present invention uses a hydroxyl group-containing acrylic resin having a molecular weight of 20,000 or less to serve as the component (B), so that even if it contains 50 parts by weight or more of the component ( B) (The combined amount of the water-soluble cellulose derivative and the hydroxyl group-containing acrylic resin (= 1 part by weight, hereinafter referred to as "the total amount of the resin") does not interfere with the development process. The paste composition can exhibit improved developability by adjusting the amount of the component (B) to 50 parts by weight or more (based on the total amount of the resin (=i 00 parts by weight)). The water-soluble cellulose derivative as component (A) may be any known water-soluble cellulose derivative including carboxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxy Propylcellulose, ethylhydroxyethylcellulose, carboxymethylethylcellulose, and hydroxypropylmethylcellulose. These cellulose derivatives may be used individually or as a mixture of two or more derivatives. -9- (6) 1311688 hydroxy-based acrylic resin serving as component (B) The type has a molecular weight of 20,000 or less and preferably 5,000 to 15,000, more preferably 8,000 to 12,000. If the molecular weight of the component (B) exceeds 20,000 and the amount of the hydroxy-containing acrylic resin is 50 parts by weight or more (Based on the combined amount of the water-soluble cellulose derivative and the hydroxyl group-containing acrylic resin (= 1 part by weight)), the developability of the composition is lowered and an undesired residue is formed. The resin is a copolymer obtained by polymerizing a hydroxyl group-containing monomer serving as a main comonomer, and if necessary, other monomers copolymerizable with the hydroxyl group-containing monomer may be used. A preferred example is a monoacetic acid formed by the reaction of acrylic acid or methacrylic acid with a monohydric alcohol having 1 to 2 carbon atoms, including methylol acrylate, methylol methacrylate, 2-hydroxyl Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate _ Vinegar, 2-hydroxybutyl acrylate, 2-hydroxybutyrate Methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate. Preferred examples of other hydroxyl-containing monomers include acrylic acid or a monoester formed by the reaction of methacrylic acid with an ethylene glycol having 1 to 10 carbon atoms, and an epoxy ester compound, which includes glycerin acrylate, glyceryl methacrylate, dipentaerythritol monoacrylate, Dipentaerythritol monomethacrylate, ε-caprolactone-modified hydroxyethyl acrylate, ε-caprolactone-modified hydroxyethyl methacrylate, and 2-hydroxy-3-phenoxypropyl Acrylate. -10- (7) 1311688 Other preferred examples of monomers copolymerizable with the hydroxyl group-containing monomer include α,^-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, citraconic acid, and horses. Acid, and fumaric acid, and anhydrides and semi-esterified products; α, cold-unsaturated carboxylic acid esters methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, acrylic acid n-Butyl ester, isobutyl acrylate, Acrylic acid second-butyl ester, cyclohexyl acrylate, 2-ethylhexyl acrylate, octadecyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate 'methacrylic acid Isopropyl propyl ester, second propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, second butyl methacrylate, cyclohexyl methacrylate, methacrylic acid 2 -ethylhexyl ester, octadecyl methacrylate, acrylate 2,2,2-trifluoromethyl ester, and methacrylate 2,2,2-trifluoromethyl ester; and styrenes such as benzene Ethylene, α-methylstyrene, and p-vinyltoluene. Other examples include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, glycidyl acrylate, and glycidyl methacrylate. These compounds may be used singly or as a mixture of two or more compounds. The photosensitive insulating paste composition of the present invention preferably contains 50 to 90 parts by weight of the hydroxyl group-containing acrylic resin, more preferably 60 to 80 parts by weight, still more preferably 65 to 75 parts by weight, based on the total amount of the resin. Amount (=1 〇〇 by weight). If the amount of the hydroxyl group-containing acrylic resin does not fall within a specific range, the desired accuracy cannot be achieved in the obtained pattern: when the amount of the hydroxyl group-containing acrylic resin is less than 50 parts by weight, the anti-developer property is lowered. However, if the amount of the resin is more than 90 parts by weight, it tends to cause a low developability of -11 - (8) 1311688 and an undesired residue may be generated during the development process. For example, if the amount of the photopolymerizable monomer is less than 50 parts by weight, an insufficient photopolymerization reaction is caused, which in turn causes dissolution of the image region during development, thereby causing image formation failure. In the comparison, when the amount of the photopolymerizable monomer is more than 90 parts by weight, the resolution of the fine image is reduced. The photopolymerizable monomer serving as component (C) may be any known photopolymerizable monomer, which may include, but is not limited to, ethylene glycol diacrylate, ethylene glycol dimethacrylate, Triethylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane triacrylate, top three Trimethylolethane acrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetraacrylate Ester, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, glyceryl acrylate, glyceryl methacrylate, and shaft Sectional (Cardo-type) epoxy diacrylates, and those which can be individually formulated with fumarate, itaconate and maleate Fumarate (meth) acrylate compound obtained by the above listed, and itaconic acid esters and maleic acid esters. The photopolymerization initiator serving as component (D) may be any general photopolymerization initiator including benzophenones, benzoin, benzoin alkyl ethers, acetophenones' Amino acetophenones, benzyls, benzyl alkyl ketals, oximes, ketals, and thioxanthones. Specific examples include 2,4-bis-dichloromethyl-6-(3-bromo-tetra-methoxy)phenyl~s-12-(9)1311688-triazine, 2,4_double Trichloromethyl-6-(2-bromo-4-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy Styrylphenyl-s-triazine, 2,4-di-trichloromethyl-6-(2-bromo-tetra-methoxy)styrylphenyl-s-triazine, 2, 4,6-trimethyl benzamidine diphenylphosphine oxide, 1 -[4-(2-hydroxyethoxy)phenyl]- 2-trans-base_2-methyl_1-propyl- 1 Monoketone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-cyclopropoxythione, 3,3 —Dimethyl_4-methoxybenzophenone, benzophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1_ (4 ten Dialkylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-benzylidene- 4'-methyldimethyl sulfide, 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid methyl ester, 4-dimethylaminobenzoic acid , 4-dimethylaminobenzoic acid butyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 4-dimethylaminobenzoic acid 2-isoamyl ester, 2,2-diethoxybenzene Ketone, benzyl dimethyl ketal, benzyl-methoxyethyl acetal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) fluorene, o-benzene Methyl benzoate, bis(4-dimethylaminophenyl) ketone, 4,4'-diethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, p-dimethylamino acetophenone, p-t-butyl butyl Chloroacetophenone, p-t-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, -two Chloro-4-tetraphenoxyacetophenone, pentyl-4-dimethylaminobenzoate, and 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer. These compounds may be used individually or as a mixture of two or more compounds of -13-(10) 1311688. The amount of the photopolymerization initiator to be used is preferably in the range of from 0.1 to 1, more preferably from 2 to 5 parts by weight, based on the combined amount of the water-soluble fiber and the photopolymerizable monomer (= 100 parts by weight) )meter. If the amount of the hair agent is less than 0.1 part by weight, the ripening property becomes low. If the photopolymerization initiator contains more than 10 parts by weight, the light is absorbed before the bottom portion is reached, and the mixture is not sufficiently cured. In addition to (A) to (D), the photosensitive insulating material of the present invention may further contain an optical additive such as a UV absorber, a sensitizer agent, a polymerization inhibitor, a plasticizer, a thickener, an organic solvent, and an antifoaming agent. Agent, inorganic or organic suspending agent. The sensitizer is added based on increasing sensitization. Sensitizers include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-diethylaminophenylidene)cyclopentanone, 2,6-bis(4-dimethylamino) Hexanone, 2,6-bis(4-dimethylaminophenylidene)-4-methyl Miller's ketone, 4,4-bis(diethylamino), 4,4~bis (two Methylamino)-chalcone, 4,4-double (bis-chalcone, p-dimethylamino cinnamyl indanone, p-tubular ketone, 2-(p-dimethylamine) Phenylvinylethylene) hydrazine, 1,3~bis(4-dimethylaminophenylidene)acetone, 1,3-carbonyl 4~diethylaminophenylidene)acetone, 3,3-carbonyl-double (7 - xiangdansu), N_phenyl-N-ethylethanolamine, N-phenyl N-tolyldiethanolamine, N-phenylethanolamine, dimethylamine isoamyl ester, isoamyl diethylaminobenzoate , 3-phenyl-5, 嚷tetradecene, and fluorenylphenyl-5-ethoxycarbonylthiotetrazolium. These oxime weights are derived from photopolymerization, but in light to paste composition, sensitizer Specific examples of dispersing agents - bis(4-phenylidene)cyclocyclohexanone, monobenzophenone ethylamino) dimethylamino- Naphthyl thiol-bis(diethylaminoethanolamine, benzoyl benzoyl sensitizer may be used in each of 14-(11) 1311688 or in a mixture of two or more. Polymerization inhibitors are used for storage. Specific examples of polymerization inhibitors include hydroquinone, hydroquinone monoester, N-nitrosodiphenylamine, phenothiazine, p-tert-butyl catechol, N-phenyl Naphthylamine, 2,6-di-t-butyl-p-methylphenol, proguanil, and pyrogallol plasticizers are added to enhance the consistency of the substrate. Specific examples of plasticizers include Phthalates such as dibutyl phthalate (DBP), dioctyl phthalate (DOP), and dihexyl phthalate (D0P), and polyethylene glycol, glycerin, And dibutyl tartrate. Antifoaming agent is to prevent the formation of bubbles in the paste or film, otherwise it will form micropores after baking. Specific examples of antifoaming agents include those based on alkylene glycol, such as Polyethylene glycol (molecular weight = 400 to 800), anthrone, or stilbene alcohol. Composition of photosensitive insulating paste used in the present invention The inorganic powder of the material may be an inorganic powder which is transparent to the light source used. Examples thereof include glass, ceramics (such as cordierite), and metal powders. More specific examples are borosilicate glass, zinc borosilicate glass. And a powder composed of barium borosilicate glass, such as Pb0-SiO2 glass, PbO-B203-SiO2 glass, ZnO-Si〇2 glass, Zn〇-B203-SiO2 glass, BiO-SiO2 glass, and Bi〇-B2O3 - Si〇2 glass, a powder composed of Na, K, Mg, Ca, Ba, Ti, Zr, and oxides thereof such as cobalt oxide, iron oxide, chromium oxide, nickel oxide, copper oxide, magnesium oxide, cerium oxide , vanadium oxide 'yttrium oxide, titanium dioxide yellow, cadmium oxide, antimony oxide, antimony oxide, magnesium oxide, and spinel; powder composed of fluorescent substances, such as ZnO · · Zn, Zn3 ( (β) -15- ( 12) !311688 P〇4 ) 2 : Mn ' Y2Si〇5 • C e, CaWO 4 · Pb, BaMgA11 4 〇 2 3 : Eu , ZnS : ( Ag , C u ), Y2O3 Eu , Y2Si05 : E u, Y3AI5O12 : Eu ' YBO3 : E XI, (Y, Cd ) B O3 : E11, GdB03 :Eu , S cB 03 : Eu , LuB〇3 : υ i ' Z112 S i 0 4 : Μ n , BaAli2 〇 i9 : Mn ' SrAl 13 〇 19 : Mn, Ci aAl) 2 〇 i9 · Mn, YBO3 : Tb, BaMgAl " 〇 23 : Mn, LuBO 3 : Tb , GdBO: Tb,
ScB03 : Tb、Sr6Si303Cl4 : Eu、ZnS : ( Cu，A1 ) 、ZnS :ScB03 : Tb, Sr6Si303Cl4 : Eu, ZnS : ( Cu, A1 ) , ZnS :
Ag、Y202S : Eu、ZnS : Zn、 （ Y，Cd ) B03 : Eu、及Ag, Y202S: Eu, ZnS: Zn, (Y, Cd) B03: Eu, and
BaMgAl2l023 : Eu ;以及金屬如鐵、鎳、鈀、鎢、銅、鋁 、銀、金、及鉑之粉末。在這些當中，以玻璃粉末及陶瓷 粉末更佳，因爲彼等具有高透明度。玻璃粉末（玻璃粉） 可提供最顯著的效果。若無機粉末不含氧化矽、氧化鋁、 或氧化鈦將更爲人喜愛，因爲這些化合物會使無機粉末變 得不透明而減少無機粉末的透光率。 雖然無機粉末之平均粒子大小可視預形成之圖形的形 狀而定，但較佳地係具有〇 · 5至1 0微米，而以1至8微 米更佳。無機粉末之平均粒子大小若大於10微米時，一 旦形成高精密度圖形會導致粗糙的表面，然而其平均粒子 大小若小於〇. 5微米將會使光散射，進而阻止光穿透至底 部。無機粉末可具有多種形狀，如球狀、塊狀、薄片狀、 或樹枝狀，並可以這些形狀之一者或其組合方式提供。 無機粉末不僅可包含黑色粉末，還可含有不同顏色之 無機顏料’如紅色、藍色、及綠色顔料。含有此類顏料之 光敏性絕緣糊料組成物可用來形成不同顏色之圖形，因此 可適於製造電漿顯示板之彩色濾光器或其他組件。該無機 -16- (13) 1311688 粉末可爲多種細粒之混合物，且每一種粒子可具有不同的 物理特性。經由利用具有不同熱軟化點的玻璃粉末或陶瓷 粉末，即可使烘烤後之收縮減至最小。這些無機粉末可依 適宜屏蔽肋材或其類似物所需之特性的形狀及物理特性而 以適當組合來混合。 具有平均粒子大小小於1 0微米（0.5至10微米）之 無機粉末，只要其特性不會損害，皆可以有機酸、無機酸 、矽烷偶合劑、以鈦酸鹽爲基礎之偶合劑、以鋁爲基礎之 偶合劑、表面活性劑、或其他表面處理劑來進行表面處理 ，以便防止粉末二度聚集並促進粉末分散。特定言之，表 面處理可依如下進行：先將表面處理劑溶解於有機溶劑或 水中。然後將無機粉末加入此溶液中並攪拌混合液。隨後 ，將溶劑蒸發並在約50至200°C下加熱殘留物達2小時之 久。另外，也可在光敏性組成物形成糊料時才將表面處理 劑加入。 本發明之光敏性絕緣糊料組成物中有機組份與無機粉 末之各別比例典型地係在5至3 5重量份範圍內及95至65 重量份範圍內，而以10至30重量份及90至70重量份範 圍內爲較佳，15至25重量份及85至75重量份範圍內更 佳，以光敏性絕緣糊料組成物之總量（=1 〇〇重量份）計 。若有機組份之量少於5重量份將產生不足的光聚合反應 。此將在顯影期間使圖像區域溶解，進而使圖像成形失敗 。比較下，若有機組份之量大於3 5重量份，則產生之圖 形一烘烤後就脫落。 光敏性絕緣糊料組成物可藉由將各組份溶解或分散於 -17- (14) 1311688 溶劑中而製備。可用於此目的之溶劑只要能展現對無機粉 末之高親合力，及使有機組份溶解得很好，並使光敏性絕 緣糊料組成物有適當的黏度，同時易於蒸發，則任一種溶 劑都可。此類溶劑之特定實例包括酮類，如二乙酮、甲基 丁基酮、二丙酮、及環己酮；醇類，如正_戊醇、4 -甲 基一2 —戊醇、環己醇、及二丙酮醇；醚醇，如乙二醇— 甲基醚、乙二醇一乙基醚、乙二醇一 丁基醚、丙二醇一甲 基醚、丙二醇一乙基醚、二乙二醇一甲基醚、二乙二醇一 乙基醚、二乙二醇二甲基醚、及二乙二醇二乙基醚；飽和 脂族一羧酸烷酯，如醋酸正- 丁酯、及醋酸戊酯；乳酸酯 ’如乳酸乙酯、及乳酸正一丁酯；以及醚酯，如甲基纖維 素醋酸酯、乙基纖維素醋酸酯、丙二醇一甲基醚醋酸酯、 丙二醇一乙基醚醋酸酯、3 -乙氧基丙酸乙酯、醋酸2一甲 氧基丁酯、醋酸3—甲氧基丁酯、醋酸4 一甲氧基丁酯、 醋酸2 —甲基一3—甲氧基丁酯、醋酸3 —甲基_3—甲氧 基丁酯、醋酸3—乙基一3 —甲氧基丁酯、醋酸2—乙氧基 丁酯、醋酸4_乙氧基丁酯、醋酸4_丙氧基丁酯、及醋 酸2-甲氧基戊酯。這些溶劑可各別使用或以二或多個溶 劑之組合物使用。 爲了使光敏性絕緣糊料組成物之黏度維持在一較佳之 範圍，溶劑之使用量較佳地係3 0 0重量份或更少，而以1 〇 至7 0重量份更佳’ 2 5至3 5重量份最佳，以有機組份與無 機粉末之總重量（=^ 0 0重量份）計。 視預定之應用而定’本發明之光敏性絕緣糊料組成物 可以液體或藉由絲網印刷術或不同的其他技巧塗布在基材 rs -18- (15) 1311688 上。在需要高精密度處理之應用，如PDPs之屏蔽肋材中 ，該組成物較佳地係塗布成光敏性薄膜。在此方法中，所 形成圖形之精確性可顯著地增進，並藉此而獲得具有高精 確度之屏蔽肋材或其類似物。光敏性薄膜係藉由將本發明 之光敏性絕緣糊料組成物塗布至一支撐膜上，然後使此薄 膜乾燥以獲得具有10至100微米厚度之薄膜而製成。舉 例之’用於此目的之支撐膜可爲一由合成樹脂，如聚對苯 二甲酸乙二酯、聚乙烯、聚丙烯、聚碳酸酯、及聚氯乙烯 所製成之15至125微米厚的撓性膜。若需要，此支撐膜 可用脫模劑處理以促進薄膜的轉移。該組成物可藉助均布 器、棒狀塗布器、線錠塗布器、滾輪塗布器、或幕塗流動 塗料器而塗布到支撐膜上。特別地，較爲人所喜歡的是使 用滾輪塗布器以便有效地形成均勻又厚的膜。當光敏性薄 膜未經使用時，可將一保護膜施加至此光敏性薄膜上以保 護光敏性糊料組成物。用於此目的之保護膜可爲一由聚對 苯二甲酸乙二酯、聚丙烯、或聚乙烯所製成之約15至125 微米厚的塗有矽酮或使矽酮烘烤過之膜。 隨後，將說明利用本發明之光敏性絕緣糊料組成物以 形成所需圖形的方法。首先，藉由塗覆或轉印技巧將該光 敏性絕緣糊料組成物塗布在基材上以形成一塗層。然後， 透過光罩將一激活光線如UV光、激元雷射、X 一射線、 及電子光束照射到該組成物塗層上以曝露出一圖像。使此 曝光之圖像在鹼性顯影劑或水中顯影。未曝光區域將溶解 於顯影劑中，而在基材上留下一圖形。需要時，可烘烤該 已組成圖形之塗層。除此之外，也可無需光罩就使該光敏 -19- (16) 1311688 性絕緣糊料組成物之塗層的整個表面曝光。依此一情況， 不用進行顯影程序即可形成一圖形。若需要時，可烘烤該 基材。當需要高精密度圖形時，可先使該光敏性薄膜剝掉 保護層，再將此光敏性絕緣糊料組成物塗層轉印至基材上 ，形成一膜層。膜層可使用或不用光罩來曝光，再剝離支 撐膜。令以光罩曝光之膜層顯影即可形成一圖形，然而， 未用光罩曝光之膜層則無需顯影過程即可熟化，若需要可 經烘烤。基材可爲玻璃、配有在基材上形成之電極如總線 電極的基材、或陶瓷基材。舉例之，在轉印光敏性絕緣糊 料組成物塗層中，此組成物塗層與基材表面接觸時係利用 熱滾輪層合機熱壓印。熱壓印較佳地係在1至5公斤/平 方公分之滾輪壓力及0.1至10.0公尺/分鐘之壓印速度下 並配合將基材之表面溫度升高至80到140°c而進行。基材 可先預熱至40至100 °C。用來使糊料組成物曝光之雷射發 射器係常用於光刻法之UV—發射器或用於製造半導體及 液晶顯示器（LCDs)的曝光裝置。 在顯影過程所用之鹼性顯影劑的鹼性組份包括鹼金屬 如鋰、鈉和鉀之氫氧化物、碳酸鹽、碳酸氫鹽、磷酸鹽、 及焦磷酸鹽；一級胺，如苄胺及丁胺；二級胺，如二甲胺 、二苄胺、及二乙醇胺；三級胺，如三甲胺、三乙胺、及 三乙醇胺；環狀胺，如嗎啉、哌嗪、及吡啶；多胺類，如 乙二胺及己二胺；氫氧化銨，如氫氧化四甲銨、氫氧化四 乙銨、氫氧化三甲基苄銨、及氫氧化三甲基苯基苄銨；氫 氧化鏑，如氫氧化三甲基毓、氫氧化二乙基甲基锍、及氫 氧化二甲基苄基銃；膽鹼；以及含矽酸鹽之緩衝劑。顯影 -20- (S) (17) 1311688 劑之形態、組成份、及濃度，及操作時間、溫度、方式（ 如浸漬、攪動、淋浴、噴灑及攪拌），以及顯影過程所用 之裝置都可以光敏性絕緣糊料組成物之特性爲基礎而適當 地選擇。 烘烤過程可在足以燒盡任何存在於光敏性絕緣糊料組 成物中之有機物質的任一溫度下進行。舉例之，此過程可 在400至600°C下進行10至90分鐘。 雖然本發明之光敏性絕緣糊料組成物可廣泛地使用於 厚膜多層電路板之製造，及電漿顯示器、電漿尋址液晶電 漿顯示器、及各種其他顯示器之製造，但還是特別適於製 造高精密度PDPs中所用的屏蔽肋材或其類似物，特定言 之，更適於製造PDPs中所用之介電質。 實施例 本發明將根據數個實施例來說明，無論如何這些實施 例並不意圖限制本發明之範圍。 實施例1 (製備光敏性絕緣糊料組成物） 在一攪拌器中將下列有機組份混合在一起達3小時以 形成溶液（固體組份=5 0 % ) : 1 5重量份之做爲水溶性纖 維素衍生物的羥丙基纖維素、3 3重量份之做爲含羥基丙烯 酸系樹脂的苯乙烯/羥乙基甲基丙烯酸酯共聚物（苯乙烯/ 羥乙基甲基丙烯酸酯=55/4 5 (重量百分比），^\\^8500) 、39重量份之做爲光聚合單體的2一羥基一 3-苯氧基丙 -21 - (18) 1311688 基丙嫌酸醋（產品名：Μ — 600A，Kyoeisha Chemical Co., Ltd.公司）、1.0重量份之做爲光聚合引發劑的2,2-二 甲氧基一2 —苯基苯乙酮（產品名：IR— 651，Ciba Geigy Ltd.公司）、12重量份之做爲增塑劑的鄰苯二甲酸二環 己酯、及100重量份之做爲溶劑的3—甲氧基一3_甲基丁 醇。將35重量份之此溶液（固體組份=50% )與82.5重量 份做爲無機粉末之玻璃粉混合/揉合以形成光敏性絕緣糊 料組成物。 (製備光敏性薄膜） 利用刀刃塗布器將該依此所得之光敏性絕緣糊料組成 物塗布到聚對苯二甲酸乙二酯支撐膜上。在1 00°c下乾燥 塗膜6分鐘以便完全去除溶劑。如此便可在支撐膜上形成 27微米厚之光敏性絕緣糊料薄膜。然後以25微米厚之聚 乙烯膜覆蓋此光敏性絕緣糊料塗層，即可完成光敏性薄膜 (光敏性薄膜之評估） 利用設定在l〇5°C之熱滾輪層合器將一預熱至8CTC之 玻璃基材與該所得之光敏性薄膜層合，同時從中剝離聚乙 烯膜。所用之空氣壓力及層合速度各別係3公斤/平方公 分和1.0公尺/分鐘。隨後，將聚對苯二甲酸乙二酯支撐膜 剝離。使用超高壓汞燈做爲光源並透過一具有正方形試驗 圖形之光罩，在5 00毫焦耳/平方公分之劑量下將紫外光 線照射到該光敏性塗膜上。爲了使圖形顯影，可將3 0 °C之 (19) 1311688 水以3公斤/平方公分之壓力噴灑至該曝光之塗膜上’直 到薄膜達成斷點時的五倍時間。本文所用之”斷點” 一詞係 表示直到未曝光區域內的物質已完全除去所花的時間。 遺留下來之線寬最小値係以測量所形成之圖形的附著 力來決定，經測量爲40微米。以SEM觀察所形成之圖形 ，頃發現係爲梯形圖形。烘烤依此方式形成之圖形以評估 其形狀安定性。烘烤過程係先以1 . 0 °C /分鐘之速率加熱薄 膜，然後再於5 80°C下維持30分鐘。烘烤過之圖形經證明 相當令人滿意。 比較性實施例1 (製備光敏性絕緣糊料組成物） 在一攪拌器中將下列有機組份混合在一起達3小時以 形成溶液：1 5重量份之做爲水溶性纖維素衍生物的羥丙基 纖維素、33重量份之做爲含羥基丙烯酸系樹脂的苯乙烯/ 羥乙基甲基丙烯酸酯共聚物（苯乙烯/羥乙基甲基丙烯酸 酯=55/4 5 (重量百分比），MW = 25000) 、39重量份之做 爲光聚合單體的2—羥基- 3 -苯氧基丙基丙烯酸酯（產品 名：Μ — 6 0 0 A，Ky 〇 e i s h a Ch e m i c al C 〇 ·, L t d .公司）、1.0 重量份之做爲光聚合引發劑的2,2—二甲氧基- 2-苯基苯 乙酮（產品名：IR- 651 ’ Ciba Geigy Ltd.公司）、12 重 量份之做爲增塑劑的鄰苯二甲酸二環己酯、及重量份 之做爲溶劑的3 —甲氧基- 3 —甲基丁醇。將3 5重量份之 此溶液與82 · 5重量份做爲無機粉末之玻璃粉揉合以形成 光敏性絕緣糊料組成物。 -23- (20) 1311688 (製備光敏性薄膜） 利用刀刃塗布器將該光敏性絕緣糊料組成物塗布到聚 對苯二甲酸乙二酯支撐膜上。在l〇(rc下乾燥塗膜6分鐘 以便完全去除溶劑。此舉可在支撐膜上形成27微米厚之 光敏性絕緣糊料薄膜。然後以2 5微米厚之聚乙烯膜覆蓋 此光敏性絕緣糊料塗層，即可完成光敏性薄膜。 (光敏性薄膜之評估） 利用設定在l〇5°C之熱滾輪層合器將一預熱至80°c之 玻璃基材與該所得之光敏性絕緣糊料薄膜層合，同時從中 剝離聚乙烯膜。所用之空氣壓力及層合速度各別係3公斤 /平方公分和1.0公尺/分鐘。隨後，將聚對苯二甲酸乙二 酯支撐膜剝離。使用超高壓汞燈做爲光源並透過一具有正 方形試驗圖形之光罩，在500毫焦耳/平方公分劑量下將 紫外光線照射到該光敏性塗膜上。爲了使圖形顯影，可將 30 °C之水以3公斤/平方公分之壓力噴灑至該曝光之塗膜 上，直到薄膜達成斷點時的五倍時間。 遺留下來之線寬最小値係以測量所形成之圖形的附著 力來決定，經測量爲40微米。然而，圖形之顯影並不完 全，並可看到殘留物。 工業應用 如前文所述，本發明之光敏性絕緣糊料組成物係含有 對組成物具優異抗顯影特性的有機組份，並適用於形成厚 -24- (21) 1311688 膜但仍具高光敏性之膜層，依此可得高精密度圖形。本發 明之光敏性絕緣糊料組成物可適於製造光敏性薄膜。BaMgAl2l023 : Eu ; and powders of metals such as iron, nickel, palladium, tungsten, copper, aluminum, silver, gold, and platinum. Among these, glass powder and ceramic powder are preferred because they have high transparency. Glass powder (glass powder) provides the most remarkable results. It is more preferred if the inorganic powder does not contain cerium oxide, aluminum oxide, or titanium oxide because these compounds make the inorganic powder opaque and reduce the light transmittance of the inorganic powder. Although the average particle size of the inorganic powder may depend on the shape of the pre-formed pattern, it is preferably from 5 to 10 μm, more preferably from 1 to 8 μm. If the average particle size of the inorganic powder is larger than 10 μm, a high-precision pattern will result in a rough surface, but an average particle size of less than 〇. 5 μm will scatter light, thereby preventing light from penetrating to the bottom. The inorganic powder may have a variety of shapes, such as spheres, blocks, flakes, or dendrites, and may be provided in one or a combination of these shapes. The inorganic powder may contain not only a black powder but also inorganic pigments of different colors such as red, blue, and green pigments. Photosensitive insulating paste compositions containing such pigments can be used to form patterns of different colors and are therefore suitable for use in the manufacture of color filters or other components for plasma display panels. The inorganic -16-(13) 1311688 powder may be a mixture of a plurality of fine particles, and each of the particles may have different physical properties. By using glass powder or ceramic powder having different thermal softening points, shrinkage after baking can be minimized. These inorganic powders may be mixed in an appropriate combination depending on the shape and physical properties of the properties required for the shielding rib or the like. An inorganic powder having an average particle size of less than 10 μm (0.5 to 10 μm) may be an organic acid, a mineral acid, a decane coupling agent, a titanate-based coupling agent, or an aluminum as long as the properties are not impaired. The base coupler, surfactant, or other surface treatment agent is surface treated to prevent secondary aggregation of the powder and promote powder dispersion. Specifically, the surface treatment can be carried out by first dissolving the surface treatment agent in an organic solvent or water. The inorganic powder is then added to the solution and the mixture is stirred. Subsequently, the solvent was evaporated and the residue was heated at about 50 to 200 ° C for 2 hours. Alternatively, the surface treatment agent may be added when the photosensitive composition forms a paste. The respective ratios of the organic component to the inorganic powder in the photosensitive insulating paste composition of the present invention are typically in the range of 5 to 35 parts by weight and 95 to 65 parts by weight, and 10 to 30 parts by weight, and It is preferably in the range of 90 to 70 parts by weight, more preferably in the range of 15 to 25 parts by weight and 85 to 75 parts by weight, based on the total amount of the photosensitive insulating paste composition (= 1 part by weight). If the amount of the organic component is less than 5 parts by weight, insufficient photopolymerization will occur. This will dissolve the image area during development, which in turn causes image formation to fail. In comparison, if the amount of the organic component is more than 35 parts by weight, the resulting pattern will fall off after baking. The photosensitive insulating paste composition can be prepared by dissolving or dispersing the components in a solvent of -17-(14) 1311688. The solvent which can be used for this purpose is any solvent as long as it exhibits a high affinity for the inorganic powder, dissolves the organic component well, and makes the photosensitive insulating paste composition have an appropriate viscosity and is easy to evaporate. can. Specific examples of such solvents include ketones such as diethyl ketone, methyl butyl ketone, diacetone, and cyclohexanone; alcohols such as n-pentanol, 4-methyl-2-pentanol, and cyclohexane Alcohol, and diacetone alcohol; ether alcohol, such as ethylene glycol - methyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; saturated aliphatic monocarboxylic acid alkyl esters, such as n-butyl acetate, And amyl acetate; lactate 'such as ethyl lactate, and n-butyl lactate; and ether esters, such as methyl cellulose acetate, ethyl cellulose acetate, propylene glycol monomethyl ether acetate, propylene glycol Ethyl ether acetate, ethyl 3-ethoxypropionate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-acetate - methoxybutyl ester, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxylate acetate Butyl ester, acetic acid 4 _Propoxybutyl ester, and 2-methoxypentyl acetate. These solvents may be used singly or in combination of two or more solvents. In order to maintain the viscosity of the photosensitive insulating paste composition in a preferred range, the solvent is preferably used in an amount of 300 parts by weight or less, and more preferably from 1 Torr to 70 parts by weight. 3 parts by weight is optimal, based on the total weight of the organic component and the inorganic powder (=^0 0 parts by weight). Depending on the intended application, the photosensitive insulating paste composition of the present invention can be applied to the substrate rs -18-(15) 1311688 liquid or by screen printing or other different techniques. In applications requiring high precision processing, such as shielding ribs for PDPs, the composition is preferably applied as a photosensitive film. In this method, the accuracy of the formed pattern can be remarkably improved, and thereby a shield rib having high precision or the like can be obtained. The photosensitive film is produced by coating the photosensitive insulating paste composition of the present invention onto a support film and then drying the film to obtain a film having a thickness of 10 to 100 μm. For example, the support film used for this purpose may be 15 to 125 μm thick made of synthetic resin such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, and polyvinyl chloride. Flexible film. If desired, the support film can be treated with a release agent to promote film transfer. The composition can be applied to the support film by means of a homogenizer, a bar coater, a wire applicator, a roller coater, or a curtain coating flow coater. In particular, it is preferred to use a roller applicator to effectively form a uniform and thick film. When the photosensitive film is not used, a protective film can be applied to the photosensitive film to protect the photosensitive paste composition. The protective film used for this purpose may be a film of about 15 to 125 μm thick coated with anthrone or anthrone, made of polyethylene terephthalate, polypropylene, or polyethylene. . Subsequently, a method of using the photosensitive insulating paste composition of the present invention to form a desired pattern will be explained. First, the photosensitive insulating paste composition is coated on a substrate by a coating or transfer technique to form a coating. Then, an activation light such as UV light, excimer laser, X-ray, and electron beam is irradiated onto the composition coating through the photomask to expose an image. The exposed image is developed in an alkaline developer or water. The unexposed areas will dissolve in the developer leaving a pattern on the substrate. The patterned coating can be baked as needed. In addition to this, the entire surface of the coating of the photosensitive -19-(16) 1311688 insulating paste composition can be exposed without a mask. In this case, a pattern can be formed without performing a developing process. The substrate can be baked if desired. When a high-precision pattern is required, the photosensitive film may be first peeled off from the protective layer, and the photosensitive insulating paste composition coating is transferred onto the substrate to form a film layer. The film layer can be exposed with or without a photomask and the support film can be peeled off. The film exposed by the reticle is developed to form a pattern, however, the film layer which is not exposed by the reticle can be cured without a development process and can be baked if necessary. The substrate may be glass, a substrate provided with an electrode formed on the substrate such as a bus electrode, or a ceramic substrate. For example, in the transfer of the photosensitive insulating paste composition coating, the composition coating is thermally embossed by a hot roller laminator when it comes into contact with the surface of the substrate. The hot stamping is preferably carried out at a roller pressure of 1 to 5 kg/cm 2 and an imprint speed of 0.1 to 10.0 m/min in conjunction with raising the surface temperature of the substrate to 80 to 140 °C. The substrate can be preheated to 40 to 100 °C. Laser emitters for exposing the paste composition are commonly used in photolithographic UV-emitters or in exposure devices for the manufacture of semiconductors and liquid crystal displays (LCDs). The alkaline component of the alkaline developer used in the development process includes alkali metals such as lithium, sodium and potassium hydroxides, carbonates, hydrogencarbonates, phosphates, and pyrophosphates; primary amines such as benzylamine and Butylamine; secondary amines such as dimethylamine, dibenzylamine, and diethanolamine; tertiary amines such as trimethylamine, triethylamine, and triethanolamine; cyclic amines such as morpholine, piperazine, and pyridine; Polyamines such as ethylenediamine and hexamethylenediamine; ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylbenzylammonium hydroxide, and trimethylphenylbenzylammonium hydroxide; hydrogen Cerium oxide, such as trimethylhydrazine hydroxide, diethylmethylhydrazine hydroxide, and dimethylbenzylhydrazine hydroxide; choline; and a buffer containing citrate. Development -20- (S) (17) 1311688 The form, composition, and concentration of the agent, as well as the operation time, temperature, mode (such as dipping, stirring, showering, spraying and stirring), and the device used in the development process can be photosensitive. The characteristics of the insulating paste composition are appropriately selected based on the characteristics. The baking process can be carried out at any temperature sufficient to burn off any organic material present in the photosensitive insulating paste composition. For example, the process can be carried out at 400 to 600 ° C for 10 to 90 minutes. Although the photosensitive insulating paste composition of the present invention can be widely used in the manufacture of thick film multilayer circuit boards, and in the manufacture of plasma displays, plasma addressed liquid crystal plasma displays, and various other displays, it is particularly suitable for Shielding ribs or the like used in the manufacture of high precision PDPs, in particular, are more suitable for the manufacture of dielectrics used in PDPs. The invention is illustrated by the following examples, which are not intended to limit the scope of the invention in any way. Example 1 (Preparation of photosensitive insulating paste composition) The following organic components were mixed together in a stirrer for 3 hours to form a solution (solid component = 50%): 15 parts by weight as water-soluble Hydroxypropylcellulose of a cellulose derivative, 33 parts by weight of a styrene/hydroxyethyl methacrylate copolymer (hydroxystyrene/hydroxyethyl methacrylate = 55) as a hydroxyl group-containing acrylic resin /4 5 (% by weight), ^\\^8500), 39 parts by weight of 2-hydroxy-3-phenoxypropan-21-(18) 1311688-based propylene vinegar as a photopolymerizable monomer (product) Name: Μ — 600A, Kyoeisha Chemical Co., Ltd.), 1.0 part by weight of 2,2-dimethoxy-2-phenylacetophenone as a photopolymerization initiator (product name: IR-651) , Ciba Geigy Ltd.), 12 parts by weight of dicyclohexyl phthalate as a plasticizer, and 100 parts by weight of 3-methoxy-3-methylbutanol as a solvent. 35 parts by weight of this solution (solid component = 50%) was mixed/kneaded with 82.5 parts by weight of glass powder as an inorganic powder to form a photosensitive insulating paste composition. (Preparation of photosensitive film) The photosensitive insulating paste composition thus obtained was applied onto a polyethylene terephthalate support film by a blade coater. The film was dried at 100 ° C for 6 minutes to completely remove the solvent. Thus, a 27 μm thick photosensitive insulating paste film can be formed on the support film. Then, the photosensitive insulating paste coating is covered with a 25 μm thick polyethylene film to complete the photosensitive film (the evaluation of the photosensitive film). The preheating is performed by a hot roller laminator set at 10 ° C. The glass substrate to 8 CTC was laminated with the obtained photosensitive film while peeling off the polyethylene film therefrom. The air pressure and laminating speed used were 3 kg/cm 2 and 1.0 m/min, respectively. Subsequently, the polyethylene terephthalate support film was peeled off. An ultraviolet light was irradiated onto the photosensitive coating film at a dose of 500 mJ/cm 2 using an ultrahigh pressure mercury lamp as a light source and through a reticle having a square test pattern. In order to develop the pattern, (19) 1311688 water at 30 °C can be sprayed onto the exposed coating film at a pressure of 3 kg/cm 2 until the film reaches five times the break point. The term "breakpoint" as used herein refers to the time it takes until the material in the unexposed area has been completely removed. The minimum line width of the remaining line is determined by measuring the adhesion of the formed pattern and is measured to be 40 microns. The pattern formed by SEM observation was found to be a trapezoidal pattern. The pattern formed in this manner is baked to evaluate its shape stability. The baking process was performed by heating the film at a rate of 1.0 ° C / min and then maintaining it at 580 ° C for 30 minutes. The baked image proved to be quite satisfactory. Comparative Example 1 (Preparation of photosensitive insulating paste composition) The following organic components were mixed together in a stirrer for 3 hours to form a solution: 15 parts by weight of hydroxy group as a water-soluble cellulose derivative Propyl cellulose, 33 parts by weight of a styrene/hydroxyethyl methacrylate copolymer (hydroxystyrene/hydroxyethyl methacrylate = 55/45 (% by weight), which is a hydroxyl group-containing acrylic resin, MW = 25000), 39 parts by weight of 2-hydroxy-3-phenoxypropyl acrylate as a photopolymerizable monomer (product name: Μ - 600 A, Ky 〇eisha Ch emic al C 〇·, L td. company), 1.0 part by weight of 2,2-dimethoxy-2-phenylacetophenone (product name: IR-651 'Ciba Geigy Ltd.), 12 weight as a photopolymerization initiator Parts are dicyclohexyl phthalate as a plasticizer, and 3-methoxy-3-methylbutanol as a solvent in parts by weight. 35 parts by weight of this solution was blended with 82.5 parts by weight of a glass powder as an inorganic powder to form a photosensitive insulating paste composition. -23- (20) 1311688 (Preparation of photosensitive film) The photosensitive insulating paste composition was applied onto a polyethylene terephthalate support film by a knife coater. The film was dried for 6 minutes at 1 Torr to completely remove the solvent. This formed a 27 μm thick photosensitive insulating paste film on the support film. The photosensitive insulation was then covered with a 25 μm thick polyethylene film. The photosensitive coating can be completed by the paste coating. (Evaluation of photosensitive film) A glass substrate preheated to 80 ° C and a photosensitive film obtained by using a hot roller laminator set at 10 ° C The insulating insulating film is laminated and the polyethylene film is peeled off therefrom. The air pressure and laminating speed used are respectively 3 kg/cm 2 and 1.0 m/min. Subsequently, polyethylene terephthalate is supported. Film peeling. Ultra-high pressure mercury lamp was used as a light source and a light mask with a square test pattern was irradiated onto the photosensitive coating film at a dose of 500 mJ/cm 2 in order to develop the pattern. Water at 30 °C is sprayed onto the exposed coating film at a pressure of 3 kg/cm 2 until the film reaches five times the break point. The remaining line width is the smallest to measure the adhesion of the formed pattern. Decide, test It is 40 μm. However, the development of the pattern is not complete, and the residue can be seen. Industrial Applicability As described above, the photosensitive insulating paste composition of the present invention contains an organic group having excellent anti-developing properties to the composition. And suitable for forming a film having a thickness of -24-(21) 1311688 film but still having high photosensitivity, thereby obtaining a high-precision pattern. The photosensitive insulating paste composition of the present invention can be suitably used for producing photosensitivity. film.
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