TWI303354B

TWI303354B -

Info

Publication number: TWI303354B
Application number: TW095101066A
Authority: TW
Inventors: Masaki Sasaki; Masao Arima
Original assignee: Taiyo Ink Mfg Co Ltd
Priority date: 2005-02-09
Filing date: 2006-01-11
Publication date: 2008-11-21
Also published as: TW200636385A; CN100582937C; KR20060090605A; JP2006220790A; CN1818780A; KR100736295B1

Description

1303354 (υ - 九、發明說明【發明所屬之技術領域】本發明係有關顯示面板用感光性樹脂組成物、及其硬化物以及由該硬化物所成之顯示面板用間隔物者。更詳細而言，係有關適合作爲形成液晶面板或碰觸面板等顯示面板用間隔物之材料的儲存穩定性、壓縮強度優越之感光性樹脂組成物，及其硬化物以及顯示面板用間隔物者。【先前技術】爲保持液晶面板中兩枚基板之間隔於一定，使用具有 - 所定之粒徑的玻璃珠、塑料珠等間隔物粒子。但是，此等、間隔物粒子，無規散佈於玻璃基板上之故，有效畫素部內存在該間隔物時，使間隔物寫入，以致射入光受散射，液晶面板之對比有降低的問題。爲解決此等問題，有藉由微影形成使用感光性樹脂組成物之間隔物的方法。 ♦ 間隔物要求在液晶面板貼合時之耐壓縮荷重的性能。但是，使用由感光性樹脂、多官能單體及光聚合引發劑構成之以往的感光性樹脂組成物所形成之間隔物硬度不足，在彩色濾色片與TFT陣列基板組裝（元件壓黏）時之高溫高壓下，塑性變形量增大，有招致作爲間隔物之機能的障礙之問題。依然殘留改善之空間。又，爲使間隔物在液晶面板中使用爲永久膜，亦要求耐熱性及耐藥品性。因此，此用途使用之感光性樹脂組成物，爲獲得作爲永久膜之特性，使用在同一分子內兼具梭 -4- 1303354 ‘ (2) ' 基與環氧基之熱硬化性樹脂（參照專利文獻1 ) ’亦有添加與黏合劑反應而得環氧樹脂之交聯劑等之情況（參照專利文獻2 )。不過，使用環氧系之交聯劑的感光性樹脂組成物時，引起交聯反應，環氧基的反應性高之故，儲存穩定性成爲問題，存在有導致操作性降低等不適宜之情況，難以使硬化物之特性與操作性兩立。專利文獻1 :特開平1 1 - 1 3 3 600號公報（申請專利範 • 圍）專利文獻2 :特開200 1 -324809號公報（申請專利範圍）【發明內容】〔發明所欲解決之課題〕本發明基於上述各項問題，其目的爲提供可形成硬度高、壓縮時塑性變形量小，且兼具作爲永久膜必要的耐熱 φ 性、耐藥品性之間隔物的感光性樹脂組成物。本發明之另一目的爲，提供將該感光性樹脂組成物使用於間隔物之形成，及以其形成之間隔物。〔課題之解決手段〕爲達成上述之目的，本發明之基本形態爲，提供一種感光性樹脂組成物，其特徵爲含有： (A )鹼可溶性之含羧基的感光性樹脂、 (B)具有乙烯性不飽和鍵之聚合性化合物、 (3) 1303354 ^ ( C )光聚合引發劑、及 (D )具有噁嗪環之化合物。本發明之較佳形態爲，提供一種顯示面板用感光性樹脂組成物，其特徵爲’該具有噁嗪環之化合物（D )爲具有含下述一般式（1 )及/或下述一般式（2 )所示之噁嗪環之基的化合物。〔化3〕1303354 (Technical Field of the Invention) The present invention relates to a photosensitive resin composition for a display panel, a cured product thereof, and a spacer for a display panel formed of the cured product. In other words, it is suitable for a photosensitive resin composition which is excellent in storage stability and compressive strength as a material for forming a spacer for a display panel such as a liquid crystal panel or a touch panel, and a cured product thereof and a spacer for a display panel. Technology] In order to keep the distance between two substrates in the liquid crystal panel constant, spacer particles such as glass beads and plastic beads having a predetermined particle size are used. However, the spacer particles are randomly dispersed on the glass substrate. Therefore, when the spacer exists in the effective pixel portion, the spacer is written, so that the incident light is scattered, and the contrast of the liquid crystal panel is lowered. To solve such problems, the photosensitive resin is formed by lithography. The method of arranging the spacers ♦ The spacers are required to be resistant to compression load when the liquid crystal panel is attached. However, the use of photosensitivity The hardness of the spacer formed by the conventional photosensitive resin composition composed of the fat, the polyfunctional monomer, and the photopolymerization initiator is insufficient, and the plasticity is high and high pressure at the time of assembly of the color filter and the TFT array substrate (component pressure bonding). The amount of deformation increases, and there is a problem that it is an obstacle to the function of the spacer. There is still room for improvement. Further, in order to use the spacer as a permanent film in the liquid crystal panel, heat resistance and chemical resistance are also required. In the photosensitive resin composition to be used for the purpose of obtaining a thermosetting resin having the same group as the epoxy group in the same molecule, a thermosetting resin having a group of 2-4-303354 '(2) ' group and an epoxy group is used (see Patent Document 1). In the case where a crosslinking agent such as an epoxy resin is reacted with a binder (see Patent Document 2), when a photosensitive resin composition of an epoxy-based crosslinking agent is used, a crosslinking reaction is caused. When the reactivity of the epoxy group is high, storage stability is a problem, and there is a possibility that the workability is lowered, and it is difficult to make the properties of the cured product and the workability stand. Patent Document 1 Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In view of the above-mentioned problems, it is an object of the present invention to provide a photosensitive resin composition which can form a spacer having high hardness and small amount of plastic deformation during compression and having a heat resistance and chemical resistance which are required for a permanent film. Another object of the present invention is to provide a photosensitive resin composition for use in the formation of a spacer and a spacer formed therewith. [Means for Solving the Problem] In order to achieve the above object, the basic form of the present invention provides a photosensitive property. The resin composition is characterized by comprising: (A) an alkali-soluble carboxyl group-containing photosensitive resin, (B) a polymerizable compound having an ethylenically unsaturated bond, and (3) a 1303354 ^ (C) photopolymerization initiator; And (D) a compound having an oxazine ring. According to a preferred embodiment of the present invention, there is provided a photosensitive resin composition for a display panel, characterized in that the compound (D) having an oxazine ring has a general formula (1) and/or the following general formula (2) A compound of the oxazine ring group shown. 〔化3〕

式中’ 爲碳數1〜12之院基，可具有取代基之環己基、可具有取代基之芳基。〔化4〕Wherein ' is a group having a carbon number of 1 to 12, a cyclohexyl group which may have a substituent, and an aryl group which may have a substituent. 〔化4〕

又，依本發明可提供一種硬化物，其特徵爲經由：使該感光性樹脂組成物進行塗佈•乾燥之形成塗膜步驟、在經該形成塗膜步驟而得之塗膜上，選擇性照射活性能量線之光硬化處理步驟、在光硬化處理步驟之後，使用鹼顯像液去除未照射部份而得圖型之鹼顯像步驟、及將鹼顯像步驟所得之圖型加熱·硬化的步驟’而得。進而，依本發明可提供，使用該感光性樹脂組成物所 (4) 1303354 形成之壓縮強度優異的顯示面板用間隔物。還有’本發明中所謂「活性能量線」，係指包含可見光線、紫外線、遠紫外線、電子線、X射線等之意。〔發明之功效〕本發明之感光性組成物含有熱硬化成份的具有噁嗪環之化合物（以下稱爲噁嗪化合物）的硬化系之故，所得硬化物具有充分的硬度、耐熱性、耐藥品性。即，本發明之感光性組成物，與以往使用環氧樹脂作爲交聯成份之情況比較’可形成保持儲存穩定性，同時高硬度、高耐熱性、耐藥品性、壓縮強度等諸特性優越之硬化物，適合於間隔物或平坦化膜等用途。並且，依本發明之感光性組成物，由於儲存穩定性優異，能提供可省略在即將使用前之二液混合的手續之操作性優異的一液型感光性樹脂組成物。〔發明之實施形態〕本發明之感光性組成物中作爲熱硬化成份添加之噁嗪化合物，係藉由熱進行開環聚合而得堅固之硬化物。又，其開環聚合催化劑係使用羧酸等酸，藉由酸催化劑之添加可使反應開始溫度下降。噁嗪化合物單獨必要200 °C之硬化溫度，本發明之感光性樹脂組成物中，含有鹼可溶性之羧基的感光性樹脂（A )中之羧基，作爲催化劑的作用之故，噁嗪環之開環聚合溫度約可降低至160 °C ° 本發明中使用之組成物，不僅含鹼可溶性之羧基的感 -7- (5) 1303354 ^ 光性樹脂（A )與具有乙烯性不飽和鍵之聚合性化合物（B )的交聯反應，噁嗪化合物之交聯結構進行複合性的作用，形成互相進入網狀鏈之結構；與以往之感光性樹脂組成物比較，全不損害儲存穩定性，可形成堅固的硬化物，能滿足間隔物所要求之高硬度、壓縮強度等各特性。就本發明之感光性樹脂組成物的各成份詳細說明如下。含有鹼可溶性之羧基的感光性樹脂（A )，可溶於鹼水 # 溶液，不限定於一分子中具有至少兩個以上之乙烯性不飽和鍵的含羧基感光性樹脂之特定者，可使用下述列舉之樹月旨（可爲低聚物及聚合物之任一種）。 (1) 在（a)不飽和羧酸與（b)具有不飽和雙鍵之 . 化合物的共聚物中，藉由附加以乙烯性不飽和基作爲側基而得之含羧基感光性樹脂。 (2) 在（c)具有環氧基與不飽和雙鍵之化合物、與 (b)具有不飽和雙鍵之化合物的共聚物中，使（a)不飽 Φ 和羧酸反應；在生成之仲羥基中，使（d )飽和或不飽和多元酸酐反應而得之含羧基感光性樹脂。 (3) 在（e)具有不飽和雙鍵之酸酐與（b)具有不飽和雙鍵之化合物的共聚物中，使（f)具有羥基與不飽和雙鍵之化合物反應而得之含羧基感光性樹脂。 (4) 使（g) —分子中具有至少兩個環氧基之多官能環氧化合物的環氧基與（h)不飽和單羧酸之羧基進行酯化反應（全酯化或部份酯化，較佳爲全酯化）；在生成之羥基中，進而使（d )飽和或不飽和多元酸酐反應而得之 -8- (6) 1303354 含羧基感光性樹脂。 (5) 在使（j)含有羥基之聚合物與（d)飽和或+ 飽和多元酸酐反應而得之含有羧基樹脂中，進而使具有環氧基與不飽和雙鍵之化合物反應而得之含羧基感％性樹脂。 (6) 在（g) —分子中具有至少兩個環氧基之多官能環氧化合物、與不飽和單羧酸（h)、及（k) 一分子中具丨有至少兩個羥基、和與環氧基反應之羥基以外的一個其他反應性基之化合物的反應生成物（I )中，使（d )飽和或不飽和多元酸酐反應而得之含羧基感光性樹脂。 (7) 由上述反應生成物（I)、與（d)飽和或不飽和多元酸酐、及（m)含不飽和基之單異氰酸酯的反應生成物所成之含不飽和基的聚羧酸胺基甲酸酯樹脂。 (8) 在（η) —分子中具有至少兩個氧雜環丁烷環之多官能氧雜環丁烷化合物中，使（h)不飽和單羧酸反應 I ，相對於所得改性氧雜環丁烷樹脂中之伯羥基，使（d ) 飽和或不飽和多元酸酐反應而得之含羧基感光性樹脂等。該（1 )之含羧基感光性樹脂，係在不飽和羧酸（a ) 與具有不飽和雙鍵之化合物（b )的共聚物之羥基的一部份上，以能獲得充分的光硬化深度之程度提升光硬化性的比例，使具有乙烯基、烯丙基、丙烯醯基、甲基丙烯醯基等乙烯性不飽和基與環氧基、酸氯化物等反應性基之化合物，與例如（甲基）丙烯酸環氧丙基酯反應，將該化合物之不飽和雙鍵導入側鏈的樹脂。該共聚物一方之單體成份 -9- (7) 1303354 的不飽和羧酸（a)具有之羧基的一部份，未反應而直接殘留之故，所得含羧基感光性樹脂，相對於鹼水溶液爲可溶性。因此，由含有如此之樹脂的組成物所形成之皮膜，在選擇性曝光後藉由於鹼水溶液中，可穩定顯像。還有，本說明書中所謂（甲基）丙烯酸酯，係丙烯酸酯與甲基丙烯酸酯之總稱的用語，其他類似者亦同。該（2 )之含羧基感光性樹脂，係在（c )分子中具有環氧基與不飽和雙鍵之化合物，例如（甲基）丙烯酸環氧丙基酯、（甲基）丙烯酸甲基環氧丙基酯等，與該（b )具有不飽和雙鍵之化合物的共聚物之環氧基上，以能獲得充分的光硬化深度之程度提升光硬化性的比例，使該（ a)不飽和羧酸之羧基反應，將該不飽和羧酸之不飽和雙鍵導入側鏈，同時在上述附加反應生成之仲羥基上使（d )多元酸酐，例如苯二甲酸酐、四氫苯二甲酸酐、六氫苯二甲酸酐等進行酯化反應，在側鏈導入羧基之樹脂。該（3 )之含羧基感光性樹脂，係在（e )具有不飽和雙鍵之酸酐，例如馬來酸酐、衣康酸酐等，與該（b)具有不飽和雙鍵之化合物的共聚物之酸酐基的一部份上，以能獲得充分的光硬化深度之程度提升光硬化性的比例，使 (f )具有羥基與不飽和雙鍵之化合物，例如（甲基）丙烯酸羥烷基酯類、在（甲基）丙烯酸酯中使己內酯反應之單體、在（甲基）丙烯酸酯中使聚己內酯低聚物反應之大分子單體等羥基反應而成半酯，將該化合物（f)之不飽和雙鍵導入側鏈的樹脂。 -10- 1303354 ‘ （8) ^ 該（4 )之含羧基感光性樹脂，係在（g )雙酚A型、雙酚F型、雙酚S型、苯酚酚醛型、甲酚酚醛型、聯苯型、聯二甲苯酚型、N-環氧丙基型等眾所周知的慣用之環氧化合物的環氧基上，以能獲得充分的光硬化深度之程度提升光硬化性的比例，使（h )(甲基）丙烯酸等不飽和羧酸之羥基反應，例如生成環氧丙烯酸酯、同時在上述附加反應生成之仲羥基上，使該（d )多元酸酐進行酯化反應 φ ，將羧基導入側鏈之樹脂。如此之含羧基感光性樹脂，光硬化性優越、同時骨架聚合物之環氧丙烯酸酯爲疏水性。因此，使用含有該樹脂之光硬化性樹脂組成物時，有效利 . 用環氧丙烯酸酯之疏水性，可提升難以進行光硬化之圖型 _ 深部的耐顯像性。其結果，在顯像及曝光步驟中，可擴大設定條件之自由度。另一方面，該（5)之含羧基感光性樹脂，係在含羧基樹脂之羧基上，以能獲得充分的光硬化深度之程度提升 # 光硬化性的比例，使該（c )具有環氧基與不飽和雙鍵之化合物的環氧基反應，將該化合物（c)之不飽和雙鍵導入側鏈的樹脂。如此之含羧基感光性樹脂，光硬化性優越，具有充分的光硬化深度。該（6)之含羧基感光性樹脂的合成反應有，在多官能環氧化合物（g )中，使不飽和單羧酸（h )〔或化合物 (k )〕反應，接著使化合物（k )〔或不飽和單羧酸（h )〕反應之第一方法；和使多官能環氧化合物（g )、與不飽和單羧酸（h)、及化合物（k)同時進行反應之第二 -11 - (9) 1303354 方法。雖可爲任一之方法，以第二方法爲具有至少兩個以上之羥基、和與環氧基反 ~個其他反應性基（例如，羧基、仲胺基 k )的具體例有，例如二羧甲基丙酸、二羥甲基丁酸、二羥甲基戊酸、二羥甲基己單羧酸；二乙醇胺、二異丙醇胺等二烷醇另一方面，該（7)之含不飽和基聚 • 樹脂的合成，以使該反應生成物（〇與$ 應，接著，相對於生成之含不飽和基聚羧，使含不飽和基之單異氰酸酯（m)反應 • 單異氰酸酯（m)之具體例有，例如藉由 . 異氰酸酯、甲基丙烯醯基氧乙基異氰酸酯酸酯（例如甲基烯二異氰酸酯、二甲苯烯佛爾酮二異氰酸酯、六亞甲基二異氰酸酯子中具有一個羥基之（甲基）丙烯酸酯類 • 反應而得之反應生成物等。該（8 )之含羧基感光性樹脂，使用環之化合物，替代藉由與不飽和單羧酸之基爲主的環氧樹脂，作爲啓始原料；在多化合物（η )中，使不飽和單羧酸（h )反氧雜環丁烷樹脂之伯羥基，進而藉由使多應，成爲結合部位難以被熱切斷之熱穩定藉由使用此含羧基感光性樹脂，可調製耐優異之鹼顯像型的光硬化性·熱硬化性樹丨佳。該一分子中應之羥基以外的等）之化合物（羥甲基乙酸、二酸等含聚羥基之胺等。羧酸胺基甲酸酯多元酸酐（d )反酸樹脂中之羥基爲佳。該不飽和使甲基丙烯醯基，或有機二異氰二異氰酸酯、異等），與該一分，以約等莫耳比具有氧雜環丁烷反應生成以仲羥官能氧雜環丁烷應，相對於改性 7元酸酐（d )反性優越的樹脂。熱性、熱穩定性指組成物。 -12- (10) 1303354 此等鹼可溶性之含羧基感光性樹脂中，以使用該（1 )、（2 )及（3 )所示之共聚合樹脂更佳。該如上述之鹼可溶性的含羧基感光性樹脂（A )，可單獨或混合使用，任一情況均以此等之合計爲組成物全量的5〜80質量份爲佳，以10〜60質量份之比例配合更佳。又，含羧基感光性樹脂，分別之酸價爲30〜25 0mg KOH/g ，較佳爲50〜150mg KOH/g;且，其雙鍵當量爲3 5 0〜2,000 ，適合使用較佳之 400〜1，5 00者。上述樹脂之酸價比 30mg KOH/g時，相對於水溶液之溶解性不充分容易造成顯像不良。另一方面，比250mg KOH/g高時，於顯像之際造成皮膜之密著的劣化、或光硬化部份（曝光部份）的溶解之故，甚不適合。進而，在含羧基之感光性樹脂的情況，感光性樹脂之雙鍵當量比2，0 0 0大時，顯像之際的操作自由度狹窄，又光硬化時必要高曝光量之故，極不適合〇本發明中所使用之具有乙烯性不飽和鍵之聚合性化合物（B )，從聚合性良好，提升所得間隔物之強度、耐熱性之點而言，以使用單官能、2官能或3官能以上之（甲基）丙烯酸酯較爲適合。上述單官能（甲基）丙烯酸酯有，例如（甲基）丙烯酸2-羥基乙基酯、卡必醇（甲基）丙烯酸酯、（甲基）丙烯酸異冰片基酯、（甲基）丙烯酸3-甲氧基丁基酯、2-( 甲基）丙烯醯基氧乙基-2-羥基丙基苯二甲酸酯等。其市售品有’例如阿洛尼庫斯Μ -1 0 1、同Μ - 1 1 1、同Μ -1 1 4 (以 (11) 1303354 上爲東亞合成股份有限公司製），卡亞拉得TC-110S、同 TC-120S (以上爲日本化藥股份有限公司製），皮斯口多 1 5 8、皮斯口多2 3 1 1 (以上爲大阪有機化學工業股份有限公司製）等。上述2官能（甲基）丙烯酸酯有，例如乙二醇二（甲基）丙烯酸酯、1,6-己二醇二（甲基）丙烯酸酯、；[，9-壬二醇二（甲基）丙烯酸酯、聚丙二醇二（甲基）丙烯酸酯、四乙二醇二（甲基）丙烯酸酯、雙苯氧基乙醇芴二丙烯酸酯等。其市售品有，例如阿洛尼庫斯M-210、同M-240 、同M-6200 (以上爲東亞合成股份有限公司製），卡亞拉得HDDA、同HX-220、同R-604 (以上爲日本化藥股份有限公司製），皮斯口多260、同312、同335 HP (以上爲大阪有機化學工業股份有限公司製）等。上述3官能以上之（甲基）丙烯酸酯有，例如三羥甲基丙烷三（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸醋、三〔（甲基）丙烯醯氧基乙基〕磷酸酯、季戊四醇四 (甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯等。其市售品有，例如阿洛尼庫斯 M-309、同 M-400、同 M-402、同 M-405、同 M-45〇、同 M-7100、同 M- 8 03 0、同 M-8 060、同 M-1310、同 Μ · 1 6 0 〇、同 M- 1 9 6 0、同 Μ - 8 1 0 0、同 Μ - 8 5 3 0、同 Μ - 8 5 6 0 、同Μ-9050、同ΤΟ-1450 (以上爲東亞合成股份有限公司製），卡亞拉得 ΤΜΡΤΑ、同 DPHA、同 DPCA-20、同 DPCA-30、同 DPCA-60、同 DPCA-120(以上爲日本化藥 -14- (12) 1303354 股份有限公司製），皮斯口多295、同300、同360、同 GPT、同3PA、同400 (以上爲大阪有機化學工業股份有限公司製）等。此等單官能、2官能或3官能以上之（甲基）丙烯酸酯，可單獨或組合使用。如上所述之具有乙烯性不飽和鍵之聚合性化合物（B )之使用量的適合範圍，相對於該含有鹼可溶性之羧基的感光性樹脂（A) 10 0質量份，爲5〜5 0質量份，更佳爲可達10〜40質量份之比例。該聚合引發劑（C )，可使用藉由照射活性能量線產生游離基之眾所周知的化合物。例如苯乙酮、2,2·二甲氧基-2-苯基苯乙酮、2，2-二乙氧基-2-苯基苯乙酮、對-二甲基胺基苯丙酮、二氯苯乙酮、三氯苯乙酮、對-叔丁基三氯苯乙酮、1-羥基環己基苯基酮、2-甲基-1-〔4-(甲硫基 )苯基〕-2-嗎啉代-丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉代苯基）-丁酮-1、N，N-二甲基胺基苯乙酮等苯乙酮類；二苯甲酮、甲基二苯甲酮、2-氯二苯甲酮、4,4’-二氯二苯甲酮、4，4’-雙二甲基胺基二苯甲酮、4，4’-雙二乙基胺基二苯甲酮、米希勒酮、4-苯甲醯基-4’-甲基二苯基硫化物等二苯甲酮類；苯偶醯、苯偶因、苯偶因甲基醚、苯偶因乙基醚、苯偶因異丙基醚、苯偶因異丁基醚等苯偶因醚類；苯乙酮二甲基酮縮醇、苯偶醯二甲基酮縮醇等酮縮醇類；噻噸酮、2-氯噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等噻噸酮類；2-甲基蒽醌、2-乙基蒽醌、2-叔丁基蒽醌、1-氯蒽醌、2-胺基蒽醌 -15- (13) 1303354 、2,3-二苯基蒽醌等蒽醌類·，苯甲醯過氧化物、異丙苯過氧化物等有機過氧化物；2，4，5 -三芳基咪唑二聚物、核黃素四丁酸酯、2-毓基苯并咪唑、2-毓基苯并噁唑、2-锍基苯并噻唑等硫醇化合物；2,4,6-三-s-三嗪、2,2,2-三溴乙醇、三溴甲基苯基颯等有機鹵素化合物；2,4,6-三甲基苯甲醯基二苯基膦氧化物等。又，其他之例有吖啶化合物類、肟酯類等。此等化合物可單獨使用，又兩種以上組合使用。進而，如上所述之光聚合引發劑（C)，可與Ν,Ν-二甲基胺基苯甲酸乙基酯、Ν，Ν-二甲基胺基苯甲酸異戊基酯、戊基-4-二甲基胺基苯甲酸酯、三乙胺、三乙醇胺等叔胺類，及沒-硫烯二乙醇等硫醚類，（酮基）香豆素、噻噸等增感色素類，以及菁、若丹明、藏紅、孔雀綠、亞甲藍等烷基硼酸鹽等光增感劑或促進劑之一種或兩種以上組合使用。該光聚合引發劑（C )之較佳組合爲，2-甲基-1-〔 4-(甲硫基）苯基〕-2-嗎啉代丙烷-1 -酮（例如吉巴·特殊化學品公司製，依魯加丘爾-907 )與2-氯噻噸酮（例如曰本化藥股份有限公司製，卡牙丘爾-CTX )、或2,4-二乙基噻噸酮（例如日本化藥股份有限公司製，卡牙丘爾DETX )、2-異丙基噻噸酮、4-苯甲醯基-4··甲基二苯基硫化物等之組合。又，如上所述之聚合引發劑（C )的使用量之較佳範圍，相對於該含有鹼可溶性之羧基的感光性樹脂（A ) 1 0 〇 -16- (14) 1303354 質量份爲0.01〜30質量份，更佳爲0.1〜20質量份。光游離基聚合引發劑之配合比例未達〇.〇 1質量份時，光硬化性惡化；另一方面，比3 0質量份多時，硬化塗膜之特性惡化，又，儲存穩定性惡化之故甚不適合。該具有噁嗪環之化合物（D )，可使用分子中具有至少一個下述一般式（3 )所示之噁嗪環含有基的噁嗪化合物，並不限定於特定之化合物。〔化5〕Further, according to the present invention, there is provided a cured product comprising: a step of forming a coating film by applying and drying the photosensitive resin composition, and a coating film obtained by the step of forming a coating film, optionally a photohardening treatment step of irradiating an active energy ray, a step of removing a non-irradiated portion using an alkali developing solution to obtain a pattern, and a pattern obtained by heating and hardening the pattern obtained by the alkali developing step after the photohardening treatment step The steps 'get it. Further, according to the present invention, it is possible to provide a spacer for a display panel which is excellent in compressive strength and which is formed by using the photosensitive resin composition (4) 1303354. Further, the term "active energy ray" as used in the present invention means that it includes visible light, ultraviolet light, far ultraviolet ray, electron beam, X-ray, and the like. [Effect of the Invention] The photosensitive composition of the present invention contains a curing compound of a compound having an oxazine ring (hereinafter referred to as an oxazine compound) which is a thermosetting component, and the obtained cured product has sufficient hardness, heat resistance, and drug resistance. Sex. In other words, the photosensitive composition of the present invention is superior in comparison with the case where an epoxy resin is conventionally used as a crosslinking component, and has excellent properties such as high hardness, high heat resistance, chemical resistance, and compressive strength. Hardened material, suitable for applications such as spacers or flattening films. In addition, the photosensitive composition of the present invention is excellent in storage stability, and it is possible to provide a one-component photosensitive resin composition which is excellent in handleability in the procedure of mixing the two liquids immediately before use. [Embodiment of the Invention] The oxazine compound to be added as a thermosetting component in the photosensitive composition of the present invention is a cured product obtained by ring-opening polymerization by heat. Further, the ring-opening polymerization catalyst is an acid such as a carboxylic acid, and the reaction initiation temperature can be lowered by the addition of an acid catalyst. The oxazine compound alone requires a curing temperature of 200 ° C. In the photosensitive resin composition of the present invention, the carboxyl group in the photosensitive resin (A) containing an alkali-soluble carboxyl group acts as a catalyst, and the oxazine ring is opened. The ring polymerization temperature can be lowered to about 160 ° C. The composition used in the present invention is not only a base-soluble carboxyl group-containing 7-(5) 1303354^ photo-resin (A) and a polymerization having an ethylenically unsaturated bond. The cross-linking reaction of the compound (B) and the cross-linking structure of the oxazine compound act as a composite to form a structure in which the mesh chain is introduced into each other; compared with the conventional photosensitive resin composition, the storage stability is not impaired. Forms a strong hardened material that meets the high hardness and compressive strength required for the spacer. The respective components of the photosensitive resin composition of the present invention will be described in detail below. The photosensitive resin (A) containing an alkali-soluble carboxyl group is soluble in the alkaline water # solution, and is not limited to a specific one of the carboxyl group-containing photosensitive resin having at least two or more ethylenically unsaturated bonds in one molecule, and can be used. The following is a list of the following (which may be either an oligomer or a polymer). (1) A carboxyl group-containing photosensitive resin obtained by adding a ethylenically unsaturated group as a side group to a copolymer of (a) an unsaturated carboxylic acid and (b) a compound having an unsaturated double bond. (2) in (c) a copolymer of a compound having an epoxy group and an unsaturated double bond, and (b) a compound having an unsaturated double bond, reacting (a) unsaturated Φ with a carboxylic acid; Among the secondary hydroxyl groups, a carboxyl group-containing photosensitive resin obtained by reacting (d) a saturated or unsaturated polybasic acid anhydride. (3) In the copolymer of (e) an acid anhydride having an unsaturated double bond and (b) a compound having an unsaturated double bond, (f) a carboxyl group-containing photosensitive reaction obtained by reacting a compound having a hydroxyl group and an unsaturated double bond Resin. (4) Esterifying (g) - an epoxy group of a polyfunctional epoxy compound having at least two epoxy groups in the molecule with a carboxyl group of (h) an unsaturated monocarboxylic acid (fully esterified or partially esterified) Further, it is preferably a full esterification); a carboxy-containing photosensitive resin obtained by reacting (d) a saturated or unsaturated polybasic acid anhydride with the resulting hydroxyl group. (5) In the case where the (j) hydroxyl group-containing polymer is reacted with (d) a saturated or + saturated polybasic acid anhydride, a carboxyl group-containing resin is further reacted with a compound having an epoxy group and an unsaturated double bond. Carboxylamine-based resin. (6) at (g) - a polyfunctional epoxy compound having at least two epoxy groups in the molecule, and at least two hydroxyl groups in the molecule of the unsaturated monocarboxylic acid (h), and (k), and A carboxyl group-containing photosensitive resin obtained by reacting (d) a saturated or unsaturated polybasic acid anhydride in the reaction product (I) of a compound other than a hydroxyl group which reacts with an epoxy group. (7) an unsaturated group-containing polycarboxylic acid amine formed from the reaction product of the above reaction product (I), (d) a saturated or unsaturated polybasic acid anhydride, and (m) an unsaturated group-containing monoisocyanate Carbamate resin. (8) In (η) - a polyfunctional oxetane compound having at least two oxetane rings in the molecule, reacting (h) an unsaturated monocarboxylic acid with respect to the resulting modified oxalate A carboxyl group-containing photosensitive resin obtained by reacting a primary hydroxyl group in a cyclobutane resin with (d) a saturated or unsaturated polybasic acid anhydride. The carboxyl group-containing photosensitive resin of (1) is a part of a hydroxyl group of a copolymer of an unsaturated carboxylic acid (a) and a compound (b) having an unsaturated double bond, so that a sufficient photohardening depth can be obtained. To the extent that the ratio of photocurability is increased, a compound having an ethylenically unsaturated group such as a vinyl group, an allyl group, an acryloyl group or a methacryl group, and a reactive group such as an epoxy group or an acid chloride is, for example, The (meth)acrylic acid glycidyl ester is reacted, and the unsaturated double bond of the compound is introduced into the resin of the side chain. a part of the carboxyl group of the unsaturated monomeric carboxylic acid (a) of the monomer component of the copolymer, 9-(7) 1303354, which remains unreacted and directly remains, thereby obtaining a carboxyl group-containing photosensitive resin relative to the aqueous alkali solution For solubility. Therefore, the film formed of the composition containing such a resin can be stably developed by the aqueous alkali solution after selective exposure. Further, in the present specification, the term "(meth)acrylate" is a generic term for acrylate and methacrylate, and the like is the same. The carboxyl group-containing photosensitive resin of (2) is a compound having an epoxy group and an unsaturated double bond in (c) a molecule, for example, a glycidyl (meth)acrylate or a methyl (meth)acrylate. a ratio of oxypropyl ester or the like to the epoxy group of the copolymer of the compound having an unsaturated double bond (b), such that a sufficient photohardening depth can be obtained to increase the ratio of photocurability, so that (a) The carboxyl group of the saturated carboxylic acid is reacted, and the unsaturated double bond of the unsaturated carboxylic acid is introduced into the side chain, and (d) a polybasic acid anhydride such as phthalic anhydride or tetrahydrophthalic acid is obtained on the secondary hydroxyl group formed by the above additional reaction. An acid anhydride, hexahydrophthalic anhydride or the like is subjected to an esterification reaction to introduce a carboxyl group-containing resin into a side chain. The carboxyl group-containing photosensitive resin of (3) is a copolymer of (e) an acid anhydride having an unsaturated double bond, such as maleic anhydride, itaconic anhydride, or the like, and (b) a compound having an unsaturated double bond. a part of the acid anhydride group which increases the photocurability ratio to a sufficient degree of photohardening depth, so that (f) a compound having a hydroxyl group and an unsaturated double bond, such as a hydroxyalkyl (meth)acrylate a monomer in which a caprolactone is reacted in a (meth) acrylate, and a hydroxyl group such as a macromonomer in which a polycaprolactone oligomer is reacted in a (meth) acrylate, and a half ester is reacted. The unsaturated double bond of the compound (f) is introduced into the resin of the side chain. -10- 1303354 ' (8) ^ The carboxyl group-containing photosensitive resin of (4) is based on (g) bisphenol A type, bisphenol F type, bisphenol S type, phenol novolac type, cresol novolac type, In the epoxy group of a well-known conventional epoxy compound such as a benzene type, a bixylenol type, or an N-epoxypropyl type, the ratio of photocurability is improved to a sufficient degree of photohardening depth, so that (h) a reaction of a hydroxyl group of an unsaturated carboxylic acid such as (meth)acrylic acid, for example, to form an epoxy acrylate, and at the same time as the secondary hydroxyl group formed by the above additional reaction, the (d) polybasic acid anhydride is subjected to an esterification reaction φ, and the carboxyl group is introduced to the side. Chain resin. Such a carboxyl group-containing photosensitive resin is excellent in photocurability and at the same time, the epoxy acrylate of the skeleton polymer is hydrophobic. Therefore, when a photocurable resin composition containing the resin is used, the hydrophobicity of the epoxy acrylate can be effectively utilized, and the pattern which is difficult to be photohardened can be improved. As a result, in the development and exposure steps, the degree of freedom in setting conditions can be expanded. On the other hand, the carboxyl group-containing photosensitive resin of the above (5) is applied to the carboxyl group of the carboxyl group-containing resin to increase the ratio of the photocurability to a sufficient degree of photohardening depth, so that the (c) has an epoxy resin. The group reacts with the epoxy group of the compound of the unsaturated double bond, and the unsaturated double bond of the compound (c) is introduced into the resin of the side chain. Such a carboxyl group-containing photosensitive resin is excellent in photocurability and has a sufficient photohardening depth. The synthesis reaction of the carboxyl group-containing photosensitive resin of (6) is carried out by reacting an unsaturated monocarboxylic acid (h) [or a compound (k)] in a polyfunctional epoxy compound (g), followed by reacting the compound (k) a first method of reacting [or unsaturated monocarboxylic acid (h)]; and a second reaction of simultaneously reacting the polyfunctional epoxy compound (g) with the unsaturated monocarboxylic acid (h) and the compound (k) 11 - (9) 1303354 Method. Although it may be any method, in the second method, there are specific examples in which at least two or more hydroxyl groups and the other reactive groups (for example, a carboxyl group or a secondary amino group k) are opposite to the epoxy group, for example, two Carboxymethylpropionic acid, dimethylolbutanoic acid, dimethylol valeric acid, dimethylol monocarboxylic acid; dialkyl alcohol such as diethanolamine or diisopropanolamine, on the other hand, (7) The synthesis of an unsaturated group-containing resin is carried out so that the reaction product (〇 and $ should be reacted with respect to the resulting unsaturated group-containing polycarboxylate to react the unsaturated group-containing monoisocyanate (m) • monoisocyanate Specific examples of (m) are, for example, by isocyanate, methacryloyloxyethyl isocyanate (for example, methylene diisocyanate, xylene ketone diisocyanate, hexamethylene diisocyanate) a (meth) acrylate having a hydroxyl group, a reaction product obtained by the reaction, etc. The carboxyl group-containing photosensitive resin of (8) uses a ring compound instead of being mainly composed of an unsaturated monocarboxylic acid. Epoxy resin, as a starting material; In the compound (η), the primary hydroxyl group of the unsaturated monocarboxylic acid (h) oxetane resin is further stabilized by heat, and the carboxyl group is difficult to be thermally cut by the use of the carboxyl group. The photosensitive resin can prepare a photocurability and thermosetting property of an alkali-developing type which is excellent in resistance, and a compound other than a hydroxyl group (such as a hydroxyl group, a diacid or the like) The amine or the like. The carboxylic acid urethane polybasic acid anhydride (d) preferably has a hydroxyl group in the acid-reducing resin. The unsaturated is a methyl methacrylate group, or an organic diisocyanuric acid ester, an isocratic group, and the like. The reaction is carried out with an oxetane reaction to form a secondary hydroxy-functional oxetane, which is superior to the modified quaternary anhydride (d). Thermal and thermal stability means composition. -12- (10) 1303354 Among these alkali-soluble carboxyl group-containing photosensitive resins, it is more preferable to use the copolymerized resin represented by the above (1), (2) and (3). Carboxyl group-containing photosensitive resin (A), which can be used singly or in combination, either It is preferable that the total amount of the composition is 5 to 80 parts by mass, and more preferably 10 to 60 parts by mass. Further, the carboxyl group-containing photosensitive resin has an acid value of 30 to 25 mg KOH / g is preferably 50 to 150 mg KOH/g; and the double bond equivalent is 3,500 to 2,000, preferably 400 to 1,500. The acid value of the above resin is 30 mg KOH/g. When the solubility in an aqueous solution is insufficient, it is likely to cause poor development. On the other hand, when it is higher than 250 mg KOH/g, the adhesion of the film or the dissolution of the photohardened portion (exposed portion) is caused at the time of development. Further, in the case of a photosensitive resin containing a carboxyl group, when the double bond equivalent ratio of the photosensitive resin is larger than 2,0 0 0, the degree of freedom of operation at the time of development is narrow, and it is necessary to be high in light hardening. The amount of exposure is extremely unsuitable for the polymerizable compound (B) having an ethylenically unsaturated bond used in the present invention, and is used in a point that the polymerizability is good and the strength and heat resistance of the obtained spacer are improved. Functional, bifunctional or trifunctional or higher (meth) acrylate Co. The above monofunctional (meth) acrylates are, for example, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylate 3 -Methoxybutyl ester, 2-(methyl)propenyloxyethyl-2-hydroxypropyl phthalate, and the like. Its commercial products are 'for example, Alonicus Μ -1 0 1 , Μ - 1 1 1 , Μ -1 1 4 (by (11) 1303354 on the East Asia Synthetic Co., Ltd.), Kayala TC-110S, TC-120S (the above is made by Nippon Kayaku Co., Ltd.), Piskou mouth 158, Piskou mouth 2 3 1 1 (above is Osaka Organic Chemical Industry Co., Ltd.), etc. . The above bifunctional (meth) acrylates are, for example, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, [,9-nonanediol di(methyl) Acrylate, polypropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, bisphenoxyethanoloxime diacrylate, and the like. Its commercial products are, for example, Alonikis M-210, the same M-240, the same M-6200 (above is East Asia Synthetic Co., Ltd.), Kayala HDDA, the same HX-220, the same R- 604 (The above is manufactured by Nippon Kayaku Co., Ltd.), Pisceso 260, 312, and 335 HP (above, Osaka Organic Chemical Industry Co., Ltd.). The above-mentioned trifunctional or higher (meth) acrylate may be, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tris(meth)acrylic acid vinegar, or tris((meth)acryloxyethyl)phosphoric acid. Ester, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like. Its commercial products are, for example, Alonikis M-309, the same M-400, the same M-402, the same M-405, the same M-45 〇, the same M-7100, the same M- 8 03 0, the same M-8 060, the same M-1310, the same Μ · 1 600 〇, the same M- 1 9 6 0, the same - 8 1 0 0, the same - 8 5 3 0, the same - 8 5 6 0, Tongyu-9050, Tongyi-1450 (above is made by East Asia Synthetic Co., Ltd.), Kayarad, same DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (above) It is made by Nippon Kayaku - 14 - (12) 1303354 Co., Ltd.), 皮斯口多多295, the same 300, the same 360, the same GPT, the same 3PA, the same 400 (the above is made by Osaka Organic Chemical Industry Co., Ltd.) . These monofunctional, bifunctional or trifunctional or higher (meth) acrylates may be used singly or in combination. The suitable range of the amount of the polymerizable compound (B) having an ethylenically unsaturated bond as described above is 5 to 50% by mass based on 100 parts by mass of the photosensitive resin (A) containing an alkali-soluble carboxyl group. More preferably, it is a ratio of up to 10 to 40 parts by mass. As the polymerization initiator (C), a well-known compound which generates a radical by irradiation of an active energy ray can be used. For example, acetophenone, 2,2. dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, p-dimethylaminopropiophenone, two Chloroacetophenone, trichloroacetophenone, p-tert-butyltrichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]- 2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, N,N-dimethylamine Acetophenones such as acetophenone; benzophenone, methylbenzophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdimethyl Diphenyl benzophenone, 4,4'-bisdiethylaminobenzophenone, michelone, 4-benzylidene-4'-methyldiphenyl sulfide, etc. Ketones; benzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers; acetophenone Ketoacetals such as dimethyl ketal and benzoin dimethyl ketal; thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethyl Thiophenones such as thioxanthone and 2,4-diisopropylthioxanthone; 2-methylindole , 2-ethyl hydrazine, 2-tert-butyl fluorene, 1-chloroindole, 2-aminoindole-15-(13) 1303354, 2,3-diphenylfluorene, etc. , organic peroxides such as benzamidine peroxide, cumene peroxide; 2,4,5-triaryl imidazole dimer, riboflavin tetrabutyrate, 2-mercaptobenzimidazole, 2 a mercaptan compound such as mercaptobenzoxazole or 2-mercaptobenzothiazole; 2,4,6-tris-triazine, 2,2,2-tribromoethanol, tribromomethylphenylhydrazine An organohalogen compound; 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or the like. Further, other examples include acridine compounds and oxime esters. These compounds may be used singly or in combination of two or more. Further, the photopolymerization initiator (C) as described above may be copolymerized with ethyl hydrazine, hydrazine-dimethylaminobenzoic acid, isoamyl hydrazine, hydrazine-dimethylaminobenzoate, pentyl- Tertiary amines such as 4-dimethylamino benzoate, triethylamine, triethanolamine, and thioethers such as non-thione diethanol, sensitizing pigments such as (keto) coumarin and thioxanthin And one or a combination of two or more kinds of photosensitizers or accelerators such as alkyl borate such as cyanine, rhodamine, saffron, malachite green, and methylene blue. A preferred combination of the photopolymerization initiator (C) is 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (for example, Jiba Special Chemistry) Manufactured by the company, Iruga Chul-907) and 2-chlorothioxanthone (such as 曰本化制药股份有限公司, Kartur-CTX), or 2,4-diethylthioxanthone ( For example, a combination of Nippon Chemical Co., Ltd., Kapon (DETX), 2-isopropylthioxanthone, 4-benzylidene-4·methyldiphenyl sulfide, and the like. Further, the preferred range of the amount of the polymerization initiator (C) to be used is 0.01% by mass of the photosensitive resin (A) 1 0 〇-16-(14) 1303354 parts of the alkali-soluble carboxyl group. 30 parts by mass, more preferably 0.1 to 20 parts by mass. When the blending ratio of the photo-radical polymerization initiator is less than 0.1 part by mass, the photocurability is deteriorated. On the other hand, when the amount is more than 30 parts by mass, the properties of the cured coating film are deteriorated, and the storage stability is deteriorated. Therefore, it is not suitable. The compound (D) having an oxazine ring can be an oxazine compound having at least one oxazine ring-containing group represented by the following general formula (3) in the molecule, and is not limited to a specific compound. 〔化5〕

…，·(3) R2 式中，R1爲碳數1〜12之烷基、可具有取代基之環己基、可具有取代之芳基。R2爲下述所示之有機基。η爲 2〜4之整數。〔化6〕(3) R2 In the formula, R1 is an alkyl group having 1 to 12 carbon atoms, a cyclohexyl group which may have a substituent, and an aryl group which may have a substitution. R2 is an organic group shown below. η is an integer of 2 to 4. [6]

更具體的噁嗪化合物之例示有，使酚化合物、甲醛、及伯胺反應而得之具有噁嗪環的化合物，由雙酚Α與甲醛 -17- (15) 1303354 及苯胺所衍生之2,2，-異亞丙基（3,4-二氫-3-苯基-2H-1，3-苯并惡嗪’或由雙酚F與甲醛及苯胺所衍生之亞甲基雙（ 3,4-二氫-3-苯基-2H-1，3-苯并噁嗪，進而，由苯酚酚醛樹脂與甲醛及苯胺所衍生之噁嗪化合物等。又’亦可使用具有兩個以上伯芳香族胺基之化合物與酚化合物、及甲醛之反應生成物的具有下述一般式（4) 所示之噁嗪環的化合物，並不限定於特定之化合物。〔化7〕More specific examples of the oxazine compound include a compound having an oxazine ring obtained by reacting a phenol compound, formaldehyde, and a primary amine, which is derived from bisphenol hydrazine and formaldehyde-17-(15) 1303354 and aniline. 2,-isopropylidene (3,4-dihydro-3-phenyl-2H-1,3-benzoxazine' or methylene bis (3, derived from bisphenol F and formaldehyde and aniline) 4-dihydro-3-phenyl-2H-1,3-benzoxazine, further, an oxazine compound derived from a phenol novolac resin, formaldehyde, and aniline. Further, it is also possible to use two or more primary aromatics. The compound having the oxazine ring represented by the following general formula (4), which is a reaction product of a compound of a group of a group with a phenol compound and formaldehyde, is not limited to a specific compound.

式中，R3爲下述所示之有機基。η爲2〜4之整數。〔化8〕In the formula, R3 is an organic group shown below. η is an integer of 2 to 4. 〔化8〕

此等噁嗪化合物中，該一般式（4 )所示之噁嗪化合物，提升硬度之效果高’更適合使用。本發明之感光性樹脂組成物中噁嗪化合物的配合里，相對於鹼可溶性感光樹脂（Α ) 1 0 〇質量份，以5〜5 〇貞里 -18- (16) 1303354 份爲佳，以10〜40質量份更佳。噁嗪化合物之配合量未達 5質量份時，組成物中之噁嗪化合物的比例少之故，不能達成顯著的物性提升。另一方面，超過5 0質量份時，鹼顯像性降低，造成解像性惡化，極不適合。本發明之感光性樹脂組成物，因應需求爲使該感光性樹脂組成物均勻溶解、調整黏度，可使用有機溶劑。有機溶劑以使各成份均勻溶解、不與各成份反應者爲佳。各成份對有機溶劑之溶解性低時，難以均勻溶解，很難確保間隔物所需求之透明性。甚不適合。此等有機溶劑之具體例有，例如甲醇、乙醇等醇類、四氫呋喃等醚類；乙二醇單甲醚、乙二醇單乙醚等二醇醚類；甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯等乙二醇烷基醚乙酸酯類；二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇二甲醚等二乙二醇類；丙二醇單甲醚、丙二醇單乙醚、丙二醇丙醚、丙二醇丁醚等丙二醇單烷基醚類；丙二醇甲醚乙酸酯、丙二醇乙醚乙酸酯、丙二醇丙醚乙酸酯、丙二醇丁醚乙酸酯等丙二醇烷基醚乙酸酯類；丙二醇甲醚丙酸酯、丙二醇乙醚丙酸酯、丙二醇丙醚丙酸酯、丙二醇丁醚丙酸酯等丙二醇烷基醚丙酸酯類；甲苯、二甲苯等芳香族烴類；甲乙酮、4-羥基-4-甲基-2-戊酮等酮類；及乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、2 -羥基丙酸乙酯、 2-羥基·2·甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、羥基乙酸甲酯、羥基乙酸乙酯、羥基乙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、3 ·羥基丙酸甲酯、3 ·羥基Among these oxazide compounds, the oxazine compound represented by the general formula (4) has a high effect of improving hardness, and is more suitable for use. The compounding of the oxazine compound in the photosensitive resin composition of the present invention is preferably 5 to 5 〇贞 -18 - (16) 1303354 parts based on the alkali-soluble photosensitive resin (Α) 10 parts by mass. 10 to 40 parts by mass is more preferable. When the amount of the oxazine compound is less than 5 parts by mass, the proportion of the oxazine compound in the composition is small, and remarkable physical property improvement cannot be achieved. On the other hand, when it exceeds 50 parts by mass, the alkali developability is lowered, and the resolution is deteriorated, which is extremely unsuitable. In the photosensitive resin composition of the present invention, an organic solvent can be used in order to uniformly dissolve the photosensitive resin composition and adjust the viscosity. The organic solvent is preferably one which dissolves each component uniformly and does not react with each component. When the solubility of each component in an organic solvent is low, it is difficult to uniformly dissolve, and it is difficult to ensure the transparency required for the spacer. Not very suitable. Specific examples of such organic solvents include, for example, alcohols such as methanol and ethanol, and ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; and methyl cellosolve acetate and B. Ethylene glycol alkyl ether acetate such as acetate, such as cellulose acetate; diethylene glycol such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether or diethylene glycol dimethyl ether; Propylene glycol monoalkyl ethers such as ether, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol butyl ether; propylene glycol alkyl ether such as propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate Ethyl ether acetates; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate and other propylene glycol alkyl ether propionates; aromatic hydrocarbons such as toluene and xylene Ketones such as methyl ethyl ketone and 4-hydroxy-4-methyl-2-pentanone; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, 2-hydroxyl 2. Methyl methacrylate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxyethyl Ethyl, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl 3-hydroxypropionate, 3-hydroxy

(17) 1303354 丙酸乙酯、3 -羥基丙酸丙酯、3 -丁氧基丙基丙酸乙酯、3 -丁氧基丙酸丙酯、3 -丁氧類等等。此等有機溶劑中，從溶解性、與各成膜形成之容易性的觀點而言，以二醇醚類酸酯類、酯類及二乙二醇類較適合使用，上混合使用。又，本發明之感光性樹脂組成物，在目的的範圍，因應需求亦可含有上述以外於此，其他成份有，.可與含有鹼可溶性樹脂中之羧基反應的交聯劑等。具體而物或氧雜環丁烷化合物等。環氧化合物有樹脂、雙酚F型環氧樹脂、雙酚S型環氧型環氧樹脂、甲酚酚醛型環氧樹脂、烷基脂、聯苯二酚型環氧樹脂、聯二甲苯酚型環氧樹脂、二環戊二烯型環氧樹脂、酚類之芳香族醛的縮合物之環氧化物、或此等環氧樹脂或含有磷原子之環氧樹脂、三環酸酯、脂環式環氧樹脂等，可單獨或兩種所周知的慣用者。氧雜環丁烷化合物有，雙酚A型氧雜雙酚F型氧雜環丁烷化合物、雙酚S型氧、苯烯二甲基型氧雜環丁烷化合物、苯酚院化合物、甲酸酣醛型氧雜環丁院化合物酸甲酯、3 - 丁氧基丙酸丁酯等酯份之反應性及塗、二醇烷基醚乙可單獨或兩種以不損及本發明之之其他成份。性之羧基的感光言，有環氧化合，雙酚A型環氧樹脂、苯酚酚醛酚酚醛型環氧樹環氧樹脂、萘型與具有酚性羥基之含有溴原子的氧丙基三聚異氰以上混合使用眾環丁烷化合物、雜環丁烷化合物酚醛型氧雜環丁、烷基酚酚醛型 -20- 1303354 * (18) ^ 氧雜環丁烷化合物、聯苯二酚型氧雜環丁烷化合物、聯二甲苯酚型氧雜環丁烷化合物、萘型氧雜環丁烷化合物、二環戊二烯型氧雜環丁烷化合物、酚類與具有酚性羥基之芳香族醛的縮合物之氧雜環丁烷化合物等，可單獨或兩種以上組合使用眾所周知的慣用者。但，添加環氧化合物造成儲存穩定性惡化之故，以添加氧雜環丁烷化合物爲佳。 φ 添加該環氧化合物或氧雜環丁烷化合物之際，在不損及儲存穩定性之範圍，可添加眾所周知的慣用之反應促進劑。 . 反應促進劑有，叔胺類、咪唑類、季鑰鹽類、叔膦類、鱗內鎗類、乙醯丙酮金屬錯合物類、或冠醚錯合物類等，此等可單獨或兩種以上組合使用。又，爲提升塗佈性可使用氟系、聚矽氧系、高分子系等眾所周知的慣用之界面活性劑、消泡劑、平坦化劑，或 # 爲提高與基板之黏著性的矽烷偶合劑等黏著助劑。如上所說明之本發明的感光性樹脂組成物，經下述說明之步驟，成爲硬化物圖型。即經：使本發明之感光性樹脂組成物進行塗佈•乾燥之形成塗膜步驟、在經該形成塗膜步驟而得之塗膜上，選擇性照射活个生能量線之光硬化處理步驟、在光硬化處理步驟之後，使用鹼顯像液去除未照射部份而得圖型之鹼顯像步驟、及 -21 - 1303354 ' (19) ^ 將鹼顯像步驟所得之圖型加熱•硬化形成硬化物圖型。 (1 )形成塗膜步驟此步驟中，使本發明之感光性樹脂組板或事先在基板上形成固體之著色感光性以下將其稱爲基板等）之上，自經塗佈之 • 物層去除溶劑等揮發成份，予以乾燥。於此，上述基板有，例如玻璃基板、酯基板、.聚酯基板、芳香族聚醯胺基板、 . 板、聚醯亞胺基板、A1基板、GaAs基板 _ 板等。此等基板可施行藉由矽烷偶合劑等、電漿處理、離子電鍍處理、濺鍍處理、真空蒸鍍處理等前處理。基板使用矽基板等時，可在該矽基板 Φ 荷結合元件（CCD)、薄膜晶體（TFT)等在該基板上塗佈感光性樹脂組成物時塗佈法、流延塗佈法、滾筒塗佈法、縫隙不旋轉塗佈機等省液塗佈機塗佈等眾所周使本發明之感光性樹脂組成物塗佈於基板由加熱使溶劑等揮發成份揮發。如此，在由感光性樹脂組成的固形份所成之層。 (2 )光硬化處理（曝光）步驟之步驟、成物，塗佈於基樹脂組成物層（感光性樹脂組成矽基板、聚碳酸聚醯胺醯亞胺基等表面平坦的基藥品之藥品處理氣相反應處理、等之表面形成電；〇 ’例如採用旋轉與旋轉塗佈法、知的塗佈方法，等之上，接著藉基板等之上形成 -22- 1303354 ^ (20) ’ 此步驟中，在該步驟（1 )所得之塗膜（以下稱爲感光性樹脂組成物層）上，選擇性照射活性能量線。於此，進行曝光時，例如以透過光罩選擇性照射活性能量線爲佳。曝光光源，通常以低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、氙氣燈、金屬鹵化物燈等較適合。又，亦可使用雷射光線等作爲曝光用活性光線。其他亦可使用電子線、α線、/3線、r線、X射線、中子 • 線等。光線係透過光罩而照射，此光罩係，例如在玻璃板之表面上設置將光線遮蔽的遮光層者。玻璃板中未設置遮光 . 層之部份爲光線透過的透光部，依此透光部之圖型，使在 . 圖型上之感光性樹脂組成物層曝光，產生未照射光線之未照射區域、與照射光線之照射區域。照射區域中之光線的照射量，依黏合劑聚合物之重量平均分子量、單體比、含量，光聚合性化合物之種類或含量，光聚合引發劑之種類 • 或含量，適當選擇。 (3 )鹼顯像步驟使完成該（2 )之步驟的基板上之塗膜顯像。於此，顯像時例如可使曝光後之感光性樹脂組成物層與顯像液接觸；具體而言，可使在其表面上形成感光性樹脂組成物層之狀態的基板，浸漬於顯像液中、或使顯像液以噴淋狀噴送。顯像液有，例如碳酸鈉、碳酸鉀、氫氧化鈉、氫氧化鉀、氫氧化四甲基銨、有機胺等鹼性化合物之 -23- (21) 1303354 " 水溶液等。藉由顯像，去除感光性樹脂組成物層中之未照射光線之未照射區域。其另一方面，光線照射區域仍然殘留形成圖型。顯像後，通常藉由水洗、乾燥，可獲得目標之圖型。 (4 )硬化步驟藉由使完成該（3)之步驟的基板上之塗膜圖型加熱 _ 而硬化，可提咼其機械強度。於此’加熱溫度通常l8〇〇C以上，較佳爲2〇(Γ(：以上 9 • 通常爲25 0 °C以下。加熱溫度爲180〜25 0 °C時，塗膜 • 之機械強度提高’耐溶劑、耐液晶性提升，甚爲適合。加熱時間通吊爲5〜120分鐘，較佳爲1〇〜9〇分鐘，更佳爲 15〜60分鐘。加熱時間爲.5〜i 20分鐘時，塗膜之機械強度提高，極爲適合。 ® 如上述之說明，使用本發明之感光性樹脂組成物所形成的硬化物之圖型，適合使用爲顯示用間隔物。【實施方式】〔實施例〕以實施例具體說明本發明如下；本發明並非限定於此等實施例者。還有，除特別規定以外，下述中之「部」爲質量份之意。 -24- 1303354 (22) 〈鹼可溶性感光性樹脂溶液之調製〉〔合成例〕在具備攪拌器、回流冷卻器 '溫度計之可分離的燒瓶中，加入偶氮雙異丁腈4 · 1質量份、丙二醇單甲醚乙酸酯 1 2 5質量份，以水浴加熱至內溫爲7 0 °C。以3小時滴加甲基丙烯酸甲酯55質量份、苯乙烯20·8質量份、甲基丙烯酸環氧丙基酯42.7質量份之混合物於其中’進行聚合反丨應。進而於70°C攪拌3小時，以GPC確認全無未反應單體存在。在此聚合物中，加入丙烯酸23.4質量份及三苯基膦0.8質量份，於80〜9反應16小時。以IR光譜確認環氧基消失後，加入四氫苯二甲酸酐45.7質量份，再於8 0t反應8小時，即得樹脂-A。還有，樹脂-A之酸價爲90mg KOH/g、以GPC之分子量（Mw)爲15,000。此樹脂清漆之固形份濃度爲60重量％。 ^ 〔實施例1〜4，及比較例〕〈感光性樹脂組成物之調製〉使用如表1所示之原料，以表2所示之配合比例配合各成份，在室溫下攪拌3小時使各成份溶解後，以孔徑 0.4 5 μιη之米利波阿過濾器過濾，即得感光性組成物（1液型組成物）。 -25- (23) 1303354 〔表1〕成分化學名或商品名感光性組成物以合成例所得之樹脂溶液光聚合引發劑 2-节基-2-二甲基胺基小（4-嗎啉代苯基）-丁烷小酮反應性稀釋劑二季戊四醇六丙烯酸酯噁嗪化合物” [l]B-a型苯并噁嗪 [2]F-a型苯并噁嗪 [3]P-a型苯并噁嗪氧雜環丁烷化合物η OXT-121 有機溶劑丙二醇單甲醚乙酸酯 * 1 :四國化成工業公司製之苯并噁嗪化合物 *2:東亞合成公司製之氧雜環丁烷化合物(17) 1303354 Ethyl propionate, propyl 3-hydroxypropionate, ethyl 3-butoxypropyl propionate, propyl 3-butoxypropionate, 3-butoxy and the like. Among these organic solvents, glycol ethers, esters, and diethylene glycols are preferably used in combination from the viewpoint of solubility and ease of formation of each film, and are used in combination. Further, the photosensitive resin composition of the present invention may contain other components in addition to the above-mentioned range, and other components may be a crosslinking agent which can react with a carboxyl group in an alkali-soluble resin. Specifically, an oxetane compound or the like. Epoxy compound resin, bisphenol F type epoxy resin, bisphenol S type epoxy type epoxy resin, cresol novolac type epoxy resin, alkyl ester, biphenyldiol type epoxy resin, dimethicone An epoxy resin, a dicyclopentadiene type epoxy resin, an epoxide of a condensate of a phenolic aromatic aldehyde, or such an epoxy resin or an epoxy resin containing a phosphorus atom, a tricyclic acid ester, or a fat A ring epoxy resin or the like can be used alone or in two conventionally known. Oxetane compounds include bisphenol A type oxabisphenol F type oxetane compound, bisphenol S type oxygen, phenylene dimethyl oxetane compound, phenol compound compound, cesium formate The reactivity of the aldehyde type oxetane compound methyl ester, butyl 3-butoxypropionate and the like, and the coating, the glycol alkyl ether B may be used alone or in combination, without damaging the other of the present invention. Ingredients. Sensitive carboxyl group, epoxidized, bisphenol A epoxy resin, phenol novolac phenolic epoxy resin, naphthalene type and oxypropyl trimeric with phenolic hydroxyl group containing bromine atom Mixing cyanide with a cyclobutane compound, a heterocyclic butane compound, a phenolic oxetane, an alkylphenol novolac type -20- 1303354 * (18) ^ an oxetane compound, a biphenyl phenol type oxalate a cyclobutane compound, a bixylenol type oxetane compound, a naphthalene type oxetane compound, a dicyclopentadiene type oxetane compound, a phenol and an aromatic aldehyde having a phenolic hydroxyl group The oxetane compound or the like of the condensate may be used alone or in combination of two or more. However, the addition of an epoxy compound causes deterioration in storage stability, and it is preferred to add an oxetane compound. φ When the epoxy compound or the oxetane compound is added, a well-known conventional reaction accelerator can be added to the extent that the storage stability is not impaired. The reaction accelerators are, for example, tertiary amines, imidazoles, quaternary phosphonium salts, tertiary phosphines, scale guns, acetoacetone metal complexes, or crown ether complexes, etc., which may be used alone or Two or more combinations are used. Moreover, in order to improve the coating property, a well-known conventional surfactant such as a fluorine-based, polyfluorene-based or polymer-based polymer, an antifoaming agent, a planarizing agent, or a decane coupling agent for improving the adhesion to a substrate can be used. Adhesive additives. The photosensitive resin composition of the present invention as described above is a cured form by the procedure described below. That is, a step of forming a coating film by coating and drying the photosensitive resin composition of the present invention, and a photohardening treatment step of selectively irradiating the living energy rays on the coating film obtained by the step of forming the coating film After the photo-hardening treatment step, the alkali imaging solution is removed by using an alkali developing solution to remove the unirradiated portion, and -21303354 ' (19) ^ The pattern obtained by the alkali imaging step is heated and hardened. Form a hardened pattern. (1) Step of forming a coating film In this step, the photosensitive resin composition sheet of the present invention or a coloring property of forming a solid on a substrate in advance is referred to as a substrate or the like, and the coating layer is applied. Remove volatile components such as solvents and dry them. Here, the substrate may be, for example, a glass substrate, an ester substrate, a polyester substrate, an aromatic polyamide substrate, a plate, a polyimide substrate, an A1 substrate, a GaAs substrate, or the like. These substrates may be subjected to pretreatment such as a decane coupling agent, a plasma treatment, an ion plating treatment, a sputtering treatment, or a vacuum evaporation treatment. When a substrate or the like is used as the substrate, the coating method, the cast coating method, and the roll coating can be applied to the substrate by applying a photosensitive resin composition to the substrate, such as a CCD or a thin film crystal (TFT). The photosensitive resin composition of the present invention is applied to a substrate by heating, such as a cloth coating method or a slit coating machine, and the like, and the volatile component such as a solvent is volatilized by heating. Thus, it is a layer formed of a solid component composed of a photosensitive resin. (2) The step of the photo-curing treatment (exposure) step, the product, and the coating of the base resin composition layer (the photosensitive resin composition 矽 substrate, the polyacrylamide fluorene imine group, etc. Gas phase reaction treatment, surface formation of electricity; 〇 'for example, using a spin and spin coating method, a known coating method, etc., and then forming a -22- 1303354 ^ (20) ' on the substrate or the like. In the coating film obtained in the step (1) (hereinafter referred to as a photosensitive resin composition layer), the active energy ray is selectively irradiated. Here, when the exposure is performed, for example, the active energy ray is selectively irradiated through the illuminating mask. Preferably, the exposure light source is usually a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. Further, laser light or the like can be used as the active light for exposure. An electron beam, an alpha line, a /3 line, an r line, an X-ray, a neutron line, etc. can be used. The light is irradiated through a reticle, for example, a light is provided on the surface of the glass plate. The light-shielding layer is shielded. The glass plate is not provided with light-shielding. The portion of the layer is the light-transmitting portion through which the light passes, and the photosensitive resin composition layer on the pattern is exposed according to the pattern of the light-transmitting portion. The unirradiated area of the unirradiated light and the irradiated area of the irradiated light. The amount of light irradiated in the irradiated area depends on the weight average molecular weight of the binder polymer, the monomer ratio, the content, and the type or content of the photopolymerizable compound. The type and content of the polymerization initiator are appropriately selected. (3) The alkali development step is used to develop a coating film on the substrate on which the step (2) is completed. Here, for example, the photosensitive property after exposure can be obtained. The resin composition layer is in contact with the developing solution; specifically, the substrate in a state in which the photosensitive resin composition layer is formed on the surface thereof is immersed in the developing liquid or the developing liquid is sprayed in a spray form. The developing solution may be, for example, a -23-(21) 1303354 " aqueous solution of a basic compound such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide or an organic amine. Like, removing the photosensitive resin group In the unexposed area of the unexposed light in the layer, on the other hand, the pattern of the light is still left to form a pattern. After the image is developed, the target pattern is usually obtained by washing with water and drying. (4) The hardening step is borrowed. The mechanical strength can be improved by heating and drying the coating film pattern on the substrate on which the step (3) is completed. Here, the heating temperature is usually l8 〇〇 C or more, preferably 2 〇 (Γ (: Above 9 • Normally below 25 0 °C. When the heating temperature is 180~25 0 °C, the mechanical strength of the coating film is improved. 'Solvent resistance and liquid crystal resistance are improved. It is suitable. The heating time is 5~120. The minute is preferably 1 〇 to 9 〇 minutes, more preferably 15 to 60 minutes. When the heating time is .5 〜i 20 minutes, the mechanical strength of the coating film is improved, which is extremely suitable. As described above, the pattern of the cured product formed using the photosensitive resin composition of the present invention is suitably used as a spacer for display. [Embodiment] [Embodiment] The present invention is specifically described by way of Examples, and the present invention is not limited to the embodiments. In addition, unless otherwise specified, the “part” below is the meaning of the mass. -24- 1303354 (22) Preparation of Alkali-Soluble Sensitive Resin Solution [Synthesis Example] Addition of azobisisobutyronitrile to 4·1 parts by mass in a separable flask equipped with a stirrer and a reflux condenser 'thermometer 1 2 5 parts by mass of propylene glycol monomethyl ether acetate was heated in a water bath to an internal temperature of 70 °C. A mixture of 55 parts by mass of methyl methacrylate, 20. 8 parts by mass of styrene, and 42.7 parts by mass of glycidyl methacrylate was added dropwise thereto for 3 hours to carry out polymerization reaction. Further, the mixture was stirred at 70 ° C for 3 hours, and it was confirmed by GPC that all of the unreacted monomers were present. To the polymer, 23.4 parts by mass of acrylic acid and 0.8 parts by mass of triphenylphosphine were added, and the mixture was reacted at 80 to 9 for 16 hours. After confirming the disappearance of the epoxy group by IR spectrum, 45.7 parts by mass of tetrahydrophthalic anhydride was added, and further reacted at 80 ° for 8 hours to obtain a resin-A. Further, the acid value of the resin-A was 90 mg KOH/g, and the molecular weight (Mw) of GPC was 15,000. The resin varnish had a solid concentration of 60% by weight. [Examples 1 to 4, and Comparative Example] <Preparation of photosensitive resin composition> Using the raw materials shown in Table 1, the components were blended in the proportions shown in Table 2, and stirred at room temperature for 3 hours. After each component was dissolved, it was filtered with a Millipona filter having a pore diameter of 0.4 5 μm to obtain a photosensitive composition (1 liquid type composition). -25- (23) 1303354 [Table 1] Ingredient chemical name or trade name photosensitive composition The resin solution photopolymerization initiator obtained by the synthesis example 2-mercapto-2-dimethylamino group small (4-morpholine) Phenyl)butane ketone reactive diluent dipentaerythritol hexaacrylate oxazine compound" [l] Ba benzoxazine [2] Fa benzoxazine [3] Pa benzoxazine oxygen Heterocyclic butane compound η OXT-121 Organic solvent propylene glycol monomethyl ether acetate * 1 : benzoxazine compound manufactured by Shikoku Chemical Industry Co., Ltd. *2: Oxetane compound manufactured by Toagosei Co., Ltd.

〔表2〕配合成分實施例1 實施例2 實施例3 實施例4 比較例1 感光性樹脂 167 167 167 167 167 光聚合引發劑 10 10 10 10 10 反應性稀釋劑 25 25 25 25 25 噁嗪化合物 (1) 20 20 (2) 20 (3) 20 氧雜環丁烷化合物 24 有機溶劑 165 165 165 141 136 -26- (24) 1303354 (1 )解像性之評估使用旋轉器，以轉速l5000rpm將上述組成物溶液佈於玻璃基板上2 0秒鐘後，在加熱板上於9 0 °C進行3 鐘之PB形成乾燥塗膜。在該所得塗膜上透過0 1〇μηι 圓點圖型的光罩，照射在3 65 nm之強度爲12mW/cm2的外線，累積光量爲1 00mJ/cm2。此時之紫外線照射係在氣氣體環境下（空氣中）進行，曝光間隙爲1〇〇μιΏ。接著，使用氫氧化四甲基銨0 · 4重量％水溶液，於 °C下顯像1 2 0秒鐘後，以純水流水洗淨3 0秒，使上述成之間隔物圖型置入烘箱中，於2 3 0 °C加熱6 0分鐘，予硬化。上述所得間隔物圖型中，圓點徑ΙΟμηι之圖型可解時爲〇，不能解像時爲X。結果如表3所示。 (2 )耐ΝΜΡ性之評估使用旋轉器，以轉速1，〇〇〇rpm將上述組成物溶液佈於玻璃基板上2 0秒鐘後，在加熱板上於9 0 °C進行3 鐘之PB形成乾燥塗膜。在該所得塗膜之全面上，照射 3 65nm之強度爲12mW/cm2之紫外線，累積光量 10 0mJ/cm2。此時之紫外線照射係在氧氣氣體環境下（氣中）進彳了，曝光間隙爲1 〇〇 μ ηι。其後，在烘箱中， 23 0°C加熱60分鐘，予以硬化。使上述所得硬化塗膜，以滲入N -甲基-2 -吡咯烷酮 NMP )之碎布擦拭’觀測擦拭表面狀態。完全無改變時塗分之紫氧 25 形以像塗分在爲空於爲 (25) 1303354 〇、表面有溶解或軟化之傷痕時爲x。 (3 )耐7 -丁內酯性使與（2 )同樣進行而得之塗膜，以滲入r _丁丙醋之碎布擦拭，觀測擦拭表面狀態。完全無改變爲Q、表面有溶解或軟化之傷痕時爲X。 (4 )鉛筆硬度使與（2)同樣進行而得之塗膜，依Jis K5 60 0-5 -4之試驗方法的標準進行，以在塗膜表面不產生傷痕之最硬的鉛筆之硬度爲鉛筆硬度。 (5 )壓縮強度形成膜厚5μιη、圓點徑30μιη之圖型，使用微細硬度計進行在23 0 °C熱硬化60分鐘之間隔物圖型的評估。測定以直徑50μηι之平面壓子，施加50mN之荷重時的變形量。其數値在0.6以下時爲〇、大於0.6時爲X。 (6 )儲存穩定性使上述之感光性組成物在40 °C之烘箱中保存14天，可觀測到膠化或黏度顯著上升時爲X、略有黏度上昇未膠化者爲〇。上述項目之試驗結果，如表3所示。[Table 2] Compositions Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Photosensitive resin 167 167 167 167 167 Photopolymerization initiator 10 10 10 10 10 Reactive diluent 25 25 25 25 25 Oxazine compound (1) 20 20 (2) 20 (3) 20 Oxetane compound 24 Organic solvent 165 165 165 141 136 -26- (24) 1303354 (1) Evaluation of resolution using a rotator at a speed of 15000 rpm After the composition solution was placed on a glass substrate for 20 seconds, PB was formed on a hot plate at 90 ° C for 3 hours to form a dried coating film. On the obtained coating film, a mask having a dot pattern of 0 1 〇 μηι was applied, and an external line having an intensity of 12 mW/cm 2 at 3 65 nm was irradiated, and the accumulated light amount was 100 mJ/cm 2 . The ultraviolet irradiation at this time was carried out in a gas atmosphere (in the air) with an exposure gap of 1 μm. Next, using tetramethylammonium hydroxide 0.4% by weight aqueous solution, the image was developed at ° C for 120 seconds, and then washed with pure water for 30 seconds, and the above-mentioned spacer pattern was placed in an oven. It was heated at 260 ° C for 60 minutes and hardened. In the above-described spacer pattern, the pattern of the dot diameter ΙΟμηι can be solved as 〇, and can not be resolved as X. The results are shown in Table 3. (2) Evaluation of tamper resistance Using a rotator, the above composition solution was placed on a glass substrate at a rotation speed of 1, rpm for 20 seconds, and then subjected to PB at 90 ° C for 3 hours on a hot plate. A dry coating film is formed. On the entire surface of the obtained coating film, ultraviolet rays having an intensity of 3 65 nm of 12 mW/cm 2 were irradiated, and the cumulative light amount was 10 m·cm/cm 2 . At this time, the ultraviolet irradiation is carried out in an oxygen gas atmosphere (in the gas), and the exposure gap is 1 〇〇 μ ηι. Thereafter, it was heated in an oven at 230 ° C for 60 minutes to be hardened. The hardened coating film obtained above was wiped with a rag impregnated with N-methyl-2-pyrrolidone NMP to observe the state of the wiping surface. When there is no change at all, the violet oxygen 25-shaped coating is x when it is coated as being empty (25) 1303354 〇, and the surface is dissolved or softened. (3) 7-butyrolactone resistance The coating film obtained in the same manner as in (2) was wiped with a rag which was infiltrated with r-butadiene vinegar, and the surface state was wiped. X when there is no change to Q at all and the surface is dissolved or softened. (4) Pencil hardness The coating film obtained in the same manner as (2) is subjected to the standard of the test method of Jis K5 60 0-5 -4, so that the hardness of the hardest pencil which does not cause scratches on the surface of the coating film is Pencil hardness. (5) Compressive strength A pattern having a film thickness of 5 μm and a dot diameter of 30 μm was formed, and a spacer pattern of heat hardening at 230 ° C for 60 minutes was evaluated using a fine hardness tester. The amount of deformation when a load of 50 mN was applied by a plane pressure of 50 μηι was measured. When the number is below 0.6, it is 〇, and when it is more than 0.6, it is X. (6) Storage stability The above-mentioned photosensitive composition was stored in an oven at 40 ° C for 14 days, and it was observed that when the gelation or viscosity was remarkably increased, X was slightly increased, and the viscosity was not increased. The test results of the above projects are shown in Table 3.

-28· (26) 1303354 〔表3〕實施例1 實施例2 實施例3 實施例4 比較例1 解像性〇〇〇〇〇耐NMP性〇〇〇〇 X 耐7 -丁內酯性〇〇〇〇 X 鉛筆硬度 5H 5H 6H 5H 3H 壓縮強度〇〇〇〇 X 儲存穩定性〇〇〇〇〇-28· (26) 1303354 [Table 3] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Resolving 〇〇〇〇〇NMP-resistant 〇〇〇〇X 7-butyrolactone-resistant 〇〇〇〇X pencil hardness 5H 5H 6H 5H 3H compressive strength 〇〇〇〇X storage stability〇〇〇〇〇

由表3所示之結果可知，在本發明之感光性組成物的實施例1〜4中，其硬化物爲高硬度，具有優越之壓縮強度、耐藥品性；又，儲存穩定性優異。As is apparent from the results shown in Table 3, in Examples 1 to 4 of the photosensitive composition of the present invention, the cured product had high hardness, excellent compressive strength and chemical resistance, and excellent storage stability.

Claims

(1) 1303354 • X. Patent Application No. 1 A photosensitive resin composition for a display panel, which comprises: (A) an alkali-soluble carboxyl group-containing photosensitive resin, and (B) an ethylenically unsaturated bond. A polymerizable compound, (C) a photopolymerization initiator, and (D) a compound having an oxazine ring. • 2) The photosensitive resin composition of claim 1, wherein the compound (D) having an oxazine ring has the following general formula (1) and/or the following general formula (2) a compound of the oxazin ring, [Formula 1]

In the formula, R] is an alkyl group having 1 to 12 carbon atoms, a cyclohexyl group which may have a substituent, and an aryl group which may have a substituent [Formula 2]

3. The photosensitive resin composition according to the first aspect of the invention, wherein the amount of the polymerizable compound (B) is 5 to 5 parts by mass based on the carboxyl group-containing photosensitive resin (A). 50 parts by mass, -30- 1303354 ^ (2) 0 The amount of the photopolymerization initiator (C) is 0.01 to 30 parts by mass based on 100 parts by mass of the carboxyl group-containing photosensitive resin (A). The compounding amount of the compound (D) having an oxazine ring is 5 to 50 parts by mass based on 100 parts by mass of the carboxyl group-containing photosensitive resin (A). The photosensitive resin composition according to any one of claims 1 to 3, wherein the hydrazine contains an oxetane compound. 5. A cured product characterized in that a photosensitive resin composition according to any one of claims 1 to 3 is coated and dried to form a coating film, and a coating film is formed thereon. The step of obtaining a selective irradiation activity on the coating film. The light hardening treatment step of the energy line, after the photo-curing treatment step, the alkali imaging step of removing the unirradiated portion by using the alkali developing solution, and The step of heating and hardening the pattern obtained by the alkali developing step is obtained. ® 6 - A spacer for a display panel, which is characterized by using the composition of any one of items 1 to 3 of the patent application. 7. A cured product characterized by: forming a coating film by coating and drying the photosensitive resin composition of claim 4, and applying a coating film to the coating film obtained by the coating film forming step a photohardening treatment step of selectively irradiating an active energy ray, a base developing step of removing a non-irradiated portion using an alkali developing solution after the photohardening treatment step, and -31 - (3) 1303354 The step of heating and hardening the pattern obtained by the developing step is obtained. A spacer for a display panel, which is characterized by using the composition of the fourth item of the patent application.

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