TW200935174A

TW200935174A - Photosensitive composition, photosensitive film, photosensitive laminate, method of forming permanent pattern, and printed board

Info

Publication number: TW200935174A
Application number: TW97136565A
Authority: TW
Inventors: Kimi Ikeda
Original assignee: Fujifilm Corp
Priority date: 2007-09-28
Filing date: 2008-09-24
Publication date: 2009-08-16
Also published as: JP2009086374A; CN101398620A

Abstract

The present photosensitive composition comprises binder, polymerization compound, filler, photo-initiating agent, and the weight average of I/O value of the said polymerization compound is 0. 52 or less.

Description

200935174 九、發明說明：【發明所屬之技術領域】本發明係關於藉由雷射曝光進行畫像形成且適於做爲耐焊劑（s ο 1 d e r - r e s i s t)材料的感光性組成物、感光性薄膜、感光性積層體、永久圖案形成方法、及印刷基板。【先前技術】以往係使用藉由在形成耐焊劑等的永久圖案之際，塗布、乾燥感光性組成物於支持體上，以形成感光層之感光 ® 性薄膜。像這樣的永久圖案之形成方法，例如在永久圖案形成之覆銅積層板等的基體上，積層感光性薄膜以形成積層體，並對該積層體的感光層進行曝光，於該曝光後，顯像感光層以使得圖案形成，然後藉由進行硬化處理等以形成永久圖案。以往，前述耐焊劑形成用的感光性組成物中係使用二新戊四醇六丙烯酸酯（以下，略記爲「DPH A」）做爲聚合性化合物（參照特開平5-9244號公報}。〇又’關於多官能單體含有爲特徴之DFR，係記載有市售之肟化合物做爲光聚合起始劑（參照特開2006-220865 號公報）。又’爲了提高進行數位圖像（DI)曝光情形中的生產性 ’已提案有藉由使用做爲光聚合起始劑之醯基肟化合物、及於分子中含有硫原子之二苯基酮化合物爲必要成分、聚合性化合物、與含有2個以上環氧基之環氧化合物，而得到在405nm雷射的圖案形成性、膜硬化性方面適合的硬化性樹脂組成物（參照特開2005-182004號公報）。 200935174 然而’在特開平5-9244號公報、特開2006_220865 號公報、及特開2005-182004號公報中，並未揭示或暗示可得到在數位圖像（DI)曝光能充分的感度，同時生物保存性優異之感光性組成物’且絶緣可靠性的加速評價，高速加速壽命試驗{ = H AST試驗）中能得到良好的結果，進而現狀係期望有進一步的改良、開發。【發明內容】本發明係有鑑於上述的現狀，以解決以往的前述各問 ^ 題，達成以下的目的爲課題。亦即，本發明之目的係提供維持顯像性的同時能提高絶緣可靠性之感光性組成物、感光性薄膜：感光性積層體、永久圖案形成方法、及印刷基板。解決課題之手段前述解決課題之手段係如下所述。亦即， < 1 > 一種感光性組成物，其特徵係含有黏結劑、聚合性化合物、塡料、及光聚合起始劑，且該聚合性化合物的 © I/O値的重量平均爲0.52以下。 <2>如前述<1>中所記載之感光性組成物’其中聚合性化合物的I/O値的重量平均爲0.43以下。 <3>如前述<1>~<2>項中任一項之感光性組成物’其中聚合性化合物係含有2個以上的聚合性基。 <4>如前述<1>~<3>項中任一項之感光性組成物’其中聚合性化合物爲二羥甲基三環癸烷二（甲基）丙烯酸酯。 <5>如前述<1>~<4>項中任一項之感光性組成物’其中光聚合起始劑爲肟衍生物。 -6 - 200935174 <6>如前述<1>~<5>項中任一項之感光性組成物，其中更含有熱交聯劑。 <7>如前述<6>中所記載之感光性組成物’其中熱交聯劑係選自於環氧化合物、氧雜環丁烷化合物、聚異氰酸酯化合物、嵌段劑與聚異氰酸酯化合物反應所得之化合物、及三聚氰胺衍生物之至少1種。 <8>—種感光性薄膜，其特徵係在支持體上含有由如前述<1>~<7>項中任一項之感光性組成物所構成之感光層 ©而形成的。 <9> 一種感光性積層體，其特徵係在基體上含有由如前述<1>~<7>項中任一項之感光性組成物所構成的感光層〇 <10> —種永久圖案形成方法，其特徵係至少含有對於由前述<1>~<7>項中任一項之感光性組成物所形成之感光層進行曝光。 <11>如前述<1〇>中所記載之永久圖案形成方法’其中〇曝光係藉由光調變手段使光線調變之後’透過配置排列微透鏡之微透鏡陣列而的進行，其中該微透鏡係具有可補償因該光調變手段中描繪部之射出面的變形所引起之像差的非球面。 <12>如前述<10>~<11>項中任一項之永久圖案形成方法，其係在曝光實施後，進行感光層的顯像。 <13>如前述<12>中所記載之永久圖案形成方法’其係在顯像實施後，進行感光層的硬化處理。 <14> —種印刷基板，其特徵係永久圖案爲藉由如前述 200935174 <10>~<13>項中任一項之永久圖案形成方法而形成的。發明之效果根據本發明時’能解決以往的各問題，可提供維持顯像性的同時能提昇絶緣可靠性之感光性組成物、感光性薄膜、感光性積層體、永久圖案形成方法、及印刷基板。【實施方式】 (感光性組成物）本發明中，感光性組成物係含有黏結劑、聚合性化合物、塡料、與光聚合起始劑，且可視需要更含有其他的成分。 <黏結劑> 前述黏結劑係以於側鏈含有酸性基與乙烯性不飽和鍵之高分子化合物、環氧丙烯酸酯化合物、等爲適宜使用的 ’此等之中，尤以於側鏈含有酸性基與乙烯性不飽和鍵之高分子化合物爲特別適宜使用的。 -於側鏈含有酸性基與乙烯性不飽和鍵之高分子化合 Ο物- 前述酸性基係可舉例如羧基、磷酸基、磺酸基等，從原料入手之點而言係以狻基爲佳。又’前述黏結劑係可使用在分子内具有至少1個可聚合的雙鍵’例如可使用（甲基）丙烯酸酯基或（甲基）丙烯醯胺基等的丙烯酸基、羧酸的乙烯酯、乙烯基醚、烯丙基醚等的各種聚合性雙鍵。更具體而言，可舉例如在含有羧基做爲酸性基的丙烯酸樹脂中，加成環狀醚基含有聚合性化合物 '例如丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、肉桂 200935174 酸等的不飽和脂肪酸的縮水甘油酯、或具有脂環族環氧基（例如在相同分子中環己烯氧化物等的環氧基）與（甲基）丙烯醯基之化合物等的含有環氧基之聚合性化合物所得到的化合物等。又’亦可舉例如在含有酸性基及羥基之丙烯酸樹脂中’加成異氰酸酯（甲基）丙烯酸乙酯等的含有異氰酸酯基之聚合性化合物所得到的化合物，在含有酸酐基之丙烯酸樹脂中’加成羥基（甲基）丙烯酸烷酯等的含有羥基之聚合性化合物所得之化合物等。又，亦可舉例如共聚合甲基 ® 丙烯酸縮水甘油酯等的環狀醚基含有聚合性化合物與（甲基）丙烯醯基烷酯等的乙烯基單體，且在側鏈的環氧基加成 (甲基）丙烯酸所得之化合物等。此等之例係可舉例如專利2763775號公報、特開平 3-172301號公報、特開2000-232264號公報等。此等之中，前述黏結劑係選自於高分子化合物的酸性基的一部份爲加成環狀醚基（例如於部分構造含有環氧基、氧雜環丁烷基之基）含有聚合性化合物、及高分子化合物〇的環狀醚基的一部份或全部爲加成羧基含有聚合性化合物中任一者之高分子化合物爲更佳。此時，與含有酸性基與環狀醚基之化合物的加成反應較佳係在觸媒存在下實施，特別是該觸媒係選自於酸性化合物及中性化合物者爲佳。此等之中，尤以從感光性組成物在經過長時間的顯像安定性之點而言，黏結劑係較佳爲在側鏈亦可含有羧基與雜環之芳香族基、及在側鏈含有乙烯性不飽和鍵之高分子化合物。 --亦可含有雜環之芳香族基-- • 9- 200935174 前述亦可含有雜環之芳香族基（以下，亦有僅稱爲「芳香族基」）係可舉例如苯環、2個〜3個的苯環形成縮合環者、苯環與5員不飽和環形成縮合環者等。前述芳香族基之具體例係可舉例如苯基、萘基、恵基、菲基、節基、二氫危基、莽基、苯并卩比略環基、苯并呋喃環基、苯并噻吩環基、吡唑環基、異噚唑環基、異噻唑環基、吲哚環基、苯并異噚唑環基、苯并異噻唑環基、咪唑環基、嗶唑環基、噻唑環基、苯并咪唑環基、苯并噚唑 © 環基、苯并噻唑環基、吡啶環基、喹啉環基、異喹啉環基、嗒阱環基、嘧啶環基、吡阱環基、呔阱環基、喹唑咐環基、喹喏啉環基、吖環丙烷環基、菲啶環基，、咔唑環基、嘌呤環基、吡喃環基、吡啶環基、哌畊環基、吲哚環基、吲哚阱環基、色烯環基、噌啉環基、吖啶環基、啡噻哄環基、四唑環基、三阱環基等。此等之中，尤以烴芳香族基爲佳，以苯基、萘基爲更佳。前述芳香族基係亦可具有取代基，前述取代基係可舉〇例如鹵素原子、具有取代基之胺基、烷氧基羰基、羥基、醚基、硫醇基、硫醚基、矽烷基、硝基、氰基、可分別具有取代基之烷基、烯基、炔基、芳基、雜環基等。前述烷基係可舉例如碳原子數爲1〜20之直鏈狀的烷基、分枝狀的烷基、環狀的烷基等。前述烷基之具體例係可舉例如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十六烷基、十八烷基、二十烷基、異丙基、異丁基、第二丁基、第三丁基、異戊基、新戊基 -10- 200935174 、1-甲基丁基、異己基、2-乙基己基、2-甲基己基基、環戊基、2 -降萡烯基等。此等之中，較佳係碳J] 〜12之直鏈狀的烷基、碳原子數3〜12之分枝狀的碳原子數5〜10之環狀的烷基。前述亦可具有烷基之取代基係可舉例如由除去之一價非金屬原子團所構成之基。此等取代基係可鹵素原子（-F、-Br、-C1、-1)、羥基、烷氧基、芳氧硫基、烷硫基、芳硫基、烷基二硫基、芳基二硫基 © 、N-烷基胺基、Ν,Ν-二烷基胺基、N-芳基胺基、n, 基胺基、Ν-烷基-Ν-芳基胺基、醯氧基、胺甲酿氧烷基胺甲醯氧基、Ν-芳基胺甲醯氧基、Ν，Ν-二院基氧基、Ν，Ν-二芳基胺甲醯氧基、Ν -烷基-Ν-芳基胺基、烷基磺醯氧基、芳基磺醯氧基、醯硫基、醯月安烷基醯胺基、Ν-芳基醯胺基、脲基、Ν’-烷基脲基、二烷基脲基、Ν’-芳基脲基、Ν’，Ν’-二芳基脲基、ν，-傷芳基脲基、Ν-烷基脲基、Ν-芳基脲基、Ν’-烷基_Ν 〇基、Ν’-烷基-Ν-芳基脲基、Ν’，Ν’-二烷基-Ν-烷基 Ν’，Ν’-二烷基-Ν-芳基脲基、Ν’-芳基-Ν-烷基脲基、 -Ν-芳基脲基、1^’，1^’-二芳基-1^烷基脲基'1^，^1，-二：芳基脲基、Ν’-烷基-Ν’-芳基-Ν-烷基脲基、ν，-院3 基-Ν-芳基脲基、烷氧基羰基胺基、芳氧基碳基月安烷基-Ν-烷氧基羰基胺基、Ν-烷基-Ν-芳氧基羯基胺芳基-Ν-烷氧基羰基胺基、Ν-芳基-Ν-芳氧基羯基胺醯基、醯基、羧基、烷氧基羰基、芳氧基羰基、胺、Ν-烷基胺甲醯基、Ν，Ν-二烷基胺甲醯基、Ν_芳基、環己冥子數1 烷基、氫原子舉例如，基、氫、胺基 ,Ν-二芳基、Ν-胺甲醯甲醯氧基、[ Ν,,Ν,-S 基-Ν’--烷基脲脲基、 Ν’-芳基专基-Ν-g -Ν’-芳基、Ν -基、Ν-，基、甲甲醯基 ;胺甲醯 -11- 200935174 基、N，N -二芳基胺甲醯基、N-烷基-N-芳基胺甲酿基、院基亞碾基、芳基亞颯基、院基擴醯基、芳基碼酸基、擴酸基（-SO3H)及其共軛鹼（稱爲磺酸酯基）' 烷氧基磺醯基、芳氧基磋釀基、亞礦釀基、N -院基亞擴酿基、N，N -二院基亞磺酿基、N-芳基亞磺酿基、Ν，Ν· —芳基亞擴酿基、N -院基 -Ν -芳基亞磺醯基、胺磺醯基、Ν_烷基胺磺醯基、ν,Ν -二烷基胺磺醯基、Ν -芳基胺磺醯基、Ν，Ν -二芳基胺磺醯基、 Ν -院基-Ν-芳基胺磺酿基、膦酸基（-ρ〇3Η；2)及其共範鹼（稱〇爲膦酸根基）、二烷基膦酸基（-p〇3 (alkyl) 2)(以下，「alkyl 」係意味著烷基）、二芳基膦酸基（_11〇3(&1^1)2)(以下，「&1^1 」係意味著萝基）、烷基芳基膦酸基（-p〇3(alkyl)(aryl))、單烷基膦酸基（-P〇3 (alkyl))及其共軛鹼（稱爲烷基膦酸根基）、單芳基膦酸基（-P〇3H (aryl))及其共軛鹼（稱爲芳基膦酸根基）、膦酸氧基（-OPO3H2)及其共軛鹼（稱爲膦酸根氧基 )、二烷基膦酸氧基（-〇P〇3H(alkyl)2)、二芳基膦酸氧基 (-OP〇3(aryl)2)、院基芳基膦酸氧基（_〇P〇3(alkyl)(aryl)) 〇、單烷基膦酸氧基（-OP〇3H(alkyl))及其共軛鹼（稱爲烷基膦酸根氧基）、單芳基膦酸氧基（-〇P〇3 H (aryl))及其共軛鹼 (稱爲芳基膦酸根氧基）、氰基、硝基、芳基、烯基、炔基、雜環基、矽烷基等。在此等取代基中的烷基之具體例係可舉例如前述的烷基。在則述取代基中的芳基之具體例係可舉例如苯基、聯苯基、奈基、甲苯基二甲苯基、茱基、異丙苯基、氯基本基、漠基本基、氯基甲基苯基、羥基苯基、甲氧基苯基 -12- 200935174 、乙氧基苯基、苯氧基苯基、乙醯氧基苯基、苯甲醯氧基苯基、甲硫基苯基、苯硫基苯基、甲基胺基苯基、二甲基胺基苯基、乙醯胺基苯基、羧基苯基、甲氧基簾基苯基、乙氧基苯基羰基、苯氧基羰基苯基、N-苯基胺甲Μ ¥苯s 、氰基苯基、磺酸基苯基、磺酸根基苯基、膦酸基苯基、膦酸根基苯基等。在前述取代基中的烯基之具體例係可舉例如乙烯基' 1-丙烯基、1-丁烯基、肉桂基、2-氯基-1-乙嫌基等。〇在前述取代基中的炔基之具體例係可舉例如乙炔基、 1-丙炔基、1-丁炔基、三甲基矽烷基乙炔基等° 在前述取代基中的醯基（RQ1C〇-)之R01係可舉例如氫原子、前述的烷基、芳基等。此等取代基之中，尤以鹵素原子（_F、_Br、_C1、―1) 、烷氧基、芳氧基、烷硫基、芳硫基、N -烷基胺基、N，N_ 二烷基胺基、醯氧基、N -烷基胺甲醯氧基、N -芳基胺甲酿氧基、醯胺基、甲醯基、醯基、羧基、烷氧基羰基、芳氧 Q 基羰基、胺甲醯基、N -烷基胺甲醯基、N，N-二院基胺甲酶基、N -芳基胺甲醯基、N -烷基-N-芳基胺甲醯基、磺酸基、磺酸酯基、胺磺醯基、N -烷基胺磺醯基、N，N -二院基胺磺醯基、N -芳基胺磺醯基、N -烷基-N-芳基胺磺醯基 '膦酸基、膦酸根基、二烷基膦酸基、二芳基膦酸基、單烷基膦酸基、烷基膦酸根基、單芳基膦酸基、芳基膦酸根基、膦酸氧基、膦酸根氧基、芳基、烯基等爲佳。又，在前述取代基中的雜環基係可舉例如吡啶基、哌啶基等，在前述取代基中的矽烷基係可舉例如三甲基矽烷 -13- 200935174 基等。另一方面，在前述烷基中的伸烷基係可舉例如將前述的碳數1〜20之烷基上的氫原子中的任一者去掉1個、而形成2價有機殘基者，例如較佳係碳原子數1〜12之直鏈狀的伸烷基、碳原子數3〜12之分枝狀的伸烷基、碳原子數5〜 10之環狀的伸烷基等。藉由組合此等取代基與伸烷基所得之取代烷基的較佳具體例，可舉例如氯基甲基、溴基甲基、2-氯基乙基、三〇氟基甲基、甲氧基甲基、異丙氧基甲基、丁氧基甲基、第二丁氧基丁基、甲氧基乙氧基乙基、烯丙氧基甲基、苯氧基甲基、甲硫基甲基、甲苯硫基甲基、吡啶甲基、四甲基哌啶甲基、N -乙醯基四甲基哌啶甲基、三甲基矽烷基甲基、甲氧基乙基、乙基胺基乙基、二乙基胺基丙基、味啉基丙基、乙醯氧基甲基、苯甲醯氧基甲基、N-環己基胺甲醯基羥乙基、N -苯基胺甲醯基羥乙基、乙醯胺基乙基、N -甲基苯甲醯基胺基丙基、2-氧基乙基、2-氧基丙基、羧基丙〇基、甲氧基羰基乙基、烯丙氧基羰基丁基、氯基苯氧基羰基甲基、胺甲醯基甲基、N-甲基胺甲醯基乙基、Ν,Ν-二丙基胺甲醯基甲基、Ν-(甲氧基苯基）胺甲醯基乙基、Ν-甲基 -Ν-(磺酸基苯基）胺甲醯基甲基、磺基丁基、磺酸根基丁基、胺磺醯基丁基、Ν-乙基胺磺醯基甲基、Ν，Ν-二丙基胺磺醯基丙基、Ν-甲苯基胺磺醯基丙基、Ν-甲基-Ν-(膦酸基苯基）胺磺醯基辛基、膦酸基丁基、膦酸根基己基、二乙基膦酸基丁基、二苯基膦酸基丙基、甲基膦酸基丁基、甲基膦酸根基丁基、甲苯基膦酸基己基、甲苯基膦酸根基己基、 -14- 200935174 膦酸氧基丙基、膦酸根氧基丁基、苄基、苯乙基、α -甲基苄基、1-甲基-1-苯基乙基、Ρ-甲基苄基、肉桂基、烯丙基、1-丙烯基甲基、2-丁烯基、2-甲基烯丙基、2-甲基丙烯基甲基、2-丙炔基、2-丁炔基、3-丁炔基等。前述芳基係可舉例如苯環、2個〜3個的苯環形成縮合環者、苯環與5員不飽和環形成縮合環者等。前述芳基之具體例係可舉例如苯基、萘基、蒽基、菲基、茚基、二氫苊基、莽基等。此等之中，以苯基、萘基 ❾爲佳。前述烷基係亦可具有取代基，具有此等取代基之芳基（以下，亦稱爲「取代芳基」）係可舉例如在前述芳基的環形成碳原子上，具有由氫原子以外的一價非金屬原子團所構成之基者做爲取代基。前述芳基亦可具有之取代基較佳係例如前述的烷基、取代院基、做爲前述烷基亦可具有之取代基所例示者。 _ 前述取代芳基之較佳具體例係可舉例如聯苯基、甲苯基、一甲苯基、来基、異丙苯基、氯基苯基、溴基苯基、氣墓苯基、氯基甲基苯基、三氟基甲基苯基、羥基苯基、氣基苯基、甲氧基乙氧基苯基、烯.丙基羥苯基、苯氧基本基、甲硫基苯基、甲苯硫基苯基、乙基胺基苯基、二乙基胺基苯基、味啉基苯基、乙醯基羥苯基、苯甲醯基羥苯基、N -環己基胺甲醯基羥苯基、N苯基胺甲醯基羥苯基、酿胺基苯基、N-甲基苯甲醯基胺基苯基、羧基苯基甲氣基裁基苯基、烯丙氧基羰基苯基、氯基苯氧基羰基苯基胺甲酶基苯基、N_甲基胺甲醯基苯基、N，N二丙基胺甲 -15- 200935174 醯基苯基、N-(甲氧基苯基）胺甲醯基苯基、N-甲基-N-(磺酸基苯基）胺甲醯基苯基、磺酸基苯基、磺酸根基苯基、胺磺醯基苯基、N -乙基胺磺醯基苯基、N，N -二丙基胺磺醯基苯基、N -甲苯基胺磺醯基苯基、N -甲基-N-(膦酸基苯基）胺磺醯基苯基、膦酸基苯基、膦酸根基苯基、二乙基隣酸基苯基、二苯基膦酸基苯基、甲基膦酸基苯基、甲基膦酸根基苯基、甲苯基膦酸基苯基、甲苯基膦酸根基苯基、烯丙基苯基、1-丙烯基甲基苯基、2-丁烯基苯基、2-甲基烯 © 丙基苯基、2 -甲基丙烯基苯基、2 -丙炔基苯基、2 -丁炔基苯基、3 -丁炔基苯基等。係可舉例如R02、RQ3、RQ4、及R05係由一價非金屬原子團所構成之基者。前述R〇2、R〇3、RG4、RQ5係可舉例如氫原子、鹵素原子、烷基、取代烷基、芳基、取代芳基等。此等之具體例係可舉例如做爲前述的例子所例示者。此等之中，尤以氫〇原子、鹵素原子、碳原子數1〜ίο之直鏈狀的烷基、分枝狀的烷基、環狀的烷基爲佳。前述烯基及炔基之較佳具體例係可舉例如乙烯基、1-丙烯基、1-丁烯基、1-戊烯基、1-己烯基、1-辛烯基、卜甲基-1-丙烯基、2-甲基-1-丙烯基、2-甲基-1-丁烯基、2-苯基-1-乙烯基、2-氯基-1-乙烯基、乙炔基、1-丙炔基、卜丁炔基、苯基乙炔基等。前述雜環基係可舉例如做爲取代烷基之取代基所例示之吡啶基等。 -16- 200935174 前述氧基（R06O-)係可舉例如由r〇6爲去掉氫原子之一價非金屬原子團所構成之基者。像這樣的氧基係可舉例如院氧基、芳氧基、醯氧基、胺甲醯氧基、N-烷基胺甲醯氧基、N-芳基胺甲醯氧基、N，N_ 二院基胺甲酿氧基、N，N -二芳基胺甲醯氧基、N_院基-N_ 芳基胺甲醯氧基、烷基磺醯氧基、芳基磺醯氧基、膦酸氧基、膦酸根氧基等爲佳。在此等中的烷基及芳基係可舉例如做爲前述的烷基、 ®取代院基、芳基、及取代芳基所例示者。又，在醯氧基中的醯基（RQ7CO-)係可舉例如r〇7爲先前的例子所列舉之烷基、取代院基、芳基以及取代芳基者。此等取代基之中，以院氧基、芳氧基、醯氧基、芳基礎醯氧基爲更佳。較佳的氧基之具體例係可舉例如甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、戊氧基、己氧基、十二烷氧基、苄氧基、烯丙氧基、苯乙基氧基、羧基乙氧基、甲氧基羰基乙氧基、乙氧基羰基乙氧基、甲氧基乙氧基、苯氧基 © 乙氧基、甲氧基乙氧基乙氧基、乙氧基乙氧基乙氧基、味啉基乙氧基、味啉基丙氧基、烯丙氧基乙氧基乙氧基、苯氧基、甲苯氧基、二甲苯氧基、茱氧基、采氧基、異丙苯基氧基、甲氧基苯氧基、乙氧基苯氧基、氯基苯氧基、溴基苯氧基、乙醯氧基、苯甲醯氧基、萘氧基、苯基磺醯基氧基、膦酸氧基、膦酸根氧基等。亦可含有醯胺基之胺基（RQ8NH -、（RQ9)(roid)N-)係可舉例如由RQ8、RQ9、及RQiQ去掉氫原子之一價非金屬原子團所構成之基。此外，R0 9與RQiQ亦可鍵結而形成環。 -17- 200935174 前述胺基係可舉例如N-烷基胺基、N，N-二烷基 N -芳基胺基、N，N-二芳基胺基、N -烷基-N -芳基胺胺基、N -烷基醯胺基、N -芳基醯胺基、脲基、Ν’ -烷、Ν，，Ν，-二烷基脲基、Ν’-芳基脲基、Ν’，Ν’-二芳基脲烷基- Ν’-芳基脲基、Ν-烷基脲基、Ν-芳基脲基、Ν’-楚烷基脲基、Ν’-烷基-Ν-芳基脲基、Ν}，Ν’-二烷基-Ν-基、Ν’-烷基-Ν’-芳基脲基、Ν’，Ν’-二烷基-Ν-烷基 Ν’，Ν’-二烷基-Ν’-芳基脲基、Ν’-芳基-Ν-烷基脲基 © 基-Ν-芳基脲基、Ν’，Ν’-二芳基-Ν-烷基脲基、Ν’，Ν’--Ν-芳基脲基、Ν’-烷基- Ν’-芳基-Ν-烷基脲基、Ν’-院芳基-Ν-芳基脲，基、院氧基鑛基胺基、芳氧基羰基胺烷基-Ν-烷氧基羰基胺基、Ν-烷基-Ν-芳氧基羰基胺芳基-Ν-烷氧基羰基胺基、Ν-芳基-Ν-芳氧基羰基胺在此等中的烷基及芳基係可舉例如做爲前述的烷基烷基、芳基、及取代芳基所例示者。又，醯胺基、醯胺基、Ν-芳基醯胺基中的醯基（R〇7CO-)之RM係如〇。此等之中，以N-烷基胺基、N，N-二烷基胺基、N-基、醯胺基爲更佳。較佳的胺基之具體例係可舉例如甲基胺基、乙、二乙基胺基、味咐基、哌啶基、吡啶基、苯基胺甲醯基胺基、乙醯胺基等。前述磺醯基（RQ11-S02-)係可舉例如由Rail爲價非金屬原子團所構成之基者。像這樣的磺醯基係可舉例如烷基磺醯基、芳基等爲佳。在此等中的烷基及芳基係可舉例如做爲前胺基、基、醯基脲基基、N，-言基-N-烷基脲脲基、、N，-芳二芳基基-N，-基、N-基、N-基等。、取代 N-烷基前所述芳基胺基胺基基、苯去掉一磺醯基述的烷 -18- 200935174 基、取代烷基、芳基、及取代芳基所例示者。前述磺醯基之具體例係可舉例如丁基磺醯基、苯基磺醯基、氯基苯基磺醯基等。前述磺酸酯基（-S〇3-)係如前所述，意味著磺酸基 (-so3h)的共軛鹼陰離子基，通常係與對陽離子一起使用爲佳。像這樣的對陽離子係可適當選擇一般習知者來使用，可舉例如鑰類（例如，銨類、鎏類、鱗類、碘類、吖啶鑰類 ® 等）、金屬離子類（例如，Na+、K+、Ca2+、Zn2 +等）。前述羰基（RQ13-CO-)係可舉例如由Row爲去掉一價非 ,金屬原子團所構成之基者。像這樣的羰基係可舉例如甲醯基、醯基、羧基、烷氧基羰基、芳氧基羰基、胺甲醯基、N-烷基胺甲醯基、N，N_ 二烷基胺甲醢基、N -芳基胺甲醯基、Ν,Ν -二芳基胺甲醯基、Ν-烷基- Ν’-芳基胺甲酸基等。在此等中的烷基及芳基係可舉例如做爲前述的烷基、取代烷基、芳基、及取代芳基 ϋ 所例示者。前述羰基係以甲醯基、醯基、羧基、烷氧基羰基、芳氧基羰基、胺甲醯基、Ν-烷基胺甲醯基、Ν，Ν-二烷基胺甲醯基、Ν-芳基胺甲醯基爲佳、甲醯基、醯基、烷氧基羰基、芳氧基羰基爲更佳。前述羰基之具體例係可舉例如甲醯基、乙醯基、苯甲醯基、羧基、甲氧基羰基、乙氧基羰基、烯丙基羥基羰基、二甲基胺基苯基乙烯基羰基、甲氧基羰基甲氧基羰基、 Ν-甲基胺甲醯基、Ν-苯基胺甲醯基、Ν，Ν-二乙基胺甲醯基 -19- 200935174 、味啉基羰基等爲適宜。前述亞颯基（Ro^-SO-)係可舉例如由R014爲去掉一價非金屬原子團所構成之基者。像這樣的亞颯基係可舉例如烷基亞颯基、芳基亞颯基、亞磺醯基、N -烷基亞磺醯基、N，N -二烷基亞磺醯基、N-芳基亞磺醯基、N，N-二芳基亞磺醯基、N-烷基-N-芳基亞磺醯基等。在此等中的烷基及芳基係可舉例如做爲前述的烷基、取代烷基、芳基、及取代芳基所例示者。此等之中 © ，尤以烷基亞楓基、芳基亞楓基爲佳。前述取代亞颯基之具體例係可舉例如己基亞碾基、苄基亞颯基、甲苯基亞楓基等爲適宜。前述膦酸基係意味著膦酸基上的一至二個羥基爲其他有機側氧基所取代者，例如前述的二烷基膦酸基、二芳基膦酸基、烷基芳基膦酸基、單烷基膦酸基、單芳基膦酸基等爲佳。此等之中，以二烷基膦酸基、二芳基膦酸基爲更佳。〇前述膦酸基之更佳具體例可舉例如二乙基膦酸基、二丁基膦酸基、二苯基膦酸基等。前述膦酸根基（-P03H2-、-P〇3H-)係如前所述，意味著來自於膦酸基（-p〇3H2)的、酸第一解離、或酸第二解離之共軛鹼陰離子基。通常係與對陽離子一同使用爲佳。像這樣的對陽離子係可適當選擇一般習知者，可舉例如各種的鎗類（銨類、鎏類、鱗類、錤類、吖啶鑰類等）、金屬離子類（Na+、K+、Ca2+、Zn2 +等}。前述膦酸根基亦可爲在膦酸基之中的羥基被取代成一 -20- 200935174 個有機側氧基者之共軛鹼陰離子基，此等具體例係可舉例如前述的單烷基膦酸基（-P〇3H(alkyl))、單芳基隣酸基 (-P03H(aryl))的共軛鹼。前述芳香族基係可使含有芳香族基之自由基聚合性化合物之1種以上、與可視需要做爲共聚合成分之其他自由基聚合性化合物之1種以上，藉由通常的自由基聚合法而可製造的。前述自由基聚合法係可舉例如一般的懸濁聚合法或溶 ®液聚合法等。前述含有芳香族基之自由基聚合性化合物較佳係例如通式（A-1}所表示之化合物、通式（A-2)所表示之化合物。200935174 IX. Description of the Invention: [Technical Field] The present invention relates to a photosensitive composition which is formed by laser exposure and is suitable as a solder resist material, a photosensitive film A photosensitive laminate, a permanent pattern forming method, and a printed substrate. [Prior Art] Conventionally, when a permanent pattern such as a solder resist is formed, a photosensitive composition is coated and dried on a support to form a photosensitive layer of a photosensitive layer. In the method of forming a permanent pattern as described above, for example, a photosensitive film is laminated on a substrate such as a copper-clad laminate having a permanent pattern to form a laminate, and the photosensitive layer of the laminate is exposed, and after the exposure, The photosensitive layer is patterned to form a pattern, and then a hardening process or the like is performed to form a permanent pattern. In the photosensitive composition for forming a solder resist, dipentaerythritol hexaacrylate (hereinafter abbreviated as "DPH A") is used as a polymerizable compound (see Japanese Patent Laid-Open Publication No. Hei 5-9244). In addition, the DFR of the polyfunctional monomer is described as a photopolymerization initiator (see JP-A-2006-220865). The productivity in the case of exposure has been proposed by using a ruthenium ruthenium compound as a photopolymerization initiator and a diphenyl ketone compound containing a sulfur atom in the molecule as an essential component, a polymerizable compound, and a content 2 The above-mentioned epoxy compound of the epoxy group is obtained, and a curable resin composition suitable for pattern formation property and film hardenability of a 405 nm laser is obtained (refer to Japanese Laid-Open Patent Publication No. 2005-182004). In the publication of Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2005-182004, which does not disclose or suggest that a sufficient sensitivity for digital image (DI) exposure can be obtained, and that the biopreservation property is excellent. The photosensitive composition 'and the accelerated evaluation of the insulation reliability, the high-speed accelerated life test {=H AST test) gave good results, and further improvements and developments are expected. DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-described current circumstances, and has been made to solve the above problems. In other words, the object of the present invention is to provide a photosensitive composition, a photosensitive film, a photosensitive laminate, a permanent pattern forming method, and a printing substrate which can improve the reliability of the development while maintaining the developability. Means for Solving the Problem The above-mentioned means for solving the problem are as follows. That is, a photosensitive composition characterized by containing a binder, a polymerizable compound, a dip, and a photopolymerization initiator, and the weight average of the I/O値 of the polymerizable compound is Below 0.52. <2> The photosensitive composition as described in the above <1> wherein the weight of the I/O値 of the polymerizable compound is 0.43 or less on average. The photosensitive composition of any one of the above-mentioned <1>, wherein the polymerizable compound contains two or more polymerizable groups. The photosensitive composition of any one of the above-mentioned <1> to <3>, wherein the polymerizable compound is dimethyloltricyclodecane di(meth)acrylate. <5> The photosensitive composition of any one of the above-mentioned <1> to <4>, wherein the photopolymerization initiator is an anthracene derivative. The photosensitive composition according to any one of the above-mentioned items, wherein the photosensitive composition further contains a thermal crosslinking agent. <7> The photosensitive composition described in the above <6> wherein the thermal crosslinking agent is selected from the group consisting of an epoxy compound, an oxetane compound, a polyisocyanate compound, a block agent, and a polyisocyanate compound. At least one of the compound obtained by the reaction and the melamine derivative. <8> A photosensitive film comprising a photosensitive layer constituting the photosensitive composition of any one of the above items <1> to <7>, which is formed on the support. <9> A photosensitive layered body comprising a photosensitive layer consisting of the photosensitive composition according to any one of the above items <1> to <7>, <10> The permanent pattern forming method is characterized in that at least the photosensitive layer formed of the photosensitive composition according to any one of the above items <1> to <7> is exposed. <11> The permanent pattern forming method described in the above <1〇>, wherein the 〇 exposure is performed by modulating light rays by means of light modulation means, and then performing the arrangement of the microlens arrays of the microlenses through the arrangement, The microlens has an aspherical surface that can compensate for aberrations caused by deformation of the exit surface of the drawing portion in the light modulation means. <12> The permanent pattern forming method according to any one of the above items <10>, wherein the photosensitive layer is developed after exposure is performed. <13> The method of forming a permanent pattern as described in the above <12>, wherein the photosensitive layer is subjected to a curing treatment after the development is performed. <14> A printed circuit board characterized in that the permanent pattern is formed by the permanent pattern forming method according to any one of the above-mentioned items 200935174 <10> to <13>. According to the present invention, it is possible to provide a photosensitive composition, a photosensitive film, a photosensitive laminate, a permanent pattern forming method, and printing which can improve the reliability of the image while maintaining the development performance. Substrate. [Embodiment] (Photosensitive composition) In the present invention, the photosensitive composition contains a binder, a polymerizable compound, a dip, and a photopolymerization initiator, and may further contain other components as needed. <Binder> The binder is a polymer compound having an acidic group and an ethylenically unsaturated bond in a side chain, an epoxy acrylate compound, or the like, which is particularly suitable for use in side chains. A polymer compound containing an acidic group and an ethylenically unsaturated bond is particularly suitably used. - a polymer compound having an acidic group and an ethylenically unsaturated bond in a side chain - the acidic group may, for example, be a carboxyl group, a phosphoric acid group or a sulfonic acid group, and it is preferred to use a mercapto group from the point of starting the raw material. . Further, the above-mentioned binder may be one having an acrylic group or a carboxylic acid having at least one polymerizable double bond in the molecule, for example, a (meth) acrylate group or a (meth) acrylamide group. Various polymerizable double bonds such as vinyl ether and allyl ether. More specifically, for example, in the acrylic resin containing a carboxyl group as an acidic group, the addition of the cyclic ether group contains a polymerizable compound such as glycidyl acrylate, glycidyl methacrylate, and cinnamon 200935174 acid. An epoxy group-containing polymerizable product of a glycidyl ester of a saturated fatty acid or an epoxy group having an alicyclic epoxy group (for example, an epoxy group such as a cyclohexene oxide in the same molecule) and a (meth) acrylonitrile group. A compound obtained by the compound or the like. In addition, for example, a compound obtained by adding an isocyanate group-containing polymerizable compound such as an isocyanate (ethyl) acrylate to an acrylic resin containing an acidic group and a hydroxyl group may be used, and in an acrylic acid group containing an acid anhydride group. A compound obtained by adding a hydroxyl group-containing polymerizable compound such as a hydroxy (meth) acrylate or the like. Further, for example, a cyclic ether group such as a copolymerized methyl glyceryl acrylate may contain a vinyl monomer such as a polymerizable compound or a (meth) propylene decyl alkyl ester, and an epoxy group in a side chain. A compound obtained by adding (meth)acrylic acid or the like. Examples of such an example include Patent No. 2,763,775, JP-A-3-172301, and JP-A-2000-232264. In the above, the binder is selected from a part of the acidic group of the polymer compound, and the addition of a cyclic ether group (for example, a group having an epoxy group or an oxetane group in a partial structure) contains a polymerization. It is more preferable that a part or all of the cyclic ether group of the compound and the polymer compound oxime is a polymer compound in which the addition carboxyl group contains a polymerizable compound. In this case, the addition reaction with the compound containing an acidic group and a cyclic ether group is preferably carried out in the presence of a catalyst, and particularly preferably the catalyst is selected from the group consisting of an acidic compound and a neutral compound. Among these, in particular, in view of the long-term development stability of the photosensitive composition, the binder is preferably an aromatic group having a carboxyl group and a heterocyclic ring in the side chain, and on the side. A polymer compound in which a chain contains an ethylenically unsaturated bond. - an aromatic group which may also contain a heterocyclic ring - 9 - 200935174 The above-mentioned aromatic group which may also contain a hetero ring (hereinafter, simply referred to as "aromatic group") may, for example, be a benzene ring or two ~3 benzene rings form a condensed ring, a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples of the aromatic group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a benzyl group, a dihydrogen group, a fluorenyl group, a benzofluorenyl group, a benzofuran ring group, and a benzo group. Thiophene ring group, pyrazole ring group, isoxazole ring group, isothiazole ring group, anthracenyl group, benzisoxazole ring group, benzisothiazole ring group, imidazole ring group, indazole ring group, thiazole Ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, pyridine ring group, quinoline ring group, isoquinoline ring group, oxime-trap ring group, pyrimidine ring group, pyridene ring Base, oxime-ring ring group, quinazolinium ring group, quinoxaline ring group, indole cyclopropyl ring group, phenanthridine ring group, carbazole ring group, anthracene ring group, pyrancyclo group, pyridine ring group, piperazine The cultivating ring group, the anthracene ring group, the hydrazine ring group, the chromene ring group, the porphyrin ring group, the acridine ring group, the phenothiaquinone ring group, the tetrazole ring group, the triple well ring group and the like. Among these, a hydrocarbon aromatic group is preferred, and a phenyl group or a naphthyl group is more preferred. The aromatic group may have a substituent, and the substituent may, for example, be a halogen atom, an amine group having a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, a thioether group or a decyl group. A nitro group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or the like which may have a substituent, respectively. The alkyl group may, for example, be a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group or a cyclic alkyl group. Specific examples of the aforementioned alkyl group include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, and ten. Trialkyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, t-butyl, t-butyl, isopentyl, neopentyl-10-200935174, 1 -methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, 2-northenyl and the like. Among these, a linear alkyl group having a carbon number of from J to 12 and a branched alkyl group having a carbon number of from 3 to 12 and having a carbon number of from 5 to 10 are preferable. The substituent which may have an alkyl group as described above may be, for example, a group consisting of a one-valent non-metal atom group removed. These substituents may be a halogen atom (-F, -Br, -C1, -1), a hydroxyl group, an alkoxy group, an aryloxythio group, an alkylthio group, an arylthio group, an alkyldithio group, an aryl group Thio-, N-alkylamino, hydrazine, fluorenyl-dialkylamino, N-arylamino, n, ylamino, fluorenyl-alkyl-fluorenyl aryl, decyloxy, Alkyl oxyalkylamine methyl methoxy, fluorenyl-arylamine methyl methoxy, hydrazine, fluorene-terpenyloxy, anthracene, fluorenyl-diarylamine, hydrazine-alkyl- Anthracene-arylamino group, alkylsulfonyloxy group, arylsulfonyloxy group, sulfonylthio group, fluorenylalkyl amide group, fluorenyl-aryl amide group, ureido group, Ν'-alkyl group Urea, dialkylureido, Ν'-arylureido, Ν', Ν'-diarylureido, ν,-injury ureido, oxime-alkylurea, oxime-arylurea , Ν'-alkyl-Ν fluorenyl, Ν'-alkyl-fluorene-arylureido, Ν', Ν'-dialkyl-fluorene-alkyl fluorene, Ν'-dialkyl-hydrazine -Arylureido, Ν'-aryl-hydrazine-alkylureido, -Ν-arylureido, 1^',1^'-diaryl-1^alkylureido'1^,^ 1,-di: arylureido, Ν'-alkyl-Ν'-aryl-hydrazine-alkylurea, ν -院3 Ν-Ν-arylureido, alkoxycarbonylamino, aryloxycarbo-alkane-anthracene-alkoxycarbonylamino, fluorenyl-alkyl-fluorenyl-aryloxy fluorenyl Amine aryl-fluorenyl-alkoxycarbonylamino, fluorenyl-aryl-fluorenyl-aryloxydecylamine fluorenyl, fluorenyl, carboxy, alkoxycarbonyl, aryloxycarbonyl, amine, fluorenyl-alkyl Aminomethyl hydrazino, anthracene, fluorene-dialkylamine-methyl fluorenyl, hydrazine-aryl, cyclohexyl-1 alkyl, hydrogen atom, for example, hydrazine, hydrogen, amine, fluorene-diaryl, hydrazine -Aminocarboxamidine, [ Ν,, Ν, -S Ν-Ν'--alkylureaurea, Ν'-aryl-yl-g-Ν'-aryl, fluorenyl-yl , Ν-, yl, methyl hydrazino; amine methyl hydrazine-11- 200935174 base, N, N-diarylamine methyl sulfhydryl, N-alkyl-N-aryl amine aryl, keaki Alkyl arylsulfonyl, aryl sulfhydryl, aryl aryl, aryl acid (-SO3H) and its conjugate base (called sulfonate) Based on the base, the sub-mineral base, the N-yard base, the N, N-two-yard sulfinyl, the N-arylsulfinyl, the Ν, the aryl-aryl Base, N - yard base - Ν - Isosulfonyl, sulfonyl, hydrazine-alkylamine sulfonyl, ν, Ν-dialkylamine sulfonyl, fluorene-arylamine sulfonyl, anthracene, fluorene-diarylamine sulfonate Sulfhydryl, fluorene-hospital-fluorene-arylamine sulfonate, phosphonic acid group (-ρ〇3Η; 2) and its co-basic base (referred to as phosphonium), dialkylphosphonic acid group (- P〇3 (alkyl) 2) (hereinafter, "alkyl" means an alkyl group) and a diarylphosphonic acid group (_11〇3 (&1^1) 2) (hereinafter, "&1^1" Means a aryl group, an alkylarylphosphonic acid group (-p〇3 (alkyl) (aryl), a monoalkylphosphonic acid group (-P〇3 (alkyl)) and its conjugate base (called Alkylphosphonate), monoarylphosphonate (-P〇3H (aryl)) and its conjugate base (referred to as arylphosphonate), phosphonic acidoxy (-OPO3H2) and its conjugate base (referred to as phosphonateoxy), dialkylphosphonic acidoxy (-〇P〇3H(alkyl) 2), diarylphosphonic acidoxy (-OP〇3 (aryl) 2), aryl aryl Phosphonic acid oxy-(〇P〇3(alkyl)(〇) 〇, monoalkylphosphonic acid oxy (-OP〇3H(alkyl)) and its conjugate base (referred to as alkylphosphonate oxy) , monoarylphosphonic acidoxy (-〇P〇3 H (aryl)) and Conjugate base (referred to as aryl phosphonate group), a cyano group, a nitro group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkyl silicon and the like. Specific examples of the alkyl group in these substituents include, for example, the aforementioned alkyl groups. Specific examples of the aryl group in the substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyldimethylphenyl group, a fluorenyl group, a cumyl group, a chloro basic group, a basal group, and a chloro group. Methylphenyl, hydroxyphenyl, methoxyphenyl-12- 200935174, ethoxyphenyl, phenoxyphenyl, ethoxylated phenyl, benzamidine phenyl, methylthiobenzene Base, phenylthiophenyl, methylaminophenyl, dimethylaminophenyl, ethenylphenyl, carboxyphenyl, methoxyphenylphenyl, ethoxyphenylcarbonyl, benzene Oxycarbonylphenyl, N-phenylamine, hydrazine, phenyl s, cyanophenyl, sulfonylphenyl, sulfonylphenyl, phosphonic phenyl, phosphonate phenyl, and the like. Specific examples of the alkenyl group in the above substituent include, for example, a vinyl '1-propenyl group, a 1-butenyl group, a cinnamyl group, a 2-chloro-1-ethyl group, and the like. Specific examples of the alkynyl group in the above substituent include, for example, an ethynyl group, a 1-propynyl group, a 1-butynyl group, a trimethyldecyl ethynyl group, etc., a fluorenyl group in the aforementioned substituent (RQ1C) The R01 of 〇-) may, for example, be a hydrogen atom, the above-mentioned alkyl group or aryl group. Among these substituents, especially a halogen atom (_F, _Br, _C1, -1), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, an N,N-dioxane Amino group, decyloxy group, N-alkylamine methyl methoxy group, N-arylamine methoxy group, decylamino group, decyl group, fluorenyl group, carboxyl group, alkoxycarbonyl group, aryloxy group Q group Carbonyl, amine-mercapto, N-alkylamine, mercapto, N,N-diamine, amine N, N-arylamine, N-alkyl-N-arylamine, mercapto , sulfonic acid group, sulfonate group, amine sulfonyl group, N-alkylamine sulfonyl group, N,N-diamine sulfonyl group, N-arylamine sulfonyl group, N-alkyl group N-arylamine sulfonyl 'phosphonic acid group, phosphonic acid group, dialkylphosphonic acid group, diarylphosphonic acid group, monoalkylphosphonic acid group, alkylphosphonic acid group, monoarylphosphonic acid group An arylphosphonate group, a phosphonic acidoxy group, a phosphonateoxy group, an aryl group, an alkenyl group or the like is preferred. Further, the heterocyclic group in the above-mentioned substituent may, for example, be a pyridyl group or a piperidinyl group, and the fluorenyl group in the above substituent may, for example, be a trimethyldecane-13-200935174 group. On the other hand, the alkylene group in the alkyl group may, for example, be one in which one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms is removed to form a divalent organic residue. For example, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 5 to 10 carbon atoms, and the like are preferable. Preferred examples of the substituted alkyl group obtained by combining these substituents with an alkylene group include, for example, a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a tris-fluoromethyl group, and a Oxymethyl, isopropoxymethyl, butoxymethyl, second butoxybutyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methyl sulfide Methyl, tolylthiomethyl, pyridylmethyl, tetramethylpiperidinemethyl, N-ethinyltetramethylpiperidinemethyl, trimethyldecylmethyl, methoxyethyl, B Aminoethyl, diethylaminopropyl, morpholinylpropyl, ethoxymethyloxy, benzhydryloxymethyl, N-cyclohexylaminemethyl hydroxyethyl, N-benzene Ketomethyl hydroxyethyl, acetamidoethyl, N-methylbenzhydrylaminopropyl, 2-oxyethyl, 2-oxypropyl, carboxypropyl thiol, methoxy Carbocarbonylethyl, allyloxycarbonylbutyl, chlorophenoxycarbonylmethyl, aminemethylmethylmethyl, N-methylamine methyl decyl ethyl, hydrazine, hydrazine-dipropylamine formazan Methyl, fluorenyl-(methoxyphenyl)amine, mercaptoethyl, fluorenyl-methyl-hydrazine-(sulfonate Aminomethylmethyl, sulfobutyl, sulfonyl butyl, sulfonyl butyl, hydrazine-ethylamine sulfonylmethyl, hydrazine, hydrazine-dipropylamine sulfonyl propyl Base, fluorene-tolylamine sulfonylpropyl, hydrazine-methyl-hydrazine-(phosphonophenyl)amine sulfonyl octyl, phosphonic butyl, phosphonic hexyl, diethylphosphonic acid Butyl, diphenylphosphonic propyl, methylphosphonic butyl, methylphosphonic butyl, tolylphosphonic hexyl, tolylphosphonate hexyl, -14- 200935174 phosphonic acid oxygen Propyl, phosphonooxybutyl, benzyl, phenethyl, α-methylbenzyl, 1-methyl-1-phenylethyl, fluorenyl-methylbenzyl, cinnamyl, allyl , 1-propenylmethyl, 2-butenyl, 2-methylallyl, 2-methylpropenylmethyl, 2-propynyl, 2-butynyl, 3-butynyl, and the like. Examples of the aryl group include a benzene ring, two to three benzene rings to form a condensed ring, and a benzene ring to form a condensed ring with a 5-membered unsaturated ring. Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group, a dihydroindenyl group, an anthracenyl group and the like. Among these, phenyl and naphthyl anthracene are preferred. The alkyl group may have a substituent, and the aryl group having such a substituent (hereinafter also referred to as "substituted aryl group") may be, for example, a carbon atom formed on the ring of the aryl group, and may have a hydrogen atom. The base of the monovalent non-metal atomic group is used as a substituent. The substituent which the aryl group may have may preferably be, for example, the above-mentioned alkyl group, substituted group, or a substituent which the above alkyl group may have. Preferred examples of the above substituted aryl group include a biphenyl group, a tolyl group, a tolyl group, a decyl group, a cumyl group, a chlorophenyl group, a bromophenyl group, a tomb phenyl group, and a chloro group. Methylphenyl, trifluoromethylphenyl, hydroxyphenyl, p-phenylene, methoxyethoxyphenyl, allylpropylhydroxyphenyl, phenoxybenyl, methylthiophenyl, Tolylthiophenyl, ethylaminophenyl, diethylaminophenyl, morpholinyl phenyl, ethyl hydroxyphenyl, benzhydryl hydroxyphenyl, N-cyclohexylamine fluorenyl Hydroxyphenyl, N-phenylamine-mercaptohydroxyphenyl, arylaminophenyl, N-methylbenzimidylphenyl, carboxyphenylmethyl phenyl, allyloxycarbonyl Phenyl, chlorophenoxycarbonylphenylamine methyl phenyl, N-methylamine decyl phenyl, N,N dipropylamine methyl-15- 200935174 nonylphenyl, N-(A Oxyphenyl)amine,mercaptophenyl, N-methyl-N-(sulfonylphenyl)amine,nonylphenyl, sulfonylphenyl, sulfonylphenyl, sulfonamide Base, N-ethylaminesulfonylphenyl, N,N-dipropylaminesulfonylphenyl, N-A Amine sulfonylphenyl, N-methyl-N-(phosphonophenyl)amine sulfonylphenyl, phosphophenyl phenyl, phosphonate phenyl, diethyl orthophenyl Diphenylphosphonic phenyl, methylphosphonic phenyl, methylphosphonic phenyl, tolylphosphonic phenyl, tolylphosphonyl phenyl, allyl phenyl, 1-propene Methylphenyl, 2-butenylphenyl, 2-methylallyl propylphenyl, 2-methylpropenylphenyl, 2-propynylphenyl, 2-butynylphenyl, 3-butynylphenyl group and the like. For example, R02, RQ3, RQ4, and R05 are based on a monovalent non-metal atomic group. Examples of the above R〇2, R〇3, RG4 and RQ5 include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group. Specific examples of such may be exemplified as the above examples. Among these, a hydroquinone atom, a halogen atom, a linear alkyl group having 1 to 30 carbon atoms, a branched alkyl group or a cyclic alkyl group is preferred. Preferred specific examples of the above alkenyl group and alkynyl group include, for example, a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1-pentenyl group, a 1-hexenyl group, a 1-octenyl group, and a methyl group-1. -propenyl, 2-methyl-1-propenyl, 2-methyl-1-butenyl, 2-phenyl-1-vinyl, 2-chloro-1-vinyl, ethynyl, 1- Propynyl, butynyl, phenylethynyl and the like. The above heterocyclic group may, for example, be a pyridyl group exemplified as a substituent of the substituted alkyl group. The above-mentioned oxy group (R06O-) is, for example, a group in which r〇6 is a valent non-metal atomic group from which a hydrogen atom is removed. Examples of the oxy group include an anthraceneoxy group, an aryloxy group, a decyloxy group, an amine methyl methoxy group, an N-alkylamine methyl methoxy group, an N-arylamine methoxy group, and N, N _. The second base amide amine, N,N-diarylamine methyl oxy, N-homo-N_ arylamine methyl methoxy, alkyl sulfonyloxy, aryl sulfonyloxy, A phosphonic acidoxy group, a phosphonic acid group or the like is preferred. The alkyl group and the aryl group in these examples are exemplified as the above-mentioned alkyl group, the substituted group, the aryl group, and the substituted aryl group. Further, the fluorenyl group (RQ7CO-) in the decyloxy group may, for example, be an alkyl group, a substituted group, an aryl group or a substituted aryl group as exemplified in the prior art. Among these substituents, an anthraceneoxy group, an aryloxy group, a decyloxy group, and an aryl-based decyloxy group are more preferable. Specific examples of preferred oxy groups include, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a dodecyloxy group, and a benzyloxy group. , allyloxy, phenethyloxy, carboxyethoxy, methoxycarbonylethoxy, ethoxycarbonylethoxy, methoxyethoxy, phenoxy, ethoxy, methoxy Ethoxyethoxy, ethoxyethoxyethoxy, morpholinylethoxy, morpholinylpropoxy, allyloxyethoxyethoxy, phenoxy, tolyloxy , xyloxy, decyloxy, oxy, cumyloxy, methoxyphenoxy, ethoxyphenoxy, chlorophenoxy, bromophenoxy, ethoxylated Base, benzamidineoxy, naphthyloxy, phenylsulfonyloxy, phosphonic acidoxy, phosphonateoxy, and the like. The amine group (RQ8NH-, (RQ9) (roid) N-) which may also contain a mercapto group may be, for example, a group consisting of RQ8, RQ9, and RQiQ to remove a valent non-metal atomic group of a hydrogen atom. In addition, R0 9 and RQiQ may also be bonded to form a ring. -17- 200935174 The aforementioned amine group may, for example, be an N-alkylamino group, an N,N-dialkyl N-arylamine group, an N,N-diarylamine group or an N-alkyl-N-aryl group. Amine amino group, N-alkyl decylamino group, N-aryl decylamino group, ureido group, Ν'-alkane, anthracene, fluorene, -dialkylureido, Ν'-arylureido, hydrazine ',Ν'-Diarylsulfanyl-Ν'-arylureido, Ν-alkylureido, Ν-arylureido, Ν'-Calylureido, Ν'-alkyl-Ν -Arylureido, Ν}, Ν'-dialkyl-fluorenyl, Ν'-alkyl-Ν'-arylureido, Ν', Ν'-dialkyl-fluorene-alkyl hydrazine ,Ν'-Dialkyl-fluorene'-arylureido, Ν'-aryl-hydrazine-alkylureido-based fluorenyl-arylurea, Ν', Ν'-diaryl-Ν- Alkylureido, Ν', Ν'--Ν-arylureido, Ν'-alkyl-Ν'-aryl-oxime-alkylureido, Ν'-院 aryl-Ν-arylurea , ketone, ortho-amine, aryloxycarbonylaminoalkyl-hydrazine-alkoxycarbonylamino, fluorenyl-alkyl-hydrazine-aryloxycarbonylamine aryl-hydrazine-alkoxycarbonylamine The alkyl group and the aryl group of the fluorenyl group, the fluorenyl-aryl-fluorene-aryloxycarbonylamine in the above may be mentioned as The alkylalkyl, aryl, and substituted aryl groups are exemplified. Further, the RM group of the fluorenyl group (R〇7CO-) in the amidino group, the fluorenylamino group, and the fluorene-aryl amide group is 〇. Among these, an N-alkylamino group, an N,N-dialkylamino group, an N- group or a decylamino group is more preferable. Specific examples of preferred amine groups include, for example, methylamino group, ethyl bromide, diethylamino group, miso base, piperidinyl group, pyridyl group, phenylamine-methylamino group, ethenyl group, and the like. . The sulfonyl group (RQ11-S02-) may, for example, be a base composed of a valence non-metal atomic group. The sulfonyl group such as this may preferably be an alkylsulfonyl group or an aryl group. The alkyl group and the aryl group in the above may, for example, be a pro-amino group, a group, a mercapto urea group, an N,-N-alkyl urea urea group, or an N,-aryl diaryl group. Base-N,-yl, N-based, N-based, and the like. Substituting the N-alkyl group for the arylamino group, benzene, and the sulfonyl group, the alkane-18-200935174 group, the substituted alkyl group, the aryl group, and the substituted aryl group are exemplified. Specific examples of the sulfonyl group include a butylsulfonyl group, a phenylsulfonyl group, and a chlorophenylsulfonyl group. The aforementioned sulfonate group (-S〇3-) is as defined above, and means that a conjugated base anion group of a sulfonic acid group (-so3h) is usually used together with a counter cation. Such a cation system can be appropriately selected and used by a general practitioner, and examples thereof include a key (for example, ammonium, anthraquinone, scaly, iodine, acridine key, etc.), and a metal ion (for example, Na+, K+, Ca2+, Zn2+, etc.). The carbonyl group (RQ13-CO-) may be, for example, a group in which a metal atom group is removed by removing a monovalent non-valent metal. Examples of the carbonyl group include a mercapto group, a mercapto group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine mercapto group, an N-alkylamine mercapto group, and an N,N-dialkylamine formamidine. A group, an N-arylaminecarbamyl group, an anthracene, an anthracene-diarylaminecarbamyl group, a fluorenyl-alkyl-anthracene-arylamine group, and the like. The alkyl group and the aryl group in the above may be exemplified as the above-mentioned alkyl group, substituted alkyl group, aryl group, and substituted aryl group. The aforementioned carbonyl group is a fluorenyl group, a fluorenyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine methyl sulfonyl group, a fluorenyl-alkylamine methyl fluorenyl group, an anthracene, a fluorenyl-dialkylamine carbaryl group, an anthracene group. The arylaminecarbamyl group is preferably a decyl group, a decyl group, a decyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. Specific examples of the carbonyl group include, for example, a decyl group, an ethyl fluorenyl group, a benzhydryl group, a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an allylhydroxycarbonyl group, and a dimethylaminophenylvinylcarbonyl group. , methoxycarbonylmethoxycarbonyl, fluorene-methylamine-methyl fluorenyl, fluorenyl-phenylamine-methyl hydrazino, hydrazine, hydrazine-diethylamine carbazino-19- 200935174, morpholinylcarbonyl, etc. suitable. The above-mentioned anthracene group (Ro^-SO-) may, for example, be a base composed of a monovalent non-metal atom group removed by R014. Examples of the fluorene group such as alkyl fluorenylene, aryl fluorenylene, sulfinylene, N-alkylsulfinylene, N,N-dialkylsulfinylene, N- An arylsulfinyl group, an N,N-diarylsulfinyl group, an N-alkyl-N-arylsulfinyl group, and the like. The alkyl group and the aryl group in the above may be exemplified as the above-mentioned alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Among these, it is preferable to use an alkylarylene group or an aryl sulfanyl group. Specific examples of the above-mentioned substituted anthracenylene group include, for example, a hexyl sulfinyl group, a benzyl fluorenylene group, a tolyl sulfoxide group, and the like. The above phosphonic acid group means that one to two hydroxyl groups on the phosphonic acid group are substituted by other organic sideoxy groups, such as the aforementioned dialkylphosphonic acid group, diarylphosphonic acid group, alkylarylphosphonic acid group. A monoalkylphosphonic acid group, a monoarylphosphonic acid group or the like is preferred. Among these, a dialkylphosphonic acid group or a diarylphosphonic acid group is more preferable. More preferably, specific examples of the phosphonic acid group include a diethylphosphonic acid group, a dibutylphosphonic acid group, and a diphenylphosphonic acid group. The aforementioned phosphonate group (-P03H2-, -P〇3H-) is as defined above, and means the first dissociation of the acid from the phosphonic acid group (-p〇3H2) or the second dissociation of the acid. Anionic group. It is usually preferred to use it together with a cation. Such a conventional cation system can be appropriately selected, and examples thereof include various types of guns (ammonium, anthraquinone, scaly, anthraquinone, acridine key, etc.), and metal ions (Na+, K+, Ca2+). Zn2 +, etc. The above-mentioned phosphonate group may also be a conjugated base anion group in which a hydroxyl group among the phosphonic acid groups is substituted into one-20 to 200935174 organic pendant oxygen groups, and specific examples thereof include the foregoing a monoalkylphosphonic acid group (-P〇3H(alkyl)), a conjugate base of a monoaryl ortho-acid group (-P03H (aryl)). The above aromatic group can radically polymerize an aromatic group One or more kinds of the above-mentioned radical polymerizable compounds, which may be used as a copolymerization component, may be produced by a usual radical polymerization method. The above-mentioned radical polymerization method may, for example, be a general one. The radical polymerization method or the solution polymerization method is preferably a compound represented by the formula (A-1) and a compound represented by the formula (A-2). Compound.

Ri R3 C=C 通式{Α·1> O—L—Ar Ο 但是，前述通式（Α-1)中，Ri、R2、及R3表示氫原子或 1價有機基。L表示有機基，不爲有機基亦可。Ar表示亦可含有雜環之芳香族基。Ri R3 C=C Formula {Α·1> O—L—Ar Ο However, in the above formula (Α-1), Ri, R2 and R3 represent a hydrogen atom or a monovalent organic group. L represents an organic group and may not be an organic group. Ar represents an aromatic group which may also contain a heterocyclic ring.

通式《A-2> 但是，前述通式（A-2)中，Ri、R2、及R3、以及、Ar 係表示與前述通式（A-1)相同之意。前述L的有機基係由非金屬原子所構成之多價有機基 ’可舉例如由1〜60個之碳原子、〇個〜1〇個之氮原子、〇個〜50個之氧原子、1個〜1〇〇個之氫原子、及〇個〜2〇個之硫原子所構成者。更具體而言，前述L的有機基係可舉例如組合下述的構 -21- 200935174 造單位所構成者、多價萘、多價μ等一 Γ I ^In the above formula (A-2), Ri, R2, R3, and Ar are the same as those of the above formula (A-1). The organic group based on L is a polyvalent organic group composed of a non-metal atom, and may, for example, be a carbon atom of 1 to 60 carbon atoms, a nitrogen atom of 1 to 1 unit, or an oxygen atom of 1 to 50 atoms, 1 One to one hydrogen atom and one to two sulfur atoms. More specifically, the organic group of L may be, for example, a combination of the following structures: 21-200935174, polyvalent naphthalene, polyvalent μ, etc.

I L — CH— — CH?- — 〇— πI L — CH— — CH?- — 〇— π

—0-—0-

OC—OC-

s—S—

前述L的連結基係亦可具有取代基，前述取代基係可舉例如前述的鹵素原子、經基、羧基、磺酸酯基、硝基、氰基、醯胺基、胺基、烷基、燦基、炔基、芳基、取代氧基、取代磺醯基、取代羰基、取代亞碾基、磺酸基、膦酸基、膦酸根基、矽烷基、雜環基。在前述通式所表示之化合物、及通式（A_2)所表示之化合物中’通式（A-1)者係從感度之點而言爲佳。又，述通式（A-1)之中，具有連結基者從安定性之點而言爲佳，前述L的有機基係從非畫像部的除去性（顯像性）之點而胃，以碳數1 ~ 4的伸烷基爲佳。前述通式（A-1)所表示之化合物係爲含有下述通式 (A-3)的構造單位之化合物。又，前述通式（A-2)所表示之化合物係爲含有下述通式（A-4)的構造單位之化合物。其中，通式（A-3)的構造單位者係從保存安定性之點而言舄佳。 -22- 200935174The linking group of L may have a substituent, and the substituent may, for example, be a halogen atom, a trans group, a carboxyl group, a sulfonate group, a nitro group, a cyano group, a decylamino group, an amine group or an alkyl group. A decyl group, an alkynyl group, an aryl group, a substituted oxy group, a substituted sulfonyl group, a substituted carbonyl group, a substituted arylene group, a sulfonic acid group, a phosphonic acid group, a phosphonic acid group, a decyl group, a heterocyclic group. Among the compounds represented by the above formula and the compounds represented by the formula (A_2), the formula (A-1) is preferred from the viewpoint of sensitivity. Further, among the above-described general formula (A-1), it is preferable that the group having a linking group is from the viewpoint of stability, and the organic group of the L is from the point of removal (developability) of the non-image portion to the stomach. It is preferred to use an alkylene group having 1 to 4 carbon atoms. The compound represented by the above formula (A-1) is a compound containing a structural unit of the following formula (A-3). Further, the compound represented by the above formula (A-2) is a compound containing a structural unit of the following formula (A-4). Among them, the structural unit of the formula (A-3) is preferred from the viewpoint of preserving stability. -22- 200935174

Rt R3Rt R3

0 通式（A-3) R2 C——O——L一Ar0 General formula (A-3) R2 C——O——L-Ar

但是，前述通式（A-3)及通式（A-4)中’ Ri、R2、及r3 、以及Ar係與前述通式（A-1)及通式（A-2)爲相同之意。 © 前述通式（A-3)及通式（A-4)中，1^及R2爲氫原子、r3 爲甲基者，從非畫像部的除去性（顯像性）之點而言爲佳。又’前述通式（A-3)的L係從非畫像部的除去性（顯像性 )之點而言，以碳數1~4的伸烷基爲佳。前述通式（A-1)所表示之化合物或通式（A_2)所表示之化合物係沒有特別地限制’可舉例如以下的例示化合物 ⑴〜（30)。However, in the above formula (A-3) and formula (A-4), ' Ri, R2, and r3, and Ar are the same as the above formula (A-1) and formula (A-2). meaning. In the above formula (A-3) and formula (A-4), 1 and R 2 are a hydrogen atom and r3 is a methyl group, and the point of removal (developability) from the non-image portion is good. Further, the L of the above formula (A-3) is preferably an alkylene group having 1 to 4 carbon atoms from the viewpoint of the removability (developability) of the non-image portion. The compound represented by the above formula (A-1) or the compound represented by the formula (A_2) is not particularly limited. Examples thereof include the following exemplified compounds (1) to (30).

23* 200935174 0⑴ Ο (9)23* 200935174 0(1) Ο (9)

α〇)〇〇)

(11)(11)

(4)(4)

(12) κ。广 Ο (5) Η(12) κ.广Ο (5) Η

(13)(13)

CI 飞。广ο叨 ^t〇r^〇 C14)CI fly.广ο叨 ^t〇r^〇 C14)

乂 ⑺ ==^：0J-(CHiCHj0乂 (7) ==^:0J-(CHiCHj0

¢15)¢15)

¢8) (16) -24- 200935174¢8) (16) -24- 200935174

(17)(17)

(18) 〇(18) 〇

(3Q) 前述例示化合物（1)-(30)之中’尤以（5)、（6)、（11)、 (I4)、及（28)爲佳，此等之中，尤以（5)及（6)從保存安定性及顯像性之點而言爲佳。前述亦可含有雜環之芳香族基在前述黏結劑中的含量係沒有特別地限制’高分子化合物的全構造單位設爲1〇〇莫耳％時’郎述通式（A_3)所表示之構造單位較佳爲含有20 -25- 200935174 莫耳/。以上、更佳爲含有3 Q莫耳。/。~ 4 5莫耳。/。。前述含量低於20莫耳/。時，保存安定性變低，超過45莫耳。/。時顯像性係爲降低。 --乙烯性不飽和鍵_ _ 目Ij述乙烯性不飽和鍵係沒有特別地限制，可視其目的做適當選擇，例如較佳爲下述通式（A_5)〜（A 7)所表示者。(3Q) Among the above-exemplified compounds (1) to (30), (5), (6), (11), (I4), and (28) are preferred, among which (5) ) and (6) are preferred from the point of preserving stability and imaging. The content of the aromatic group which may contain a hetero ring in the above-mentioned binder is not particularly limited. When the total structural unit of the polymer compound is 1% mol%, the structural unit represented by the general formula (A_3) Preferably, it contains 20 - 25 - 200935174 mole /. More preferably, it contains 3 Q moles. /. ~ 4 5 mo ears. /. . The aforementioned content is less than 20 mol/. When the preservation stability is lowered, it exceeds 45 m. /. The temporal imaging is reduced. The ethylenically unsaturated bond is not particularly limited, and may be appropriately selected depending on the purpose. For example, those represented by the following general formulae (A-5) to (A7) are preferred.

通式（A-5} 〇 -Y-C-C=C 通式卩-6} R5 Rfe R11 Z-Cr c _General formula (A-5} 〇 -Y-C-C=C General formula 卩-6} R5 Rfe R11 Z-Cr c _

Rg R10 通式 <A_7> 但是，前述通式（A-5)~(A-7)中，係各自獨立表示1價有機基。X及Y係各自獨立、表示氧原子、硫原子、或-N-R4。Ζ表示氧原子、硫原子、-N-R4、或伸苯基。R4 ® 表示氫原子、或1價有機基。前述通式（A-5)中，RdS各自獨立例如氫原子、可具有取代基之烷基等爲佳，氫原子、甲基爲自由基反應性高爲更佳。前述R2及R3係各自獨立、可舉例如氫原子、鹵素原子、胺基、羧基、烷氧基羰基、磺酸基、硝基、氰基、可具有取代基之烷基、可具有取代基之芳基、可具有取代基之院氧基、可具有取代基之芳氧基 '可具有取代基之院基胺基、可具有取代基之芳基胺基、可具有取代基之烷基磺醯 -26- 200935174 基、可具有取代基之芳基磺醯基等，氫原子、羧基、烷氧基羰基、可具有取代基之烷基、可具有取代基之芳基係以自由基反應性高爲更佳。前述R4係可舉例如可具有取代基之烷基等爲佳，以氫原子、甲基、乙基、異丙基爲自由基反應性高爲更佳。此處，所導入之前述取代基係可舉例如烷基、烯基、炔基、芳基、烷氧基、芳氧基、鹵素原子、胺基、烷基胺基、芳基胺基、羧基、烷氧基羰基、磺酸基、硝基、氰基 ® 、醯胺基、烷基磺醯基、芳基磺醯基等。前述通式（A-6)中，r4~r8係可舉例如氫原子、_素原子、胺基、二烷基胺基、羧基、烷氧基羰基、磺酸基、硝基、氰基 '可具有取代之烷基、可具有取代之芳基、可具有取代之院氧基、可具有取代之芳氧基、可具有取代之烷基胺基 '可具有取代之芳基胺基、可具有取代之烷基磺醯基、可具有取代之芳基磺醯基等爲佳，以氫原子、羧基、院氧基簾基、可具有取代之烷基、可具有取代之芳基爲更 ©佳。所導A之前述取代基係可例示如前述通式（A-5)中所舉例者。則述通式（A-7)中，R9係可舉例如氫原子、可具有取代之院基等爲佳’氫原子、甲基係以自由基反應性高爲更佳〇削述Rio、Ru係各自獨立、例如氫原子、鹵素原子、月安基一院基胺基、殘基、院氧基羯基、礦酸基、硝基、氰基飞具有取代之烷基、可具有取代之芳基、可具有取 -27- 200935174 代之院氧基、可具有取代之芳氧基、可具有取代之烷基胺基、可具有取代之芳基胺基、可具有取代之烷基磺醯基、可具有取代之芳基磺醯基等爲佳，氫原子、羧基、烷氧基簾基、可具有取代之烷基、可具有取代之芳基係以自由基反應性高爲更佳。此處’所導入之前述取代基係可例示如通式（A_5)中所舉例者。前述Z係表示氧原子、硫原子、-nr1；3_、或可具有取代 ©之伸苯基。R13表示可具有取代之烷基等，氫原子、甲基、乙基、異丙基係.以自由基反應性高爲更佳。前述通式（A-5)~(A-7)所表示之側鏈乙烯性$飽和鍵之中’尤以通式（A-5)者係聚合反應性高且感度高而爲更佳〇前述乙烯性不飽和鍵在前述高分子化合物中的含量係沒有特別地限制，以0.5 m e q / g ~ 3 · 0 m e q / g爲佳、 1 . Omeq/g~3 . Omeq/g爲較佳、1 · 5 m e q / g ~ 2.8 m e q / g 爲特 O 佳。前述含量低於〇.5meq/g時，由於硬化反應量減少而變成低感度’比3. Omeq/g多時，則保存安定性係爲劣化。此處’前述含量（meq/g)係可藉由例如碘價滴定來進行測定。將前述通式（A-5)所表示之乙烯性不飽和鍵導入至側鏈的方法係沒有特別地限制，例如可藉由使於側鏈含有羧基之高分子化合物、與具有乙烯性不飽和鍵及環氧基之化合物進行加成反應而可得到。前述於側鏈含有羧基之高分子化合物係可例如使含有 -28- 200935174 羧基之自由基聚合性化合物的1種以上、與可視需要做爲共聚合成分之其他自由基聚合性化合物的1種以上’藉由一般的自由基聚合法而製造，前述自由基聚合法係可舉例如懸濁聚合法、溶液聚合法等。前述具有乙烯性不飽和鍵及環氧基之化合物係只要含有此等即可，沒有特別地限制，例如下述通式（A- 8 )所表示之化合物及通式（A-9)所表示之化合物爲佳。 H2〇=C h $-0—Lr<^CH2 通式（A-8> 但是，前述通式（A-8)中Rg R10 Formula <A_7> However, in the above formulae (A-5) to (A-7), each represents a monovalent organic group. X and Y are each independently represented by an oxygen atom, a sulfur atom, or -N-R4. Ζ represents an oxygen atom, a sulfur atom, -N-R4, or a phenyl group. R4 ® represents a hydrogen atom or a monovalent organic group. In the above formula (A-5), each of RdS is preferably independently a hydrogen atom, an alkyl group which may have a substituent, and the like, and a hydrogen atom or a methyl group is preferably a radical having a high reactivity. R2 and R3 are each independently and may, for example, be a hydrogen atom, a halogen atom, an amine group, a carboxyl group, an alkoxycarbonyl group, a sulfonic acid group, a nitro group, a cyano group, an alkyl group which may have a substituent, and may have a substituent. An aryl group, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a aryl group which may have a substituent, an aryl group which may have a substituent, and an alkyl sulfonium which may have a substituent -26- 200935174, an arylsulfonyl group which may have a substituent, etc., a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are highly reactive with a radical For better. The R4 may be, for example, an alkyl group which may have a substituent, and the like, and a hydrogen atom, a methyl group, an ethyl group or an isopropyl group may have a high radical reactivity. Here, the substituent to be introduced may, for example, be an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amine group, an alkylamino group, an arylamine group or a carboxyl group. , alkoxycarbonyl, sulfonate, nitro, cyano®, decylamino, alkylsulfonyl, arylsulfonyl and the like. In the above formula (A-6), r4 to r8 may, for example, be a hydrogen atom, a sulfonium atom, an amine group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfonic acid group, a nitro group or a cyano group. a aryl group which may have a substituted alkyl group, a aryl group which may have a substituent, a substituted oxy group, a substituted aryloxy group, a substituted alkylamino group which may have a substitution, may have a substituted alkylsulfonyl group, a substituted arylsulfonyl group, etc., preferably a hydrogen atom, a carboxyl group, an alkoxy group, a substituted alkyl group, and a substituted aryl group. . The aforementioned substituent of the A is a exemplified by the above formula (A-5). In the above formula (A-7), R9 may, for example, be a hydrogen atom, a substituted substituent, or the like, preferably a hydrogen atom, and a methyl group may have a higher radical reactivity, and may be described as Rio or Ru. Individually independent, for example, a hydrogen atom, a halogen atom, a sulfhydryl group, a residue, a thiol group, a mineral acid group, a nitro group, a cyano group, a substituted alkyl group, and a substituted aromatic group. The base may have an alkyloxy group which may be substituted from -27 to 200935174, an aryloxy group which may have a substitution, an alkylamine group which may have a substitution, an arylamine group which may have a substitution, and an alkylsulfonyl group which may have a substitution Further, a substituted arylsulfonyl group or the like is preferable, and a hydrogen atom, a carboxyl group, an alkoxy group, a substituted alkyl group, and a substituted aryl group are more preferably a radical reactive property. The aforementioned substituent introduced here can be exemplified by the formula (A-5). The aforementioned Z system represents an oxygen atom, a sulfur atom, -nr1; 3_, or a phenyl group which may have a substitution of ©. R13 represents an alkyl group which may have a substituent, etc., and a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group. It is more preferable that the radical reactivity is high. Among the side chain ethylenicity-saturated bonds represented by the above formulas (A-5) to (A-7), the formula (A-5) is particularly preferred because of its high polymerization reactivity and high sensitivity. The content of the above-mentioned ethylenically unsaturated bond in the above polymer compound is not particularly limited, and is preferably 0.5 meq / g to 3 · 0 meq / g, and 1. Omeq / g ~ 3. Omeq / g is preferable. 1 · 5 meq / g ~ 2.8 meq / g is especially good. When the content is less than 〇5 meq/g, the amount of hardening reaction is reduced to become low sensitivity. When the amount is less than 3. Omeq/g, the storage stability is deteriorated. Here, the aforementioned content (meq/g) can be measured by, for example, iodine titration. The method of introducing the ethylenically unsaturated bond represented by the above formula (A-5) into the side chain is not particularly limited, and for example, it can be made by a polymer compound having a carboxyl group in a side chain and having an ethylenic unsaturated property. A bond and a compound of an epoxy group are obtained by an addition reaction. In the above-mentioned polymer compound having a carboxyl group in the side chain, for example, one or more kinds of radical polymerizable compounds having a carboxyl group of -28 to 200935174 may be used, and one or more other radical polymerizable compounds which may be used as a copolymerization component may be used. 'The production is carried out by a general radical polymerization method, and examples of the radical polymerization method include a suspension polymerization method and a solution polymerization method. The compound having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it contains such a compound, and is represented by, for example, a compound represented by the following formula (A-8) and a formula (A-9). The compound is preferred. H2〇=C h $-0—Lr<^CH2 Formula (A-8> However, in the above formula (A-8)

Ri表示氫原子或甲基。Li 表示有機基Ri represents a hydrogen atom or a methyl group. Li represents an organic group

Η H2〇=CΗ H2〇=C

Ο通式（Α-9> ,R2ΟGeneral formula (Α-9>, R2

C r°- 但是，前述通式（Α-9)中 R2表示氫原子或甲基。L2 表示有機基。W表示4~7員環的脂肪族烴基。前述通式（A-8)所表示之化合物及通式（A-9)所表示之化合物之中’尤以通式（A-8)所表示之化合物爲佳，前述通式（A-8)中，1^係以碳數1〜4的伸烷基者爲更佳。前述通式（A-8)所表示之化合物或通式（A_9)所表示之化合物係沒有特別地限制，可舉例如以下的例示化合物 (3 1卜（40) » -29- (36) 200935174C r° - However, in the above formula (Α-9), R2 represents a hydrogen atom or a methyl group. L2 represents an organic group. W represents an aliphatic hydrocarbon group of a 4 to 7 membered ring. Among the compounds represented by the above formula (A-8) and the compound represented by the formula (A-9), the compound represented by the formula (A-8) is preferred, and the above formula (A-8) is preferred. Among them, 1^ is preferably an alkyl group having 1 to 4 carbon atoms. The compound represented by the above formula (A-8) or the compound represented by the formula (A-9) is not particularly limited, and examples thereof include the following exemplified compounds (3 1 (40) » -29- (36) 200935174

(39)(39)

(40) 前述含有羧基之自由基聚合性化合物係例如丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、異巴豆酸、順丁烯二酸、 P -羧基苯乙烯等，特佳者係可舉例如丙烯酸、甲基丙烯酸等。前述導入側鏈之導入反應係可舉例如藉由在以三乙基胺、苄基甲基胺等的3級胺、氯化十二烷基三甲基銨、氯化四甲基銨、氯化四乙基銨等的4級銨鹽、吡啶、三苯基膦等做爲觸媒之有機溶劑中，以反應溫度5 0。(： ~ 1 5 0 °C使其反應數小時~數十小時來進行。於前述側鏈具有乙烯性不飽和鍵之構造單位係沒有特別地限制，例如較佳爲下述通式（A- 1 0)所表示之構造、通 -30- 200935174 式（A-1 1)所表示之構造、及由此等之混合所表示者(40) The carboxyl group-containing radical polymerizable compound is, for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, P-carboxystyrene or the like, and particularly preferred examples are Such as acrylic acid, methacrylic acid and the like. The introduction reaction of the introduced side chain may be, for example, a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride or chlorine. A tetrabasic ammonium salt such as tetraethylammonium, pyridine or triphenylphosphine is used as an organic solvent in a catalyst at a reaction temperature of 50. (: ~ ~ 150 ° C, the reaction is carried out for several hours to several tens of hours. The structural unit having an ethylenically unsaturated bond in the side chain is not particularly limited, and for example, the following formula (A- is preferred). 1 0) The structure represented by the structure, the structure represented by the formula (A-1 1), and the mixture represented by the above

但是，前述通式（A-10)及通式（A-11)中，Ra~Rc表示氫原子或1價有機基。Ri表示氫原子或甲基。Ll表示可具有連結基之有機基。前述通式（A-10)所表示之構造乃至通式（A—n)所表示之構造在高分子化合物中的含量係以20莫耳％以上爲佳、 20莫耳％~50莫耳％爲較佳、25莫耳％~45莫耳％爲特佳。前述含量低於20莫耳。/。的話，由於硬化反應量少而變成低感度，比50莫耳％多時，則保存安定性劣化。 --羧基-- 本發明的高分子化合物中，爲了提高非畫像部除去性等的各性能，亦可具有羧基。前述羧基係藉由使具有酸基之自由基聚合性化合物共聚合，而可賦予至前述高分子化合物。具有此等自由基聚合性之酸基係可舉例如羧酸、磺酸、磷酸基等，以羧酸爲特佳。前述具有羧基之自由基聚合性化合物係沒有特別地限制，可視其目的做適當選擇，可舉例如丙烯酸、甲基丙烯酸 '衣康酸、巴豆酸、異巴豆酸、順丁烯二酸、P-羧基苯乙烯等，此等之中，尤以丙烯酸、甲基丙烯酸、P-羧基苯 -31- 200935174 乙烯爲佳。此等係可單獨1種使用、亦可倂用2種以上。前述羧基在黏結劑中的含量係l.〇meq/g~4.0meq/g ’以1.5meq/g~3.0meq/g爲佳。前述含量低於i.〇meq/g 的話，顯像性係變得不充分，超過4.Omeq/g時係變得容易受到因鹼水顯像所引起的畫像強度損害。前述高分子化合物係以提昇畫像強度等的各性能爲目的的話，除了前述的自由基聚合性化合物以外，可進而與其他的自由基聚合性化合物共聚合爲佳。〇前述其他的自由基聚合性化合物係可舉例如選自於丙烯酸酯類、甲基丙烯酸酯類、苯乙烯類等之自由基聚合性化合物等。具體而言，可舉例如丙烯酸烷酯等的丙烯酸酯類、丙烯酸芳基酯、甲基丙烯酸烷酯等的甲基丙烯酸酯類、芳基甲基丙烯酸酯、苯乙烯、烷基苯乙烯等的苯乙烯類、烷氧基苯乙烯、鹵化苯乙烯等。前述丙烯酸酯類係以烷基的碳原子數爲1~20者爲佳〇，可舉例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸戊酯、丙烯酸乙基己酯、丙烯酸辛酯、丙烯酸第三辛酯、丙烯酸氯乙基酯、丙烯酸2,2 -二甲基羥基丙基酯、丙烯酸5-羥基戊基酯、三羥甲基丙烷單丙烯酸酯、新戊四醇單丙烯酸酯、丙烯酸縮水甘油酯、丙烯酸苄酯、丙烯酸甲氧基苄酯、丙烯酸糠基酯、丙烯酸四氫糠基酯等。前述丙烯酸芳基酯係可舉例如丙烯酸苯基酯等。前述甲基丙烯酸酯類係以烷基的碳原子爲1~2〇者爲 -32- 200935174 佳，可舉例如甲基丙烯酸甲酯、甲基丙烯酸乙基酯、甲基丙烯酸丙基酯、甲基丙烯酸異丙基酯、甲基丙烯酸戊基酯、甲基丙烯酸己基酯、甲基丙烯酸環己基酯、甲基丙烯酸苄酯、甲基丙烯酸氯基苄酯、甲基丙烯酸辛基酯、甲基丙烯酸4-羥基丁基酯、甲基丙烯酸5-羥基戊基酯、甲基丙烯酸2，2 -二甲基-3-羥基丙基酯、三羥甲基丙烷單甲基丙烯酸酯、新戊四醇單甲基丙烯酸酯、甲基丙烯酸縮水甘油酯、甲基丙烯酸糠基酯、甲基丙烯酸四氫糠酯等。 ❺ 前述甲基丙烯酸芳基酯係可舉例如甲基丙烯酸苯基酯、甲基丙烯酸甲苯酚基酯、甲基丙烯酸萘基酯等。前述苯乙烯類係可舉例如甲基苯乙烯、二甲基苯乙烯、三甲基苯乙嫌、乙基苯乙烯、二乙基苯乙嫌、異丙基苯乙烯、丁基苯乙烯、己基苯乙烯、環己基苯乙烯、癸基苯乙烯、苄基苯乙烯、氯基甲基苯乙烯、三氟甲基苯乙烯、乙氧基甲基苯乙烯、乙醯氧基甲基苯乙嫌等。前述烷氧基苯乙烯係可舉例如甲氧基苯乙烯、4 -甲氧 Q 基-3-甲基苯乙烯、二甲氧基苯乙烯等。前述鹵化苯乙烯係可舉例如氯基苯乙烯、二氯基苯乙嫌、三氯苯乙稀、四氣基苯乙嫌、五氯基本乙嫌、漠本乙烯、二溴苯乙烯、碘苯乙烯、氟代苯乙烯、三氟苯乙烯、 2 -溴-4-三氟甲基苯乙烯、4 -氟代-3-三氟甲基苯乙烯等。此等之自由基聚合性化合物係可單獨1種使用、亦可倂用2種以上。本發明中，在合成高分子化合物之際所使用的溶媒係沒有特別地限制，可視其目的做適當的適當地選擇’可舉 -33- 200935174 例如二氯乙烯、環己酮、甲基乙基酮、丙酮、甲醇、丙醇、丁醇、乙二醇單甲基醚、乙二醇單乙基醚氧基乙基乙酸酯、1-甲氧基-2-丙醇、1-甲氧基- 2-酸酯、N，N-二甲基甲醯胺、N，N -二甲基乙醯胺、二、甲苯、乙酸乙酯、乳酸甲酯、乳酸乙酯等。此等獨1種使用、亦可混合2種以上使用。本發明中，高分子化合物的分子量以質量平均計，以10,000以上爲佳、10,000〜50,000爲更佳。 © 量平均分子量低於10, 〇〇〇時硬化膜強度係爲不足 50,00 0時則顯像性有降低之傾向。又，在本發明中，高分子化合物中亦可具有未單體。此時，前述單體在前述高分子化合物中的含佳爲15質量％以下。本發明中，高分子化合物係可單獨1種使用、ί 種以上使用。又，亦可混合其他的高分子化合物來此時，前述其他的高分子化合物在前述本發明高分〇物中的含量以5 0質量。/。以下爲佳、3 0質量％以下爲 <環氧丙烯酸酯化合物> 前述環氧丙烯酸酯化合物係具有來自環氧化合架，且分子中具有乙烯性不飽和雙鍵與羧基之化合這樣的化合物係可以例如使多官能環氧化合物與残單體進行反應’進而附加多鹼酸酐之方法等來得到前述多官能環氧化合物係可舉例如聯二甲苯醒酚型環氧樹脂（「ΥΧ4000 ;日本環氧樹脂公司製」等之混合物、具有異三聚氰酸酯骨架等之雜環式環、乙醇、2-甲丙基乙甲亞礦係可單分子量前述質，超過尽應的量係較奕混合2 使用。子化合更佳。物之骨 '物。像 :基含有〇 ί型或雙等）或此氧樹脂（ -34- 200935174 「TEPIC;日產化學工業公司製」、「ARALDITE PT810 ；汽巴特殊化學品公司製」等）、雙酚A型環氧樹脂、雙酚F 型環氧樹脂、加氫雙酚A型環氧樹脂、雙酚S型環氧樹脂、酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、鹵化酚酚醛清漆型環氧樹脂、縮水甘油基胺型環氧樹脂（例如，四縮水甘油基二胺基二苯基甲烷等）、海因型環氧樹脂、脂環族環氧樹脂、三羥基苯基甲烷型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、四苯基乙烷型環氧樹脂、縮水甘油基酞酸〇樹脂、四縮水甘油基二甲苯酚乙烷樹脂、萘基含有環氧樹月旨（「ESN-190，ESN-36〇 ;新曰鐵化學公司製」、「 HP-4032,EXA-4750，EXA-4700 ;大日本油墨化學工業公司製」等）、具有二環戊二烯骨架之環氧樹脂（「 HP-7200,HP-7200H ；大日本油墨化學工業公司製」等} :藉由酚、〇-甲酚、萘酚等的酚化合物與具有酚性羥基之芳香族醛的縮合反應所得之多酚化合物、與環氧氯丙烷的反應物；由酚化合物與二乙烯基苯或二環戊二烯等的二烯〇烴化合物之加成反應所得到的多酚化合物、與環氧氯丙烷之反應物；4 -乙烯基環己烯-1-氧化物的開環聚合物經過乙酸等環氧化者；三縮水甘油基異三聚氰酸酯等的具有雜環之環氧樹脂；甲基丙烯酸縮水甘油酯共聚合系環氧樹脂（「 CP-50S,CP-50M ；日本油脂公司製」等）、環己基順丁烯二醯亞胺與甲基丙烯酸縮水甘油酯之共聚合環氧樹脂；選自於酚及甲酚之1種與P -羥基苯甲醛縮合物經縮水甘油基醚化之環氧樹脂；貳（縮水甘油基羥苯基）弗型環氧樹脂；貳（縮水甘油基羥苯基）金剛烷型環氧樹脂等。此等係可單 -35- 200935174 獨1種使用、亦可倂用2種以上。又，羧基含有單體之例子可舉例如（甲基）丙烯酸、乙烯基安息香酸、順丁烯二酸、順丁烯二酸單烷酯、反丁烯二酸、衣康酸、巴豆酸、肉桂酸、山梨酸、α-氰基肉桂酸、丙烯酸二聚物；另外，2-羥（甲基）丙烯酸乙酯等的具有羥基之單體與順丁烯二酸酐、酞酸酐、環己烷二羧酸酐等的環狀酸酐之加成反應物；與鹵素含有羧氧化合物之反應生成物、ω-羧基-聚己內酯單（甲基）丙烯酸酯等。另外，市〇售品係可使用東亞合成化學工業（股）製的ARONIX Μ-5300 ' Μ-5400、Μ-5500 及 Μ-5600、新中村化學工業（股）製的NK ESTER CB-1及CBX-1、共榮社油脂化學工業（股）製的HOA-MP及HOA-MS、大阪有機化學工業（股）製的 VISCOAT #2100等。此等係可單獨1種使用、亦可倂用2 種以上。又，多鹼酸酐係亦可使用例如琥珀酸酐、甲基琥珀酸酐、2,3-二甲基琥珀酸酐、2,2-二甲基琥珀酸酐、乙基琥〇珀酸酐、十二碳烯基琥珀酸酐、壬烯基琥珀酸、順丁烯二酸酐、甲基順丁烯二酸酐、2,3 -二甲基順丁烯二酸酐、2_ 氯基順丁烯二酸酐、2,3 -二氯基順丁烯二酸酐、溴基順丁烯二酸、衣康酸酐、檸康酸酐、順烏頭酸、酞酸酐、四氫酞酸酐、四氯基酞酸酐、四溴基酞酸酐、六氫酞酸酐 '甲基四氫酞酸酐、甲基六氫酞酸酐、橋亞甲基四氫酞酸酐、甲基橋亞甲基四氫酞酸酐、氯菌酸及5-(2,5 -二氧基四氫咲喃基）-3-甲基·3-環己烯-1,2-二羧酸酐等的二鹼酸酐、偏苯三酸酐、均苯四甲酸酐、3，3，，4,4，-二苯基酮四羧酸等的多 -36- 200935174 鹼酸酐等。此等係可單獨1種使用、亦可倂用2種以上。使其分別依序反應以得到環氧丙烯酸酯，惟使彼等反應之比率係相對於多官能環氧化合物的環氧基1當量，羧基含有單體的羧基爲〇·8~1·2當量、較佳爲0_9~1.1當量，多鹼酸酐爲〇.1~1.〇當量、較佳爲0.3-1.0當量。又，在特開平5-7052 8號公報中記載的具有弗骨架之環氧丙烯酸酯（不具有羧基之化合物）加成酸酐所得之化合物等，亦可利用做爲本發明的環氧丙烯酸酯。〇前述環氧丙烯酸酯化合物的分子量係以 1，000~100,000爲佳、2,000~50,000爲更佳°該分子量低於i，qoo時，感光層表面的黏性變強，且在後述感光層的硬化後，膜質變脆，或表面硬度係爲劣化，超過100,000 時，顯像性係爲劣化。又，樹脂的合成也變得困難。前述黏結劑在前述感光性組成物中的固體成分含量係以5 ~ 8 0質量％爲佳、1 0 ~ 7 0質量％爲更佳。前述黏結劑在前述感光性組成物中的固體成分含量係〇以5質量％~80質量％爲佳、1〇質量％~70質量％爲更佳。該固體成分含量低於5質量％時，感光層的膜強度係容易變弱，且該感光層表面的黏性係爲惡化，超過80質量％時，曝光感度係爲降低。 <聚合性化合物> 前述聚合性化合物係在I/O値的重量平均爲〇·52以下之範圍的話，沒有特別地限制，可視其目的做適宜地選擇〇又，前述聚合性化合物的I/O値的重量平均爲〇·43以 -37- 200935174 下爲佳，以分子中具有2個以上的聚合性基之化合物、例如二羥甲基三環癸烷二（甲基）丙烯酸酯（三環癸烷二甲醇二（甲基）丙烯酸酯）爲佳。此處’二羥甲基三環癸烷二丙烯酸酯（三環癸烷二甲醇二丙烯酸酯、NK ESTER Α-DCP)的構造式係於下述例示爲通式（B-1)。However, in the above formula (A-10) and formula (A-11), Ra to Rc represent a hydrogen atom or a monovalent organic group. Ri represents a hydrogen atom or a methyl group. L1 represents an organic group which may have a linking group. The structure represented by the above formula (A-10) or the structure represented by the formula (A-n) is preferably 20 mol% or more, 20 mol% to 50 mol% in the polymer compound. It is preferably from 25 mol% to 45 mol%. The foregoing content is less than 20 moles. /. In the case where the amount of hardening reaction is small, the sensitivity is low, and when it is more than 50% by mole, the storage stability is deteriorated. -Carboxyl group - The polymer compound of the present invention may have a carboxyl group in order to improve various properties such as non-image portion removability. The carboxyl group can be imparted to the polymer compound by copolymerizing a radical polymerizable compound having an acid group. The acid group having such a radical polymerizable property may, for example, be a carboxylic acid, a sulfonic acid or a phosphoric acid group, and particularly preferably a carboxylic acid. The radical polymerizable compound having a carboxyl group is not particularly limited, and may be appropriately selected depending on the intended purpose, and examples thereof include acrylic acid, methacrylic acid 'itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and P-. Among the carboxystyrenes and the like, among these, acrylic acid, methacrylic acid, and P-carboxybenzene-31-200935174 ethylene are preferred. These may be used alone or in combination of two or more. The content of the carboxyl group in the binder is preferably from 1.5 meq/g to 3.0 meq/g. When the content is less than i.〇meq/g, the imaging property is insufficient, and when it exceeds 4.Omeq/g, it is likely to be damaged by the image strength caused by alkali water development. In addition to the above-mentioned radically polymerizable compound, the polymer compound may be further copolymerized with other radical polymerizable compounds.其他 The other radically polymerizable compound is, for example, a radical polymerizable compound selected from the group consisting of acrylates, methacrylates, and styrenes. Specific examples thereof include acrylates such as acrylates, methacrylates such as aryl acrylates and alkyl methacrylates, aryl methacrylates, styrenes, and alkylstyrenes. Styrene, alkoxystyrene, halogenated styrene, and the like. The acrylate type is preferably one having an alkyl group having 1 to 20 carbon atoms, and examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, and ethyl hexyl acrylate. Octyl acrylate, trioctyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, neopentyl alcohol Monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, decyl acrylate, tetrahydrofurfuryl acrylate, and the like. The acryl aryl ester may, for example, be phenyl acrylate or the like. The methacrylate type is preferably -32 to 200935174 in which the carbon atom of the alkyl group is 1 to 2, and examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and A. Isopropyl acrylate, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, methyl 4-hydroxybutyl acrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, neopentyl Alcohol monomethacrylate, glycidyl methacrylate, decyl methacrylate, tetrahydrofurfuryl methacrylate, and the like.前述 The aryl methacrylate may, for example, be phenyl methacrylate, cresyl methacrylate or naphthyl methacrylate. The aforementioned styrenes may, for example, be methylstyrene, dimethylstyrene, trimethylbenzene, ethylstyrene, diethylbenzene, isopropylstyrene, butylstyrene, hexyl. Styrene, cyclohexylstyrene, mercaptostyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, ethoxylated methylbenzene, etc. . The alkoxystyrene may, for example, be methoxystyrene, 4-methoxy Q-methyl-3-methylstyrene or dimethoxystyrene. The aforementioned halogenated styrene may, for example, be chlorostyrene, dichlorophenyl benzene, trichlorophenylethylene, tetrakilyphenylene, tetrachloroethylene, chloroethylene, dibromostyrene, iodobenzene. Ethylene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, and the like. These radically polymerizable compounds may be used alone or in combination of two or more. In the present invention, the solvent to be used in the synthesis of the polymer compound is not particularly limited, and may be appropriately and appropriately selected depending on the purpose. - Reference may be made - 33 - 200935174 For example, dichloroethylene, cyclohexanone, methyl ethyl Ketone, acetone, methanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether oxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy Base-2-ester, N,N-dimethylformamide, N,N-dimethylacetamide, di-, toluene, ethyl acetate, methyl lactate, ethyl lactate, and the like. These may be used alone or in combination of two or more. In the present invention, the molecular weight of the polymer compound is preferably 10,000 or more, more preferably 10,000 to 50,000, based on the mass average. © The amount average molecular weight is less than 10, and when the strength of the cured film is less than 50,00, the development property tends to decrease. Further, in the present invention, the polymer compound may have a non-monomer. In this case, the content of the monomer in the polymer compound is preferably 15% by mass or less. In the present invention, the polymer compound may be used alone or in combination of two or more. Further, other polymer compounds may be mixed. In this case, the content of the other polymer compound in the high-order bismuth of the present invention is 50% by mass. /. In the following, it is preferably 30% by mass or less of the <epoxy acrylate compound> The epoxy acrylate compound has a compound derived from an epoxidation frame and having a combination of an ethylenically unsaturated double bond and a carboxyl group in the molecule. For example, a method of reacting a polyfunctional epoxy compound with a residual monomer, and further adding a polybasic acid anhydride, etc., to obtain the polyfunctional epoxy compound may be, for example, a dimethyl ketone type epoxy resin ("ΥΧ4000; Japan A mixture of the epoxy resin company, etc., a heterocyclic ring having an isomeric cyanate skeleton, an ethanol, or a 2-methylpropyl methine ore can be a single molecular weight, and the amount exceeding the amount is more than奕 Mixing 2 is used. Sub-combination is better. The bone of the object is like: the base contains 〇ί or double, or the oxygen resin (-34- 200935174 "TEPIC; manufactured by Nissan Chemical Industries Co., Ltd.", "ARALDITE PT810; Ciba Specialty Chemicals Co., Ltd., bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol S epoxy resin, phenol novolak ring Oxygen tree , cresol novolac type epoxy resin, halogenated phenol novolak type epoxy resin, glycidyl amine type epoxy resin (for example, tetraglycidyl diaminodiphenylmethane, etc.), hydantoin epoxy resin , alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylethane type epoxy resin, glycidyl ruthenium ruthenate resin, tetraglycidyl group The dimethyl phenol ethane resin and the naphthyl group contain an epoxy resin ("ESN-190, ESN-36"; manufactured by Shinkai Iron Chemical Co., Ltd.", "HP-4032, EXA-4750, EXA-4700; Epoxy resin having a dicyclopentadiene skeleton ("HP-7200, HP-7200H; manufactured by Dainippon Ink Chemical Industry Co., Ltd."): by phenol, hydrazine-cresol, naphthalene a polyphenol compound obtained by a condensation reaction of a phenol compound such as a phenol with an aromatic aldehyde having a phenolic hydroxyl group, and a reaction product with epichlorohydrin; a diene such as a phenol compound and divinylbenzene or dicyclopentadiene Polyphenol compound obtained by addition reaction of a hydrocarbon compound, and epichlorohydrin a reactant; a ring-opening polymer of 4-vinylcyclohexene-1-oxide undergoes epoxidation such as acetic acid; a heterocyclic epoxy resin such as triglycidyl isocyanurate; Copolymerized epoxy resin of glycidyl acrylate copolymerized epoxy resin ("CP-50S, CP-50M; manufactured by Nippon Oil Co., Ltd."), cyclohexylmethyleneimine and glycidyl methacrylate An epoxy resin selected from the group consisting of phenol and cresol and a p-hydroxybenzaldehyde condensate glycidyl etherified; hydrazine (glycidyl hydroxyphenyl) fluorene epoxy resin; hydrazine (glycidyl group) Hydroxyphenyl) adamantane type epoxy resin or the like. These can be used alone or in combination of two or more types. Further, examples of the carboxyl group-containing monomer include, for example, (meth)acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, Cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer; in addition, a hydroxyl group-containing monomer such as ethyl 2-hydroxy(meth)acrylate and maleic anhydride, phthalic anhydride, cyclohexane An addition reaction product of a cyclic acid anhydride such as a dicarboxylic acid anhydride; a reaction product containing an carboxyoxy compound with a halogen; ω-carboxy-polycaprolactone mono(meth)acrylate; In addition, the market sales system can use ARONIX Μ-5300 'Μ-5400', Μ-5500 and Μ-5600 made by East Asia Synthetic Chemical Industry Co., Ltd., NK ESTER CB-1 by Xinzhongcun Chemical Industry Co., Ltd. and CBX-1, HOA-MP and HOA-MS manufactured by Kyoei Oil & Fat Chemical Industry Co., Ltd., and VISCOAT #2100 manufactured by Osaka Organic Chemical Industry Co., Ltd. These may be used alone or in combination of two or more. Further, as the polybasic acid anhydride, for example, succinic anhydride, methyl succinic anhydride, 2,3-dimethylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, ethyl succinic anhydride, dodecenyl group can also be used. Succinic anhydride, nonenyl succinic acid, maleic anhydride, methyl maleic anhydride, 2,3-dimethyl maleic anhydride, 2-chloro-maleic anhydride, 2,3 - two Chloromethyl maleic anhydride, bromo maleic acid, itaconic anhydride, citraconic anhydride, cis-aconitic acid, phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, hexahydrogen Indane anhydride 'methyltetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, benzylidene tetrahydrophthalic anhydride, methyl bridged methylene tetrahydrophthalic anhydride, chloric acid and 5-(2,5-dioxo Dibasic anhydride such as tetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3,,4,4,- Poly-36-200935174 alkali anhydride or the like of diphenyl ketone tetracarboxylic acid or the like. These may be used alone or in combination of two or more. They are sequentially reacted to obtain epoxy acrylates, except that the ratio of their reactions is 1 equivalent to the epoxy group of the polyfunctional epoxy compound, and the carboxyl group of the carboxyl group-containing monomer is 〇·8 to 1.2 equivalents. Preferably, it is 0_9 to 1.1 equivalents, and the polybasic acid anhydride is 〇.1 to 1. 〇 equivalent, preferably 0.3-1.0 equivalent. Further, a compound obtained by adding an acid anhydride of an epoxy acrylate having a fluorene skeleton (a compound having no carboxyl group), which is described in JP-A-5-7052, can be used as the epoxy acrylate of the present invention. The molecular weight of the epoxy acrylate compound is preferably from 1,000 to 100,000, more preferably from 2,000 to 50,000. When the molecular weight is lower than i, qoo, the viscosity of the surface of the photosensitive layer becomes strong, and the photosensitive layer is described later. After hardening, the film quality becomes brittle, or the surface hardness is deteriorated, and when it exceeds 100,000, the development property is deteriorated. Moreover, the synthesis of the resin also becomes difficult. The content of the solid content of the above-mentioned binder in the photosensitive composition is preferably from 5 to 80% by mass, more preferably from 10 to 70% by mass. The solid content of the above-mentioned binder in the photosensitive composition is preferably 5% by mass to 80% by mass, more preferably 1% by mass to 70% by mass. When the content of the solid content is less than 5% by mass, the film strength of the photosensitive layer is likely to be weak, and the viscosity of the surface of the photosensitive layer is deteriorated. When the content is more than 80% by mass, the exposure sensitivity is lowered. <Polymerizable compound> The polymerizable compound is not particularly limited as long as the weight average of I/O値 is in the range of 〇·52 or less, and the polymerizable compound I can be appropriately selected depending on the purpose. The weight of /O値 is preferably 〇43, which is preferably -37-200935174, and a compound having two or more polymerizable groups in the molecule, such as dimethylol tricyclodecane di(meth)acrylate ( Tricyclodecane dimethanol di(meth)acrylate) is preferred. Here, the structural formula of 'dimethylol tricyclodecane diacrylate (tricyclodecane dimethanol diacrylate, NK ESTER Α-DCP) is exemplified below as the general formula (B-1).

前述I / Ο値的重量平均之上限値，例如從提昇絶緣可靠性之觀點而言，以0.5 2爲較佳、0.4 3爲特佳。前述I/O値的重量平均之下限値，例如從提高解析性之觀點而言，以0.350爲較佳、0.380爲更佳、0.400爲特佳調整前述黏結劑的I/O値之重量平均的方法，可藉由適 φ 當選擇構成共聚物之單體的種類、及聚合該單體之際的聚合比（含量）中至少任一者’以調整至規定的範圍。前述I/O値係將亦稱爲（無機性値）/(有機性値）之各種有機化合物的極性爲有機槪念地處理之値，且依各官能基設定參數之官能基寄予法之一。前述〗/〇値的詳細內容係在有機槪念圖（甲田善生著、三共出版（1984)); KUMAMOTO PHARMACEUTICAL BULLETIN,第 1 號、第 1~16 項（1954 年）；化學的領域、第11卷、第10號、719~725項（1957年 );香料品期刊（Fragrance Journal)、第 34號、第 97~111 項（1979年）；香料品期刊、第50號、第79~82項（1981年） -38- 200935174 等的文獻中有詳細地説明。前述I/O値的槪念係將化合物的性質區分爲表示共價性之有機性基、與表示離子結合性之無機性基，全部的有機化合物係以在命名爲有機軸與無機軸之直行座標上定位每1點位置來表示。所謂的前述無機性値係有機化合物所具有的各種取代基或鍵等對於沸點的影響力大小，以羥基爲基準所數値化者。具體而言，由於直鏈醇的沸點曲線與直鏈烯烴的沸點 ® 曲線之距離係取自碳數5的附近時爲約10 0°C，所以將每1 個羥基的影響力規定爲數値100，基於此數値基而將各種取代基或是各種鍵等的對於沸點之影響力予以數値化之値，係爲有機化合物所具有的取代基之無機性値。例如， -COOH基的無機性値爲150，雙鍵的無機性値爲2。因此，某種的有機化合物之無機性値係意味者該化合物所具有的各種取代基或鍵等的無機性値之總和。所謂的前述有機性値係以分子内的亞甲基爲單位，並 ® 以代表該亞甲基之碳原子的沸點之影響力爲基準而規定的。亦即，因爲直鏈飽和烴化合物在碳數5~10附近每加1個碳所引起的沸點上昇之平均値爲2 0 °C，所以以此爲基準將 1個碳原子的有機性値規定爲20，並以此爲基礎，將各種取代基或鍵等的對於沸點之影響力予以數値化之値爲有機性値。例如，硝基（-N02)的有機性値爲70。前述I/O値係越接近0則表示爲非極性（疏水性、有機性大）的有機化合物，越大則表示爲極性（親水性、無機性大）的有機化合物。 -39- 200935174 又，I / 〇値的重量平均係將例如聚合性化合物A以a重量％、B以b重量％的比率混合使用聚合性化合物之情形 (a + b=100)，計算爲I/O値的重量平均=(A的I/O値X a/100 + B 的 I/O 値 xb/100)。以下，說明前述I/O値的計算方法之一例。新戊四醇四丙烯酸酯的I /〇値係依照以下的方法來計算無機性値及有機性値，並藉由下述式計算（無機性値）/( 有機性値）而求得。〇新戊四醇四丙烯酸酯由於具有17個碳原子，所以新戊四醇四丙烯酸酯的有機性値係以20(碳原子的有機性値 )x 17(碳原子數）= 340來計算。，新戊四醇四丙烯酸酯的無機性値係由於新戊四醇四丙烯酸酯具有4個羧基、4個雙鍵，所以新戊四醇四丙烯酸酯的無機性値係6 0 (酯基的無機性値）X 4 (酯基的個數）+ 2 (雙鍵的無機性値卜4(雙鍵的個數）= 248 因此，可知新戊四醇四丙烯酸酯的I/O値係248(前述 Q 共聚物的無機性値）/340(前述共聚物的有機性値）= 〇·729 〇此外，在本發明中的「聚合性化合物」係不包含黏結劑中所含有的聚合性化合物。前述聚合性化合物在前述感光性組成物固體成分中的固體成分含量係以5質量％ ~ 5 0質量％爲佳、1 〇質量％ ~ 4 0 質量。/。爲更佳。該固體成分含量低於5質量％時，會有顯像性的惡化、曝光感度的降低等的問題產生’超過50質量％時，感光層的黏著性係變得過強而爲不佳。 -40- 200935174 <塡料（無機塡充劑）> 前述塡料（無機塡充劑）由於係有能提高永久圖案的表面硬度、能降低抑制線膨張係數、可降低抑制硬化層本身的介電率或電介質損耗角正切之機能’所以適合使用於本發明的感光性組成物。前述塡料（無機塡充劑）係沒有特別地限制’可從眾所周知者中適當地選擇，可舉例如高嶺土、硫酸鋇、鈦酸鋇、氧化矽粉、微粉狀氧化矽、氣相法二氧化砂、無定形二 Ο氧化矽、結晶性二氧化矽、熔融二氧化矽、球狀二氧化矽、滑石、黏土、碳酸鎂、碳酸鈣、氧化鋁、氫氧化鋁、雲母等。，前述塡料（無機塡充劑）的平均粒徑係低於3 v m爲佳、 O.ly m爲更佳。該平均粒徑爲3/z m以上時，由於光散射而解析度變差。前述塡料（無機塡充劑）的添加量係以5質量％~75質量 %爲佳' 8質量％〜7 0質量％爲較佳、1 0質量。/。~ 6 5質量。/。爲〇特佳。該添加量低於5質量％時，無法充分地使線膨張係數降低，超過90質量％時，在感光層表面形成硬化膜之情形中，該硬化膜的膜質變脆，在使用永久圖案形成配線之情形中，做爲配線保護膜的機能係爲受損。另外，亦可視需要添加有機微粒子。適宜的有機微粒子係沒有特別地限制，可視其目的做適當地選擇，可舉例如三聚氰胺樹脂、苯并胍胺樹脂、交聯聚苯乙烯樹脂等。又，可使用由平均粒徑爲吸油量爲 100m2/g~200m2/g左右之二氧化矽、交聯樹脂所構成之 -41- 200935174 球狀多孔質微粒子等。由於前述塡料（無機塡充劑）中含有平均粒徑爲〇· 1 // m~2 /z m的粒子，所以伴隨印刷配線基板的薄型化，永久圖案即使薄層化爲厚度5ym~20/zm，塡料（無機塡充劑）粒子也不會破壞永久圖案的表裏兩面，其結果即使在高加速度試驗（HAST)中亦沒有樹枝狀晶體發生，且可成爲耐熱性、耐濕性優異之永久圖案。 <光聚合起始劑> ® 前述光聚合起始劑係使用肟衍生物。又，亦可視需要含有其他的光聚合起始劑。前述肟衍生物係沒有特別地限制，可視其目的做適當選擇’以具有至少芳香族基之化合物爲佳，以具有下述通式（I)及通式（II)中任一者所示之部分構造的化合物爲更佳。前述肟衍生物係亦可倂用2種以上。The upper limit of the weight average of the above I / Ο値 is, for example, preferably 0.5 2 and 0.4 3 from the viewpoint of improving the insulation reliability. The lower limit of the weight average of the I/O 値, for example, from the viewpoint of improving the resolution, the weight average of the I/O 前述 of the above-mentioned binder is preferably adjusted at 0.350, more preferably 0.380, and more preferably 0.400. The method can be adjusted to a predetermined range by selecting at least one of the type of the monomer constituting the copolymer and the polymerization ratio (content) at the time of polymerizing the monomer. The above-mentioned I/O lanthanide is also known as one of the functional groups of the various organic compounds of (inorganic 値)/(organic 値), which are treated organically, and one of which is set according to each functional group. . The details of the above 〗 / 〇値 are in the organic mourning map (Katata Satoshi, San Gong Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, 1~16 (1954); the field of chemistry, the 11th Volume, No. 10, 719-725 (1957); Fragrance Journal, No. 34, No. 97-111 (1979); Journal of Spices, No. 50, No. 79-82 (1981) -38- 200935174 and the like are described in detail. The entanglement of the aforementioned I/O値 distinguishes the properties of the compound into an organic group representing covalentity and an inorganic group indicating ionic bonding, and all of the organic compounds are straightforward in the organic axis and the inorganic axis. The coordinates are located at every 1 o'clock position. The influence of the various substituents, bonds, and the like of the inorganic lanthanide-based organic compound on the boiling point is determined by the number of hydroxyl groups. Specifically, since the boiling point curve of the linear alcohol and the boiling point of the linear olefin are from the vicinity of the carbon number of 5, about 10 ° C, the influence of each hydroxyl group is defined as a number. 100. The influence of the boiling point on various substituents or various bonds based on the number of sulfhydryl groups is an inorganic enthalpy of a substituent of the organic compound. For example, the -COOH group has an inorganic enthalpy of 150 and the double bond has an inorganic enthalpy of 2. Therefore, the inorganic lanthanum of a certain organic compound means the sum of inorganic ruthenium of various substituents or bonds which the compound has. The above-mentioned organic oxime is defined by a methylene group in the molecule, and ® is defined based on the influence of the boiling point of the carbon atom representing the methylene group. That is, since the average enthalpy of the boiling point rise caused by the linear saturated hydrocarbon compound per carbon addition of 5 to 10 is 20 ° C, the organic enthalpy of one carbon atom is defined as a reference. On the basis of 20, on the basis of this, the influence of various substituents or bonds on the boiling point is counted as organic enthalpy. For example, the organic enthalpy of nitro (-N02) is 70. The closer the I/O system is to 0, the more organic compound which is non-polar (hydrophobic or organic), and the larger the organic compound which is polar (hydrophilic and inorganic). Further, the weight average of I / 〇値 is, for example, a case where the polymerizable compound A is mixed with a polymerizable compound at a ratio of a% by weight and B at a ratio of b% by weight (a + b = 100), and is calculated as I. /O値 weight average = (A I / O 値 X a / 100 + B I / O 値 xb / 100). Hereinafter, an example of the calculation method of the aforementioned I/O値 will be described. The I/N of the pentaerythritol tetraacrylate was calculated by the following method to calculate the inorganic hydrazine and the organic hydrazine, and was calculated by the following formula (inorganic enthalpy) / (organic enthalpy). Since neopentyltetraol tetraacrylate has 17 carbon atoms, the organic lanthanide of neopentyltetraol tetraacrylate is calculated by 20 (organic enthalpy of carbon atoms) x 17 (number of carbon atoms) = 340. , Inorganic lanthanide of pentaerythritol tetraacrylate. Since pentaerythritol tetraacrylate has 4 carboxyl groups and 4 double bonds, the inorganic lanthanide of neopentyltetraol tetraacrylate is 60 (ester-based). Inorganic 値) X 4 (number of ester groups) + 2 (inorganic bismuth of double bond 4 (number of double bonds) = 248 Therefore, it is known that I/O 値 248 of pentaerythritol tetraacrylate (Inorganic enthalpy of the Q copolymer) / 340 (organic enthalpy of the copolymer) = 〇·729 〇 In addition, the "polymerizable compound" in the present invention does not contain a polymerizable compound contained in the binder. The solid content of the polymerizable compound in the solid content of the photosensitive composition is preferably 5% by mass to 50% by mass, and more preferably 1% by mass to 40% by mass. When the amount is less than 5% by mass, the problem of deterioration in developability and deterioration in exposure sensitivity may occur. When the content exceeds 50% by mass, the adhesion of the photosensitive layer is too strong and is not good. -40- 200935174 <塡 ( (Inorganic 塡 ))> The above-mentioned mash (inorganic sputum) can be improved due to The surface hardness of the permanent pattern, the function of suppressing the coefficient of expansion of the line, and the function of suppressing the dielectric constant of the hardened layer itself or the dielectric loss tangent are suitable for use in the photosensitive composition of the present invention. The agent is not particularly limited' and may be appropriately selected from well-known ones, and examples thereof include kaolin, barium sulfate, barium titanate, cerium oxide powder, finely divided cerium oxide, fumed silica, and amorphous bismuth. Cerium oxide, crystalline cerium oxide, molten cerium oxide, spherical cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, etc., the aforementioned cerium (inorganic cerium) The average particle diameter is preferably less than 3 vm, more preferably O.ly m. When the average particle diameter is 3/zm or more, the resolution is deteriorated by light scattering. The aforementioned pigment (inorganic chelating agent) The amount of addition is preferably from 5% by mass to 75% by mass, preferably from 8% by mass to 7% by mass, and preferably from 10% by mass to 5% by mass. When the mass is %, the linear expansion coefficient cannot be sufficiently reduced. When the cured film is formed on the surface of the photosensitive layer at a content of more than 90% by mass, the film quality of the cured film becomes brittle, and in the case where wiring is formed using a permanent pattern, the function as a wiring protective film is impaired. The organic fine particles may be added as needed. The suitable organic fine particle system is not particularly limited, and may be appropriately selected depending on the intended purpose, and examples thereof include a melamine resin, a benzoguanamine resin, a crosslinked polystyrene resin, and the like. The average particle size is -41-200935174 spherical porous fine particles composed of cerium oxide and crosslinked resin having an oil absorption of about 100 m2/g to 200 m2/g. The average amount of the above-mentioned pigment (inorganic chelating agent) is average. Since the particle diameter is 〇·1 //m~2 /zm, the thickness of the printed wiring board is reduced, and even if the permanent pattern is thinned to a thickness of 5 μm to 20/zm, the pigment (inorganic chelating agent) particles are not The both sides of the front surface of the permanent pattern are destroyed, and as a result, dendritic crystals are not generated even in the high acceleration test (HAST), and the permanent pattern excellent in heat resistance and moisture resistance can be obtained. <Photopolymerization initiator> ® The above photopolymerization initiator is an anthracene derivative. Further, other photopolymerization initiators may be contained as needed. The above-mentioned anthracene derivative is not particularly limited, and may be appropriately selected as the compound having at least an aromatic group, and has the following formula (I) and formula (II). Partially constructed compounds are preferred. The above anthracene derivatives may be used in combination of two or more kinds.

Ar ~(c (Y1) = N -0—Y2) m 通式⑴Ar ~(c (Y1) = N -0—Y2) m General formula (1)

Ar -(c〇-C(Y') = N-O-Y2) 通式（ll> 但是，前述通式（I)及（II)中’ Ar係表示芳香族基及雜環基中任一者。Y1係表示氫原子及一價取代基中任一者， Y2係表示脂肪族基、芳香族基、雜環基、C〇Y3、CO2Y3、及CONY4Y5中任一者。γ3、γ4、及…係表示脂肪族基、芳香族基、及雜環基中任一者。m係表示1以上的整數。前述Y1係較佳爲氫原子、脂肪族基、及芳香族基中任一者。前述Y2係較佳爲脂肪族基、-CO-(脂肪族基）、-CO-( 芳香族基）、-CO-(雜環基）、-C〇2-(脂肪族基）、-C〇2-(芳 -42- 200935174 香族基）、及- C〇2-(雜環基）中任一者。前述Y3及Y4係較佳爲脂肪族基及芳香族基中任—者。 BIJ述照衍生物係亦可爲前述通式（I)及通式（i 1)所表示之構造透過連結基複數鍵結所構成之化合物。此外’前述通式（I)及通式（II)中，前述脂肪族基係表示各自亦可具有取代基之院基、烯基、炔基，前述芳香族基係表不各自亦可具有取代基之芳基、雜環（雜環）基，前述一價取代基係表示鹵素原子、亦可具有取代基之胺基、院 ®氧基羰基、羥基、醚基、硫醇基、硫醚基' 矽烷基、硝基、氰基、各自亦可具有取代基之烷基、烯基、炔基、芳基、雜環華。前述芳香族基係可舉例如1個〜3個的苯環形成縮合環者、苯環與5員不飽和環形成縮合環者，具體例係可舉例如苯基、萘基、蒽基、菲基、茚基、二氫苊基、苐基，其中尤以具有苯基及萘基中任一者之基爲佳，具有萘基之基爲特佳。〇又，此等之芳香族基係亦可具有取代基，彼等之取代基係可舉例如去掉氫原子獨一價非金屬原子團所構成之基。可舉例如後述的烷基、取代烷基、或取代烷基中做爲取代基所表示者等。又，前述雜環（雜環）基係可舉例如吡咯環基、呋喃環基、噻吩環基、苯并吡咯環基、苯并呋喃環基、苯并噻吩環基、吡唑環基、異噚唑環基、異噻唑環基、吲哚環基、苯并異卩f唑環基、苯并異噻唑環基、咪唑環基、噚唑環基、噻唑環基、苯并咪唑環基、苯并噚唑環基、苯并噻唑環 -43- 200935174 基、吡啶環基、喹啉環基、異喹啉環基、嗒阱環基、嘧啶環基、卩比哄環基、呔哄環基、喹唑啉環基、喹喏啉環基、叱環丙院環基、菲啶環基'咔唑環基、嘌呤環基、耻喃環基、吡啶環基、哌哄環基、味啉環基、吲哚環基、吲哚畊環基、色烯環基、噌啉環基、吖啶環基、啡噻哄環基、四唑環基、二阱環基等，其中尤以呋喃環基、噻吩環基、咪哩環基、噻唑環基、苯并噻唑環基、吡啶環基、吲吸環基、吖啶環基爲特佳。 © 又，此等之雜環基係亦可具有取代基，彼等取代基係可舉例如去掉氫原子的1價非金屬原子團所構成之基。可舉例如後述的院基、取代院基、或取代院基中做爲取代基所表示者。則述一價取代基係以鹵素原子、亦可具有取代基之胺基、烷氧基鑛基、羥基、醚基、硫醇基、硫醚基、矽烷基、硝基、氰基、各自亦可具有取代基之烷基、烯基、炔基、芳基、雜環基爲佳。〇又’前述由非金屬原子所構成之1價取代基係以各自亦可具有取代基之院基、烯基、炔基、芳基、雜環基爲佳。前述亦可具有取代基之烷基係可舉例如碳原子數爲1 〜20之直鏈狀、分枝狀、及環狀的烷基，其具體例係可舉例如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十六烷基、十八烷基、二十烷基、異丙基、異丁基、第二丁基、第三丁基、異戊基、新戊基、1-甲基丁基、異己基、2-乙基己基、2 -甲基己基、環己基、環戊基、2_降萡烯基。此 -44- 200935174 等之中，以碳原子數1〜12之直鏈狀、碳原子數3〜12之分枝狀、以及碳原子數5〜10之環狀的烷基爲更佳。前述亦可具有取代基之烷基的取代基係可舉例如由去掉氫原子的一價非金屬原子所構成之取代基’較佳例子係可舉例如鹵素原子（-F、-Br、-C1、-1)、羥基、烷氧基、芳氧基、氫硫基、烷硫基、芳硫基、烷基二硫基、芳基二硫基、胺基、N-烷基胺基、N，N-二烷基胺基、N-芳基胺基、 N，N -二芳基胺基、N -烷基-N-芳基胺基、醯氧基、胺甲醯 © 氧基、N-烷基胺甲醯氧基、N-芳基胺甲醯氧基、N，N-二烷基胺甲醯氧基、N，N:二芳基胺甲醯氧基、N-烷基-N-芳基胺甲醯氧基、烷基磺醯氧基、芳基磺醯氧基、醯硫基、醯胺基、N-烷基醯胺基、N-芳基醯胺基、脲基、Ν’-烷基脲基、Ν’，Ν’-二烷基脲基、Ν’-芳基脲基、Ν’，Ν’-二芳基脲基、Ν’-烷基- Ν’-芳基脲基、Ν-烷基脲基、Ν-芳基脲基、Ν’-烷基- Ν-烷基脲基、Ν’-烷基-Ν-芳基脲基、Ν’，Ν’-二烷基-Ν-烷基脲基、Ν’，Ν’-二烷基-Ν-芳基脲基、Ν’-芳基-Ν-烷基脲基、Ν ΐ-Ο 芳基-Ν-芳基脲基、Ν’，Ν’-二芳基-Ν-烷基脲基、Ν’，Ν’-二芳基芳基脲基、Ν’-烷基-Ν’-芳基-Ν-烷基脲基、Ν’-烷基 -Ν’-芳基-Ν-芳基脲基、烷氧基羰基胺基、芳氧基羰基胺基、Ν-烷基-Ν-烷氧基羰基胺基、Ν-烷基-Ν-芳氧基羰基胺基、Ν-芳基-Ν-烷氧基羰基胺基、Ν-芳基-Ν-芳氧基羰基胺基、甲醯基、醯基、羧基、烷氧基羰基、芳氧基羰基、胺甲醯基、Ν-烷基胺甲醯基、Ν，Ν-二烷基胺甲醯基、Ν-芳基胺甲醯基、Ν,Ν-二芳基胺甲醯基、Ν-烷基-Ν-芳基胺甲醯基、烷基亞颯基、芳基亞楓基、烷基磺醯基、芳基磺醯基、 -45- 200935174 磺酸基（-S〇3H)及其共軛鹼（稱爲磺酸酯基}、烷氧基磺醯基、芳氧基磺醯基、亞磺醯基、N-烷基亞磺醯基、N，N-二烷基亞磺醯基、N-芳基亞磺醯基、Ν,Ν-二芳基亞磺醯基、N-烷基-Ν-芳基亞磺醯基、胺磺醯基、Ν -烷基胺磺醯基、ν，Ν-二烷基胺磺醯基、Ν -芳基胺磺醯基、Ν，Ν-二芳基胺磺醯基、Ν -烷基-Ν-芳基胺磺醯基、膦酸基（-Ρ〇3η2)及其共軛鹼（稱爲膦酸根基）、二烷基膦酸基（-P〇3(alkyl)2)「alkyl =烷基，以下相同」、一方基麟酸基（_P〇3(aryl)2)「aryl =芳基 Ο ，以下相同」、烷基芳基膦酸基（-?〇3(&11^1)(&71))、單烷基膦酸基（-P〇3(alkyl))及其共軛鹼（稱爲烷基膦酸根基）、單芳基膦酸基（-P〇3H(aryl))及其共軛鹼（稱爲芳基膦酸炉基）、膦酸氧基（-OPO3H2)及其共軛鹼（稱爲膦酸根氧基}、二烷基膦酸氧基（-OP03H(alkyl)2)、二芳基膦酸氧基 (-OP〇3(aryl)2)、烷基芳基膦酸氧基卜 OP〇3(alky1)(aryiH 、單烷基膦酸氧基（-ΟΡΟ 3 H (alky 1))及其共軛鹼（稱爲烷基膦酸根氧基）、單芳基膦酸氧基（-〇P〇3H(aryl))及其共軛鹼〇 (稱爲芳基膦酸根氧基）、氰基、硝基、芳基、烯基、炔基、雜環基、矽烷基等。此等取代基中的烷基之具體例係可舉例如前述的烷基，前述取代基中的芳基之具體例係可舉例如苯基、聯苯基、萘基、甲苯基、二甲苯基、菜基、異丙苯基、氯基苯基、溴基苯基、氯基甲基苯基、羥基苯基、甲氧基苯基、乙氣基本基、本氧基苯基、乙醯氧基苯基、苯甲醯氧基苯基、甲硫基苯基、苯硫基苯基、甲基胺基苯基、二甲基胺基苯基、乙醯胺基苯基、羧基苯基、甲氧基羰基苯基、乙氧 -46- 200935174 基苯基鑛基 '苯氧基羰基苯基、N_苯基胺甲醯基苯基、氰基苯基、擴酸基苯基、磺酸根基苯基、膦酸基苯基、膦酸根基苯基等。又’前述取代基中的烯基之例子可舉例如乙烯基、1_ 丙烯基、1-丁烯基、肉桂基、2-氯基-1-乙烯基等，前述取代基中的炔基之例子可舉例如乙炔基、1-丙炔基' 1-丁炔基、三甲基矽烷基乙炔基等。前述取代基中的雜環基係可舉例如吡啶基、哌啶基、 ©等。前述取代基中的矽烷基係可舉例如三甲基矽烷基等。前述取代基中亦可含有醯基（RQ1CO -)，該醯基係可舉例如該RQ1爲例如氫原子、上述的烷基、芳基者。醯基（RQ1CO-)的RQ1係可舉例如氫原子、以及前述烷基、芳基。此等之取代基之中，更較佳者係可舉例如鹵素原子（-F、-Br、-C1、-1)、烷氧基、芳氧基、烷硫基、芳硫基、N -烷基胺基、N，N -二烷基胺基、醯氧基、N -烷基胺甲醯〇氧基、N-芳基胺甲醯氧基、醯胺基、甲醯基、醯基、羧基、烷氧基羰基、芳氧基羰基、胺甲醯基、N-烷基胺甲醯基、Ν,Ν-二烷基胺甲醯基、N-芳基胺甲醯基、N-烷基-N-芳基胺甲醯基、磺酸基、磺酸酯基、胺磺醯基、Ν-烷基胺磺醯基、Ν，Ν -二烷基胺磺醯基、Ν -芳基胺磺醯基、Ν -烷基- Ν-芳基胺磺醯基、膦酸基、膦酸根基、二烷基膦酸基、二芳基膦酸基、單烷基膦酸基、烷基膦酸根基、單芳基膦酸基、芳基膦酸根基、膦酸氧基、膦酸根氧基、芳基、烯基。另一方面，取代烷基中的伸烷基，係可舉例如將前述 -47- 200935174 碳數1〜20之烷基上的氫原子去掉任一個而成爲2價有機殘基者，較佳係可舉例如碳原子數1〜12之直鏈狀、碳原子數3〜12之分枝狀以及碳原子數5〜1〇之環狀的伸烷基。藉由組合此等取代基與伸烷基所得之取代烷基的較佳具體例係可舉例如氯基甲基、溴基甲基、2 -氯基乙基、三氟基甲基、甲氧基甲基、異丙氧基甲基、丁氧基甲基、第二丁氧基丁基、甲氧基乙氧基乙基、烯丙氧基甲基、苯氧基甲基、甲硫基甲基、甲苯硫基甲基、吡啶甲基、四甲基哌〇啶甲基、N -乙醯基四甲基哌啶甲基、三甲基矽烷基甲基、甲氧基乙基、乙基胺基乙基、二乙基胺基丙基、味啉基丙基、乙醯氧基甲基、苯甲醯氧基甲基、N -環己基胺甲醯基羥乙基、N-苯基胺甲醯基羥乙基、乙醯胺基乙基、N-甲基苯甲醯基胺基丙基、2-氧基乙基、2-氧基丙基、羧基丙基、甲氧基羰基乙基、烯丙氧基羰基丁基、氯基苯氧基羰基甲基、胺甲醯基甲基、N -甲基胺甲醯基乙基、N，N -二丙基胺甲醯基甲基、N-(甲氧基苯基）胺甲醯基乙基、N -甲基- N- ( 〇磺酸基苯基）胺甲醯基甲基、磺基丁基、磺酸根基丁基、胺磺醯基丁基、N-乙基胺磺醯基甲基、N，N-二丙基胺磺醯基丙基、N -甲苯基胺磺醯基丙基、N -甲基-N-(膦酸基苯基）胺磺醯基辛基、膦酸基丁基、隣酸根基己基、二乙基膦酸基丁基、二苯基膦酸基丙基、甲基膦酸基丁基、甲基膦酸根基丁基、甲苯基膦酸基己基、甲苯基膦酸根基己基、膦酸氧基丙基、膦酸根氧基丁基、苄基、苯乙基、α -甲基苄基、1-甲基-1-苯基乙基、ρ-甲基苄基、肉桂基、烯丙基、 1-丙烯基甲基、2-丁烯基、2-甲基烯丙基、2-甲基丙烯基 -48- 200935174 甲基、2-丙炔基、2-丁炔基、3-丁炔基等。前述芳基係可舉例如1個〜3個的苯環形成縮合環者、苯環與5員不飽和環形成縮合環者，具體例係可舉例如苯基、萘基、蒽基、菲基、茚基、二氫苊基、弗基，此等之中以苯基、萘基爲更佳。前述取代芳基係可使用在前述芳基的環形成碳原子上 ’由去掉氫原子的一價非金屬原子團所構成之基做爲取代基者。較佳取代基的例子係可舉例如前述的烷基、取代烷 ©基 '以及之前取代烷基中做爲取代基所表示者。前Μ取代芳基之較佳具體例係可舉例如聯苯基、甲苯基、二甲苹基、莱基、異丙苯基、氯基苯基、溴基苯基、氟基苯基、氯基甲基苯基、三氟基甲基苯基、羥基苯基、甲氧基苯基、甲氧基乙氧基苯基、烯丙基羥苯基、苯氧基苯基、甲硫基苯基、甲苯硫基苯基、乙基胺基苯基、二乙基胺基苯基、味啉基苯基、乙醯基羥苯基、苯甲醯基羥苯基、Ν-環己基胺甲醯基羥苯基、[苯基胺甲醯基羥苯基、 Ο 乙酸胺基苯基、Ν -甲基苯甲醯基胺基苯基、羧基苯基、甲氧基簾基苯基、烯丙氧基羰基苯基、氯基苯氧基羰基苯基、胺甲酿基苯基、Ν -甲基胺甲醯基苯基、Ν，Ν-二丙基胺甲醯基苯基、Ν-(甲氧基苯基}胺甲醯基苯基、Ν-甲基-Ν-(磺酸基苯基）胺甲醯基苯基、磺酸基苯基、磺酸根基苯基、胺磺醯基苯基、Ν -乙基胺磺醯基苯基、Ν，Ν -二丙基胺磺醯基苯基、Ν-甲苯基胺磺醯基苯基、ν-甲基-Ν-(膦酸基苯基）胺擴酿基苯基、膦酸基苯基、膦酸根基苯基、二乙基膦酸基苯基 '二苯基膦酸基苯基、甲基膦酸基苯基、甲基膦酸 -49- 200935174 根基苯基、甲苯基膦酸基苯基、甲苯基鱗酸根基苯基、烯丙基苯基、1-丙烯基甲基苯基、2 -丁烯基苯基、2 -甲基烯丙基苯基、2-甲基丙烯基苯基、2-丙炔基苯基、2-丁炔基苯基、3 -丁炔基苯基等。前述烯基、前述取代烯基、前述炔基、及前述取代炔基（-C(R〇2) = C(R03)(R04)、及-C 三 C(R〇5))，係可使用 R〇2' R〇3、RCM、ROS爲由一價非金屬原子所構成之基者。 R〇2、R〇3、R04、R0 5係以氫原子、鹵素原子、烷基、〇取代烷基、芳基、及取代芳基爲佳，此等之具體例係可舉例如做爲前述之例所表示者。此等之中，尤以氫原子、鹵素原子、碳原子數1〜10之直鏈狀、分枝狀 '環狀的烷基爲更佳。具體而言，可舉例如乙烯基、1-丙烯基、1-丁烯基、 1-戊烯基、1-己烯基、1-辛烯基、1-甲基-1-丙烯基、2-甲基-1-丙烯基、2-甲基-1-丁烯基、2-苯基-1-乙烯基、2-氯基-1-乙烯基、乙炔基、1-丙炔基、1-丁炔基、苯基乙炔 ©基等。雜環基係可舉例如做爲取代烷基之取代基所例示之吡啶基等。上述取代氧基（RG6〇-)係可使用RQ6爲去掉氫原子的一價非金屬原子所構成之基者。較佳的取代氧基係可舉例如烷氧基、芳氧基、醯氧基、胺甲醯氧基、N -烷基胺甲醯氧基、N-芳基胺甲醯氧基、N，N-二烷基胺甲醯氧基、N，N-二芳基胺甲醯氧基、N-烷基-N-芳基胺甲醯氧基、烷基磺醯氧基、芳基磺醯氧基、膦酸氧基、膦酸根氧基。此等之中的 -50- 200935174 烷基、以及芳基係可舉例如前述做爲烷基、取代烷基以及芳基、取代芳基所例示者。又，醯氧基中的醯基（R〇7C〇-) 係可舉例如R〇7爲先前的例子所列舉之烷基、取代烷基、芳基以及取代芳基者。此等取代基之中，以烷氧基、芳氧基、醯氧基、芳基磺醯氧基爲更佳。較佳取代氧基之具體例係可舉例如甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、戊氧基、己氧基、十一院氣基、节氧基、稀丙氧基、苯乙基氧基、羧基乙氧基、甲氧基羰基乙氧基、乙氧基羰基 ^ 乙氧基、甲氧基乙氧基、苯氧基乙氧基、甲氧基乙氧基乙氧基、乙氧基乙氧基乙氧基、味啉基乙氧基、味啉基丙氧基、嫌丙氧基乙氧基乙氧基' 苯氧基、甲苯氧基、二甲苯氧基、采氧基、釆氧基、異丙苯基氧基、甲氧基苯氧基、乙氧基苯氧基、氯基苯氧基、溴基苯氧基、乙醯氧基、苯甲醯氧基、萘氧基、苯基磺醯基氧基、膦酸氧基、膦酸根氧基等。醯胺基亦可含有之取代胺基（R08NH -、（RQSKROit^N-) Ο 係可使用由R〇8、R09、RG1G爲去掉氫原子的一價非金屬原子團所構成之基者》此外，9與以1()亦可鍵結以形成環。取代胺基之較佳之例可舉例如N-烷基胺基、N，N-二烷基胺基、N -芳基胺基、N，N -二芳基胺基、N-烷基-N-芳基胺基、醯胺基、N-烷基醯胺基、N-芳基醯胺基、脲基、Ν’-烷基脲基、Ν’，Ν’-二烷基脲基、Ν’-芳基脲基、Ν’，Ν’-二芳基脲基、Ν’-烷基- Ν’-芳基脲基、Ν-烷基脲基、Ν-芳基脲基' Ν’-烷基-Ν-烷基脲基、Ν’-烷基-Ν-芳基脲基、N’，N’-二烷基-N-烷基脲基、N’-烷基-N’-芳基脲基、N’，N’-二烷基-N-烷基脲 -51- 200935174 基、N，，N，-二烷基- N，-芳基脲基、N，-芳基-N-烷基脲基、N’-芳基-N-芳基脲基、N，，N，-二芳基-N-烷基脲基、N，，N’-二芳基-N-芳基脲基、N，-烷基-N，-芳基-N-烷基脲基、N’-院基 -Ν，-芳基-Ν-芳基脲基、烷氧基羰基胺基、芳氧基鑛基胺基、Ν-烷基-Ν-烷氧基羰基胺基、Ν-烷基-Ν-芳氧基羰基胺基、Ν-芳基-Ν-烷氧基羰基胺基、Ν-芳基-Ν-芳氧基羰基胺基。此等之中的烷基、芳基係可舉例如做爲前述的烷基' $ 代烷基、以及芳基、取代芳基所例示者，在醯胺基' 〇基醯胺基、Ν-芳基醯胺基中醯基（RQ7CO-)的R〇7係如前所述。此等之中，更佳者係可舉例如N-烷基胺基、N，N-二院基胺基、N-芳基胺基、醯胺基。較佳取代胺基之具體例係可舉例如甲基胺基、乙基胺基、二乙基胺基、味啉基、哌11定基、吡啶基、苯基胺基、苯甲醯基胺基、乙醯胺基等。取代磺醯基（R011-S〇2-)係可使用由R〇ii爲去掉一價非金屬原子團所構成之基者。更佳的例子係可舉例如烷基磺醯基、芳基磺醯基。此等之中的烷基、芳基係可舉例如〇在前述做爲烷基、取代烷基、以及芳基、取代芳基所例示者。像這樣的取代磺醯基之具體例係可舉例如丁基磺醯基、苯基磺醯基、氯基苯基磺醯基等。磺酸酯基（-so3-)係如前所述，意味者磺酸基（-so3h) 的共軛鹼陰離子基，通常係與對陽離子一同使用爲佳。像這樣的對陽離子係可舉例如一般習知者，亦即各種的鑰類（銨類、鎏類、鱗類、鎮類、吖啶鎗類等）、以及金屬離子類 (Na+、K+ ' Ca2+、Zn2 +等}。取代羰基（R〇i3-CO-)係可使用R〇13爲一價非金屬原子 -52- 200935174 所構成之基者。取代羰基之較佳之例可舉例如甲醯基、醯基、羧基、院氧基羰基、芳氧基羰基、胺甲醯基、N院基胺甲醯基、N，N-二烷基胺甲醯基、N-芳基胺甲醯基、N，N_ 二芳基胺甲醯基、N-烷基- Ν’-芳基胺甲醯基。此等之中的烷基、芳基係可舉例如前述做爲烷基、取代院基、以及芳基、取代芳基所例示者。此等之中，更佳的取代羯基係可舉例如甲醯基、醯基、羧基、烷氧基羰基、芳氧基羰基、胺甲醯基、Ν-烷基胺甲醯基、Ν，Ν-二烷基胺甲醯基、[芳 ©基胺甲醯基，尤佳者係可舉例如甲醯基 '醯基、院氧基羰基以及芳氧基羰基。較佳的取代羰基之具體例係可舉例如甲醯基、乙醯基、苯甲醯基、羧基、甲氧朞羰基、乙氧基羰基、烯丙基羥基羰基、二甲基胺基苯基乙烯基羰基、甲氧基羰基甲氧基羰基、Ν-甲基胺甲醯基、Ν-苯基胺甲醯基、Ν，Ν-二乙基胺甲醯基、味啉基羰基等。取代亞楓基（RQ14-SO-)係可使用RQM爲去掉一價非金屬原子團所構成之基者。較佳例子係可舉例如烷基亞碾基〇、芳基亞颯基、亞磺醯基、N-烷基亞磺醯基、N，N-二烷基亞磺醯基、N-芳基亞磺醯基、N，N-二芳基亞磺醯基、N-烷基-N-芳基亞磺醯基。此等之中的烷基、芳基係可舉例如前述做爲烷基、取代烷基、以及芳基、取代芳基所例示者。此等之中，更佳的例子係可舉例如烷基亞颯基、芳基亞颯基。像這樣的取代亞颯基之具體例係可舉例如己基亞碾基、苄基亞楓基、甲苯基亞颯基等。取代膦酸基係意味著在膦酸基上的一或二個經基被其他的有機側氧基所取代，較佳的例子係可舉例如前述的二 -53- 200935174 烷基鱗酸基、二芳基膦酸基、烷基芳基膦酸基、單烷基膦酸基、單芳基膦酸基。此等之中係以二烷基膦酸基、以及二芳基膦酸基爲更佳。像這樣的具體例係可舉例如二乙基膦酸基、二丁基膦酸基、二苯基膦酸基等。膦酸根基（-P〇3H2·、-P〇3H-)係如前所述，意味著來自膦酸基（-P〇3H2)的酸第一解離、或酸第二解離之共軛鹼陰離子基。通常係與對陽離子一同使用爲佳。像這樣的對陽離子係可舉例如一般習知者，亦即各種的鑰類（銨類、鎏類 © 、鐵類、銚類、吖啶鑰類等）、以及金屬離子類（Na+、K + 、Ca2+、Zn2 +等）。取代膦酸根基係在前述，的取代膦酸基之中，羥基被一個有機側氧基所取代者之共軛鹼陰離子基，具體例係可舉例如前述的單烷基膦酸基（_P〇3 H (alkyl))、單芳基膦酸基 (-P03H(aryl))的共軛鹼。前述肟衍生物係以下述通式（III)及通式（IV)中任一者所表示的化合物爲更佳。Ar - (c 〇 - C (Y') = NO - Y2) Formula (ll) However, in the above formulae (I) and (II), "Ar" means any of an aromatic group and a heterocyclic group. Y1 represents any one of a hydrogen atom and a monovalent substituent, and Y2 represents an aliphatic group, an aromatic group, a heterocyclic group, C〇Y3, CO2Y3, and CONY4Y5. γ3, γ4, and ... Any of an aliphatic group, an aromatic group, and a heterocyclic group. The m system represents an integer of 1 or more. The Y1 is preferably a hydrogen atom, an aliphatic group, or an aromatic group. Preferably, it is an aliphatic group, -CO-(aliphatic group), -CO-(aromatic group), -CO-(heterocyclic group), -C〇2-(aliphatic group), -C〇2 Any one of -(aryl-42-200935174 aromatic group) and -C〇2-(heterocyclic group). The above Y3 and Y4 are preferably any of an aliphatic group and an aromatic group. The derivative may be a compound composed of a complex bond of a linking group represented by the above formula (I) and formula (i 1). Further, in the above formula (I) and formula (II) , the aforementioned aliphatic group means each hospital which may also have a substituent And an alkenyl group or an alkynyl group, wherein the aromatic group has an aryl group or a heterocyclic (heterocyclic) group which may have a substituent, and the monovalent substituent is a halogen atom or an amine group which may have a substituent. , oxycarbonyl, hydroxy, ether, thiol, thioether 'decyl, nitro, cyano, each of which may also have a substituent alkyl, alkenyl, alkynyl, aryl, heterocyclic In the above-mentioned aromatic group, for example, one to three benzene rings form a condensed ring, and a benzene ring forms a condensed ring with a 5-membered unsaturated ring. Specific examples thereof include a phenyl group, a naphthyl group, and a fluorenyl group. , phenanthryl, fluorenyl, indanyl, fluorenyl, especially preferably having a phenyl group and a naphthyl group, and a naphthyl group is particularly preferred. The base system may have a substituent, and examples of the substituent include, for example, a group in which a hydrogen atom is a monovalent non-metal atom group, and an alkyl group, a substituted alkyl group or a substituted alkyl group to be described later is used. The substituent represented by the substituent, etc. Further, the heterocyclic (heterocyclic) group may, for example, be a pyrrole ring group or a furan ring. , thiophene ring group, benzopyrrole group, benzofuran ring group, benzothiophene ring group, pyrazole ring group, isoxazole ring group, isothiazole ring group, anthracene ring group, benzoisoindole ring a cyclic group, a benzisothiazole ring group, an imidazole ring group, a carbazole ring group, a thiazole ring group, a benzimidazole ring group, a benzoxazole ring group, a benzothiazole ring-43-200935174 group, a pyridine ring group, Quinoline ring group, isoquinoline ring group, oxime-trap ring group, pyrimidine ring group, indole ring group, anthracene ring group, quinazoline ring group, quinoxaline ring group, anthracycline ring group, Phenanthrylcycloyl 'carbazole ring group, anthracene ring group, sigmocycline group, pyridine ring group, piperidinyl group, porphyrin ring group, anthracene ring group, hydrazine ring group, chromene ring group, fluorene a porphyrinyl group, an acridine ring group, a phenothiaquinone ring group, a tetrazole ring group, a ditrapped ring group, etc., among which a furan ring group, a thiophene ring group, a fluorenyl ring group, a thiazole ring group, a benzothiazole ring The base, the pyridine ring group, the oxime ring group, and the acridine ring group are particularly preferred. Further, the heterocyclic group may have a substituent, and the substituents may be, for example, a group composed of a monovalent non-metal atom group from which a hydrogen atom is removed. For example, the following can be used as a substitute for a hospital base, a substitute base, or a substitute base. The monovalent substituent is a halogen atom, an amine group which may have a substituent, an alkoxy mineral group, a hydroxyl group, an ether group, a thiol group, a thioether group, a decyl group, a nitro group, a cyano group, and each An alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group which may have a substituent is preferred. Further, the above-mentioned monovalent substituent composed of a non-metal atom is preferably a group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group which may have a substituent. The alkyl group which may have a substituent may, for example, be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and specific examples thereof include methyl group, ethyl group and ethyl group. Base, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosane Base, isopropyl, isobutyl, t-butyl, tert-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, Cyclohexyl, cyclopentyl, 2-norbornyl. In the above-mentioned -44-200935174, etc., a linear chain having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable. The substituent of the alkyl group which may have a substituent may, for example, be a substituent composed of a monovalent non-metal atom from which a hydrogen atom is removed. Preferred examples thereof include a halogen atom (-F, -Br, -C1). ,-1), hydroxy, alkoxy, aryloxy, thiol, alkylthio, arylthio, alkyldithio, aryldithio, amine, N-alkylamine, N , N-dialkylamino, N-arylamino, N,N-diarylamino, N-alkyl-N-arylamine, decyloxy, aminecarboxamide oxy, N -alkylamine methyl methoxy, N-arylamine methyl methoxy, N,N-dialkylamine methyl methoxy, N,N: diarylamine methyl methoxy, N-alkyl- N-arylamine methyl methoxy, alkyl sulfonyloxy, aryl sulfonyloxy, sulfonylthio, decylamino, N-alkyl decylamino, N-aryl decylamino, ureido ,Ν'-alkylureido, Ν', Ν'-dialkylureido, Ν'-arylureido, Ν', Ν'-diarylureido, Ν'-alkyl-Ν'- Arylureido, fluorene-alkylureido, fluorene-arylureido, Ν'-alkyl-hydrazine-alkylureido, Ν'-alkyl-oxime-arylureido, Ν', Ν' -dialkyl-anthracene-alkane Urea, Ν', Ν'-dialkyl-fluorene-arylureido, Ν'-aryl-hydrazine-alkylureido, Ν ΐ-Ο aryl-Ν-arylureido, Ν', Ν'-Diaryl-hydrazine-alkylureido, Ν', Ν'-diarylarylureido, Ν'-alkyl-Ν'-aryl-Ν-alkylureido, Ν'- Alkyl-Ν'-aryl-fluorene-arylureido, alkoxycarbonylamino, aryloxycarbonylamino, fluorenyl-alkyl-hydrazine-alkoxycarbonylamino, fluorenyl-alkyl-hydrazine -aryloxycarbonylamino, fluorenyl-aryl-hydrazine-alkoxycarbonylamino, fluorenyl-aryl-fluorenyl-aryloxycarbonylamino, decyl, fluorenyl, carboxy, alkoxycarbonyl, Aryloxycarbonyl, amine mercapto, fluorenyl-alkylamine, mercapto, anthracene, quinone-dialkylamine, mercapto, fluorene-arylamine, mercapto, fluorene-diarylamine , Ν-alkyl-fluorene-arylamine, fluorenyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, -45- 200935174 sulfonate (-S 〇3H) and its conjugate base (referred to as sulfonate group}, alkoxysulfonyl, aryloxysulfonyl, sulfinyl, N-alkylsulfinyl, N, N-di Alkylsulfinyl, N-arylsulfinyl, , fluorene-diarylsulfinyl, N-alkyl-fluorene-arylsulfinyl, amine sulfonyl, hydrazine-alkylamine sulfonyl, ν, Ν-dialkylamine sulfonyl , Ν-arylamine sulfonyl, anthracene, fluorene-diarylamine sulfonyl, fluorenyl-alkyl-arylenesulfonyl, phosphonic acid (-Ρ〇3η2) and its conjugate base (referred to as phosphonate group), dialkylphosphonic acid group (-P〇3 (alkyl) 2) "alkyl = alkyl, the same below", one cyanoic acid group (_P〇3 (aryl) 2) "aryl = aryl hydrazine, the same as the following", alkyl arylphosphonic acid group (-?? 3 (& 11^1) (& 71)), monoalkylphosphonic acid group (-P〇3 (alkyl)) And its conjugate base (referred to as alkylphosphonate), monoarylphosphonate (-P〇3H (aryl)) and its conjugate base (referred to as arylphosphonic acid furnace base), phosphonic acid oxy group (-OPO3H2) and its conjugate base (referred to as phosphonateoxy), dialkylphosphonic acidoxy (-OP03H(alkyl) 2), diarylphosphonic acidoxy (-OP〇3 (aryl) 2 ), alkyl aryl phosphonic acid oxy oxi, OP 〇 3 (alky1) (aryiH, monoalkylphosphonic acid oxy (- ΟΡΟ 3 H (alky 1)) and its conjugate base (referred to as alkylphosphonate oxygen) , a monoarylphosphonic acidoxy group (-〇P〇3H(ar) Yll)) and its conjugate base 〇 (referred to as arylphosphonate oxy), cyano, nitro, aryl, alkenyl, alkynyl, heterocyclic, decyl and the like. Specific examples of the alkyl group in the substituents include, for example, the above-mentioned alkyl group, and specific examples of the aryl group in the above substituent include, for example, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. , vegetable base, cumyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethyl basic, present oxyphenyl, ethoxylated Phenylphenyl, benzhydryloxyphenyl, methylthiophenyl, phenylthiophenyl, methylaminophenyl, dimethylaminophenyl, ethylaminophenyl, carboxyphenyl, Methoxycarbonylphenyl, ethoxy-46- 200935174 phenyl phenyl phenyloxycarbonylphenyl, N-phenylamine methyl phenyl, cyanophenyl, phenyl sulfonate Base phenyl, phosphonic phenyl, phosphonate phenyl, and the like. Further, examples of the alkenyl group in the above substituent include, for example, a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group, a 2-chloro-1-vinyl group, and the like, and examples of the alkynyl group in the above substituent. For example, an ethynyl group, a 1-propynyl '1-butynyl group, a trimethyl decyl ethynyl group, etc. are mentioned. The heterocyclic group in the above substituent may, for example, be a pyridyl group, a piperidinyl group, or a ruthenium group. The fluorenyl alkyl group in the above substituent may, for example, be a trimethyl decyl group. The above substituent may further contain a mercapto group (RQ1CO-), and examples of the mercapto group include, for example, a hydrogen atom, the above alkyl group, and an aryl group. The RQ1 of the mercapto group (RQ1CO-) may, for example, be a hydrogen atom or the above alkyl group or aryl group. Among these substituents, more preferred are, for example, a halogen atom (-F, -Br, -C1, -1), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and N- Alkylamino, N,N-dialkylamino, decyloxy, N-alkylamine, methyloxy, N-arylamine, methoxy, decyl, decyl, fluorenyl , carboxy, alkoxycarbonyl, aryloxycarbonyl, aminecarbamyl, N-alkylamine, mercapto, anthracene, fluorenyl-dialkylamine, fluorenyl, N-arylamine, fluorenyl, N- Alkyl-N-arylaminecarbamyl, sulfonate, sulfonate, sulfonyl, fluorenyl-alkylamine sulfonyl, fluorene, fluorene-dialkylamine sulfonyl, fluorene-aryl Amidoxime, fluorenyl-alkyl-arylenesulfonyl, phosphonic acid, phosphonate, dialkylphosphonic acid, diarylphosphonic acid, monoalkylphosphonic acid, alkane A phosphinyl group, a monoarylphosphonic acid group, an arylphosphonate group, a phosphonic acidoxy group, a phosphonateoxy group, an aryl group, an alkenyl group. On the other hand, the alkylene group in the substituted alkyl group may, for example, be a hydrogen atom on the alkyl group having 1 to 20 carbon atoms of -47 to 200935174, and may be a divalent organic residue. For example, a linear form having 1 to 12 carbon atoms, a branched form having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 1 ring carbon atoms may be mentioned. Preferred specific examples of the substituted alkyl group obtained by combining these substituents with an alkylene group include, for example, a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, and a methoxy group. Methyl, isopropoxymethyl, butoxymethyl, t-butoxybutyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthio Methyl, tolylthiomethyl, pyridylmethyl, tetramethylpiperidinylmethyl, N-ethinyltetramethylpiperidinemethyl, trimethyldecylmethyl, methoxyethyl, B Aminoethyl, diethylaminopropyl, morpholinylpropyl, ethoxymethyloxy, benzhydryloxymethyl, N-cyclohexylaminemethyl hydroxyethyl, N-benzene Methylaminomethylhydroxyethyl, acetaminoethyl, N-methylbenzimidylpropyl, 2-oxyethyl, 2-oxypropyl, carboxypropyl, methoxy Carbonylethyl, allyloxycarbonylbutyl, chlorophenoxycarbonylmethyl, aminecarboxymethyl, N-methylamine, decylethyl, N,N-dipropylamine Methyl, N-(methoxyphenyl)amine, mercaptoethyl, N-methyl-N- (anthracenesulfonic acid) Phenyl)amine,mercaptomethyl, sulfobutyl, sulfonylbutyl, sulfonylbutyl, N-ethylaminesulfonylmethyl, N,N-dipropylamine sulfonyl Propyl, N-tolylaminesulfonylpropyl, N-methyl-N-(phosphonophenyl)aminesulfonyloctyl, phosphonic butyl, ortho-hexyl, diethylphosphine Butyl butyl, diphenylphosphonyl propyl, methylphosphonic butyl, methylphosphonic butyl, tolylphosphonic hexyl, tolylphosphonate hexyl, phosphonic acid oxypropyl , phosphonateoxybutyl, benzyl, phenethyl, α-methylbenzyl, 1-methyl-1-phenylethyl, ρ-methylbenzyl, cinnamyl, allyl, 1- Propenylmethyl, 2-butenyl, 2-methylallyl, 2-methylpropenyl-48- 200935174 methyl, 2-propynyl, 2-butynyl, 3-butynyl, etc. . The aryl group may be, for example, one to three benzene rings forming a condensed ring, and a benzene ring and a five-membered unsaturated ring forming a condensed ring. Specific examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthryl group. Further, a phenyl group or a naphthyl group is more preferred among the fluorenyl group, the indanyl group and the fluorenyl group. The above substituted aryl group may be one which is a substituent composed of a monovalent non-metal atom group from which a hydrogen atom is removed, on the ring-forming carbon atom of the above aryl group. Examples of preferred substituents include, for example, those described above for the alkyl group, the substituted alkane group, and the previously substituted alkyl group. Preferred specific examples of the pre-substituted aryl group include, for example, a biphenyl group, a tolyl group, a dimethylphenyl group, a lysyl group, a cumyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group, and a chlorine group. Methylphenyl, trifluoromethylphenyl, hydroxyphenyl, methoxyphenyl, methoxyethoxyphenyl, allylhydroxyphenyl, phenoxyphenyl, methylthiobenzene Base, tolylthiophenyl, ethylaminophenyl, diethylaminophenyl, morpholinylphenyl, ethoxylated hydroxyphenyl, benzhydrylhydroxyphenyl, anthracene-cyclohexylamine Nonylhydroxyphenyl, [phenylamine-mercaptohydroxyphenyl, guanylacetic acid aminophenyl, fluorenyl-methylbenzhydrylaminophenyl, carboxyphenyl, methoxyphenylphenyl, ene Propyloxycarbonylphenyl, chlorophenoxycarbonylphenyl, amine methyl phenyl, hydrazine-methylamine methyl phenyl, hydrazine, hydrazine-dipropylamine methyl phenyl, hydrazine (methoxyphenyl}amine-methyl-nonylphenyl, fluorenyl-methyl-hydrazine-(sulfonylphenyl)amine-formylphenyl, sulfonylphenyl, sulfonylphenyl, aminesulfonate Phenyl, oxime-ethylamine sulfonylphenyl, hydrazine, hydrazine-dipropylamine sulfonylphenyl, Ν-Tolylamine sulfonylphenyl, ν-methyl-hydrazine-(phosphonophenyl)amine, phenyl, phosphophenyl phenyl, phosphonate phenyl, diethylphosphonic acid Phenyl 'diphenylphosphonylphenyl, methylphosphonic phenyl, methylphosphonic acid-49- 200935174 base phenyl, tolylphosphonic phenyl, tolyl phenyl phenyl, allyl Phenylphenyl, 1-propenylmethylphenyl, 2-butenylphenyl, 2-methylallylphenyl, 2-methylpropenylphenyl, 2-propynylphenyl, 2- a butynylphenyl group, a 3-butynylphenyl group, etc. The above alkenyl group, the aforementioned substituted alkenyl group, the aforementioned alkynyl group, and the aforementioned substituted alkynyl group (-C(R〇2) = C(R03)(R04), And -C C (R〇5)), R〇2' R〇3, RCM, and ROS can be used as a base composed of monovalent non-metal atoms. R〇2, R〇3, R04, R0 5 is preferably a hydrogen atom, a halogen atom, an alkyl group, an anthracene-substituted alkyl group, an aryl group, or a substituted aryl group, and specific examples thereof include those shown in the above examples. In particular, a hydrogen atom, a halogen atom, a linear one having a carbon number of 1 to 10, and a branched 'cyclic alkyl group are Specifically, for example, a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1-pentenyl group, a 1-hexenyl group, a 1-octenyl group, and a 1-methyl-1-propenyl group are mentioned. , 2-methyl-1-propenyl, 2-methyl-1-butenyl, 2-phenyl-1-vinyl, 2-chloro-1-vinyl, ethynyl, 1-propynyl And a 1-butynyl group, a phenyl acetylene group, etc. The heterocyclic group may, for example, be a pyridyl group exemplified as a substituent of a substituted alkyl group. The above substituted oxy group (RG6〇-) may be RQ6. A base composed of a monovalent non-metal atom of a hydrogen atom is removed. Preferred substituted oxygen groups include, for example, an alkoxy group, an aryloxy group, a decyloxy group, an amine methyloxy group, and an N-alkylamine formazan. Oxy, N-arylamine methyloxy, N,N-dialkylamine methyloxy, N,N-diarylaminemethyloxy, N-alkyl-N-arylamine Alkoxy, alkylsulfonyloxy, arylsulfonyloxy, phosphonic acidoxy, phosphonateoxy. The -50-200935174 alkyl group and the aryl group among these may, for example, be exemplified as the alkyl group, the substituted alkyl group, and the aryl group or the substituted aryl group. Further, the fluorenyl group (R〇7C〇-) in the decyloxy group may, for example, be an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group as exemplified in the above examples. Among these substituents, an alkoxy group, an aryloxy group, a decyloxy group or an arylsulfonyloxy group is more preferred. Specific examples of the preferred substituted oxy group include, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an eleventh gas group, and an oxy group. , diloxyoxy, phenethyloxy, carboxyethoxy, methoxycarbonylethoxy, ethoxycarbonyl^ethoxy, methoxyethoxy, phenoxyethoxy, methoxy Ethoxyethoxy, ethoxyethoxyethoxy, morpholinylethoxy, morpholinylpropoxy, propyloxyethoxyethoxy 'phenoxy, tolyloxy ,xyloxy,oxy,decyloxy, cumyloxy, methoxyphenoxy, ethoxyphenoxy, chlorophenoxy, bromophenoxy, ethoxylated Base, benzamidineoxy, naphthyloxy, phenylsulfonyloxy, phosphonic acidoxy, phosphonateoxy, and the like. Further, the substituted amine group (R08NH-, (RQSKROit^N-)) may be a base composed of a monovalent non-metal atom group in which R〇8, R09, and RG1G are a hydrogen atom removed. 9 and 1() may also be bonded to form a ring. Preferred examples of the substituted amine group include, for example, an N-alkylamino group, an N,N-dialkylamino group, an N-arylamino group, and N. N-diarylamino, N-alkyl-N-arylamine, decylamino, N-alkylnonylamino, N-aryldecylamine, ureido, Ν'-alkylureido ,Ν',Ν'-dialkylureido, Ν'-arylureido, Ν', Ν'-diarylureido, Ν'-alkyl-Ν'-arylureido, Ν-alkane Urea-urea, Ν-arylureido- Ν'-alkyl-oxime-alkylureido, Ν'-alkyl-oxime-arylureido, N',N'-dialkyl-N-alkane Urea group, N'-alkyl-N'-arylureido group, N',N'-dialkyl-N-alkylurea-51- 200935174 base, N, N,-dialkyl-N ,-arylureido, N,-aryl-N-alkylureido, N'-aryl-N-arylureido, N,,N,-diaryl-N-alkylureido, N,,N'-diaryl-N-arylureido, N,-alkyl-N,-aryl-N- Urea group, N'-homo-anthracene, -aryl-fluorene-arylureido group, alkoxycarbonylamino group, aryloxy ore group, fluorenyl-alkyl-hydrazine-alkoxycarbonylamine Base, fluorenyl-alkyl-fluorene-aryloxycarbonylamino group, fluorenyl-aryl-fluorenyl-alkoxycarbonylamino group, fluorenyl-aryl-fluorene-aryloxycarbonylamino group. The base group and the aryl group may, for example, be exemplified as the above alkyl 'alkyl group, and an aryl group or a substituted aryl group, and may be exemplified in the fluorenyl 'mercapto fluorenylamino group and the fluorene-aryl decylamino group. The R〇7 group of the mercapto group (RQ7CO-) is as described above. Among them, more preferred are, for example, an N-alkylamino group, an N,N-di-systemylamino group, and an N-arylamine. Specific examples of the preferred substituted amine group include, for example, a methylamino group, an ethylamino group, a diethylamino group, a morpholinyl group, a piperidinyl group, a pyridyl group, a phenylamino group, Benzylamino group, etidinyl group, etc. The substituted sulfonyl group (R011-S〇2-) can be used as a base composed of R〇ii as a monovalent non-metal atom group removed. More preferred examples are For example, an alkylsulfonyl group or an arylsulfonyl group may, for example, be an alkyl group or an aryl group. The above is exemplified as an alkyl group, a substituted alkyl group, and an aryl group or a substituted aryl group. Specific examples of the substituted sulfonyl group such as butyl sulfonyl group, phenyl sulfonyl group, and chlorobenzene are mentioned. Sulfosyl group, etc. The sulfonate group (-so3-) is as defined above, meaning that the conjugated base anion group of the sulfonic acid group (-so3h) is usually used together with the cation. Examples of the cation system include those conventionally known, that is, various kinds of keys (ammonium, anthraquinone, scaly, town, acridine gun, etc.), and metal ions (Na+, K+'Ca2+, Zn2+). Wait}. The substituted carbonyl group (R〇i3-CO-) can be used as a base composed of a monovalent non-metal atom -52-200935174. Preferred examples of the substituted carbonyl group include, for example, a fluorenyl group, a fluorenyl group, a carboxyl group, an oxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group, a N-based amine mercapto group, and an N,N-dialkylamine group. Indenyl, N-arylamine, mercapto, N,N-diarylamine, N-alkyl-Ν'-arylamine, mercapto. The alkyl group and the aryl group among these may, for example, be exemplified as the alkyl group, the substituted group, and the aryl or substituted aryl group. Among these, a more preferred substituted fluorenyl group may, for example, be a fluorenyl group, a fluorenyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group, a fluorenyl-alkylamine carbaryl group, an anthracene group, The fluorene-dialkylamine-methyl fluorenyl group and the aryl group are, for example, a fluorenyl group, a methoxycarbonyl group and an aryloxycarbonyl group. Specific examples of the preferred substituted carbonyl group include, for example, a decyl group, an ethyl fluorenyl group, a benzamyl group, a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an allylhydroxycarbonyl group, and a dimethylaminophenyl group. A vinylcarbonyl group, a methoxycarbonylmethoxycarbonyl group, a fluorene-methylamine-methyl fluorenyl group, a fluorenyl-phenylamine-methyl fluorenyl group, an anthracene, a fluorene-diethylamine methyl fluorenyl group, a morpholinylcarbonyl group, and the like. The substituted yttrium group (RQ14-SO-) system can use RQM as a base for removing a monovalent non-metal atomic group. Preferred examples include, for example, an alkyl sulfinium group, an aryl fluorenylene group, a sulfinyl group, an N-alkyl sulfinylene group, an N,N-dialkyl sulfinylene group, and an N-aryl group. Sulfosyl, N,N-diarylsulfinyl, N-alkyl-N-arylsulfinyl. The alkyl group and the aryl group among these may, for example, be exemplified as the alkyl group, the substituted alkyl group, and the aryl group or the substituted aryl group. Among these, a more preferable example is an alkyl fluorenylene group or an aryl fluorenylene group. Specific examples of the substituted anthracene group like this may, for example, be a hexyl sulfinyl group, a benzyl sulfinyl group or a tolylylene group. The substituted phosphonic acid group means that one or two mercapto groups on the phosphonic acid group are substituted by other organic side oxy groups, and preferred examples thereof include the above-mentioned bis-53-200935174 alkyl squarylate group, Diarylphosphonic acid group, alkylarylphosphonic acid group, monoalkylphosphonic acid group, monoarylphosphonic acid group. Among these, a dialkylphosphonic acid group and a diarylphosphonic acid group are more preferred. Specific examples thereof include a diethylphosphonic acid group, a dibutylphosphonic acid group, and a diphenylphosphonic acid group. The phosphonate group (-P〇3H2·, -P〇3H-) is as described above, meaning that the acid is first dissociated from the phosphonic acid group (-P〇3H2), or the second base dissociated conjugate base anion base. It is usually preferred to use it together with a cation. Examples of the cation-based system include a variety of key types (ammonium, anthraquinone, iron, anthraquinone, acridinium, etc.) and metal ions (Na+, K + ). , Ca2+, Zn2+, etc.). The substituted phosphonic acid group is a conjugated base anion group in which the hydroxyl group is substituted by an organic side oxy group among the above-mentioned substituted phosphonic acid groups, and specific examples thereof include the aforementioned monoalkylphosphonic acid group (_P〇). 3 H (alkyl), a conjugate base of a monoarylphosphonic acid group (-P03H (aryl)). The above anthracene derivative is more preferably a compound represented by any one of the following formula (III) and formula (IV).

❹❹

通式（iv> 但是，前述通式（III)及通式（IV)中’ 係表示與通式 ⑴及通式（II)中的γι爲相同之意’ Y12係與通式⑴及通式 (II)中的Υ2爲相同之意。 -54- 200935174 前述R1〇1係以氫原子及脂肪族基中任一者爲較佳’特別是碳原子數1〜之脂肪族基爲佳。前述脂肪族基係可舉例如甲基、乙基、丙基、辛基、烯丙基等。前述Y12係以-CO-(脂肪族基）爲特佳。前述Y12中的脂肪族基係以碳原子數1〜10之脂肪族基爲佳。具體而言，例如甲基、乙基、丙基、丁基、辛基、環己基、苄基等爲佳。 ® 前述肟衍生物的其他具體之例係可舉例如特開 2001- 233842號公報 '特表2004-534797號公報、及特表 2002- 5197,3 2號公報等中所揭示之化合物、以及下述構造式所表示之化合物等。〇 -55- 200935174However, in the above formula (III) and formula (IV), 'the meaning is the same as γι in the formula (1) and the formula (II), and the formula Y1 and the formula (1) and the formula Υ2 in (II) is the same. -54- 200935174 The above R1〇1 is preferably one of a hydrogen atom and an aliphatic group, particularly an aliphatic group having 1 to 1 carbon atom. Examples of the aliphatic group include a methyl group, an ethyl group, a propyl group, an octyl group, an allyl group, etc. The Y12 system is particularly preferably -CO-(aliphatic group). The aliphatic group in the above Y12 is carbon. The aliphatic group having 1 to 10 atomic atoms is preferred. Specifically, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a cyclohexyl group, a benzyl group or the like is preferred. For example, a compound disclosed in JP-A-2004-534797, JP-A-2004-534797, and JP-A-2002-5197-1, and the like, and a compound represented by the following structural formula may be mentioned. 〇-55- 200935174

Ο n-o-c-ch3Ο n-o-c-ch3

ηη

y 上述構造式中，R係表示n-C3H7、n-C8H17、莰烷、及 P-CH3C6H4 中任一者。 -56- 200935174y In the above structural formula, R represents any of n-C3H7, n-C8H17, decane, and P-CH3C6H4. -56- 200935174

上述構造式中，R係表示n-C3H7、及p-CH3C6H4中任一者。In the above structural formula, R represents any one of n-C3H7 and p-CH3C6H4.

coch3 I 0Coch3 I 0

\N\N

3 -57- 2009351743 -57- 200935174

-58 200935174-58 200935174

CH3"Y^N 〇 COC2H5 CH3^^N_0-C0C3H7 cH3Nv^N-〇-C〇2CH3 1 ΟΗ3\^Ν-〇-〇〇2〇2Η5 ^ p II 〇CH3 0CH3 och3 心 3 O och3CH3"Y^N 〇 COC2H5 CH3^^N_0-C0C3H7 cH3Nv^N-〇-C〇2CH3 1 ΟΗ3\^Ν-〇-〇〇2〇2Η5 ^ p II 〇CH3 0CH3 och3 heart 3 O och3

CH3x^N-0-C0N(C2H5)2 och3 前述肟衍生物亦可適當地使用下述通式（5)所表示之肟衍生物。 -59- 200935174 Ν，0-γ2 (Y5)m—Ar^A ^ 通式00 但是’前述通式（V)中，γ2、ΑΓ係表示與通式⑴及（ΙΙ) 中的有相同在 R ΙΒ 1」< 意。m表示〇以上的整數。Υ5表示取代基，m 爲2以上的情形中，該Ys係可相同、亦可不同。a表示4、5 ' 6及7貝環中任—者，此等之環係可含有各雜原子。 mi述通式（V)所表示之肟衍生物的其中，尤以下述通式 (vi)所表示之化合物爲較佳，以下述通式（νπ)及（νιπ)中任一者所示之化合物爲特佳。，Ν，0—γ2 (Υ5)“Φ 通式 ΟCH3x^N-0-C0N(C2H5)2 och3 The above anthracene derivative may suitably be an anthracene derivative represented by the following formula (5). -59- 200935174 Ν,0-γ2 (Y5)m—Ar^A ^ Formula 00 However, in the above formula (V), γ2 and lanthanide are the same as those in the formulae (1) and (ΙΙ) in R. ΙΒ 1”< meaning. m represents an integer above 〇. In the case where Υ5 represents a substituent and m is 2 or more, the Ys may be the same or different. a represents 4, 5 '6 and 7 shell rings, and these ring systems may contain each hetero atom. In the above, the anthracene derivative represented by the formula (V) is preferably a compound represented by the following formula (vi), and is represented by any one of the following formulae (νπ) and (νιπ). The compound is particularly good. ,Ν,0—γ2 (Υ5) “Φ General formula Ο

但是，前述通式（VI)中’ Υ2、Υ5、m、及心係表示與通式（V)中的有相同之意。X係表示〇、及S中的任—者。A 係表示5及6員環中任一者。However, in the above formula (VI), 'Υ2, Υ5, m, and a cardioid system have the same meanings as in the formula (V). The X system indicates 〇 and any of S. Line A indicates any of the 5 and 6 member rings.

通式（VII》通式<νιιι> 但是，前述通式（VII)及通式（VIII)中，Y6係表示亦可 -60- 200935174 具有取代基之烷基。i表示〇~6中的任、整數。口表示烷基、烷氧基、芳氧基、齒素原子、磺醯基、及醯氧基中的任 -者’ ！爲2以上之情形，該可相同、亦可不同。χχΑ 係表示與通式（VI)者有相同之意。前述通式（V)及（VI)中，取代基係沒有特別地限制’可舉例如烷基、烷氧基、芳氧基、_素原子、擴醯基、醯氧基、硝基、醯胺基等。此等之中，尤以烷基、院氧基、方氧基、鹵素原子、磺醯基、及酿氧基中的任一 ®者爲佳。此處’前述通式（V)所表示之肟衍生物的具體例係可舉例如下述構造，式（1) ~ (5 4 )所表示之化合物，惟在本發明係並不受限於此等。In the above formula (VII) and formula (VIII), Y6 represents an alkyl group which may have a substituent at -60 to 200935174. i represents a group of 〇~6. Any one of the alkyl group, the alkoxy group, the aryloxy group, the dentate atom, the sulfonyl group, and the decyloxy group is not more than 2, and may be the same or different. The oxime is the same as the formula (VI). In the above formulae (V) and (VI), the substituent is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an aryloxy group, and _. a single atom, a fluorenyl group, a decyloxy group, a nitro group, a decylamino group, etc. Among these, especially an alkyl group, an alkoxy group, a aryloxy group, a halogen atom, a sulfonyl group, and a methoxy group The specific example of the anthracene derivative represented by the above formula (V) is, for example, a compound represented by the following formulas (1) to (5 4 ), but in the present invention. The system is not limited to this.

-61- 200935174 〇<^^Ph oypn：D〇0 ..οό ^° cy<-61- 200935174 〇<^^Ph oypn:D〇0 ..οό ^° cy<

構造式（1) 構造式（2) 構造式（3) 構造式（4) 構造式（5) 構造式（6)Structural formula (1) Structural formula (2) Structural formula (3) Structural formula (4) Structural formula (5) Structural formula (6)

構造式（12)Structural formula (12)

構造式（7) 構造式（8) 構造式（9) 檐造式（10) 構造式⑴） ^Ac n-OAc i Μβα〇ά ( n』Ac N-OAC 〇ώ OMe N，〇AC ,構造式（13)構造式〇4) < 構造式（15) 檐造式（16) 構造式（17) .OAcStructural formula (7) Structural formula (8) Structural formula (9) Formula (10) Structural formula (1)) ^Ac n-OAc i Μβα〇ά ( n』Ac N-OAC 〇ώ OMe N, 〇AC, structure Equation (13) Structural formula ) 4) < Structural formula (15) Modification formula (16) Structural formula (17) .OAc

OMe 檐造式OS)OMe Creative OS)

OMe 構造式（19) N，OAcOMe Construction (19) N, OAc

構造式（22) 檐造式（20) 構造式（21)Structural formula (22) Modular (20) Structural formula (21)

構造式(23) 構造式（24) 構造式(25)Structural formula (23) Structural formula (24) Structural formula (25)

• OAc• OAc

OAcOAc

檐造式(26) 構造式（27) 構造式（28)Manufacturing (26) Structural formula (27) Structural formula (28)

-62- 200935174-62- 200935174

構造式(29) 構造式（30) 構造式(31)Structural formula (29) Structural formula (30) Structural formula (31)

檐造式(40) 構造式（41)Manufacturing (40) Construction (41)

構造式(45) 構造式(46)Structural formula (45) Structural formula (46)

檐造式（32) 構造式（33) OAcManufacturing (32) Structural Formula (33) OAc

構造式（34)Structural formula (34)

檐造式（37〉構造式(38) 構造式(39)Fabrication (37> Structural Formula (38) Structural Formula (39)

構造式（42) 檐造式(43) 構造式(44)Structural formula (42) Modular (43) Structural formula (44)

OMeOMe

構造式(52) 樽造式¢3) 構造式(54) 但是，前述構造式（1)~(54)中，Me表示甲基。Ph表示苯基。Ac表示乙醯基。前述肟衍生物的含量係例如以固體成分換算爲〇 0.1~15質量％爲佳、0.5~10質量％爲較佳、1.0〜8.0質量％爲特佳。比0.1質量％少之情形中感度降低，難以得到充分硬度的硬化膜，比1 5質量％多之情形中，不僅薄膜化時的黏性惡化，而且由於Tg降低而使得硬化膜變脆。 -其他的光聚合起始劑- 前述其他的光聚合起始劑係在具有起始前述聚合性化合物聚合之能力的範圍內即可，沒有特別地限制，可從眾所周知的光聚合起始劑之中做適當地選擇，例如，對於紫外線領域至可見光線有感光性者爲佳，亦可爲與光激發之 -63- 200935174 增感劑產生某些作用而生成活性自由基之活性劑，亦可爲根據單體的種類可起始陽離子聚合之起始劑。又，前述光聚合起始劑係含有至少1種在波長約 300nm~800nm的範圍内具有至少約50的分子吸光係數之成分爲佳。前述波長係330nm~500nm爲更佳。前述其他的光聚合起始劑係可舉例如鹵化烴衍生物（例如，具有三畊骨架者、具有噚二唑骨架者等）、六芳基聯二咪唑、有機過氧化物、硫化合物、酮化合物、吖啶化合〇物、金屬茂類等。具體而言，可舉例如特開2005-25843 1 號公報中所記載之化合物等。此等之中，從感光層的感度、保存性、及感光層與基板之黏附性等的觀點，以酮化合物及吖啶化合物爲佳。前述其他的光聚合起始劑係可單獨1 種使用、亦可倂用2種以上》前述光聚合起始劑在前述感光性組成物中的固體成分含量係以0 · 1質量％ ~ 3 0質量％爲佳、0.5質量％ ~ 2 0質量％爲較佳、0.5質量％ ~ 1 5質量。/。爲特佳。〇 <其他的成分> 前述其他的成分係可舉例如熱交聯劑、黏附促進劑、增感劑、熱聚合抑制劑、可塑劑、著色劑（著色顔料或染料 )、等’另外亦可倂用其他的助劑類（例如，導電性粒子、塡充劑、消泡劑、難燃劑、流平劑、剝離促進劑、抗氧化劑、香料、表面張力調整劑、鏈移動劑等）》藉由適當含有此等’可調整作爲目的之感光性薄膜的安定性、照相性、膜物性等的性質。 -熱交聯劑- -64- 200935174 前述熱交聯劑係沒有特別地限制，可視其目的做適當地選擇，爲了改良使用前述感光性薄膜所形成之感光層於硬化後的膜強度，在不對顯像性等造成不良影響之範圍內，可使用例如於1分子内具有至少2個環氧乙烷基之環氧化合物、於1分子内具有至少2個氧雜環丁烷基之氧雜環丁烷化合物，可舉例如特開2 0 0 7 - 4 7 7 2 9號公報中所記載的具有環氧乙烷基之環氧化合物、於Θ位具有烷基之環氧化合物、具有氧雜環丁烷基之氧雜環丁烷化合物、聚異氰酸酯化〇合物、聚異氰酸酯及其衍生物的異氰酸酯基與嵌段劑反應所得之化合物等。又，前述熱交聯劑係可使用三聚氰胺衍生。該三聚氰胺衍生物係可舉例如羥甲基三聚氰胺、烷基化羥甲基三聚氰胺（羥甲基經甲基、乙基、丁基等醚化的化合物）等。此等係可單獨1種使用、亦可倂用2種以上。此等之中，從保存安定性良好、且感光層的表面硬度或硬化膜的膜強度本身能有效提昇之點而言，以烷基化羥甲基三聚氰胺爲佳〇、六甲基化羥甲基三聚氰胺爲特佳。前述熱交聯劑在前述感光性組成物固體成分中的固體成分含量係以1質量。~ 5 0質量％爲佳、3質量％ ~ 3 0質量％爲更佳。該固體成分含量低於1質量％時，係認爲硬化膜的膜強度沒有提昇，超過5 0質量％時’會產生顯像性的降低或曝光感度的降低。 -黏附促進劑- 爲了提昇各層間的黏附性、或感光層與基體的黏附性 ’各層上亦可使用眾所周知所謂的黏附促進劑。 -65- 200935174 前述黏附促進劑係可舉例如特開平5- 1 1439號公報、特開平5-341532號公報、及特開平6-43638號公報等中所記載之黏附促進劑爲適宜。具體而言，可舉例如本并咪唑、苯并曙哇、苯并噻嗖、2 -氫硫基苯并咪嗖、2 -氫硫基本并曙唑、2 -氫硫基苯并噻唑、3_味啉基甲基_1_苯基_三唑 -2-硫酮、3-味啉基甲基-5-苯基·曙二哇硫酮、5·胺基 -3-味啉基甲基-噻二哩-2-硫酮、及2-氫硫基_5_甲硫基_噻二哩、三哩、四哩、苯并三哩、竣基苯并三哩、胺基含有 © 苯并三唑、矽烷偶合劑等。前述黏附促進劑的含量係相對於前述感光層的總成分，以0.0 0 1質量％ ~ 2 0質量％爲佳、0.0 1質量％ ~ 1 0質量。/〇爲較佳、0 · 1質量。/。~ 5質量％爲特佳。 -增感劑- 前述感光性組成物係亦可含有增感劑。前述增感劑係在曝光前述感光層以進行顯像之情形中，從該感光層曝光部分之厚度在該曝光及顯像後不會變化〇且可使前述光的最小能量（感度）提昇之觀點，倂用前述增感劑爲特佳。前述增感劑係可配合前述光照射手段（例如，可見光線或紫外光及可見光雷射等）做適當地選擇。前述增感劑係可藉由活性能量線成爲激發狀態，與其他物質（例如’自由基產生劑、酸產生劑等）進行相互作用（例如’能量移動、電子移動等），而可產生自由基或酸等的有用基。前述增感劑係含有至少1種選自於縮環系化合物、胺基 -66- 200935174 苯基酮系化合物、多核芳香族類、具有酸性核者、具有鹼性核者、具有螢光增白劑核者，亦可視需要含有其他的增感劑。增感劑係從提高感度之點而言，更以雜縮環系化合物、胺基二苯基酮系化合物爲佳，特別是雜縮環系化合物爲佳。 --縮環系化合物-- 在前述例示化合物之中’芳香族環或雜環被縮環之化合物（縮環系化合物）係以雜縮環系化合物爲佳。前述雜縮 ® 環系化合物係意味著在環中具有雜元素之多環式化合物，在前述環之中較佳係含有氮原子。前述雜縮環系化合物係可舉例如雜縮環系酮化合物。前述雜縮環系酮化合物之中，尤以吖啶酮化合物及硫咄嗣化合物爲更佳，此等之中尤以硫岫酮化合物爲特佳。具體而言，前述雜縮環系酮化合物係可舉例如吖啶酮、氯基吖啶酮、N -甲基吖啶酮、N -丁基吖啶酮、N-丁基-氯基吖啶酮、等的吖啶酮化合物；硫灿酮、異丙硫基咄酮 Ο 、2,4 -二乙硫基卩[li酮、1-氯基-4 -丙氧基硫卩[1]嗣、 QuantacureQTX等的硫卩山酮化合物；3-(2 -苯并呋喃甲醯基）-7 -二乙基胺基香豆素、3-(2 -苯并呋喃甲醯基）-7-(1-吡咯烷基）香豆素、3-苯甲醯基-7-二乙基胺基香豆素、3-(2-甲氧基苯甲醯基）-7-二乙基胺基香豆素、3_(4_二甲基胺基苯甲醯基）-7-二乙基胺基香豆素、3,3’-羰基貳（5,7-二-n-丙氧基香豆素）、3,3’-羰基貳（7-二乙基胺基香豆素）、3-苯甲醯基-7-甲氧基香豆素、3-(2 -呋喃甲醯基）-7 -二乙基胺基香豆素、3-(4 -二乙基胺基肉桂醯基）-7 -二乙基胺基香豆素 -67- 200935174 、7 -甲氧基- 3- (3 -吡啶羰基）香豆素、3_苯甲醯基_5,7_二丙氧基香豆素、7 -苯并三唑-2-基香豆素、7_二乙基胺基_4_ 甲基香豆素、又’特開平5-19475號、特開平7-27102 8號、特開 2002-363206 號、特開 2002-363207 號、特開 2002-363208號、特開2002-363209號公報等中所記載之香豆素化合物、等的香豆素類等。又’可舉例如眾所周知的多核芳香族類（例如，芘、茈、三鄰亞苯）、卩ill嗶類（例如’螢光素、曙紅、赤蘚紅鈉鹽〇、若丹明B、玫瑰紅）、花青類（例如，靛羰花青、硫羰花青、氧雜羰花青）、部花青類（例如，部花青、羰部花青）、噻护類（例如，硫堇、亞甲藍、甲苯胺藍）、蒽醌類（例如，蒽醌）、方形鎗類（例如，方形鑰）等。前述增感劑的含量係相對於前述感光性組成物的總固體成分，以〇 . 〇 1質量。/。~ 4質量％爲佳、〇 · 〇 2質量％ ~ 2質量％爲較佳、0 · 0 5質量％ ~ 1質量％爲特佳。前述含量爲低於〇·〇1質量％時，感度係爲降低，超過4 φ 質量％時，圖案的形狀係爲惡化。在前述感光性組成物中的前述增感劑、與光聚合起始劑之含量的質量比係以〔（增感劑）/ (肟衍生物）〕 = 1/ 0•卜1/100爲佳、1/1~1/50 爲更佳。前述增感劑的含量、與前述光聚合起始劑的含量之質量比在上述的範圍外時，感度降低且感度的經時變化係爲惡化。 -熱聚合抑制劑- 前述熱聚合抑制劑係可爲了防止在前述感光層中前述 -68- 200935174 聚合性化合物的熱聚合或經時聚合而添加。前述熱聚合抑制劑係可舉例如4 -甲氧基酚、氫醌、烷基或芳基取代氫醌、第三丁基鄰苯二酚 '焦掊酚、2_羥基二苯基嗣、4-甲氧基-2-羥基二苯基酮、氯化銅（1)、啡噻阱、氯醌、萘基胺、/5 -萘酚、2,6-二-第三丁基-4-甲酚、2，2，-亞甲基貳（4-甲基-6-第三丁基酚）、吡啶、硝基苯、二硝基苯、苦味酸、4_甲苯胺、亞甲藍、銅與有機螯合劑反應物、水楊酸甲酯、及啡噻阱、亞硝基化合物、亞硝基化合物 ©與A1之螯合物等。前述熱聚合抑制劑的含量係相對於前述聚合性化合物，以Ο · Ο Ο 1質量％〜5質量。/。爲佳、〇 . 〇 0 5質量。/。~ 2質量。/〇爲較佳、〇.〇1質量％~1質量％爲特佳。前述含量低於0.001質量％時，保存時的安定性降低，超過5質量％時，對於活性能量線的感度係爲下降。 -可塑劑- 前述可塑劑係可爲了調控前述感光層的膜物性（可撓〇性）而添加。前述可塑劑係可舉例如酞酸二甲酯、酞酸二丁酯、酞酸二異丁酯、酞酸二庚酯、酞酸二辛酯、酞酸二環己酯、酞酸二-十三烷酯、酞酸丁基苄酯、酞酸二異癸酯、酞酸二苯酯、酞酸二烯丙酯、酞酸辛基癸醯酯等的酞酸酯類；三乙二醇二乙酸酯、四乙二醇二乙酸酯、二甲基乙二醇酞酸、乙基鄰苯二甲醯基乙基乙醇酸酯、甲基鄰苯二甲醯基乙基乙醇酸酯、丁基鄰苯二甲醯基丁基乙醇酸酯、三乙二醇二癸酸酯等的乙二醇酯類；三甲苯酚基磷酸酯、三苯基磷 -69- 200935174 酸酯等的磷酸酯類；4 -甲苯磺醯胺、苯磺醯胺、N -正丁基苯磺醯胺、N-正丁基乙醯胺等的醯胺類；二異丁基己二酸酯、二辛基己二酸酯、二甲基癸二酸酯、二丁基癸二酸酯、二辛基癸二酸酯、二辛基壬二酸酯、二丁基蘋果酸酯等的脂肪族二鹼酸酯類；檸檬酸三乙酯、檸檬酸三丁酯、丙三醇三乙醯酯、月桂酸丁酯、4,5-二環氧環己烷-1,2-二羧酸二辛酯等、聚乙二醇、聚丙二醇等的二醇類。前述可塑劑的含量係相對於前述感光性組成物的總成 Ο 分，以〇· 1質量％~50質量。/。爲佳、0.5質量。/。~40質量％爲較佳、1質量％~30質量％爲特佳。 -著色顔料- 前述著色顔料係沒有特別地限制，可視其目的做適當地選擇，例如，維多利亞純藍BO(C.1.42595)、金胺 (C.I.41000)、脂溶黑 HB(C.I.26150)、莫諾賴特黃 GT(C.I. 顏料黃12)、永久黃GR(C.I.顏料黃17)、永久黃HR(C.I.顏料黃83)、永久洋紅FBB(C.I.顔料紅146)、霍斯特帕姆紅〇 ESB(C.I_顏料紫19)、永久玉紅FBH(C.I.顏料紅11)法斯特爾粉紅B蘇普拉（C.I.顏料紅81)莫納斯特拉爾堅固藍（C.i. 顏料藍15)、莫諾賴特堅固黑B(C.I.顏料.黑1)、碳、C.I. 顏料紅97、C.I.顏料紅122、C.I.顏料紅149、C.I.顏料紅 168、C.I.顏料紅 177、C.I.顏料紅 180、C.I.顏料紅 192、 C.I.顏料紅215、C.I,顔料綠7、C_I_顏料綠36、C.I.顏料藍15: 1、C.I.顏料藍15: 4、C.I·顏料藍15: 6、C.I.顏料藍22、C.I.顏料藍60、C.I.顏料藍64等。此等係可單獨1 種使用、亦可倂用2種以上。又’可視需要使用從眾所周知 -70- 200935174 的染料之中所適當地選擇的染料。前述著色顔料在前述感光性組成物中的固體成分含量 ’係可考慮永久圖案形成之際感光層的曝光感度、解析性等而決定，且因前述著色顔料的種類而有所不同，惟一般係以0.01質量。/。〜10質量％爲佳、0.05質量％~5質量％爲更佳。 (感光性薄膜）本發明的感光性薄膜係在支持體上積層感光性組成物〇所構成之感光層而成的。較佳係在前述感光層上積層保護層而成，可視需要更積層緩衝層、氧遮斷層（PC層）等的其他的層來構成。 β 前述感光性薄膜的形態係沒有特別地限制，可視其目的做適當地選擇，可舉例如有：在前述支持體上依序具有前述感光層、前述保護層而形成之形態；在前述支持體上依序具有前述PC層、前述感光層、前述保護層而形成之形態；在前述支持體上依序具有前述緩衝層、前述PC層、前〇述感光層、前述保護層而形成之形態等。此外，前述感光層係可爲單層、亦可爲複數層。 <感光層> 前述感光層在前述感光性薄膜中設置之處係沒有特別地限制，可視其目的做適當選擇，通常係積層於前述支持體上。前述感光層係在後述之曝光步驟中，藉由受光來自光照射手段的光線而具有η個射出之描繪部的光調變手段，調變來自前述光照射手段的光線之後，以通過具有可補償因 -71- 200935174 爲前述描繪部中射出面的變形所引起的像差之非球面的微透鏡所配置排列之微透鏡陣列的光線，來使其曝光者爲佳 0 在曝光顯像前述感光層之情形中，該感光層的曝光部分之厚度係在該曝光及顯像後沒有變化、且於前述曝光中所使用光的最小能量係以100mJ/cm2以下爲佳、 70mJ/cm2以下爲更佳。前述曝光中所使用光的最小能量係超過100mJ/cm2時，由於生產間隔時間（tact time)變長 ®而爲不佳。此處，「該感光層的曝光部分之厚度係在該曝光及顯像後沒有變化、且於前述曝光中所使用光的最小能量」係所謂的顯像感度，例如可從表示曝光前述感光層時的前述曝光中所使用光的能量（曝光量）、與接續前述曝光由前述顯像處理所生成之前述硬化層的厚度之關係圖表（感度曲線）而求得。前述硬化層的厚度係可根據前述曝光量增加而增加，〇隨後與其與前述曝光前的前述感光層之厚度成大致相同且大致固定。前述顯像感度係藉由讀取前述硬化層的厚度爲大致固定時的最小曝光量所求得之値。此處，前述硬化層的厚度與前述曝光前之前述感光層的厚度係在± 1 V m以内時，認爲前述硬化層的厚度不因曝光及顯像而變化。Structural Formula (52) 樽 ¢ 3) Structural Formula (54) However, in the above structural formulae (1) to (54), Me represents a methyl group. Ph stands for phenyl. Ac represents an ethyl group. The content of the anthracene derivative is preferably, for example, 0.1 to 15% by mass in terms of solid content, more preferably 0.5 to 10% by mass, even more preferably 1.0 to 8.0% by mass. When the amount is less than 0.1% by mass, the sensitivity is lowered, and it is difficult to obtain a cured film having sufficient hardness. When the amount is more than 15% by mass, not only the viscosity at the time of film formation is deteriorated, but also the cured film becomes brittle due to a decrease in Tg. - Other photopolymerization initiators - The other photopolymerization initiators described above may be within a range having the ability to initiate polymerization of the above polymerizable compound, and are not particularly limited, and may be used from a well-known photopolymerization initiator. Suitable choices, for example, those that are sensitive to ultraviolet light to visible light, or active agents that generate some action by photoexciting the -63-200935174 sensitizer, or The initiator for cationic polymerization can be initiated depending on the kind of the monomer. Further, the photopolymerization initiator preferably contains at least one component having a molecular absorption coefficient of at least about 50 in a wavelength range of about 300 nm to 800 nm. The aforementioned wavelength system is preferably 330 nm to 500 nm. The other photopolymerization initiators mentioned above may, for example, be halogenated hydrocarbon derivatives (for example, those having a three-till skeleton, having an oxadiazole skeleton, etc.), hexaarylbiimidazole, an organic peroxide, a sulfur compound, and a ketone. a compound, an acridine compound, a metallocene or the like. Specifically, for example, a compound described in JP-A-2005-25843 1 or the like can be mentioned. Among these, a ketone compound and an acridine compound are preferred from the viewpoints of the sensitivity of the photosensitive layer, the preservability, and the adhesion between the photosensitive layer and the substrate. The other photopolymerization initiators may be used alone or in combination of two or more. The photopolymerization initiator has a solid content of 0.1 to 1% by mass in the photosensitive composition. The mass % is preferably 0.5% by mass to 200% by mass, preferably 0.5% by mass to 15% by mass. /. It is especially good. 〇<Other components> The other components mentioned above may, for example, be a thermal crosslinking agent, an adhesion promoter, a sensitizer, a thermal polymerization inhibitor, a plasticizer, a coloring agent (coloring pigment or dye), etc. Other additives (for example, conductive particles, chelating agents, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain shifting agents, etc.) can be used. The properties of stability, photographic properties, film properties, and the like of the photosensitive film which is intended to be adjusted are appropriately contained. - Thermal crosslinking agent - 64-200935174 The above-mentioned thermal crosslinking agent is not particularly limited, and may be appropriately selected depending on the purpose thereof, in order to improve the film strength of the photosensitive layer formed by using the photosensitive film after hardening, in the case of For example, an epoxy compound having at least two ethylene oxide groups in one molecule and an oxygen heterocyclic ring having at least two oxetanyl groups in one molecule can be used within a range in which adverse effects such as development are caused. The butane compound may, for example, be an epoxy compound having an oxirane group, an epoxy compound having an alkyl group at a fluorene group, or an oxa compound, which is described in JP-A-2007-47 7 2-9. A compound obtained by reacting an isocyanate group of a cyclobutane group, a polyisocyanate compound, a polyisocyanate and a derivative thereof with a block agent. Further, the above thermal crosslinking agent can be derived using melamine. The melamine derivative may, for example, be methylol melamine or alkylated methylol melamine (a compound in which a methylol group is etherified with a methyl group, an ethyl group or a butyl group). These may be used alone or in combination of two or more. Among these, from the viewpoint of good preservation stability, and the surface hardness of the photosensitive layer or the film strength of the cured film itself can be effectively improved, alkylated methylol melamine is preferred, and hexamethylated hydroxyl group is preferred. Melamine is particularly preferred. The thermal crosslinking agent has a solid content of 1 part by mass in the solid content of the photosensitive composition. More preferably, it is more preferably 50% by mass, and more preferably 3% by mass to 30% by mass. When the content of the solid content is less than 1% by mass, the film strength of the cured film is not improved, and when it exceeds 50% by mass, the decrease in developability or the decrease in exposure sensitivity may occur. - Adhesion promoter - In order to improve the adhesion between the layers or the adhesion of the photosensitive layer to the substrate. A so-called adhesion promoter is also known for use on each layer. The adhesion promoter described in, for example, Japanese Laid-Open Patent Publication No. Hei 5- No. Hei. Specific examples thereof include Benzimidazole, Benzopyrene, Benzothiazin, 2-Hydroxythiobenzimidazole, 2-Hydroxysulfanylcarbazole, 2-Hydroxythiobenzothiazole, and 3 _ porphyrinylmethyl_1_phenyl-triazole-2-thione, 3-tyrosolinylmethyl-5-phenylanthracene bis- thione, 5-amino-3-ylidene -thiadiin-2-thione, and 2-hydrothio-5-methylthio-thiadiazepine, triterpenoid, tetraterpene, benzotriazine, mercaptobenzotriazine, amine group containing Benzotriazole, decane coupling agent, and the like. The content of the adhesion promoter is preferably 0.001% by mass to 20% by mass, and 0.01% by mass to 10% by mass based on the total composition of the photosensitive layer. /〇 is better, 0 · 1 quality. /. ~ 5 mass% is especially good. - Sensitizer - The photosensitive composition may further contain a sensitizer. In the case where the sensitizer is exposed to the photosensitive layer for development, the thickness of the exposed portion from the photosensitive layer does not change after the exposure and development, and the minimum energy (sensitivity) of the light can be improved. In view of the above, it is particularly preferable to use the aforementioned sensitizer. The sensitizer may be appropriately selected in combination with the above-described light irradiation means (for example, visible light or ultraviolet light and visible light laser). The sensitizer can be excited by an active energy ray, and interacts with other substances (for example, 'free radical generator, acid generator, etc.) (for example, 'energy movement, electron movement, etc.), and can generate free radicals. Or a useful group such as an acid. The sensitizer contains at least one selected from the group consisting of a condensed ring compound, an amine group -66-200935174 phenyl ketone compound, a polynuclear aromatic compound, an acid nucleus, a basic nucleus, and a fluorescent whitening. The nucleator may also contain other sensitizers as needed. The sensitizer is preferably a heterocyclic ring compound or an aminodiphenyl ketone compound from the viewpoint of improving the sensitivity, and particularly preferably a heterocyclic ring compound. - condensed ring-based compound - Among the above-exemplified compounds, a compound in which an aromatic ring or a heterocyclic ring is condensed (a condensed ring compound) is preferably a heterocyclic ring compound. The above-mentioned hybrid ® ring-based compound means a polycyclic compound having a hetero element in the ring, and preferably contains a nitrogen atom among the above rings. The above heterocyclic ring compound may, for example, be a heterocyclic ketone compound. Among the above heterocyclic ketone compounds, an acridone compound and a sulfonium compound are particularly preferable, and among these, a thioxanthone compound is particularly preferable. Specifically, the above heterocyclic ketone compound may, for example, be acridone, chloroacridone, N-methylacridone, N-butylacridone or N-butyl-chloroacridine. Ketone, etc. acridone compounds; thioxanthone, isopropylthioxanthone oxime, 2,4-diethylthio fluorene [li ketone, 1-chloro-4-propoxy oxime [1] 嗣, thioacene ketone compound such as QuantacureQTX; 3-(2-benzofurancarbenyl)-7-diethylamino coumarin, 3-(2-benzofuranyl)-7-( 1-pyrrolidinyl)coumarin, 3-benzylidene-7-diethylamine coumarin, 3-(2-methoxybenzimidyl)-7-diethylamine Bean, 3_(4-dimethylaminobenzimidyl)-7-diethylaminocoumarin, 3,3'-carbonylindole (5,7-di-n-propoxycoumarin , 3,3'-carbonyl hydrazine (7-diethylaminocoumarin), 3-benzylidene-7-methoxycoumarin, 3-(2-furylmethyl)- 7-Diethylamino coumarin, 3-(4-diethylamino cinnamyl)-7-diethylamino coumarin-67- 200935174, 7-methoxy- 3- ( 3-pyridinecarbonyl)coumarin, 3-benzylidene- 5,7-dipropoxycoumarin 7-benzotriazol-2-ylcoumarin, 7-diethylamino _4_methylcoumarin, and 'Special Kaiping 5-19475, Special Kaiping 7-27102 No. 8, Special Open 2002- A coumarin compound or the like, such as a coumarin compound described in JP-A-2002-363209, JP-A-2002-363209, and the like. Further, for example, well-known polynuclear aromatics (for example, ruthenium, osmium, tri-o-phenylene) and 卩ill oxime (for example, 'luciferin, ruthenium, erythrosine sodium salt, rhodamine B, Rose red), cyanine (for example, carbocyanine, thiocarbocyanine, oxacarbocyanine), merocyanine (for example, merocyanine, carbonyl chloroform), thiophene (for example, Thiopurine, methylene blue, toluidine blue), terpenoids (eg, hydrazine), square guns (eg, square keys), and the like. The content of the sensitizer is 〇质量 1 by mass based on the total solid content of the photosensitive composition. /. ~ 4% by mass is preferred, 〇 · 〇 2% by mass to 2% by mass is preferred, and 0. 5% by mass to 1% by mass is particularly preferred. When the content is less than 质量·〇1% by mass, the sensitivity is lowered, and when it exceeds 4 φ% by mass, the shape of the pattern is deteriorated. The mass ratio of the content of the sensitizer and the photopolymerization initiator in the photosensitive composition is preferably [(sensitizer) / (deuterium derivative)] = 1/0•b 1/100. , 1/1~1/50 is better. When the ratio of the content of the sensitizer to the content of the photopolymerization initiator is outside the above range, the sensitivity is lowered and the temporal change in sensitivity is deteriorated. - Thermal polymerization inhibitor - The thermal polymerization inhibitor may be added in order to prevent thermal polymerization or polymerization over time of the above-mentioned -68-200935174 polymerizable compound in the photosensitive layer. The above thermal polymerization inhibitor may, for example, be 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, tert-butyl catechol 'pyrophenol, 2-hydroxydiphenyl fluorene, 4- Methoxy-2-hydroxydiphenyl ketone, copper chloride (1), morphine trap, chloranil, naphthylamine, /5-naphthol, 2,6-di-t-butyl-4-methyl Phenol, 2,2,-methylene hydrazine (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper A chelate compound with an organic chelating agent, a methyl salicylate, a morphine, a nitroso compound, a nitroso compound, and A1. The content of the thermal polymerization inhibitor is from 1% by mass to 5% by mass based on the above polymerizable compound. /. For better, 〇. 〇 0 5 quality. /. ~ 2 quality. /〇 is preferred, 〇.〇1% by mass to 1% by mass is particularly good. When the content is less than 0.001% by mass, the stability at the time of storage is lowered, and when it exceeds 5% by mass, the sensitivity to the active energy ray is decreased. - Plasticizer - The aforementioned plasticizer can be added for controlling the film properties (teleability) of the photosensitive layer. The aforementioned plasticizer may, for example, be dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate or di-decanoic acid. Trialkyl esters, butyl benzyl phthalate, diisononyl phthalate, diphenyl phthalate, diallyl phthalate, octyl decyl phthalate, etc.; triethylene glycol diethyl Acid ester, tetraethylene glycol diacetate, dimethyl glycol phthalic acid, ethyl phthalic acid ethyl glycolate, methyl phthalic acid ethyl glycolate, butyl Ethylene glycol esters such as phthalic acid butyl glycolate, triethylene glycol dicaprate, etc.; phosphates such as trimethylphenol phosphate, triphenylphosphonium-69-200935174 acid ester ; 4 - toluene sulfonamide, benzene sulfonamide, N - n - butyl benzene sulfonamide, phthalamides such as N-n-butyl acetamide; diisobutyl adipate, dioctyl Aliphatic dibasic acid esters such as diester, dimethyl sebacate, dibutyl sebacate, dioctyl sebacate, dioctyl sebacate, dibutyl malate; Triethyl citrate, tributyl citrate, C3 A glycol such as polyethylene glycol, butyl laurate or tetraoctyl 4,5-diepoxycyclohexane-1,2-dicarboxylate, or polyethylene glycol or polypropylene glycol. The content of the plasticizer is 〇·1 mass% to 50 mass% with respect to the total composition of the photosensitive composition. /. Good, 0.5 quality. /. It is particularly preferable that it is preferably 40% by mass and 1% by mass to 30% by mass. - Coloring Pigment - The aforementioned coloring pigment is not particularly limited and may be appropriately selected depending on the purpose thereof, for example, Victoria Pure Blue BO (C.1.42595), gold amine (CI41000), fat-soluble black HB (CI26150), Mo Norit Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Magenta FBB (CI Pigment Red 146), Horst Palm Red 〇 ESB (C.I_Pigment Violet 19), Permanent Jade Red FBH (CI Pigment Red 11) Faster Pink B Supra (CI Pigment Red 81) Monastral Strong Blue (Ci Pigment Blue 15), Mono Wright Strong Black B (CI Pigment. Black 1), Carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI, Pigment Green 7, C_I_Pigment Green 36, CI Pigment Blue 15: 1, CI Pigment Blue 15: 4, CI·Pigment Blue 15: 6, CI Pigment Blue 22, CI Pigment Blue 60 , CI Pigment Blue 64, etc. These may be used alone or in combination of two or more. Further, a dye appropriately selected from the dyes well-known as -70-200935174 can be used as needed. The content of the solid content of the coloring pigment in the photosensitive composition is determined in consideration of exposure sensitivity and resolution of the photosensitive layer in the formation of a permanent pattern, and is different depending on the type of the coloring pigment, but generally Take 0.01 mass. /. It is preferably 10% by mass or more, preferably 0.05% by mass to 5% by mass. (Photosensitive film) The photosensitive film of the present invention is obtained by laminating a photosensitive layer composed of a photosensitive composition on a support. It is preferable to form a protective layer on the photosensitive layer, and it is also possible to form a buffer layer or another layer such as an oxygen barrier layer (PC layer) as needed. The form of the photosensitive film is not particularly limited, and may be appropriately selected depending on the purpose, and may be, for example, a form in which the photosensitive layer and the protective layer are sequentially provided on the support; and the support is provided. a form in which the PC layer, the photosensitive layer, and the protective layer are formed in this order, and the buffer layer, the PC layer, the front surface photosensitive layer, and the protective layer are sequentially formed on the support. . Further, the photosensitive layer may be a single layer or a plurality of layers. <Photosensitive layer> The photosensitive layer is not particularly limited in the photosensitive film, and may be appropriately selected depending on the purpose, and is usually laminated on the support. In the exposure step described later, the photosensitive layer has a light modulation means that receives n light-emitting portions by receiving light from the light-irradiating means, and modulates the light from the light-irradiating means to compensate -71-200935174 is the light of the microlens array in which the aspherical microlenses of the aberration caused by the deformation of the exit surface in the drawing portion are arranged, so that the exposure is better. The photosensitive layer is exposed and exposed. In this case, the thickness of the exposed portion of the photosensitive layer is not changed after the exposure and development, and the minimum energy of the light used in the exposure is preferably 100 mJ/cm 2 or less, and more preferably 70 mJ/cm 2 or less. . When the minimum energy of the light used in the above exposure exceeds 100 mJ/cm2, it is not preferable because the production time (tact time) becomes longer. Here, the "the thickness of the exposed portion of the photosensitive layer is such that the minimum energy of the light used in the exposure after the exposure and development" is a so-called development sensitivity, for example, the exposure of the photosensitive layer can be indicated. The energy (exposure amount) of the light used in the exposure described above is obtained by a graph (sensitivity curve) relating to the thickness of the hardened layer which is formed by the development process described above. The thickness of the hardened layer may be increased in accordance with the increase in the amount of exposure described above, and then substantially equal to and substantially constant from the thickness of the photosensitive layer before the exposure. The development sensitivity is obtained by reading the minimum exposure amount when the thickness of the hardened layer is substantially fixed. Here, when the thickness of the hardened layer and the thickness of the photosensitive layer before the exposure are within ± 1 V m, it is considered that the thickness of the hardened layer is not changed by exposure and development.

前述硬化層及前述曝光前之前述感光層的厚度之測定方法係沒有特別地限制，可視其目的做適當選擇，可舉例使用膜厚測定裝置、表面粗糙度測定機（例如，SU RFC OM -72- 200935174 1400D(東京精密公司製））等所測定之方法。前述感光層的厚度係沒有特別地限制，可視其適當選擇，例如以m-lOOy m爲佳、5/z m~70/z 佳。前述感光層的形成方法係可舉例如將本發明的光性組成物溶解於水或溶劑中，經乳化或分散以調性組成物溶液，並藉由將該溶液直接塗布、乾燥至持體上而進行積層之方法。〇前述感光性組成物溶液的溶劑係沒有特別地限視其目的做適當地選擇，可舉例如甲醇、乙醇、正異丙醇、正丁醇、，第二丁醇、正己醇等的醇類；丙基乙基酮、甲基異丁基酮、環己酮、二異丁基酮等 :乙酸乙酯、乙酸丁酯、乙酸-正戊酯、硫酸甲酯、酯、酞酸二甲酯、安息香酸乙酯、及乙酸甲氧基丙酯類；甲苯、二甲苯、苯、乙基苯等的芳香族烴類化碳、三氯乙烯、氯仿、1，1，1-三氯基乙烷、氯化〇、單氯基苯等的鹵化烴類；四氫呋喃、二乙基醚、單甲基醚、乙二醇單乙基醚、1-甲氧基-2-丙醇等的二甲基甲醯胺、二甲基乙醯胺、二甲亞颯、環丁颯等係可單獨1種使用、亦可倂用2種以上。又，亦可所周知的界面活性劑。前述塗布的方法係沒有特別地限制，可視其目當地選擇，可舉例如使用旋轉塗布機、狹縫旋轉塗輥塗機、凹模塗布機、簾式塗布機等，以直接塗布支持體之方法。目的做 m爲更前述感製感光前述支制，可丙醇、酮、甲的酮類丙酸乙酯等的 :四氯亞甲基乙二醇 1醚類；等。此添加眾的做適布機、至前述 -73- 200935174 前述乾燥的條件亦可根據各成分、溶媒的種類、使用比例等而不同，惟通常係在60°c ~ 1 l〇°C的溫度且30秒鐘 ~ 15分鐘左右。本發明中，前述感光層係藉由含有黏結劑、聚合性化合物、與塡料，以及可視需要含有其他成分之感光性組成物而形成的。 <支持體> 前述支持體係沒有特別地限制’可視其目的做適當選 Ο 擇，前述感光層爲可剝離且光的透射性爲良好者爲佳，進而以表面的平滑性良好爲更佳。，前述支持體較佳係以合成樹脂製且透明者，可舉例如聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚丙烯、聚乙烯、三乙酸纖維素、二乙酸纖維素、聚（甲基）丙烯酸烷酯、聚（甲基）丙烯酸酯共聚物、聚二氯乙烯、聚乙烯醇、聚碳酸酯、聚苯乙烯、賽璐玢、聚偏二氯乙烯共聚物、聚醯胺、聚醯亞胺、二氯乙烯·乙酸乙烯酯共聚物、聚四氟乙烯 Q 、聚三氟乙烯、纖維素系薄膜、耐綸薄膜等的各種的塑膠薄膜，此等之中，尤以聚對苯二甲酸乙二酯爲特佳。此等係可單獨1種使用、亦可倂用2種以上。前述支持體的厚度係沒有特別地限制，可視其目的做適當選擇，例如以2//m~150/zm爲佳、5ym~100/zm爲較佳、8；uni~5〇em爲特佳。前述支持體係可爲單層、亦可具有多層構成。前述支持體的形狀係沒有特別地限制，可視其目的做適當選擇，以長尺狀爲佳。前述長尺狀的支持體之長度係 -74- 200935174 沒有特別地限制，可舉例如爲10m~20,000m之長度者。 <保護層> 前述感光性薄膜係亦可在前述感光層上形成保護層。前述保護層係可舉例如前述支持體中所使用者、紙、層壓聚乙烯、聚丙烯而成之紙等，此等之中，尤以聚乙烯薄膜、聚丙烯薄膜爲佳。前述保護層的厚度係沒有特別地限制，可視其目的做適當選擇，例如以5" m~100/£ m爲佳、8/z m~50；ci m爲較〇佳、l〇em~30;zm 爲特佳。前述支持體與保護層之組合（支持體/保護層）係可舉例如聚對苯二甲酸乙二酯/聚丙烯、聚對苯二甲酸乙二酯/ 聚乙烯、聚二氯乙烯/賽璐玢、聚醯亞胺/聚丙烯、聚對苯二甲酸乙二酯/聚對苯二甲酸乙二酯等。又，藉由表面處理支持體及保護層之至少任一面，可調整層間黏著力。前述支持體的表面處理係可爲了提高與前述感光層的黏著力而實施，可舉例如下塗層的塗設、電暈放電處理、火焰處理〇、紫外線照射處理、高頻照射處理、輝光放電照射處理、活性電漿照射處理、雷射光線照射處理等。又，前述支持體與前述保護層的静摩擦係數係以 0.3-1.4爲佳、0.5-1.2爲更佳。前述静摩擦係數低於0.3時，由於過滑而會在成輥狀之情形中發生捲繞偏差，超過1.4時係變得難以捲繞成良好的輥狀。前述感光性薄膜係例如捲取成圓筒狀的卷芯，且以長尺狀捲繞成輥狀來保管爲佳。前述長尺狀的感光性薄膜之 -75- 200935174 長度係沒有特別地限制，例如可從10m~20,000m的範圍做適當地選擇。又，爲了讓使用者方便使用，亦可進行分切加工，將l〇〇m~l，OOOm範圍的長尺體形成爲輥狀。此外，該情形中，前述支持體係捲取成爲最外側爲佳。又，前述輥狀的感光性薄膜亦可分切成薄片狀。於保管之際，從保護端面、防止邊緣熔融之觀點，於端面設定分隔物（特別是防濕性者、放入乾燥劑者）爲佳，又以使用捆包或透濕性低的原料爲佳。〇前述保護層係爲了調整前述保護層與前述感光層之黏著性，亦可進行表面處理。在前述表面處理、例如在前述保護層的表面，形成由聚有機矽氧烷、氟化聚烯烴、聚氟乙烯、聚乙烯醇等的聚合物所構成之下塗層。該下塗層的形成係可在將前述聚合物的塗布液塗布至前述保護層的表面後，藉由在30°c~150°c、乾燥1分鐘~30分鐘而形成。前述乾燥之際的溫度係以5(TC ~ 120°C爲特佳。 <其他的層> 〇前述感光性薄膜中其他的層係沒有特別地限制，可視其目的做適當地選擇，例如亦可具有緩衝層、氧遮斷層（PC 層）、剝離層、黏著層、光吸收層、表面保護層等的層。此等之層係可具有單獨1種、亦可具有2種以上。又，前述感光層上亦可具有保護層。 <感光性薄膜的製造方法> 前述感光性薄膜係可例如以下述之方法來製造。首先，將前述感光性組成物中所含有的材料溶解於水或溶劑中，使其乳化或分散，以調製感光性薄膜用的感光 -76- 200935174 性組成物溶液。前述溶媒係可舉例如與前述感光性組成物溶液之溶劑相同者。接著，於前述支持體上塗布前述感光性組成物溶液，使其乾燥以形成感光層，而可製造感光性薄膜。前述感光性組成物溶液的塗布方法係可舉例如上述的方法。前述感光性薄膜由於使用前述感光性組成物’所以耐 Ο電鍍性、感度、顯像性、及黏附性係爲良好’且可適當使用於保護膜、層間絶緣膜、及耐焊劑圖案等永久圖案等的各種圖案形成用、彩色濾光片、柱材、肋材、間隔村、隔壁等的液晶構造構件之製造用、全息照相、微型機械、樣張（proof)等的圖案形成用等’特別是可適當使用於印刷基板的永久圖案形成用。特別是由於前述感光性薄膜係該薄膜的厚度爲均一的，所以在形成永久圖案之際’即使永久圖案（保護膜、層間〇絶緣膜、耐焊劑等）薄層化，在高加速度試驗（HAST)中亦不會產生樹枝狀晶體，且因爲可得到耐熱性、耐濕性優異之高精細永久圖案’所以對基材的積層可更精細地進行。 (感光性積層體）前述感光性積層體係在基體上至少具有前述感光層’ 且可視其目的積層適當地選擇之其他的層而形成。 <基體> 前述基體係爲形成感光層之被處理基體、或本發明感光性薄膜之至少感光層被轉印之被轉印體者’沒有特別地 -77- 200935174 限制，可視其目的做適當地選擇，例如可從表面平滑性高者至具有某些凸凹之表面中任意地選擇。板狀的基體爲佳 ’可使用所謂的基板。具體而言，可舉例如眾所周知的印刷配線板製造用的基板（印刷基板）、玻璃板（鈉鈣玻璃板等）、合成樹脂性的薄膜、紙、金屬板等。 <感光性積層體的製造方法> 前述感光性積層體的製造方法，第1態様係可舉例如將前述感光性組成物塗布至前述基體表面並乾燥之方法，第2 © 態樣係可舉例如將前述感光性薄膜中的至少感光層一邊進行加熱及加壓中至少任一者、一邊進行轉印、積層之方法〇前述第1態樣之感光性積層體的製造方法係在前述基體上，塗布及乾燥前述感光性組成物以形成感光層。前述塗布及乾燥的方法係沒有特別地限制，可視其目的做適當地選擇，可舉例如將前述感光性組成物溶解於水或溶劑中，使其乳化或分散以調製感光性組成物溶液，並〇藉由將該溶液直接塗布、乾燥，以積層至前述基體表面之方法。前述塗布方法及乾燥條件係沒有特別地限制，可視其目的做適當地選擇，可以與前述感光性薄膜中所使用者爲相同之方法及條件來進行。前述第2態樣之感光性積層體的製造方法，係將本發明的感光性薄膜一邊進行加熱及加壓中至少任一者、一邊進行積層至前述基體的表面。此外，前述感光性薄膜具有前述保護層之情形中，較佳係剝離該保護層並積層至前述基 -78- 200935174 體以使得前述感光層爲重疊的。前述加熱溫度係沒有特別地限制，可視其目的做適當地選擇，例如以15~180°C爲佳、60~140°C爲更佳。前述加壓的壓力係沒有特別地限制，可視其目的做適當地選擇，例如以〇.l~l.〇MPa爲佳、0.2~0.8MPa爲更佳〇前述進行加熱中至少任一者之裝置係沒有特別地限制，可視其目的做適當地選擇，可舉例如層壓機（例如，大成 © 層壓機公司製VP-II、Nichigo Motor(股）製 VP130)等爲適宜。前述感光性薄膜，及前述感光性積層體由於使用前述感光性組成物，所以感度、顯像性、及黏附性爲良好，可更有效率地形成高精細的永久圖案，且能適當使用於保護膜、層間絶緣膜、及耐焊劑圖案等永久圖案等的各種圖案形成用、彩色濾光片、柱材、肋材、間隔材、隔壁等的液晶構造構件的製造用、全息照相、微型機械、樣張（proof)等〇的圖案形成用等，特別是可適當使用於印刷基板的永久圖案形成用。特別是由於前述感光性薄膜係厚度爲均一的，所以在形成永久圖案之際，即使永久圖案（保護膜、層間絶緣膜、耐焊劑等）爲薄層化，在高度加速壽命試驗（HAST)中亦不會有樹枝狀晶體發生，且因爲得到耐熱性、耐濕性優異之高精細的永久圖案，所以對基材的積層可更精細地進行。 (永久圖案形成方法）前述永久圖案形成方法係至少含有曝光步驟，亦可含 •79- 200935174 有適當選擇之顯像步驟等的其他步驟。此外，圖案形成裝置係可經由前述圖案形成方法之説明而明白得知，係具備前述感光性積層體，且至少含有光照射手段與光調變手段。 <曝光步驟> 前述曝光步驟係對於前述感光層進行曝光之步驟。關於前述感光層、及基體的材料係如上所述。前述曝光的對象係在前述感光層之範圍即可，沒有特〇別地限制，可視其目的做適當選擇，例如，如上所述，對於將感光性組成物一邊進行加熱及加壓中之至少任一者、一邊，積層於基體上所形成之感光性積層體中的感光層進行曝光爲佳。前述曝光係沒有特別地限制，可視其目的做適當地選擇，可舉例如數位曝光、類比曝光等，惟此等之中以數位曝光爲佳。前述類比曝光係沒有特別地限制，可視其目的做適當〇地選擇，可舉例如透過具有規定圖案之光罩，以（超）高壓水銀燈、氙氣燈、鹵素燈等進行曝光之方法。前述數位曝光若係不使用前述光罩進行即可，沒有特別地限制，可視其目的做適當選擇，較佳係例如移動至少具備光照射手段及光調變手段之曝光頭、與前述感光層中之至少任一者’且對於前述感光層，藉由前述光調變手段並根據圖案情報一邊調變自前述光照射手段射出的光線、一邊自前述曝光頭進行照射以實施數位曝光。前述數位曝光中所使用的光源若爲能發射紫外線至近 -80- 200935174 紅外線的光源即可，沒有特別地限制，可視其目的做適當地選擇，例如可使用（超）高壓水銀燈、氙氣燈、碳弧燈、鹵素燈、及複印機用等的螢光管、或雷射光等的公知光源，此等之中尤以（超）高壓水銀燈、雷射光爲佳、雷射光爲更佳。所謂的（超）高壓水銀燈係將水銀封入至石英玻璃管等之放電燈，並提高設定水銀的蒸氣壓以提昇發光效率者。線狀光譜之中，可爲利用ND濾光片等而僅使用1波長之線 © 狀光譜，亦可使用具有複數個線狀光譜之光線。前述雷射光的「雷射」係爲Light Amplification by S t i m ιι 1 a t e d E m i s s i ο η o f R a d i a t i ο η (由誘導放出之光的增幅）的頭字語。前述發射雷射光之裝置係可舉例如利用在育有反轉分布之物質中所發生的誘導放出現象，且藉由光波的增幅、發振，產生出相干性與定向性進一步增強的單色光之發振器及增幅器爲適宜。前述雷射光之激發媒質係有結晶、玻璃、液體、色素〇、氣體等，可使用來自此等媒質中之固體雷射、液體雷射、體雷射、半導體雷射等的眾所周知的雷射。具體而言，氣體雷射係可舉例如Ar離子雷射（364nm、 351nm}、Kr 離子雷射（356nm、351nm)、He-Cd 雷射 (3 2 5nm)，固體雷射係可舉例如YAG雷射、YV04雷射 (l，064nm)、YAG雷射或YV04雷射的2倍波（532nm)、3倍波（355nm)、4倍波（266nm)、導波型波長變換元件與 AlGaAs、InGaAs半導體之組合（380nm~400nm)、導波型波長變換元件與AlGalnP或AlGaAs半導體t之組合 *81- 200935174 (3 Ο Ο n m ~ 3 5 Ο n m)、A1 G a I η N (3 5 Ο n m ~ 4 7 Ο n m)等。此等之中適宜的雷射光從成本面而言，可舉例如AlGalnN半導體雷射（市售InGaN系半導體雷射375nm或405nm)在生產性面有高輸出功率的355nm雷射。前述雷射光的波長係例如以200nm~ 1，500nm爲佳、 300nm~800nm 爲較佳、330nm~500nm 爲更佳、 350nm~420nm 爲特佳。 -光調變手段- © 前述光調變手段係可舉例如有具有η個的描繪部、且根據前述圖案情報以控制前述描繪部之方法爲代表性的方法。具體而言，可舉例如數位微反射裝置（DMD)、或 MEMS(Micro Electro Mechanical Systems，微電子機械系統）類型的空間光調變元件（SLM ; Spacial Light Modulator)、藉由電氣光學效果以調變透射光之光學元件 (PLZT元件）、液晶光快門（FLC)等，此等之中尤以DMD爲適宜。The method for measuring the thickness of the hardened layer and the photosensitive layer before the exposure is not particularly limited, and may be appropriately selected depending on the purpose thereof, and a film thickness measuring device or a surface roughness measuring machine (for example, SU RFC OM-72) may be used. - 200935174 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)). The thickness of the photosensitive layer is not particularly limited, and may be appropriately selected, for example, preferably m-100 y m or more preferably 5/z m to 70/z. The method for forming the photosensitive layer may be, for example, dissolving the photoactive composition of the present invention in water or a solvent, emulsifying or dispersing to adjust the composition solution, and directly coating and drying the solution onto the support. And the method of layering. The solvent of the photosensitive composition solution is not particularly limited, and may be appropriately selected, and examples thereof include alcohols such as methanol, ethanol, n-isopropanol, n-butanol, and second butanol or n-hexanol. ; propyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, etc.: ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ester, dimethyl phthalate , benzoic acid ethyl ester, and methoxypropyl acetate; aromatic hydrocarbonized carbon such as toluene, xylene, benzene, ethylbenzene, trichloroethylene, chloroform, 1,1,1-trichloro a halogenated hydrocarbon such as an alkane, a ruthenium chloride or a monochlorobenzene; a dimethyl group such as tetrahydrofuran, diethyl ether, monomethyl ether, ethylene glycol monoethyl ether or 1-methoxy-2-propanol The carbamide, dimethyl acetamide, dimethyl hydrazine, and cyclobutyl hydrazine may be used alone or in combination of two or more. Further, a well-known surfactant can also be used. The method of coating described above is not particularly limited, and may be selected from the viewpoint of the coating, for example, by a spin coater, a slit spin coater, a die coater, a curtain coater, or the like, to directly coat the support. . The purpose is to make m the sensitization of the above-mentioned support, such as propanol, ketone or methyl ketone propionate: tetrachloromethylene glycol 1 ether; The above-mentioned drying conditions can be varied depending on the components, the type of the solvent, the ratio of use, etc., but usually at a temperature of 60 ° C to 1 l ° ° C. And 30 seconds ~ 15 minutes or so. In the present invention, the photosensitive layer is formed by containing a binder, a polymerizable compound, a coating material, and a photosensitive composition which may optionally contain other components. <Support> The support system is not particularly limited. It is preferable that the photosensitive layer is peelable and the light transmittance is good, and the smoothness of the surface is better. . The support is preferably made of a synthetic resin and is transparent, and examples thereof include polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, and cellulose diacetate. , polyalkyl (meth) acrylate, poly (meth) acrylate copolymer, polydichloroethylene, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, poly Various plastic films such as decylamine, polyamidiamine, dichloroethylene/vinyl acetate copolymer, polytetrafluoroethylene Q, polytrifluoroethylene, cellulose-based film, nylon film, etc. It is particularly preferred to use polyethylene terephthalate. These may be used alone or in combination of two or more. The thickness of the support is not particularly limited, and may be appropriately selected depending on the purpose, for example, preferably 2//m to 150/zm, preferably 5ym to 100/zm, and 8; uni~5〇em is particularly preferable. . The aforementioned support system may be a single layer or a multilayer structure. The shape of the aforementioned support is not particularly limited, and may be appropriately selected depending on the purpose thereof, and is preferably a long shape. The length of the long-length support is -74 to 200935174, and is not particularly limited, and may be, for example, a length of 10 m to 20,000 m. <Protective layer> The photosensitive film may form a protective layer on the photosensitive layer. The protective layer may, for example, be a user of the above-mentioned support, paper, paper obtained by laminating polyethylene or polypropylene, and the like, and particularly preferably a polyethylene film or a polypropylene film. The thickness of the protective layer is not particularly limited, and may be appropriately selected according to the purpose, for example, 5 " m~100/£ m is better, 8/zm~50; ci m is better, l〇em~30; Zm is especially good. The combination of the support and the protective layer (support/protective layer) may, for example, be polyethylene terephthalate/polypropylene, polyethylene terephthalate/polyethylene, polydichloroethylene/cellulose.玢, polyimide/polypropylene, polyethylene terephthalate/polyethylene terephthalate, and the like. Further, the adhesion between the layers can be adjusted by surface-treating at least one of the support and the protective layer. The surface treatment of the support may be carried out in order to improve the adhesion to the photosensitive layer, and examples thereof include coating of a coating, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high-frequency irradiation treatment, and glow discharge irradiation. Treatment, active plasma irradiation treatment, laser irradiation treatment, and the like. Further, the static friction coefficient of the support and the protective layer is preferably from 0.3 to 1.4 and more preferably from 0.5 to 1.2. When the static friction coefficient is less than 0.3, the winding deviation occurs in the form of a roll due to excessive slip, and when it exceeds 1.4, it becomes difficult to wind up into a good roll shape. The photosensitive film is preferably wound into a cylindrical core, and is preferably wound into a roll shape in a long shape for storage. The length of the long-length photosensitive film of -75 to 200935174 is not particularly limited, and can be appropriately selected, for example, from the range of 10 m to 20,000 m. Further, in order to make it easy for the user to use, it is also possible to perform slitting processing to form a long-length body in the range of l〇〇m~l, OOOm into a roll shape. Further, in this case, it is preferable that the aforementioned support system winding is the outermost side. Further, the roll-shaped photosensitive film may be cut into a sheet shape. In the case of storage, it is preferable to set a separator on the end surface (particularly for moisture prevention and desiccant) from the viewpoint of protecting the end surface and preventing the edge from melting, and using a raw material having a low packing or a low moisture permeability. good.前述 The protective layer may be subjected to surface treatment in order to adjust the adhesion between the protective layer and the photosensitive layer. In the surface treatment, for example, on the surface of the protective layer, a coating layer composed of a polymer of polyorganosiloxane, fluorinated polyolefin, polyvinyl fluoride, polyvinyl alcohol or the like is formed. The formation of the undercoat layer can be carried out by applying the coating liquid of the polymer to the surface of the protective layer, followed by drying at 30 ° C to 150 ° C for 1 minute to 30 minutes. The temperature at the time of the drying is particularly preferably 5 (TC to 120 ° C. <Other layers> The other layer of the photosensitive film is not particularly limited, and may be appropriately selected depending on the purpose, for example It may have a layer such as a buffer layer, an oxygen barrier layer (PC layer), a release layer, an adhesive layer, a light absorbing layer, a surface protective layer, etc. These layers may be used alone or in combination of two or more. Further, the photosensitive layer may have a protective layer. <Method for Producing Photosensitive Film> The photosensitive film may be produced, for example, by the following method. First, a material contained in the photosensitive composition is dissolved in The emulsion or the solvent is emulsified or dispersed to prepare a photosensitive composition solution for a photosensitive film. The solvent is, for example, the same as the solvent of the photosensitive composition solution. The photosensitive composition solution is applied onto the support and dried to form a photosensitive layer, whereby a photosensitive film can be produced. The coating method of the photosensitive composition solution is, for example, the above method. Since the photosensitive film is used as the photosensitive composition, it is excellent in plating resistance, sensitivity, developability, and adhesion, and can be suitably used for permanent patterns such as a protective film, an interlayer insulating film, and a solder resist pattern. For the production of liquid crystal structural members such as various pattern forming, color filters, pillars, ribs, spacers, partitions, etc., holograms, micromachines, proofs, etc., etc. It can be suitably used for the formation of a permanent pattern on a printed substrate. In particular, since the photosensitive film is uniform in thickness, a permanent pattern (protective film, interlayer insulating film, solder resist) is formed when a permanent pattern is formed. Thin layering, dendritic crystals are not produced in the high acceleration test (HAST), and the high-precision permanent pattern excellent in heat resistance and moisture resistance can be obtained, so that the laminate of the substrate can be finer. (Photosensitive Laminate) The photosensitive laminate system has at least the photosensitive layer ' on the substrate and can be appropriately selected depending on the intended laminate [Others] The above-mentioned base system is a substrate to be processed to form a photosensitive layer, or a transferable body in which at least a photosensitive layer of the photosensitive film of the present invention is transferred is not particularly -77-200935174 The limitation can be appropriately selected depending on the purpose, and can be arbitrarily selected, for example, from a surface smoothness to a surface having some unevenness. The plate-shaped substrate is preferably 'a so-called substrate can be used. Specifically, for example, A known substrate (printed substrate) for producing a printed wiring board, a glass plate (such as a soda-lime glass plate), a synthetic resin film, paper, a metal plate, etc. <Method for Producing Photosensitive Laminate> < In the method for producing a laminate, the first embodiment may be, for example, a method in which the photosensitive composition is applied onto the surface of the substrate and dried, and the second embodiment may be, for example, at least one of the photosensitive films. A method of transferring and laminating at least one of heat and pressure, and a method for producing a photosensitive laminate of the first aspect is applied to the substrate Drying the photosensitive composition to form a photosensitive layer. The method of coating and drying is not particularly limited, and may be appropriately selected depending on the purpose, and for example, the photosensitive composition may be dissolved in water or a solvent, emulsified or dispersed to prepare a photosensitive composition solution, and The method of laminating the solution to the surface of the substrate by directly coating and drying the solution. The coating method and the drying conditions are not particularly limited, and may be appropriately selected depending on the purpose, and may be carried out in the same manner and under the conditions as those employed in the photosensitive film. In the method of producing the photosensitive laminate of the second aspect, the photosensitive film of the present invention is laminated on the surface of the substrate while performing at least one of heating and pressurization. Further, in the case where the photosensitive film has the above protective layer, it is preferred to peel off the protective layer and laminate it to the aforementioned substrate -78-200935174 so that the photosensitive layers are overlapped. The heating temperature is not particularly limited, and may be appropriately selected depending on the purpose thereof, and is preferably, for example, 15 to 180 ° C and more preferably 60 to 140 ° C. The pressurizing pressure system is not particularly limited, and may be appropriately selected depending on the purpose thereof, for example, a device having at least one of heating, preferably 0.2 to 0.8 MPa, more preferably 0.2 to 0.8 MPa. It is not particularly limited, and may be appropriately selected depending on the purpose, and may be, for example, a laminating machine (for example, VP-II manufactured by Daewoo Co., Ltd., VP130 manufactured by Nichigo Motor Co., Ltd.) or the like. In the photosensitive film and the photosensitive laminate, since the photosensitive composition is used, sensitivity, developability, and adhesion are good, and a high-definition permanent pattern can be formed more efficiently, and can be suitably used for protection. For the production of liquid crystal structural members such as various patterns such as a film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern, a color filter, a pillar, a rib, a spacer, and a partition, hologram, micromachine, It is used for forming a pattern such as proof, and the like, and can be suitably used for forming a permanent pattern of a printed circuit board. In particular, since the thickness of the photosensitive film is uniform, even when a permanent pattern (a protective film, an interlayer insulating film, a solder resist, etc.) is formed into a permanent pattern, in a highly accelerated life test (HAST) Also, dendrites do not occur, and since a high-definition permanent pattern excellent in heat resistance and moisture resistance is obtained, the lamination of the substrate can be performed more finely. (Permanent Pattern Forming Method) The above-described permanent pattern forming method includes at least an exposure step, and may include other steps such as an appropriate selection step of the image from 79 to 200935174. Further, the pattern forming apparatus can be understood from the above description of the pattern forming method, and includes the photosensitive layered body and at least a light irradiation means and a light modulation means. <Exposure Step> The aforementioned exposure step is a step of exposing the photosensitive layer. The materials regarding the photosensitive layer and the substrate are as described above. The object to be exposed may be in the range of the photosensitive layer, and is not particularly limited, and may be appropriately selected depending on the purpose. For example, as described above, at least one of heating and pressurizing the photosensitive composition is used. On the other hand, it is preferred that the photosensitive layer laminated in the photosensitive laminate formed on the substrate is exposed. The above-mentioned exposure system is not particularly limited, and may be appropriately selected depending on the purpose thereof, and may be, for example, digital exposure, analog exposure, etc., but digital exposure is preferred among these. The analog exposure system is not particularly limited, and may be appropriately selected depending on the purpose, and may be, for example, a method of exposing an (ultra) high pressure mercury lamp, a xenon lamp, a halogen lamp or the like through a mask having a predetermined pattern. The above-mentioned digital exposure is not particularly limited, and may be appropriately selected depending on the purpose thereof. For example, it is preferable to move an exposure head having at least a light irradiation means and a light modulation means, and the photosensitive layer. At least one of the photosensitive layers is irradiated with the light emitted from the light irradiation means by the light modulation means according to the pattern information, and is irradiated from the exposure head to perform digital exposure. The light source used in the above-mentioned digital exposure may be a light source capable of emitting ultraviolet rays to near-80 to 200935174 infrared rays, and is not particularly limited, and may be appropriately selected depending on the purpose thereof, for example, (ultra) high pressure mercury lamp, xenon lamp, carbon may be used. A known light source such as a fluorescent tube such as an arc lamp, a halogen lamp, or a copying machine, or a laser beam, etc., among which (super) high pressure mercury lamp, laser light, and laser light are more preferable. The so-called (ultra) high-pressure mercury lamp system encloses mercury into a discharge lamp such as a quartz glass tube, and raises the vapor pressure of the mercury to increase the luminous efficiency. Among the linear spectra, it is possible to use only a line of one wavelength using an ND filter or the like, or a light having a plurality of linear spectra. The "laser" of the aforementioned laser light is the head word of Light Amplification by S t i m ι i 1 a t e d E m i s s i ο η o f R a d i a t i ο η (increased by the induced light emission). The apparatus for emitting laser light is, for example, a monochromatic light which is enhanced by coherence and orientation by utilizing an induced release image which occurs in a material having an inverted distribution and which is amplified and oscillated by light waves. The vibrator and the amplifier are suitable. The excitation medium for the laser light is crystal, glass, liquid, pigment, gas, or the like, and a well-known laser such as a solid laser, a liquid laser, a body laser, or a semiconductor laser from such a medium can be used. Specifically, the gas laser system may be, for example, an Ar ion laser (364 nm, 351 nm}, a Kr ion laser (356 nm, 351 nm), a He-Cd laser (3 25 nm), and a solid laser system such as YAG. Laser, YV04 laser (l, 064 nm), YAG laser or YV04 laser 2 times wave (532 nm), 3 times wave (355 nm), 4 times wave (266 nm), guided wave type wavelength conversion element and AlGaAs, Combination of InGaAs semiconductor (380nm~400nm), combination of guided wave type wavelength conversion element and AlGalnP or AlGaAs semiconductor t*81- 200935174 (3 Ο ~ nm ~ 3 5 Ο nm), A1 G a I η N (3 5 Ο From the cost side, for example, an AlGalnN semiconductor laser (a commercially available InGaN-based semiconductor laser of 375 nm or 405 nm) has high output power on a productive surface, such as nm ~ 4 7 Ο nm). The wavelength of the laser light is preferably 200 nm to 1,500 nm, preferably 300 nm to 800 nm, more preferably 330 nm to 500 nm, and particularly preferably 350 nm to 420 nm. - Optical modulation means - © The optical modulation means may be, for example, a method in which n drawing units are provided and the drawing unit is controlled based on the pattern information. Specifically, for example, a digital micro-reflecting device (DMD), or a MEMS (Micro Electro Mechanical Systems) type spatial light modulation element (SLM; Spacial Light Modulator), by electro-optics The effect is to modulate the transmitted optical element (PLZT element), liquid crystal shutter (FLC), etc., among which DMD is particularly suitable.

前述使用D M D之情形，來自光源的光線係可藉由適合的光學系統照設置前述DMD上，且使前述DMD中來自二維並排的各反射鏡之反射光經過其他的光學系統等，而在感光層上形成二維並排的光點之像。就這樣光點與光點之間係沒有沒有受到曝光，但將前述二維並排的光點之像對於二維並排的方向，稍稍往傾斜的方向移動時，藉由使最初列的光點與光點之間的後方列之光點曝光，可曝光感光層的全面。前述DMD係可藉由控制各反射鏡的角度，且前述光點係進行ON-OFF控制，而可形成畫像圖案。藉由排列具 -82- 200935174 有如此前述DMD之曝光頭來使用的話，可對應於各種寬度的基板。前述DMD係將前述光點的亮度一邊進行ON或OFF的2 階調、一邊使用反射鏡階調型空間調變元件時，可進行256 階調的曝光。又，前述光調變手段較佳係根據形成之圖案情報，具有生成控制信號之圖案信號生成手段。此時，前述光調變手段係根據前述圖案信號生成手段所生成之控制信號來調〇變光。前述控制信號係沒有特別地限制，可視其目的做適當地選擇，可舉例如數位信號爲適宜。，另一方面，前述光調變手段之另一代表性方法，係可舉例如使用多角鏡之方法。此處，多角鏡（polygon mirror) 係在周圍具有一連串的平面反射面之回轉構件。前述多角鏡係將來自光源的光反射並照射至感光層上，而反射光的光點係可藉由該平面鏡的回轉來進行掃瞄。對於該掃瞄方〇向成直角地移動基板的話，可曝光基板上感光層的全面。而且，來自光源的光強度係可藉由以適合的方法控制 ON-OFF、或控制爲中間調，而可形成畫像圖案。此時，藉由使來自光源的光線爲複數條的話，可縮短掃瞄時間。前述光調變手段係可舉例如其他使用特開平 5-150175公報中所記載之多角鏡進行描繪之例；特表 2004-523101公報（國際公開第2002/039793號手冊）中所記載的視覺性取得下部層畫像的一部份，並利用使用多角鏡之裝置以使得上部層的位置與下部層位置一致’以進 -83- 200935174 行曝光之例；具有特開2004-56080公報中所記載之DMD 以進行曝光之例；具備特表2002-523905公報中所記載之多角鏡的曝光裝置、具備特開2001-255661公報中所記載之多角鏡的曝光裝置、特開2003-50469公報中所記載之 DMD、LD、多次曝光之組合例；特開2003-156853公報中所記載的根據基板的部位改變曝光量之曝光方法之例；特開2005-43576公報中所記載的進行位置偏差調整之曝光方法之例等。 ® -光照射手段- 前述光照射手段、亦即光的照射方法係沒有特別地限制，前述的曝光光源係可視其目的做寧當選擇，來自此等光源的光線係可舉例如合成2以上來進行爲適宜，照射合成 2以上的光線之雷射光（合波雷射光）係爲特別適宜。前述合波雷射光的照射方法係沒有特別地限制，可視其目的做適當選擇，可舉例如藉由複數個的雷射光源、多模式光纖、與聚光來自該複數個的雷射光源所照射之雷射〇光並與前述多模式光纖結合之集合光學系統，構成合波雷射光而進行照射之方法爲適宜。前述雷射光的光束徑係沒有特別地限制，可視其目的做適當選擇，從濃色離隔壁的解析度之觀點而言，以高斯光束的Ι/e2値爲5// m~30// m爲佳、7# m爲更佳〇前述雷射光可根據畫像資訊進行空間光調變爲佳。因此，因爲該目的，使用空間光調變元件之前述DMD爲佳。具有前述光調變手段、及前述光照射手段之曝光裝置 -84- 200935174 係可使用例如特開2005-222039號公報、特開 2005-258431號公報、特開2006-30966號公報等中所記載的裝置，惟前述曝光裝置並不受限於此。 <顯像步驟> 前述顯像係可藉由去除前述感光層的未曝光部分而進行。前述未硬化領域的除去方法係沒有特別地限制，可視其目的做適當地選擇，可舉例如使用顯像液以除去之方法 ©等。前述顯像液係沒有特別地限制，可視其目的做適當選擇，可舉例如鹼性水溶液、水系顯像液、有機溶劑等，此 > 等之中，尤以弱鹼性的水溶液爲佳。該弱鹼性水溶液的鹼成分係可舉例如氫氧化鋰、氫氧化鈉、氫氧化鉀、碳酸鋰、碳酸鈉、碳酸鉀、碳酸氫鋰、碳酸氫鈉、碳酸氫鉀、磷酸鈉、磷酸鉀、焦磷酸鈉、焦磷酸鉀、硼砂等。前述弱鹼性水溶液的pH係例如以約8 ~ 1 2爲佳、約 Ο 9 ~ 1 1爲更佳。前述弱鹼性的水溶液係可舉例如0.1質量 % ~ 5質量％的碳酸鈉水溶液或碳酸鉀水溶液等。前述顯像液的溫度係可配合前述感光層的顯像性而適當地選擇，例如以約2 5。(： ~ 4 0 °C爲佳。前述顯像液係可與界面活性劑、消泡劑、有機鹼（例如，伸乙二胺、乙醇胺、氫氧化四甲基銨、二乙三胺、三乙五胺、味啉、三乙醇胺等）、或促進顯像用的有機溶劑（例如’醇類、酮類、酯類、醚類、醯胺類、內酯類等）等合倂使用。又’前述顯像液係可爲混合水或鹼性水溶液、與有 -85- 200935174 機溶劑之水系顯像液，亦可爲有機溶劑單獨。前述圖案的形成中’亦可包含例如硬化處理步驟、飩刻步驟、電鍍步驟等。此等係可單獨1種使用、亦可倂用2 種以上。 <硬化處理步驟> 前述圖案的形成方法係在進行形成保護膜、層間絶緣膜、耐焊劑圖案等的永久圖案、或形成彩色濾光片之永久圖案形成方法的情形中，在前述顯像步驟後，具備對於感 ® 光層進行硬化處理之硬化處理步驟爲佳。前述硬化處理步驟係沒有特別地限制，可視其目的做適當選擇，可舉例如全面曝光處理、全面加熱處理等爲適宜。前述全面曝光處理的方法係可舉例如在前述顯像後，曝光前述永久圖案形成之前述積層體上的全面之曝光方法。藉由該全面曝光，在形成前述感光層之感光性組成物中可促進樹脂的硬化，且使前述永久圖案的表面硬化。〇前述進行全面曝光之裝置係沒有特別地限制，可視其目的做適當選擇，可舉例如超高壓水銀燈等的UV曝光機、氙氣燈使用的曝光機、雷射曝光機等爲適宜。曝光量係通常爲 10mJ/cm2~2,000mJ/cm2。前述全面加熱處理的方法係可舉例如在前述顯像之後，加熱前述永久圖案形成之前述積層體上的全面之加熱方法。藉由該全面加熱，可提高前述永久圖案表面的膜強度〇前述全面加熱中的加熱溫度係以12〇°C ~250°C爲佳、 -86- 200935174 120°C~200°C爲更佳。該加熱溫度低於12CTC時，無法藉由加熱處理而提昇膜強度，超過250 °C時，前述感光性組成物中產生樹脂分解，膜質係變弱易脆。前述全面加熱中的加熱時間係以1 0分~ 1 2 0分爲佳、1 5 分〜60分爲更佳。前述進行全面加熱之裝置係沒有特別地限制，可從眾所周知的裝置之中視其目的做適當地選擇，可舉例如乾式烘箱、加熱板、IR加熱器等。 © 前述圖案的形成方法在藉由405nm的雷射曝光之直接描繪中，可使用於必須防止因氧而使得感光層之感度降低之各種圖案的形成等、可適當使用於兼具高密度化與高生產性之圖案形成。在前述永久圖案形成方法中，藉由前述永久圖案形成方法所形成之永久圖案係爲前述保護膜或前述層間絶緣膜時，可保護配線避免來自外部的衝撃或彎曲，特別是在前述層間絶緣膜之情形中，例如，對於多層配線基板或組裝〇配線基板等的半導體或構件之高密度封裝係爲有用。前述永久圖案形成方法由於使用前述感光性組成物’ 所以可適當使用於保護膜、層間絶緣膜、及耐焊劑圖案等永久圖案等的各種圖案形成用、彩色濾光片、柱材、肋材、間隔材、隔壁等的液晶構造構件的製造、全息照相、微型機械、樣張（proof)等的製造，特別是可適當使用於印刷基板的永久圖案形成。實施例以下，本發明係藉由實施例來更具體地説明’本發明 -87- 200935174 係不超出其主旨之範圍內，且不限定於以下的實施例。此外，沒有特別地預先限定的話，「份」係爲質量基準。 (實施例1) -感光性薄膜的製造- 在做爲支持體之厚度16//m的聚對苯二甲酸乙二酯薄膜（東麗股份有限公司製、16 FB 50)上，塗布下述的組成所構成之感光性組成物溶液且乾燥，以在前述支持體上形成厚度30// m的感光層。在前述感光層上積層做爲保護層之 © 厚度20#m的聚丙烯薄膜（王子特殊紙股份有限公司製、 ARUFUN E-200)，以製造感光性薄膜。 <感光性組成物溶液 > 的組成下述黏結劑1的溶液...................1 〇〇質量份三環癸院二丙’稀酸酯（商品名：NK ester A-DCP).... ........................................ism&m 下述式1-2所表示之光聚合起始劑.......1.0質量份下述式S-1所表示之增感劑............0.7質量份〇 EPOTOHTO YD-8125(環氧等量 170g/eq.東都化成股份有限公司製、雙酚A系環氧樹脂）.........8.9質量份氰胍...............................〇 . 5質量份顔料分散液........................80.21質量份 MEGAFAC F-780F(大日本油墨股份有限公司製）的 30質量％甲基乙基酮溶液...................0.2質量份此外，前述顔料分散液係以電動硏磨機M_250(IGAR 公司製），預先混合硫酸鋇（堺化學股份有限公司製、B30)30 質量份、前述黏結劑1的溶液50質量份、酞菁藍〇. ;l 6質量 -88- 200935174 份、與蒽醌系黃色顔料（PY2 4) Ο. 〇 7質量份之後，使用直徑 1 .Omm的氧化锆珠粒，以周速9m/s進行3小時分散而調製的0In the case of using the DMD described above, the light from the light source can be disposed on the DMD by a suitable optical system, and the reflected light from the two-dimensional side-by-side mirrors in the DMD passes through other optical systems or the like, and is exposed to light. An image of two-dimensional side-by-side light spots is formed on the layer. In this way, there is no exposure between the light spot and the light spot, but when the image of the two-dimensional side-by-side light spot is moved in a direction slightly inclined to the two-dimensional side by side, by making the light spot of the first column The spot of the rear column between the spots is exposed to expose the entire layer of the photosensitive layer. The DMD can form an image pattern by controlling the angle of each of the mirrors and performing ON-OFF control of the above-mentioned light spots. By arranging the exposure head of the above-mentioned DMD with the -82-200935174, it is possible to correspond to substrates of various widths. The DMD is capable of performing 256-step exposure when a mirror-level spatial modulation element is used while the brightness of the light spot is turned ON or OFF. Further, it is preferable that the optical modulation means has a pattern signal generating means for generating a control signal based on the formed pattern information. In this case, the optical modulation means adjusts the dimming based on the control signal generated by the pattern signal generating means. The aforementioned control signal is not particularly limited, and may be appropriately selected depending on the purpose thereof, and for example, a digital signal is suitable. On the other hand, another representative method of the above optical modulation means can be exemplified by a method using a polygon mirror. Here, the polygon mirror is a rotating member having a series of planar reflecting surfaces around it. The polygon mirror reflects light from the light source and illuminates the photosensitive layer, and the light spot of the reflected light can be scanned by the rotation of the plane mirror. By moving the substrate at right angles to the scanning direction, the entire photosensitive layer on the substrate can be exposed. Moreover, the light intensity from the light source can be formed into an image pattern by controlling ON-OFF in a suitable manner or controlling to a midtone. At this time, the scanning time can be shortened by making the light from the light source a plurality of lines. The above-mentioned optical modulation means is exemplified by the use of a polygon mirror described in Japanese Laid-Open Patent Publication No. Hei 5-150175, and the visibility described in Japanese Patent Publication No. 2004-523101 (International Publication No. 2002/039793). Obtaining a part of the lower layer image and using a device using a polygon mirror such that the position of the upper layer coincides with the position of the lower layer is taken as an example of exposure to -83-200935174; and it is described in Japanese Laid-Open Patent Publication No. 2004-56080 An example of the exposure of the DMD, and the exposure apparatus of the polygon mirror described in the Japanese Patent Publication No. 2002-523905, and the exposure apparatus of the polygon mirror described in JP-A-2001-255661, JP-A-2003-50469 An example of a combination of DMD, LD, and multiple exposures; an example of an exposure method for changing an exposure amount according to a portion of a substrate described in Japanese Laid-Open Patent Publication No. 2003-156853; Examples of exposure methods, etc. ® - Light irradiation means - The light irradiation means, that is, the light irradiation method is not particularly limited, and the above-mentioned exposure light source can be selected according to the purpose, and the light from the light source can be, for example, a combination of 2 or more. It is particularly preferable to perform laser light (combined laser light) which is suitable for irradiation with light of 2 or more. The method of irradiating the combined laser light is not particularly limited, and may be appropriately selected depending on the purpose thereof, and may be irradiated by, for example, a plurality of laser light sources, multimode optical fibers, and concentrated light from the plurality of laser light sources. A method in which the laser beam is combined with the multi-mode optical fiber and the combined optical system is combined to form a combined laser light and irradiated is suitable. The beam path of the aforementioned laser light is not particularly limited, and may be appropriately selected depending on the purpose. From the viewpoint of the resolution of the rich color from the partition wall, the Ι/e2 高 of the Gaussian beam is 5//m~30//m. For better, 7# m is better, the aforementioned laser light can be better adjusted according to the portrait information. Therefore, for this purpose, it is preferable to use the aforementioned DMD of the spatial light modulation element. The exposure apparatus of the above-mentioned light-modulating means, and the above-mentioned light-irradiation means - 84-200935174 can be described, for example, in JP-A-2005-222039, JP-A-2005-258431, JP-A-2006-30966, and the like. The device is only limited to the aforementioned exposure device. <Production Step> The above-described development can be carried out by removing the unexposed portion of the photosensitive layer. The removal method in the uncured field is not particularly limited, and may be appropriately selected depending on the purpose, and for example, a method of removing using a developing solution, etc., may be mentioned. The above-mentioned developing liquid system is not particularly limited, and may be appropriately selected depending on the intended purpose, and examples thereof include an alkaline aqueous solution, a water-based developing liquid, and an organic solvent. Among them, a weakly alkaline aqueous solution is preferable. The alkali component of the weakly alkaline aqueous solution may, for example, be lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate or potassium phosphate. , sodium pyrophosphate, potassium pyrophosphate, borax, and the like. The pH of the weakly alkaline aqueous solution is preferably, for example, about 8 to 12, more preferably about 9 to 11. The weakly alkaline aqueous solution may, for example, be a 0.1% by mass to 5% by mass aqueous sodium carbonate solution or a potassium carbonate aqueous solution. The temperature of the above-mentioned developing liquid can be appropriately selected in accordance with the developability of the above-mentioned photosensitive layer, for example, about 25 cm. (: ~ 40 ° C is preferred. The above imaging liquid can be combined with surfactants, antifoaming agents, organic bases (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, three) Ethyl pentaamine, porphyrin, triethanolamine, etc., or an organic solvent for promoting development (for example, 'alcohols, ketones, esters, ethers, guanamines, lactones, etc.), etc. The above-mentioned developing liquid may be a mixed water or an alkaline aqueous solution, or a water-based developing liquid having a solvent of -85-200935174, or may be an organic solvent alone. The formation of the pattern may also include, for example, a hardening treatment step, The etching step, the plating step, etc. These may be used alone or in combination of two or more. <The curing step> The method for forming the pattern is to form a protective film, an interlayer insulating film, and a solder resist. In the case of a permanent pattern such as a pattern or a permanent pattern forming method for forming a color filter, it is preferable to provide a hardening treatment step for hardening the photosensitive layer after the developing step. Special restrictions, The appropriate selection may be, for example, a full exposure treatment or a total heat treatment. The method of the overall exposure treatment may be, for example, a comprehensive exposure of the laminate formed by exposing the permanent pattern after the development. The exposure method can promote the hardening of the resin and harden the surface of the permanent pattern in the photosensitive composition forming the photosensitive layer. The apparatus for performing overall exposure is not particularly limited, and The purpose is suitably selected, for example, a UV exposure machine such as an ultrahigh pressure mercury lamp, an exposure machine for a xenon lamp, a laser exposure machine, etc. The exposure amount is usually 10 mJ/cm 2 to 2,000 mJ/cm 2 . The method may be, for example, heating the entire heating method on the laminated body formed by the permanent pattern after the development, and by the overall heating, the film strength of the surface of the permanent pattern may be increased, and the heating in the overall heating may be performed. The temperature is preferably 12 ° C ~ 250 ° C, -86 - 200935174 120 ° C ~ 200 ° C is better. The heating temperature At 12 CTC, the film strength cannot be increased by heat treatment. When the temperature exceeds 250 ° C, the resin is decomposed in the photosensitive composition, and the film quality is weak and brittle. The heating time in the overall heating is 10 minutes. 1 2 0 is preferably divided into 15 minutes to 60. The apparatus for performing overall heating is not particularly limited, and may be appropriately selected from among well-known apparatuses depending on the purpose thereof, and may be, for example, a dry oven or a heating. Plate, IR heater, etc. © The method of forming the pattern described above, in the direct drawing by laser exposure at 405 nm, can be suitably used for forming various patterns that must prevent the sensitivity of the photosensitive layer from being lowered by oxygen. It is a combination of high density and high productivity. In the foregoing permanent pattern forming method, when the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, the wiring can be protected from punching or bending from the outside, particularly in the interlayer insulating film. In this case, for example, it is useful for a multilayer wiring board or a high-density package of a semiconductor or a member in which a wiring board or the like is assembled. The permanent pattern forming method can be suitably used for various pattern formations such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern, a color filter, a pillar, and a rib, because the photosensitive composition is used. The production of a liquid crystal structural member such as a spacer or a partition, production of a hologram, a micromachine, a proof, or the like can be suitably used for permanent pattern formation of a printed substrate. EXAMPLES Hereinafter, the present invention is more specifically described by the examples, and the present invention is not limited to the scope of the invention, and is not limited to the following examples. Further, the "parts" are based on quality unless otherwise specified. (Example 1) - Production of a photosensitive film - The polyethylene terephthalate film (16 FB 50, manufactured by Toray Industries, Inc.) having a thickness of 16/m as a support was applied as follows. The photosensitive composition solution composed of the composition was dried and formed into a photosensitive layer having a thickness of 30/m on the support. A polypropylene film (manufactured by Oji Paper Co., Ltd., ARUFUN E-200) having a thickness of 20 #m was laminated on the photosensitive layer to produce a photosensitive film. <Photosensitive composition solution> Composition of the following bonding agent 1.................. 1 〇〇 mass part of the three-ring brothel Acid ester (trade name: NK ester A-DCP)........................................ .ism&m The photopolymerization initiator represented by the following formula 1-2. 1.0 part by mass of the sensitizer represented by the following formula S-1. .......0.7 parts by mass 〇EPOTOHTO YD-8125 (epoxy equivalent 170g/eq. Dongdu Chemical Co., Ltd., bisphenol A epoxy resin).........8.9 quality Parts of cyanogen...............................〇. 5 parts by mass of pigment dispersion........ ................80.21 parts by mass of MEGAFAC F-780F (manufactured by Dainippon Ink Co., Ltd.) 30% by mass methyl ethyl ketone solution........ In the above-mentioned pigment dispersion liquid, 30 parts by mass of barium sulfate (manufactured by Daicel Chemical Co., Ltd., B30) was previously mixed with an electric honing machine M_250 (manufactured by IGAR Co., Ltd.). 50 parts by mass of the above-mentioned binder 1 , phthalocyanine blue 〇.; 16 mass - 88 - 200935174 parts, and lanthanide yellow pigment (PY2 4) Ο. 〇 7 parts by mass, 1 .Omm diameter zirconia beads at a peripheral speed 9m / s for 3 hours to prepare a dispersion of the 0

S-1 (合成例1)黏結劑1的合成在l，000mL三頸燒瓶中加入1-甲氧基-2-丙醇159g，並於氮氣流下、加入至85°C。於其中花2小時，滴下甲基丙烯酸苄酯63.4g、甲基丙烯酸72.3g、V-601(和光純藥製 )4.15g的1-甲氧基-2-丙醇159g溶液。滴下終了後，再加熱5小時進行反應。其次，停止加熱，以得到甲基丙烯酸苄酯/甲基丙烯酸（30/70莫耳％比）的共聚物。接著，將前述共聚物溶液之中的120.0 g移至300mL三頸燒瓶中，加入甲基丙烯酸縮水甘油酯16.6g、p-甲氧基酚〇. 16g並攪拌使其溶解。溶解後，加入三苯基膦3_0g並加熱至100 °C，以進行加成反應。以氣相色譜法確認甲基丙 -89- 200935174 烯酸縮水甘油酯消失後，停止加熱。加入1-甲氧基-2-丙醇 38g，以調製酸價112mgKOH/g、質量平均分子量15,000 、固體成分3 0質量％的黏結劑1的溶液。 -於基體的積層- 前述基體係於覆銅積層板（無通孔、銅厚度12^ m)的表面施加化學硏磨處理而調製的。前述感光性薄膜的感光層係以與前述覆銅積層板相接的方式，一邊剝離前述感光性薄膜中的保護薄膜、一邊使用真空層壓機（Nichigo Motor( © 股）製、VP130)來積層至該覆銅積層板上，以調製依序積層有前述覆銅積層板、前述感光層、與前述聚對苯二甲酸乙二酯薄膜（支持體）之積層體。，壓延條件係抽真空的時間爲40秒、壓延溫度爲70°C、壓延壓力爲〇.2MPa、加壓時間爲10秒。關於前述積層體係如下所述，來進行感度的評價。 <感度> 將前述積層體於室溫（23 °C、55% RH)靜置10分鐘。使〇用INPREX IP-3000(富士軟片公司製、畫素間距= l.〇M m) ，利用從〇.5mJ/cm2、以2 W2倍間隔至500inj/cm2之不同光能量的光線，將L/S(線寬/間距）= 50/zm/50/zm的圖案資訊照射、曝光於所得之前述積層體的感光層表面，以使得L/S(線寬/間距）= 50/ζιη/50μιη的線寬圖案硬化。於室溫靜置10分鐘後，從前述感光性積層體剝離取下前述支持體，將30°C的1質量％碳酸鈉水溶液以噴霧壓〇.15MPa、最短顯像時間的2~3倍的時間（或40~60秒）噴霧顯像於覆銅積層板上感光層的全面，以除去未硬化的領域。使用雷射 -90- 200935174 顯微鏡（VK-9500、KEYENCE公司製；對物透鏡50倍）來測定像這樣所得之L = 50/zm的圖案線寬，並將線寬爲50μπι 之曝光量設爲感度（最適曝光量）。結果表示於表1。 -顯像及硬化處理- 從前述積層體剝掉聚對苯二甲酸乙二酯薄膜（支持體} ，並將30°C的1質量％碳酸鈉水溶液以0· 15MPa的壓力，對前述感光層的全面噴霧6 0秒鐘，以溶解去除未硬化的領域。然後，進行水洗、乾燥，以形成永久圖案。〇 <顯像性> 從前述積層體剝掉聚對苯二甲酸乙二酯薄膜（支持體），並將30°c的1質量％碳酸鈉水溶液以0.1 5MPa的壓力，對覆銅積層板上前述感光層的全面進行噴霧，測定從噴霧碳酸鈉水溶液開始，到溶解去除覆銅積層板上的感光層所需要的時間，並將其當作最短顯像時間。該最短顯像時間越短，顯像性係爲優異。結果係表示於表1。 <絶緣可靠性的評價（HAST試驗）> 〇除了使用銅厚12//Π1的覆銅積層板，以線寬/間距 = 50μ m/50/z m的方式配線形成爲梳齒型者來作爲前述基材以外，針對以與前述永久圖案之形成方法相同方式作成之永久圖案，進行HAST試驗並評價樹枝狀晶體與絶緣電阻 (Ω )» HAST試驗中係使用高加速度試驗器，將電子構件模組在溫度爲1 3 0 °C且相對濕度爲8 5 %的雰圍氣中，於施加 200小時的電壓10V後，於同條件下測定導體隆起部分的絶緣電阻（Ω)，隨後進行導體隆起部分的樹枝狀晶體觀察進行如以下之評價。結果’係表示於表1。 -91- 200935174 〔評價基準〕〇：無樹枝狀晶體 X :有樹枝狀晶體 <生物保存性的評價> 將前述積層體在室溫（23°c、55%RH)下，密閉於防濕袋（黑色聚乙烯製的筒狀袋、膜厚：SO/zm、水蒸氣透過率 :25g/m2_24hr以下）開始，於40°C下保存3天之後，藉由與前述最短顯像時間的評價中相同的方法，來測定前述最 ©短顯像時間，於前述最短顯像時間的評價中所得之値設爲 to，於保存3天後的前述最短顯像時間之値設爲h，以算出 U/U之填。但是，在測定“時，即使進行60秒鐘噴霧顯像亦無法去除前述感光層之情形記爲「X」。所得之値越接近1 ，意味著生物保存性係爲優異。結果係表示於表1。 <解析度的評價> 將前述積層體靜置於室溫（23°C、55%RH) 10分鐘。使用INPREX IP-3000(富士軟片股份有限公司製、畫素間距〇 =l.〇ym)，將直徑40/zm~直徑400/zm且每ΙΟ/zm的圓孔圖案資訊，以前述最適曝光量照射於所得之前述積層體的感光層表面，並進行各穴徑的圖案曝光。於室溫靜置10分鐘後，以與前述最短顯像時間的評價中相同的方法，且根據前述的方法所得之最短顯像時間的2倍時間進行噴霧顯像，以去除未硬化領域。以光學顯微鏡觀察像這樣所得之硬化樹脂圖案的表面，並將硬化樹脂圖案上沒有堵塞、波紋等的異常之最小圓孔徑當作解析度。該解析度係數値越小越爲良好。結果係表示於表1。 -92- 200935174 (實施例2) 除了將三環癸烷二丙烯酸酯（商品名：NK ESTER A-DCP)取代爲三環癸烷二甲基丙烯酸酯（商品名：NK ESTER DCP)以外，以與實施例1同樣的方式，製造積層體及永久圖案，並以與實施例1同樣的方式’進行感度、顯像性、生物保存性、解析性及絶緣可靠性的評價。結果係表示於表1。 {實施例3}S-1 (Synthesis Example 1) Synthesis of the binder 1 159 g of 1-methoxy-2-propanol was placed in a 1,000 mL three-necked flask, and added to 85 ° C under a nitrogen stream. After 2 hours, a solution of 63.4 g of benzyl methacrylate, 72.3 g of methacrylic acid, and 4.15 g of 1-methoxy-2-propanol of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. After the completion of the dropwise addition, the reaction was further carried out by heating for 5 hours. Next, the heating was stopped to obtain a copolymer of benzyl methacrylate/methacrylic acid (30/70 mol%). Next, 120.0 g of the copolymer solution was transferred to a 300 mL three-necked flask, and 16.6 g of glycidyl methacrylate and 16 g of p-methoxyphenol oxime were added and stirred to dissolve. After the dissolution, 3-0 g of triphenylphosphine was added and heated to 100 ° C to carry out an addition reaction. After confirming the disappearance of methyl propyl-89-200935174 olefinic acid glycidyl ester by gas chromatography, the heating was stopped. 38 g of 1-methoxy-2-propanol was added to prepare a solution of the binder 1 having an acid value of 112 mgKOH/g, a mass average molecular weight of 15,000, and a solid content of 30% by mass. - Lamination of the substrate - The above-mentioned base system was prepared by applying a chemical honing treatment to the surface of a copper clad laminate (without via holes, copper thickness of 12 μm). The photosensitive layer of the photosensitive film is laminated with a vacuum laminator (made by Nichigo Motor Co., Ltd., VP130) while peeling off the protective film in the photosensitive film so as to be in contact with the copper-clad laminate. To the copper clad laminate, a laminate of the copper clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) is laminated in this order. The rolling conditions were a vacuuming time of 40 seconds, a rolling temperature of 70 ° C, a rolling pressure of 〇. 2 MPa, and a pressurizing time of 10 seconds. Regarding the above-described laminated system, the sensitivity was evaluated as described below. <Sensitivity> The laminate was allowed to stand at room temperature (23 ° C, 55% RH) for 10 minutes. Using INPREX IP-3000 (manufactured by Fujifilm Co., Ltd., pixel spacing = l.〇M m), using light of different light energies from 〇5mJ/cm2, 2 W2 times to 500inj/cm2, L Pattern information of /S (line width/pitch) = 50/zm/50/zm is irradiated and exposed on the surface of the photosensitive layer of the obtained laminate, so that L/S (line width/pitch) = 50/ζιη/50μιη The line width pattern is hardened. After standing at room temperature for 10 minutes, the support was removed from the photosensitive laminate, and a 1% by mass aqueous sodium carbonate solution at 30 ° C was spray-pressed at 15 MPa and 2 to 3 times the shortest development time. The time (or 40 to 60 seconds) is sprayed onto the entire layer of the photosensitive layer on the copper clad laminate to remove the uncured areas. Using a laser-90-200935174 microscope (VK-9500, manufactured by KEYENCE Co., Ltd.; 50 times the objective lens), the pattern line width of L = 50/zm thus obtained was measured, and the exposure amount of the line width of 50 μm was set to Sensitivity (optimal exposure). The results are shown in Table 1. - development and hardening treatment - peeling off the polyethylene terephthalate film (support) from the above laminated body, and applying a 1% by mass aqueous sodium carbonate solution at 30 ° C to the photosensitive layer at a pressure of 0.15 MPa. Full-spraying for 60 seconds to dissolve and remove the unhardened area. Then, it is washed with water and dried to form a permanent pattern. 〇 <Developability> Peel off polyethylene terephthalate from the aforementioned laminate a film (support), and a 30% by mass of a 1% by mass aqueous sodium carbonate solution was sprayed on the copper-clad laminate on the copper-clad laminate at a pressure of 0.15 MPa, and the measurement was started from the sprayed sodium carbonate aqueous solution to the dissolution and removal. The time required for the photosensitive layer on the copper laminate is regarded as the shortest development time. The shorter the shortest development time, the better the imaging performance. The results are shown in Table 1. <Insulation reliability Evaluation (HAST test)> In addition to the copper-clad laminate having a copper thickness of 12//1, the wire-width/pitch=50 μm/50/zm is used to form a comb-tooth type as the base material. A method for forming a permanent pattern Permanent pattern made in the same way, performing HAST test and evaluation of dendrites and insulation resistance (Ω) » In the HAST test, a high-acceleration tester was used, and the electronic component module was at a temperature of 130 ° C and a relative humidity of 8 In a 5% atmosphere, after applying a voltage of 10 V for 200 hours, the insulation resistance (Ω) of the conductor ridge portion was measured under the same conditions, and then dendritic observation of the conductor ridge portion was performed as follows. It is shown in Table 1. -91- 200935174 [Evaluation Criteria] 〇: no dendrites X: dendrites < evaluation of biopreservability> The laminate was at room temperature (23 ° C, 55% RH) , sealed in a moisture-proof bag (barrel bag made of black polyethylene, film thickness: SO/zm, water vapor transmission rate: 25 g/m2_24 hr or less), and stored at 40 ° C for 3 days, with the shortest In the same method as in the evaluation of the development time, the most short development time was measured, and the 値 obtained in the evaluation of the shortest development time was set to, and the shortest development time after 3 days of storage was set. For h, to calculate U/U However, in the case of "measurement", the case where the photosensitive layer could not be removed even after 60 seconds of spray development was described as "X". The closer the obtained 値 is to 1, the superior the biopreservation property is. Table 1. <Evaluation of Resolution> The laminate was allowed to stand at room temperature (23 ° C, 55% RH) for 10 minutes. INPREX IP-3000 (Fuji Film Co., Ltd., pixel spacing 〇 = L.〇ym), the circular hole pattern information of diameter 40/zm~ diameter 400/zm and per ΙΟ/zm is irradiated onto the surface of the photosensitive layer of the obtained laminated body with the above-mentioned optimum exposure amount, and each hole diameter is performed. Pattern exposure. After standing at room temperature for 10 minutes, spray development was carried out in the same manner as in the evaluation of the shortest development time described above, and twice as long as the shortest development time obtained by the above method, to remove the uncured field. The surface of the hardened resin pattern thus obtained was observed with an optical microscope, and the smallest circular aperture having no abnormality such as clogging or waviness on the cured resin pattern was taken as the resolution. The smaller the resolution coefficient 値 is, the better. The results are shown in Table 1. -92- 200935174 (Example 2) Except that tricyclodecane diacrylate (trade name: NK ESTER A-DCP) was substituted with tricyclodecane dimethacrylate (trade name: NK ESTER DCP), In the same manner as in Example 1, a laminate and a permanent pattern were produced, and evaluation of sensitivity, developability, biopreservability, resolution, and insulation reliability was performed in the same manner as in Example 1. The results are shown in Table 1. {Example 3}

G 除了將三環癸烷二丙烯酸酯（商品名：NK ESTER A-DCP)取代爲三羥甲基丙烷三甲基丙烯酸酯（商品名：NK ESTER tmpt)以外，以與實施例1同樣的方式，製造積層體及永久圖案，並以與實施例1同樣的方式，進行感度、顯像性、生物保存性、解析性、及絶緣可靠性的評價。結果係表示於表1。 (實施例4) 除了將上述式1-2所表示之光聚合起始劑，取代爲下述 Ο 式1 -1所表示之光聚合起始劑以外，以與實施例1同樣的方式’製造積層體及永久圖案，並以與實施例1同樣的方式，進行感度、顯像性、生物保存性、解析性、及絶緣可靠性的評價。結果係表示於表1。G In the same manner as in Example 1, except that tricyclodecane diacrylate (trade name: NK ESTER A-DCP) was substituted with trimethylolpropane trimethacrylate (trade name: NK ESTER tmpt) The laminate and the permanent pattern were produced, and the sensitivity, developability, biopreservability, analytical properties, and insulation reliability were evaluated in the same manner as in Example 1. The results are shown in Table 1. (Example 4) The photopolymerization initiator represented by the above formula 1-2 was produced in the same manner as in Example 1 except that it was replaced by the photopolymerization initiator represented by the following formula 1-1. In the same manner as in Example 1, the laminate and the permanent pattern were evaluated for sensitivity, developability, biopreservability, analytical properties, and insulation reliability. The results are shown in Table 1.

(實施例5丨除了將上述式1_2所表示之光聚合起始劑取代爲 -93- 200935174(Example 5 丨 except that the photopolymerization initiator represented by the above formula 1_2 was replaced with -93- 200935174

Irgacure907(汽巴特殊化學品製）以外，以與實施例1同樣的方式，製造積層體及永久圖案，並以與實施例1同樣的方式，進行感度、顯像性、生物保存性、解析性、及絶緣可靠性的評價。結果係表示於表1。 (比較例1) 除了將三環癸烷二丙烯酸酯（商品名：NK ESTER A-DCP)取代爲乙氧基化三羥甲基丙烷三丙烯酸酯（商品名 :NK ESTER A-TMPT)以外，以與實施例1同樣的方式’ fc製造積層體及永久圖案，並以與實施例1同樣的方式’進行感度、顯像性、生物保存性、解析性、及絶緣可靠性的評價。結果係表不於表1。 (比較例2) 除了將三環癸烷二丙烯酸酯（商品名：NK ESTER A-DCP)取代爲新戊四醇四丙烯酸酯（商品名：NK ESTER A-TMMT)以外，以與實施例1同樣的方式，製造積層體及永久圖案，並以實施例1同樣的方式，進行感度、顯像性、〇生物保存性、解析性、及絶緣可靠性的評價。結果係表示於表1。 (比較例3} 除了將三環癸烷二丙烯酸酯（商品名：NK ESTER A-DCP)取代爲二新戊四醇六丙烯酸酯（商品名：kayarad DPHA、日本化藥股份有限公司製）以外，以與實施例1同樣的方式，製造積層體及永久圖案，並以與實施例1同樣的方式，進行感度、顯像性、生物保存性、解析性、及絶緣可靠性的評價。結果係表示於表1。 -94- 200935174In the same manner as in Example 1, except that Irgacure 907 (manufactured by Ciba Specialty Chemicals), a laminate and a permanent pattern were produced, and sensitivity, developability, biopreservability, and resolution were carried out in the same manner as in Example 1. And evaluation of insulation reliability. The results are shown in Table 1. (Comparative Example 1) Except that tricyclodecane diacrylate (trade name: NK ESTER A-DCP) was substituted with ethoxylated trimethylolpropane triacrylate (trade name: NK ESTER A-TMPT), In the same manner as in Example 1, a laminate and a permanent pattern were produced, and the sensitivity, developability, biopreservability, analytical properties, and insulation reliability were evaluated in the same manner as in Example 1. The results are shown in Table 1. (Comparative Example 2) Example 1 was prepared except that tricyclodecane diacrylate (trade name: NK ESTER A-DCP) was substituted with pentaerythritol tetraacrylate (trade name: NK ESTER A-TMMT). In the same manner, in the same manner as in Example 1, the laminate and the permanent pattern were produced, and the evaluation of sensitivity, developability, bioaccumulation, resolution, and insulation reliability was performed. The results are shown in Table 1. (Comparative Example 3) Except that tricyclodecane diacrylate (trade name: NK ESTER A-DCP) was substituted with dipentaerythritol hexaacrylate (trade name: kayarad DPHA, manufactured by Nippon Kayaku Co., Ltd.) The laminate and the permanent pattern were produced in the same manner as in Example 1, and the sensitivity, developability, biopreservability, analytical properties, and insulation reliability were evaluated in the same manner as in Example 1. Expressed in Table 1. -94- 200935174

聚合性化合物光聚合起始劑感度 (mJ/cm2) 顯像性 (秒）生保存性解析性 (η孔）絕緣可靠性檯類 I/O値樹枝狀結晶絕緣電阻 (Q) 綜合評價實施例1 NK ESTER A-DCP 0.428 1-2 34 12 1.2 60jUm 〇 6 xlO7 〇實施例2 NK ESTER DCP 0.385 1-2 34 14 1.1 60 μ m 〇 7Χ107 ◎ 賁施例3 NK ESTER TMPT 0.517 1-2 34 10 1.2 60// m 〇 5Χ107 ΔΟ 實施例4 NK ESTER A-DCP 0.428 1-1 50 11 1.2 60// m 〇 6Χ107 〇實施例5 NK ESTER A-DCP 0.428 Irgacure907 340 14 X 60/i m 〇 6Χ107 〇比較例1 NK ESTER A-TMPT 0.620 1-2 24 10 1.2 60 jU m X 3 xlO7 X 比較例2 NK ESTER A-TMMT 0.729 1-2 24 10 1.2 QOfim X 2Χ107 X 比較例3 kayarad DPHA 0.720 1-2 24 10 1.1 60 y m X 2Χ107 X 由表1的結果，實施例1~5與比較例1~3相比，已知由於聚合性化合物的I /〇値的重量平均低、且聚合性化合物爲 : 疏水化，所以在維持顯像性的同時可提昇絶緣可靠性。產業上的利用可能性本發明的感光性薄膜由於可維持顯像性且同時提昇絶緣可靠性，且可更有效率地形成高精細的永久圖案，所以可適合使用於保護膜、層間絶緣膜、及耐焊劑圖案等的永久圖案等的各種圖案形成、彩色濾光片、柱材、肋材、間隔材、隔壁等的液晶構造構件的製造、全息照相、微型機械、樣張（proof)的製造等，特別是可適合使用於印刷基板的永久圖案形成用。〇本發明的圖案形成方法由於使用前述感光性組成物，所以可適合使用於保護膜、層間絶緣膜、及耐焊劑圖案等的永久圖案等的各種圖案形成用、彩色濾光片、柱材、肋材、間隔材、隔壁等的液晶構造構件的製造、全息照相、微型機械、樣張（proof)的製造等，特別是可適合使用於印刷基板的永久圖案形成。【圖式簡單說明】 Μ。【主要元件符號說明】 Μ。 -95-Polymeric compound photopolymerization initiator sensitivity (mJ/cm2) Development (second) Biopreservation resolution (η hole) Insulation reliability type I/O値 dendritic insulation resistance (Q) Comprehensive evaluation example 1 NK ESTER A-DCP 0.428 1-2 34 12 1.2 60jUm 〇6 xlO7 〇Example 2 NK ESTER DCP 0.385 1-2 34 14 1.1 60 μ m 〇7Χ107 ◎ Example 3 NK ESTER TMPT 0.517 1-2 34 10 1.2 60// m 〇5Χ107 ΔΟ Example 4 NK ESTER A-DCP 0.428 1-1 50 11 1.2 60// m 〇6Χ107 〇Example 5 NK ESTER A-DCP 0.428 Irgacure907 340 14 X 60/im 〇6Χ107 〇Comparative Example 1 NK ESTER A-TMPT 0.620 1-2 24 10 1.2 60 jU m X 3 xlO7 X Comparative Example 2 NK ESTER A-TMMT 0.729 1-2 24 10 1.2 QOfim X 2Χ107 X Comparative Example 3 kayarad DPHA 0.720 1-2 24 10 1.1 60 ym X 2Χ107 X From the results of Table 1, Examples 1 to 5 are compared with Comparative Examples 1 to 3, and it is known that the weight of I /〇値 of the polymerizable compound is low on average, and the polymerizable compound is: hydrophobic Therefore, the insulation reliability can be improved while maintaining the imaging performance. INDUSTRIAL APPLICABILITY The photosensitive film of the present invention can be suitably used for a protective film, an interlayer insulating film, because it can maintain development and at the same time improve insulation reliability, and can form a high-definition permanent pattern more efficiently. And various pattern formation such as permanent patterns such as a solder resist pattern, manufacture of liquid crystal structural members such as color filters, pillars, ribs, spacers, and partition walls, manufacturing of holograms, micromachines, and proofs, etc. In particular, it can be suitably used for the formation of a permanent pattern for a printed substrate. In the pattern forming method of the present invention, since the photosensitive composition is used, it can be suitably used for various pattern formation, color filters, pillars, and the like, such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern. The manufacture of liquid crystal structural members such as ribs, spacers, and partition walls, production of holograms, micromachines, proofs, and the like can be suitably used for permanent pattern formation on printed boards. [Simple description of the diagram] Μ. [Main component symbol description] Μ. -95-

Claims

200935174 X. Patent application scope: 1. A photosensitive composition characterized by comprising a binder 'polymerizable compound, a dip material, and a photopolymerization initiator, and the weight of the polymerizable compound is 0.5 2 or less. 2. The photosensitive composition of claim 1 wherein the weight of the I/O値 of the polymerizable compound is 〇.43 or less. 3. The photosensitive composition of claim 1 wherein the polymerizable compound contains two or more polymerizable groups. 4. The photosensitive composition of claim 1, wherein the polymerizable compound is dimethylol tricyclodecane di(meth)acrylate. 5. The photosensitive composition as claimed in claim 1 wherein the photopolymerization initiator is an anthracene derivative. 6. The photosensitive composition of claim 1, wherein the photosensitive composition further comprises a thermal crosslinking agent. 7. The photosensitive composition of claim 6, wherein the thermal crosslinking agent is selected from the group consisting of an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a block agent with a polyisocyanate compound. And at least one of melamine derivatives. A photosensitive film comprising a photosensitive layer composed of a photosensitive composition according to the first aspect of the patent application, which is formed on a support. A photosensitive laminate comprising a photosensitive layer comprising a photosensitive composition according to the first aspect of the patent application. A method of forming a permanent pattern, characterized in that it contains at least a photosensitive layer formed of the photosensitive composition of the first aspect of the patent application. -96- 200935174 * 11. The method of forming a permanent pattern according to claim 10, wherein the exposure is performed by modulating the light by means of light modulation, and then performing the arrangement of the microlens array of the microlenses through the arrangement, wherein The microlens system has an aspherical surface that can compensate for aberrations caused by deformation of the exit surface of the drawing portion in the light modulation means. 12. The method of forming a permanent pattern according to the first aspect of the patent application, wherein the exposure of the photosensitive layer is performed after the exposure is performed. 13. The permanent pattern forming method according to claim 12, wherein the photosensitive layer is hardened after the development of 1 image. A printed substrate 'characteristically permanent pattern is formed by a permanent pattern forming method as in claim 10 of the patent application.

-97- 200935174 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 〇 j\w

8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: