TW201242931A - Oxime ester compound and photoinitiator containing said compound - Google Patents

Oxime ester compound and photoinitiator containing said compound Download PDF

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TW201242931A
TW201242931A TW101104967A TW101104967A TW201242931A TW 201242931 A TW201242931 A TW 201242931A TW 101104967 A TW101104967 A TW 101104967A TW 101104967 A TW101104967 A TW 101104967A TW 201242931 A TW201242931 A TW 201242931A
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TWI541221B (en
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Kiyoshi Murata
Takeo Oishi
Koichi Kimijima
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Adeka Corp
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Abstract

An oxime ester compound represented by general formula (1) [wherein R1 to R4 are each OR11, COOR11, or the like; R11 is a hydrogen atom, a C1-20 alkyl group, a C6-30 aryl group, a C7-30 arylalkyl group, or a C2-20 heterocyclic group, the hydrogen atoms of these groups being optionally replaced by -CR21=CR22R23, -CO-CR21=CR22R23, -O-CO-CR21=CR22R23, or the like (wherein R21 to R23 have the same meanings as defined above for R11); X is a sulfur atom, NR33 (wherein R33 is a hydrogen atom, a C1-20 alkyl group, or the like), or the like; a is an integer of 0 to 4; b is an integer of 1 to 5; and at least one of the R4 moieties is a group having -CR21=CR22R23, -CO-CR21=CR22R23, -O-CO-CR21=CR22R23 or the like].

Description

201242931 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種用作感光性組合物所使用之光聚合起 始劑的新穎肟酯化合物、含有該化合物之光聚合起始劑、 使具有乙烯性不飽和鍵之聚合性化合物含有該光聚合起始 劑而成之感光性组合物、及該感光性組合物之硬化物。 【先前技術】 感光性組合物係於具有乙烯性不飽和鍵之聚合性化合物 中添加有光聚合起始劑者，可藉由照射能量射線（光）而聚 合硬化，故而可用於光硬化性油墨、感光性印刷版、各種 光阻劑等。 作為上述感光性組合物所使用之光聚合起始劑，於專利 文獻1〜3中提出有肟酯化合物。 然而’於專利文獻1〜3所記載之肟酯化合物之中，感光 度另人滿意度之肟酯化合物存在可見光區域之穿透率較 低，無法於彩色濾光片中獲得所需之顏色之問題（尤其是 用於保護膜之類之要求透明性之用途之感光性組合物、或 使用藍色之顏料或色素之彩色濾光片用光阻劑中，若混合 有吸收380〜450 nm之化合物，則亮度、色純度會降低）， 又，可見光區域之穿透率較高之两醋化合物存在感光度無 法充分令人滿意之問題，業界正尋求兼具兩個特性之光聚 合起始劑。 又要求彩色濾光片等所使用之含有著色料之著色鹼顯 影性感光性樹脂組合物為高感光度，必需使光阻劑中之光 162338.doc 201242931 聚合起始劑成為高濃度。然而，高濃度之光聚合起始劑會 引起由顯影性之惡化而導致之殘渣之產生、由昇華物而導 致之遮罩或加熱爐之污染等。 先前技術文獻 專利文獻 專利文獻1:曰本專利特開2000_80068號公報 專利文獻2:日本專利特開2001·233842號公報 專利文獻3:日本專利第3860170號公報 【發明内容】 發明所欲解決之問題 本發明所欲解決之問題點為：迄今為止尚無具有令人滿 意之感光度、且可見光區域之穿透率較高、昇華性較低之 光聚合起始劑。 因此，本發明之目的在於提供一種穩定性優異、低昇華 性、顯影性優異、可見光區域之穿透率較高、有效吸收 365 nm等近紫外線光而活化之高感光度之光聚合起始劑。 解決問題之技術手段 本發明者等人進行努力研究，結果獲得如下見解：若使 用作光聚合起始劑之化合物於製成樹脂組合物時與樹脂等 . 反應，或於能量射線（光）照射時與樹脂等反應，則與未與 樹脂等反應而直接以化合物之狀態存在之情形相比成為低 昇華性。 本發明係基於上述見解而成者，且提供下述通式（1)所 表示之肟酯化合物、及含有該化合物而成之光聚合起始 I62338.doc -4- (1) (1)201242931 劑。 [化i]201242931 VI. [Technical Field] The present invention relates to a novel oxime ester compound used as a photopolymerization initiator for a photosensitive composition, a photopolymerization initiator containing the compound, and having A polymerizable composition in which a polymerizable compound having an ethylenically unsaturated bond contains the photopolymerization initiator, and a cured product of the photosensitive composition. [Prior Art] The photosensitive composition is a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator is added thereto, and can be polymerized and hardened by irradiation with an energy ray (light), so that it can be used for a photocurable ink. , photosensitive printing plates, various photoresists, etc. As the photopolymerization initiator used in the above photosensitive composition, an oxime ester compound is proposed in Patent Documents 1 to 3. However, among the oxime ester compounds described in Patent Documents 1 to 3, the oxime ester compound having satisfactory sensitivity is lower in the visible light region, and the desired color cannot be obtained in the color filter. Problems (especially for photosensitive compositions such as protective films that require transparency, or for color filters using blue pigments or pigments, if mixed with absorption of 380 to 450 nm In the case of compounds, the brightness and color purity are lowered. Moreover, the two vinegar compounds having a high transmittance in the visible light region have a problem that the sensitivity cannot be sufficiently satisfactory, and the industry is seeking a photopolymerization initiator having both characteristics. . Further, it is required that the color base photosensitive photosensitive resin composition containing a coloring material used in a color filter or the like has high sensitivity, and it is necessary to make the light in the photoresist 162338.doc 201242931 a polymerization initiator to a high concentration. However, a high concentration of the photopolymerization initiator causes the generation of residue due to deterioration of developability, the mask caused by the sublimate, the contamination of the furnace, and the like. CITATION LIST Patent Literature Patent Literature 1: Patent Publication No. 2000-80068 Patent Document 2: Japanese Patent Laid-Open No. 2001-233842. Patent Document 3: Japanese Patent No. 3860170 (Invention) The problem to be solved by the invention The problem to be solved by the present invention is that there has been no photopolymerization initiator having a satisfactory sensitivity, a high transmittance in a visible light region, and a low sublimation property. Therefore, an object of the present invention is to provide a photopolymerization initiator which is excellent in stability, low in sublimation property, excellent in developability, high in transmittance in a visible light region, and effective in absorbing high-sensitivity light such as 365 nm. . MEANS FOR SOLVING THE PROBLEMS The inventors of the present invention have made an effort to obtain a result of using a compound which is a photopolymerization initiator to react with a resin or the like in the preparation of a resin composition, or to irradiate with an energy ray (light). When it reacts with a resin, etc., it is low sublimation property compared with the case where it does not react with a resin etc. and it exists in the state of a compound. The present invention is based on the above findings, and provides an oxime ester compound represented by the following formula (1), and a photopolymerization initiation group I62338.doc -4- (1) (1) 201242931 Agent. [i]

(式中，Ri、R2、R3及r4分別獨立表示ri丨、⑽丨1、 COOR11、SR11、SO^i、c〇NRi2Ri3或 CN , R"、R12及R13分別獨立表示氫原子、或作為碳原子 1〜20之院基、碳原子數為6〜3()之芳基、碳原子數為 芳基烷基或碳原子數為2〜2〇之雜環基的取代基， R11、R12及R13所表示之取代基之氫原子可進而經⑽、 COR21、SR21、NR22R23、c〇nr22r23、视22 〇r23、他〜〇· OCOR23、-C(=N-OR21)_r22、C(=N 〇c〇r21) r22 cn 鹵 素原子、-COOR21、-CR21=cr22r23、_c〇 cr21 = cr22r23、 •0_C0_CI121 = C：R22R23、·Ν=〇〇或環氧基等取代， R 、R及r23分別獨立表示氫原子、或作為碳原子數為 1〜20之烷基、碳原子數為6〜3〇之芳基、碳原子數為7〜3〇之 芳基烷基或碳原子數為2〜20之雜環基的取代基， R 、R及尺所表示之取代基之氫原子可進而經CN、 鹵素原子、羥基或羧基取代， R11、R12、R13、r21、尺^及尺^所表示之取代基之伸烷基 部分可藉由-0-、-8-、-(：00-、-0(：0-、"1124-、_1^24(：00- 、-OCONR24-、-SCO-、-COS-、-OCS-或-CSO-中斷 1〜5 162338.doc 201242931 次， R表不氫原子、碳原子數為^20之院基、碳原子數為 6〜30之芳基、碳原子數為7〜3〇之芳基烷基或碳原子數為 2〜20之雜環基，(wherein, Ri, R2, R3 and r4 each independently represent ri丨, (10)丨1, COOR11, SR11, SO^i, c〇NRi2Ri3 or CN, and R", R12 and R13 each independently represent a hydrogen atom or as a carbon a substituent of a group of 1 to 20 atoms, an aryl group having 6 to 3 carbon atoms, a heterocyclic group having an arylalkyl group or a carbon number of 2 to 2, R11 and R12; The hydrogen atom of the substituent represented by R13 may further be via (10), COR21, SR21, NR22R23, c〇nr22r23, 2222 〇r23, 〜〇·OCOR23, -C(=N-OR21)_r22, C(=N 〇 C〇r21) r22 cn halogen atom, -COOR21, -CR21=cr22r23, _c〇cr21 = cr22r23, •0_C0_CI121 = C: R22R23, ·Ν=〇〇 or epoxy, etc., R, R and r23 are represented independently a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 3 carbon atoms, an arylalkyl group having 7 to 3 carbon atoms, or a carbon number of 2 to 20 The substituent of the heterocyclic group, the hydrogen atom of the substituent represented by R, R and the ruthen may be further substituted by CN, a halogen atom, a hydroxyl group or a carboxyl group, and substituted by R11, R12, R13, r21, ruthenium and ruthenium. Base extension The alkyl moiety can be represented by -0-, -8-, -(:00-, -0(:0-, "1124-, _1^24(:00-, -OCONR24-, -SCO-, -COS) -, -OCS- or -CSO-interruption 1~5 162338.doc 201242931 times, R is a hydrogen atom, a group of carbon atoms of ^20, an aryl group having 6 to 30 carbon atoms, and the number of carbon atoms is 7 to 3 〇 arylalkyl or a heterocyclic group having 2 to 20 carbon atoms,

Rl1、Rl2、Rl3、R21、R22及R23所表示之取代基之院基部 分可具有分支側鏈，亦可為環狀烷基，又，尺^與…3及r22 ‘ 與R23亦可分別一起形成環， X表不氧原子、硫原子、硒原子、cr31r32、c〇、nr33 或 PR34， R 、R 、R33及R34分別獨立表示氫原子、或作為碳原 子數為1〜20之烷基、碳原子數為6〜3〇之芳基或碳原子數為 7〜3 0之芳基统基的取代基， R 、R 、R3及R34所表示之取代基之烷基部分可具有 为支側鍵’亦可為環狀院基，R3 1、R32、R33及R34所表示 之取代基之烷基末端可為不飽和鍵，R3丨、R32、尺33及尺34 亦可分別獨立地與鄰接之任意苯環一起形成環， a表示0〜4之整數， b表示1〜5之整數， R4 之至少一者為具有 cr21=cr22r23、c〇 cr2 丨=cr22r23 - 、-O-CO-CR2丨=CR22R23、-N=O0或環氧基之基）》 又’本發明提供一種含有上述光聚合起始劑、及具有乙 稀性不飽和鍵之聚合性化合物而成之感光性組合物。 又，本發明提供一種使上述感光性組合物含有賦予鹼顯 影性之化合物而成之鹼顯影性感光性樹脂組合物。 162338.doc •6- 201242931 又，本發明提供一種使上述鹼顯影性感光性樹脂組合物 進而含有著色料而成之著色鹼顯影性感光性樹脂組合物。 又，本發明提供一種對上述感光性組合物、上述鹼顯影 性感光性樹脂組合物或上述著色驗顯影性感光性樹脂組合 物照射能量射線而成之硬化物。 發明之效果 本發明之肟酯化合物為可見光區域之穿透率較高，對 365 nm(i射線）等明線有效率地產生自由基，並用作光聚合 起始劑者。又，若將本發明之肟酯化合物作為光聚合起始 劑而調配於樹脂組合物中使用，則與具有聚合性基之樹脂 反應，故而昇華物較少，進而可提高硬化物之耐熱性。 【實施方式】 以下，對本發明之肟酯化合物及含有該化合物之光聚合 起始劑進行詳細說明。 本發明之肟酯化合物係上述通式（1)所表示之新穎化合 物m該㈣化合物在藉由狀雙鍵之兩個幾^ 異構物，但本發明並非對該等加以區別者。 即，於本說明書中，上述通式⑴、及下述表示上述通 式（1)所表示之化合物之較佳形態之通式（2)、及例示化合 物No. 1〜Ng’39之化學結構式僅表示兩個幾何異構物中之— 者，但本發明之肟酯化合物並不限定於該等式所表示之幾 何異構物’亦可為另—幾何異構物，亦可為^個幾何異構 物之混合物。 作為上述通式（1)中之R11、R丨2、R丨3、、r22、r23 162338.doc 201242931 R 、R31、R32、R33及R34所表示之碳數為i〜2〇之烷基，例 如可列舉：曱基、乙基、丙基、異丙基、丁基、異丁基、 第二丁基、第三丁基、戊基、異戊基 '第三戊基、己基、 庚基、辛基、異辛基、2-乙基己基、第三辛基、壬基、異 壬基、癸基、異癸基、十一烷基、十二烷基、十四烷基、 十六烷基、十八烷基、二十烷基、環戊基、環己基、環己 基曱基等。 作為上述通式（1)中之R"、R丨2、r13、r21、r22、r23、 R R 、R 、R及R34所表示之碳原子數為6〜30之芳 基，例如可列舉：苯基、甲苯基、二甲苯基、乙基苯基、 萘基、蒽基、菲基、及經上述烷基取代一個以上之苯基、 聯苯基、萘基、蒽基等。 作為上述通式（1)中之Rll、r12、rI3、r2丨、r22、尺23、 R R 、R 、R及尺34所表示之碳原子數為7〜30之芳基 烷基’例如可列舉：节基、α甲基苄基、αα二甲基节 基、苯基乙基等。 作為上述通式（1)中之、R丨2、R〗3、r2丨、r22、尺23及 R24所表示之可經取代之碳原子數為2〜2〇之雜環基，例如 可較佳地列舉：°比絲、喃基、㈣基、四氫 吱喊基、二氧雜環戊基、苯并十坐·2•基、四氫㈣基、〇比 洛烧基、料絲、（錢基"g錢基、異㈣燒基、 …坐院基、異十线基、μ基n基、咪似等5〜7 員雜環。 作為上述通式（1)中R12與 、R22與R23可—起形成之環 162338.doc 201242931 及 R31、R32、r33 如可較佳地列舉· iSj與鄰接之苯環-起形成之環，例 I料環、味環、㈣胺環等W ^襄、本 二’:二上述通式⑴中可取代aw 之函素原子，可列舉氟、氣、漠、峨。 又 ’ R"、R、Rl3、r21、r22、r23所表示 伸烧基部分可藉HS_、·。。。…。c。t之 •NR24co〇…〇c〇 24 叫-、 中斯 i p cos-、-ocs或-cso· -人，此時進行中斷之配位基可為—種或兩種以上 之基’於為可連續進行中斷之基之情形時，亦可兩個以上 相連而進行中斷。x，上述取代基之烧基部分可具有分支 側鏈，亦可為環狀烷基。The base portion of the substituent represented by Rl1, Rl2, Rl3, R21, R22 and R23 may have a branched side chain or a cyclic alkyl group, and the ruler and ...3 and r22' and R23 may also be respectively used together. Forming a ring, X represents an oxygen atom, a sulfur atom, a selenium atom, cr31r32, c〇, nr33 or PR34, and R, R, R33 and R34 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, a substituent having an aryl group having 6 to 3 carbon atoms or an aryl group having 7 to 30 carbon atoms, and an alkyl moiety of a substituent represented by R, R, R3 and R34 may have a branch side The bond ' can also be a ring-shaped base. The alkyl end of the substituent represented by R3 1, R32, R33 and R34 can be an unsaturated bond, and R3丨, R32, 33 and 34 can also be independently adjacent to each other. Any benzene ring forms a ring together, a represents an integer of 0 to 4, b represents an integer of 1 to 5, and at least one of R4 has cr21=cr22r23, c〇cr2 丨=cr22r23 - , -O-CO-CR2丨=CR22R23, -N=O0 or a group of an epoxy group) Further, the present invention provides a polymerizable compound containing the above photopolymerization initiator and having an ethylenically unsaturated bond A photosensitive composition. Moreover, the present invention provides an alkali-developable photosensitive resin composition obtained by containing the alkali-developing compound in the photosensitive composition. Further, the present invention provides a color base-developable photosensitive resin composition obtained by further containing a coloring material in the alkali-developable photosensitive resin composition. Moreover, the present invention provides a cured product obtained by irradiating an energy ray to the photosensitive composition, the alkali-developable photosensitive resin composition, or the coloring-developing photosensitive resin composition. EFFECTS OF THE INVENTION The oxime ester compound of the present invention has a high transmittance in a visible light region, efficiently generates radicals for an open line such as 365 nm (i-ray), and is used as a photopolymerization initiator. In addition, when the oxime ester compound of the present invention is used as a photopolymerization initiator in a resin composition, it reacts with a resin having a polymerizable group, so that the sublimate is less, and the heat resistance of the cured product can be improved. [Embodiment] Hereinafter, the oxime ester compound of the present invention and a photopolymerization initiator containing the same will be described in detail. The oxime ester compound of the present invention is a novel compound represented by the above formula (1). The compound (4) is a mixture of two isomers of a double bond, but the present invention is not intended to distinguish them. That is, in the present specification, the chemical formula of the general formula (2) and the exemplified compound No. 1 to Ng'39 which are the preferred forms of the compound represented by the above formula (1), and the following formula The formula represents only two geometric isomers, but the oxime ester compound of the present invention is not limited to the geometric isomer represented by the equation 'may be another geometric isomer, or may be ^ a mixture of geometric isomers. As the alkyl group represented by R11, R丨2, R丨3, r22, r23 162338.doc 201242931 R, R31, R32, R33 and R34 in the above formula (1), the carbon number is i 〜2〇, For example, an alkyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a 'p-pentyl group, a hexyl group, a heptyl group are exemplified. , octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexa Alkyl, octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclohexyldecyl and the like. Examples of the aryl group having 6 to 30 carbon atoms represented by R", R丨2, r13, r21, r22, r23, RR, R, R and R34 in the above formula (1) include benzene. a group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, and one or more phenyl groups, a biphenyl group, a naphthyl group, an anthracenyl group and the like substituted by the above alkyl group. The arylalkyl group having 7 to 30 carbon atoms represented by R11, r12, rI3, r2丨, r22, 尺23, RR, R, R and the rule 34 in the above formula (1) can be exemplified. : a benzyl group, an αmethylbenzyl group, an αα dimethyl group, a phenylethyl group, or the like. The heterocyclic group having 2 to 2 ring carbon atoms represented by R 2 , R 3 , r 2 丨, r 22 , 尺 23 and R 24 in the above formula (1) can be, for example, The best examples are: ° filament, thiol, (tetra), tetrahydro fluorenyl, dioxolane, benzoxanthene, tetrahydro (tetra), indole, and filament. (Qianji "g Qianji, Xing (4) base, ... sitting base, hetero-line base, μ-based n-base, imitation, etc. 5~7 member heterocycle. As R12 and in the above formula (1) R22 and R23 can form a ring 162338.doc 201242931 and R31, R32, r33, for example, a ring formed by iSj and an adjacent benzene ring, such as a ring, a taste ring, a (tetra)amine ring, etc. W ^ 襄, 本二': Two of the above-mentioned general formula (1) can replace the atom of aw atom, which can be exemplified by fluorine, gas, desert, bismuth. Also, 'R", R, Rl3, r21, r22, r23 The base part can be borrowed from HS_, ·......c.t•NR24co〇...〇c〇24 called-, Zhongsi ip cos-, -ocs or -cso·-person, at this time the interrupted ligand Can be one or more than two bases When the base of the case, may be connected to two or more interrupt .x, burning portion of the group may have a substituent group of branched side chains, it may also be a cyclic alkyl group.

於本發明之肟酯化合物之中，上述通式（1)中，X 子或NR33 ’ R33為可具有分支側鏈、亦可為環狀烷基之碳 原子數為1〜20之烷基的化合物；及下述通式（2)所表示之 化合物尤其是感光度較高，又，容易製造，故而較佳。 [化2]In the oxime ester compound of the present invention, in the above formula (1), X or NR33' R33 is an alkyl group which may have a branched side chain or a cyclic alkyl group having 1 to 20 carbon atoms. The compound and the compound represented by the following formula (2) are particularly preferred because they have high sensitivity and are easy to manufacture. [Chemical 2]

(式中，H1、R2、R3、R4、乂及3與上述通式⑴相同，尺5與 上述通式（1)中之R4相同’至少R5為至少具有一個選自_CR21 = CR22R23、_c〇-CR21=CR22R23、-〇-CO-CR21=CR22R23、-N=C=0 162338.doc -9· 201242931 及環氧基t之結構之基，e表示〇〜4之整數）。 式(2)所表示之化合物中，r5具有_cr2|=cr22r23 由與反：或·〇_°〇-(：Κ21，221123之化合物藉 由與反應性軔宾Β θ 士于& m 表現出、 和雙鍵之樹脂組合物組合而 =較…熱性，故而進而較佳，又，由於Π 有-N=C=〇或環氧基之化合物藉由與醇、胺、 有 活性氫之樹脂組合而表現出敕古夕紂也以 八有 衣見出較问之耐熱性，故而同樣進而 較佳。 又’就更高地發揮本發明之效果而言，上述通式⑴及 (2)中之R及R2較佳為碳原子數為i，尤其是碳原子數為 1〜1〇、特別是碳原子數為卜4)之院基，上述通式⑴及⑺ 中之a較佳為0〜1，上述通式⑴中之b較佳為υ，上述 式（2)中之c較佳為〇〜〗。 # 就進而高地發揮本發明之效果而言，上述r3較佳為氣原 子。基於相同之理由，上述χ較佳為硫原子。基於相同之 理由，較佳為上述R4為OR11或C〇〇Rll，且該R"為碳原子 數為1〜20之烷基、尤其是碳原子數為1〜10之烷基、特別是 碳原子數為1〜6之烷基，該Rh所具有之氫原子中之少一者 經-OCO-CR2】 = CR22R23取代，於該-0C0-CR21=CR22R23 中， R為風原子或甲基’ R22及R23為氫原子。於該情形時， -oco-cr21=cr22r23於取代OR"之R"所具有之氫原子之情 形時較佳為鍵結於距該OR11之氧原子最遠之位置上之碳原 子’於取代COORniRn所具有之氫原子之情形時較佳為 鍵結於距該COOR11之COO基最遠之位置上之碳原子。 162338.doc •10· 201242931 又，較佳為b為1，R4為相對於X所鍵結之碳原子而鍵結於 對位上。 作為上述通式（1)所表示之本發明之肟酯化合物之較佳 之具體例，可列舉以下之化合物No. 1〜No.39之化合物。但 本發明不受以下化合物任何限制。 [化 3-1] 化合物No. 1Wherein H1, R2, R3, R4, 乂 and 3 are the same as the above formula (1), and the ruler 5 is the same as R4 in the above formula (1) 'at least R5 has at least one selected from the group consisting of _CR21 = CR22R23, _c 〇-CR21=CR22R23, -〇-CO-CR21=CR22R23, -N=C=0 162338.doc -9·201242931 and the structure of the epoxy group t, and e represents an integer of 〇~4). In the compound represented by the formula (2), r5 has _cr2|=cr22r23 and the compound of the reverse: or · 〇_°〇-(:Κ21,221123 by the reactivity of the compound 轫 Β θ 士 & m The combination of the resin composition with the double bond and the heat of the double bond is further preferred, and further, since the compound having -N=C=〇 or an epoxy group is a resin with an alcohol, an amine or an active hydrogen In combination, it is shown that the ancient 纣 纣 见 见 纣 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八 八R and R2 are preferably a group having a carbon number of i, particularly a carbon number of 1 to 1 Å, particularly a carbon number of 4), and a of the above formulas (1) and (7) is preferably 0. 1, b in the above formula (1) is preferably υ, and c in the above formula (2) is preferably 〇~. # Further, in order to exert the effect of the present invention, the above r3 is preferably a gas atom. For the same reason, the above hydrazine is preferably a sulfur atom. For the same reason, it is preferred that R4 is OR11 or C〇〇Rll, and the R" is an alkyl group having 1 to 20 carbon atoms, particularly an alkyl group having 1 to 10 carbon atoms, particularly carbon. An alkyl group having an atomic number of 1 to 6, and one of the hydrogen atoms of the Rh is substituted by -OCO-CR2] = CR22R23, and in the -0C0-CR21=CR22R23, R is a wind atom or a methyl group. R22 and R23 are a hydrogen atom. In this case, -oco-cr21=cr22r23 is preferably a carbon atom that is bonded to the oxygen atom farthest from the OR11 in the case of replacing the hydrogen atom of the OR", in place of COORniRn. In the case of a hydrogen atom, it is preferably a carbon atom bonded to the position farthest from the COO group of the COOR 11. Further, preferably, b is 1, and R4 is bonded to the para position with respect to the carbon atom to which X is bonded. Preferred examples of the oxime ester compound of the present invention represented by the above formula (1) include the following compounds No. 1 to No. 39. However, the present invention is not limited by any of the following compounds. [Chem. 3-1] Compound No. 1

化合物No.2Compound No. 2

化合物No.3Compound No.3

化合物No.4Compound No. 4

化合物No.5Compound No. 5

化合物No.6Compound No.6

化合物No.7Compound No. 7

化合物No.8Compound No. 8

162338.doc • 11 · 201242931 [化 3-2] 化合物No.9162338.doc • 11 · 201242931 [Chem. 3-2] Compound No. 9

化合物No.12 化合物Νο.13Compound No.12 Compound Νο.13

ο -12 162338.doc 201242931 [化 3-3] 化合物No.16ο -12 162338.doc 201242931 [Chemical 3-3] Compound No.16

化合物No. 17Compound No. 17

化合物No.20Compound No.20

化合物No.22Compound No. 22

162338.doc -13- 201242931 [化 3-4] 化合物No.24 化合物No.25162338.doc -13- 201242931 [Chemical 3-4] Compound No.24 Compound No.25

化合物No.26 化合物Νο.27Compound No.26 Compound Νο.27

V 化合物Νο.28V compound Νο.28

Λ 化合物Νο.30Λ Compound Νο.30

-14- 162338.doc 201242931 [化 3-5] 化合物Νο.32-14- 162338.doc 201242931 [Chemical 3-5] Compound Νο.32

上述通式（1)所表示之本發明之肟酯化合物並無特別限 定，例如可依照日本專利特開2000-80068號公報所記載之 方法而製造。作為方法之一，可根據下述反應式1，藉由 以下之方法而製造。首先，藉由於路易斯酸存在下使酮體 與（甲基）丙烯酸反應而獲得（曱基）丙烯酸酯體。繼而，使 該（甲基）丙烯酸酯體與亞硝酸酯於鹽酸存在下反應，接著 與酸酐或醯氣反應而獲得上述通式（1)所表示之本發明之肟 162338.doc 15 201242931 酯化合物。於下述反應式丨中記載有x為硫原子之情形曰 X為氧原子、碼原子、CR”R”、NR33slpR34者亦^按昭： 述方法製造。 •… [化4] (反應式1)The oxime ester compound of the present invention represented by the above formula (1) is not particularly limited, and it can be produced, for example, according to the method described in JP-A-2000-80068. One of the methods can be produced by the following method according to the following Reaction Scheme 1. First, a (mercapto) acrylate body is obtained by reacting a ketone body with (meth)acrylic acid in the presence of a Lewis acid. Then, the (meth) acrylate body is reacted with a nitrite ester in the presence of hydrochloric acid, followed by reaction with an acid anhydride or helium gas to obtain the oxime 162338.doc 15 201242931 ester compound of the present invention represented by the above formula (1). . In the following reaction formula, it is described that x is a sulfur atom, X is an oxygen atom, a code atom, CR"R", or NR33slpR34 is also produced according to the method described. •... [Chemical 4] (Reaction 1)

胴逋胴逋

(甲基）丙烯狡酯體 彳。〜。兮成—★〜。。廣又 ㈣ 本發明之肟明《 、。人丨 (式中，R1及R2與上述通式(1)相同）。 以上說明之本發明之新穎肟酯化合物可用作光聚合起始 劑 本發明之光聚合起始劑含有至少一種本發明之肟酯化合 物，尤其疋可用作具有乙烯性不飽和鍵之聚合性化合物之 光聚合起始劑》本發明之光聚合起始劑中之本發明之肟酯 化合物之含量較佳為30〜1〇〇質量。/。，更佳為5〇〜1〇〇質量 %。本發明之光聚合起始劑除本發明之肟酯化合物以外， 亦可含有其他光聚合起始劑《作為其他光聚合起始劑，可 使用先前已知之化合物，例如可列舉：二苯曱酮、苯基聯 苯基酮、1-經基-1-苯甲醯基環己院、安息香、苄基二甲基 縮酮、1-苄基-1-二甲基胺基-1-(4，·咪啉基苯甲醯基）丙烷、 2-味琳基-2-(4·-甲基巯基）苯甲醯基丙燒、硫雜蒽酮、卜氣-4 -丙氧基硫雜蒽酮、異丙基硫雜蒽酿j、二乙基硫雜蒽銅、 乙基蒽酿、4-本甲醯基-4·-甲基二笨基硫謎、安息香丁 162338.doc 16- 201242931 醚、2-羥基-2-苯曱醯基丙烷、2-羥基-2-(4·-異丙基）苯曱醯 基丙烷、4-丁基笨甲醯基三氣甲烷、4-苯氧基笨甲醯基二 氣曱烷、苯曱醯基曱酸甲酯、1，7·雙（9·-吖啶基）庚烷、9-正丁基-3,6-雙（2’-咮啉基異丁醯基）咔唑、2-甲基-4,6-雙（三 氣曱基）-均三啡、2-笨基-4,6-雙（三氯甲基）-均三畊、2-萘 基-4,6-雙（三氣曱基）_均三畊、2,2_雙（2_氣苯基）_4,5,4,，5·_ 四苯基-1-2'-聯咪唑、4,4-偶氮雙異丁腈、三苯基膦、樟腦 醌、Ν-1414、Ν-1717、Ν-1919、ΡΖ-408、NCI-831、NCI- 930(ADEKA股份有限公司製造）、IRGACURE369、(Meth) propylene oxime ester 彳. ~.兮成—★〜. . Guang (4) The invention of the invention ",. Human 丨 (wherein R1 and R2 are the same as those of the above formula (1)). The novel oxime ester compound of the present invention described above can be used as a photopolymerization initiator. The photopolymerization initiator of the present invention contains at least one oxime ester compound of the present invention, and particularly ruthenium can be used as a polymerizable property having an ethylenically unsaturated bond. Photopolymerization initiator of the compound The content of the oxime ester compound of the present invention in the photopolymerization initiator of the invention is preferably 30 to 1 Å by mass. /. More preferably 5〇~1〇〇% by mass. The photopolymerization initiator of the present invention may contain, in addition to the oxime ester compound of the present invention, other photopolymerization initiators. As other photopolymerization initiators, previously known compounds may be used, and for example, diphenyl fluorenone may be mentioned. Phenylbiphenyl ketone, 1-carbyl-1-benzhydrylcyclohexyl, benzoin, benzyldimethylketal, 1-benzyl-1-dimethylamino-1-(4 ,·Morolinylbenzimidyl)propane, 2-mylinyl-2-(4·-methylindenyl)benzhydrylpropanone, thioxanthone, Bu-4-propoxythiazepine Anthrone, isopropyl thioxanthene, diethyl thiazinium copper, ethyl hydrazine, 4-benmethanyl-4·-methyldiphenylthiol, benzoin 162338.doc 16- 201242931 Ether, 2-hydroxy-2-phenylmercaptopropane, 2-hydroxy-2-(4.-isopropyl)benzoxanylpropane, 4-butyl benzomethyl sulfhydryl tri-methane, 4-benzene Oxybenzamide-dioxadecane, methyl benzoquinone decanoate, 1,7-bis(9--acridinyl)heptane, 9-n-butyl-3,6-bis (2' - porphyrinyl isobutyl hydrazino) oxazole, 2-methyl-4,6-bis(trimethyl decyl)-s-trisyl, 2-phenyl-4,6-bis(trichloromethyl)- Tillage, 2-naphthyl-4,6-bis(trioxanyl)_three-plowed, 2,2_bis(2-hydrophenyl)_4,5,4,5·_ tetraphenyl-1 -2'-biimidazole, 4,4-azobisisobutyronitrile, triphenylphosphine, camphorquinone, Ν-1414, Ν-1717, Ν-1919, ΡΖ-408, NCI-831, NCI-930 ( ADEKA Co., Ltd.), IRGACURE369,

IRGACURE907、IRGACURE OXE 01、IRGACURE OXE ”遇虱化本曱醯、下述通式（4)〜（6)所表 於使用該等本發明之肟酯化合物以外之光 形時可使用一種或組合兩種以上使用。 02(BASF公司製造）' 過氧化苯曱醯、 之光 示之化合物等。於使用該等本發明之 聚合起始劑之情形時，可使用一種或 [化5]IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE ” can be used in combination with the oxime ester compounds of the present invention, and the following formulas (4) to (6) can be used in combination with Use of the above. 02 (manufactured by BASF Corporation) 'Phenyl peroxide, a compound of light, etc. In the case of using the polymerization initiator of the present invention, one or [5] may be used.

(式中，R1、R2及 R33 或烷基，η為〇〜5) » [化6](wherein R1, R2 and R33 or alkyl, η is 〇~5) » [Chemical 6]

162338.doc -17· 201242931 (式中，R1、R2及R33與上述通式⑴相同，,及11與上述通 式（4)相同，R’1及尺，2與111及112相同，尺⑴與尺”相同，丫,3與 Y3相同，R8表示二醇殘基或二硫醇殘基，Z5表示氧原子或 硫原子）。 [化7]162338.doc -17·201242931 (wherein R1, R2 and R33 are the same as the above formula (1), and 11 is the same as the above formula (4), R'1 and ruler, 2 are the same as 111 and 112, and the ruler (1) Like the ruler, 丫, 3 is the same as Y3, R8 represents a diol residue or a dithiol residue, and Z5 represents an oxygen atom or a sulfur atom).

(式中，R、R2及R33與上述通式⑴相同，與上述通 式⑷相同，Ζ6表示氧原子、硫原子或砸原子，Α表示雜環 基’ t為〇〜5之整數’ u為〇或1)。 繼而，對本發明之感光性組合物進行詳細說明。 本發明之感光性組合物含有⑷本發明之光聚合起始劑 及(B)具有乙烯性不飽和鍵之聚合性化合物作為必需成 分，並組合含有（C)無機化合物、（D)著色料、溶劑等成分 作為任意成分。 於本發明之感光性組合物中，（A)本發明之光聚合起始 劑之含量並無特別限定’本發明之感光性組合物中之本發 明之㈣化合物之含量相對於（B)具有乙料不飽和鍵之 聚合性化合物量份㈣為成為質量份，更佳為 成為1〜50質量份，最佳為成為5〜3〇質量份。 作為上述（B)具有乙烯性不飽和鍵之聚合性化合物並 162338.doc 201242931 無特別限定，可使用先前用於感光性組合物者，例如可列 舉：乙烯、丙烯、丁烯、異丁烯、氣乙烯、偏二氣乙烯、 偏二氟乙烯、四氟乙烯等不飽和脂肪族烴；（曱基）丙烯 酸、α-氣丙烯酸、衣康酸、順丁烯二酸、檸康酸、反丁烯 二酸、雙環庚烯二甲酸、丁烯酸、異丁烯酸、乙烯基乙 酸、烯丙基乙酸、肉桂酸、山梨酸、中康酸、琥珀酸單[2_ (甲基）丙烯醢氧基乙基]酯、鄰苯二甲酸單[2_(曱基）丙烯醯 氧基乙基]酯、ω-羧基聚己内酯單（甲基）丙烯酸酯等之於兩 末端具有羧基與羥基之聚合物之單（曱基）丙烯酸酯；羥基 乙基（曱基）丙烯酸酯/順丁烯二酸酯、羥基丙基（曱基）丙烯 酸酯/順丁烯二酸酯、二環戊二烯/順丁烯二酸酯或具有 羧基與2個以上之（甲基）丙烯醯基之多官能（甲基）丙烯酸酯 等不飽和多元酸；（曱基）丙烯酸_2_羥基乙酯、（曱基）丙烯 酸-2-羥基丙酯、（曱基）丙烯酸縮水甘油酯、下述化合物 Νο.ΛΙ〜No.A4、（甲基）丙烯酸曱酯 ' (曱基）丙烯酸丁酯、 (甲基）丙烯酸異丁酯、（曱基）丙烯酸第三丁酯、（甲基）丙烯 酸環己酯、（甲基）丙烯酸正辛酯、（甲基）丙烯酸異辛酯、 (曱基）丙烯酸異壬酯、（曱基）丙烯酸硬脂酯、（曱基）丙烯酸 月桂酯、（甲基）丙烯酸甲氧基乙酯、（甲基）丙烯酸二甲基 胺基曱酯、（曱基）丙烯酸二曱基胺基乙酯、（曱基）丙烯酸 胺基丙酯、（甲基）丙烯酸二甲基胺基丙酯、（甲基）丙烯酸 乙氧基乙酯、（曱基）丙烯酸聚（乙氧基）乙酯、（甲基）丙烯酸 丁氧基乙氧基乙酯、（曱基）丙烯酸乙基己酯、（甲基）丙烯 酸苯氧基乙酯、（甲基）丙烯酸四氫呋喃酯、（甲基）丙烯酸 162338.doc -19- 201242931 乙婦醋、（甲基）丙稀酸稀丙賴、（甲基）丙稀酸节醋、乙二 醇一（曱基）丙稀酸g旨、二乙二醇二（甲基）丙埽酸醋、三乙 二醇二（甲基）丙稀酸醋1乙二醇二（甲基）丙烯酸醋、丙 二醇二（曱基）丙稀酸醋、U•丁二醇二（曱基）丙烯酸醋、 Μ·己二醇二（曱基）丙稀酸醋、三經甲基乙烧三（甲基）丙婦 酸醋、三經甲基丙统三（甲基）丙稀酸醋、4戊四醇六（甲 基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、季戊四醇四 (甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、三環癸烷 二甲醇二（甲基）丙烯酸酯、異氰尿酸三曱基）丙烯醯基乙 基]酯、聚酯（甲基）丙烯酸酯低聚物等不飽和一元酸及多元 醇或多元酚之酯；（甲基）丙烯酸鋅、（甲基）丙烯酸鎂等不 飽和多元酸之金屬鹽’順丁烯二酸酐、衣康酸酐、檸康酸 酐、曱基四氫鄰苯二甲酸酐、四氫鄰苯二甲酸酐、三烷基 四氫鄰苯二甲酸酐、5-(2,5-二氧代四氫呋喃基）-3_曱基·3_ 環己烯-1，2-二羧酸酐、三烷基四氫鄰苯二甲酸酐_順丁烯 二酸酐加成物、十二烯基琥轴酸酐、甲基雙環庚烯二曱酸 酐等不飽和多元酸之酸酐；（甲基）丙烯醯胺、亞甲基雙（甲 基）丙烯醯胺、二乙三胺三（甲基）丙烯醯胺、苯二甲基雙 (甲基）丙烯醢胺、α-氣丙烯醯胺、Ν-2-羥基乙基（曱基）丙 烯醯胺等不飽和一元酸及多元胺之酿胺；丙烯醛等不飽和 醛；（甲基）丙烯腈、α_氣丙烯腈、偏二氰乙烯、氰化烯丙 基等不飽和腈；苯乙烯、4-曱基苯乙烯、4-乙基苯乙烯、 4-甲氧基苯乙烯、4-羥基苯乙烯、4-氯苯乙烯、二乙烯基 苯、乙烯基甲苯、乙烯基苯甲酸、乙烯基苯驗'乙烯基磺 162338.doc -20· 201242931 酸、4-乙烯基苯磺酸、乙烯基节基曱醚、乙烯基节基縮水 甘油醚等不飽和芳香族化合物；甲基乙烯基酮等不飽和 酮；乙烯基胺、烯丙基胺、沁乙烯基吡咯烷酮、乙烯基哌 咬等不飽和胺化合物；；^丙醇、巴豆醇等乙婦醇；乙稀基 曱醚、乙烯基乙醚、正丁基乙烯醚、異丁基乙烯醚、烯丙 基縮水甘油醚等乙烯醚；順丁烯二醯亞胺、N_苯基順丁烯 -酿亞胺N環己基順丁歸二亞胺等不飽和酿亞胺類； 節、1-甲基節等節類；丁二稀、異戍二稀、氣丁二稀 等脂肪族共輛二烯類；聚笨乙烯、聚（甲基）丙稀酸甲醋、 聚（甲基）㈣m、聚#氧料之於聚合物分子键之 末端具有單（甲基）丙烯酿基之巨單體類；氣乙稀、偏二氣 乙稀、細二乙烯醋、鄰笨二甲酸二稀丙醋、鱗酸三稀 丙酯、異氰尿酸三烯丙酯、乙烯基硫醚、乙烯基咪唑、乙 稀基十坐琳、乙烯基°卡。坐、乙稀基料烧鲷、乙烯基吨 咬3I基之乙稀基單體及聚異氛酸輯化合物之乙稀基胺 基甲酸醋化合物、含經基之乙稀基單體及聚環氧化合物之 乙烯基環氧化合物。 [化8] 化合物No.Al(wherein R, R2 and R33 are the same as the above formula (1), and are the same as the above formula (4), wherein Ζ6 represents an oxygen atom, a sulfur atom or a ruthenium atom, and Α represents a heterocyclic group 't is an integer of 〇~5'. 〇 or 1). Next, the photosensitive composition of the present invention will be described in detail. The photosensitive composition of the present invention contains (4) a photopolymerization initiator of the present invention and (B) a polymerizable compound having an ethylenically unsaturated bond as an essential component, and contains (C) an inorganic compound, (D) a coloring material, and A component such as a solvent is used as an optional component. In the photosensitive composition of the present invention, (A) the content of the photopolymerization initiator of the present invention is not particularly limited. The content of the compound of the present invention (4) in the photosensitive composition of the present invention has a content relative to (B) The component (4) of the polymerizable compound of the ethylenic unsaturated bond is preferably 1 to 50 parts by mass, more preferably 5 to 3 parts by mass. The (B) polymerizable compound having an ethylenically unsaturated bond and 162, 338.doc 201242931 is not particularly limited, and those which have been previously used for a photosensitive composition can be used, and examples thereof include ethylene, propylene, butylene, isobutylene, and ethylene ethylene. , an unsaturated aliphatic hydrocarbon such as ethylene dimer, vinylidene fluoride or tetrafluoroethylene; (mercapto)acrylic acid, α-gas acrylic acid, itaconic acid, maleic acid, citraconic acid, and antibutene Acid, bicycloheptene dicarboxylic acid, crotonic acid, methacrylic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono[2_(methyl)acryloxyethyl) a single ester of a polymer having a carboxyl group and a hydroxyl group at both ends, such as ester, phthalic acid mono [2_(fluorenyl) propylene oxyethyl ester], ω-carboxy polycaprolactone mono(meth) acrylate (fluorenyl) acrylate; hydroxyethyl (mercapto) acrylate / maleate, hydroxypropyl (decyl) acrylate / maleate, dicyclopentadiene / cis-butene Diacid ester or polyfunctional group having a carboxyl group and two or more (meth) acrylonitrile groups (A Unsaturated polybasic acid such as acrylate; (2-mercapto)acrylic acid 2-hydroxyethyl ester, (mercapto)acrylic acid 2-hydroxypropyl ester, (mercapto)acrylic acid glycidyl ester, the following compound Νο.ΛΙ~ No. A4, decyl (meth) acrylate 'butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, (A) Base n-octyl acrylate, isooctyl (meth)acrylate, isodecyl (decyl) acrylate, stearyl (decyl) acrylate, lauryl (meth) acrylate, methoxy (meth) acrylate Ethyl ester, dimethylamino methacrylate (meth) acrylate, decylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate Ester, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, ethylhexyl (decyl)acrylate , (meth)acrylic acid phenoxyethyl ester, (meth)acrylic acid tetrahydrofuran ester, (methyl) Esoic acid 162338.doc -19- 201242931 Epoxy vinegar, (meth) acrylic acid dilute, (meth) acrylic acid vinegar, ethylene glycol mono(indenyl) acrylate acid, two Glycol di(methyl)propionic acid vinegar, triethylene glycol di(methyl) acrylate vinegar 1 ethylene glycol di(meth)acrylic acid vinegar, propylene glycol di(decyl) acrylate vinegar, U• Butanediol di(indenyl)acrylic acid vinegar, hydrazine hexanediol di(indenyl) acrylate vinegar, trimethyl ethene tris(methyl) propylene vinegar, trimethyl methacrylate Methyl) acrylate vinegar, 4 pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclic Unsaturated monobasic acid such as decane dimethanol di(meth) acrylate, trimethyl sulfhydryl isocyanate, polyester (meth) acrylate oligomer, and polyhydric or polyhydric phenol a metal salt of an unsaturated polybasic acid such as zinc (meth)acrylate or magnesium (meth)acrylate, maleic anhydride, itaconic anhydride, citraconic anhydride Mercaptotetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3_indolyl·3_ ring Unsaturated hexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methyl bicycloheptene phthalic anhydride Polybasic acid anhydride; (meth) acrylamide, methylene bis(meth) acrylamide, diethylenetriamine tris(meth) acrylamide, benzyl bis(methyl) acrylamide And unsaturated monobasic acids such as α-aluminum decylamine, hydrazine-2-hydroxyethyl(fluorenyl) acrylamide and polyamines; unsaturated aldehydes such as acrolein; (meth)acrylonitrile, α_ An unsaturated nitrile such as acrylonitrile, vinylidene cyanide or cyanyl allyl; styrene, 4-mercaptostyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyl toluene, vinylbenzoic acid, vinyl benzene test 'vinyl sulfonate 162338.doc -20· 201242931 acid, 4-vinylbenzenesulfonic acid, vinyl fluorenyl hydrazine Ether, ethylene An unsaturated aromatic compound such as a glycidyl ether; an unsaturated ketone such as methyl vinyl ketone; an unsaturated amine compound such as a vinylamine, an allylamine, a fluorenylvinylpyrrolidone or a vinylpiperidine; , ethenyl alcohol such as crotyl alcohol; vinyl ether such as ethyl ether, vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; maleimide, N_ Unsaturated brewed imines such as phenyl-cis-butene-imine, N-cyclohexyl-cis-diimide, etc.; knots, 1-methyl nodal, etc.; And other aliphatic dienes; polystyrene, poly(methyl) methacrylate, poly(methyl)(tetra)m, poly(oxygen) having mono(meth) propylene at the end of the polymer molecular bond Giant monomer of brewing base; ethylene ethylene, diethylene glycol, fine divinyl vinegar, diisopropyl acetonate, trisyl propyl citrate, triallyl isocyanurate, vinyl sulphur Ether, vinyl imidazole, ethylene base ten sitting, vinyl ° card. Sit, ethylene base simmering, vinyl ton bite 3I based ethylene monomer and polyiso-acid compound compound ethylene glycol carboxylic acid acetate compound, vinyl group containing vinyl group and poly ring A vinyl epoxy compound of an oxygen compound. [Chemical 8] Compound No. Al

[化9] 化合物No.A2[Chemistry 9] Compound No. A2

162338.doc •21· 201242931 [化 ίο] 化合物No,A3 [化 11] 化合物ΝαΑ4 又，作為（B)具有乙烯性不飽和鍵之聚合性化合物可 使用丙烯酸酯之共聚物、或苯酚及/或甲酚酚醛清漆環氧 樹脂、具有多官能環氧基之聚苯基甲烷型環氧樹脂\環氧 丙烯酸酯樹脂、及使下述通式（3)所表示之環氧化合物=環 氧化合物與不飽和一元酸作用、進而與多元酸酐作用而獲 得之樹脂。於該等中，較佳為使下述通式（3)所表示之環氧 化合物等環氧化合物與不飽和一元酸作用、進而與多元酸 酐作用而獲得之樹脂。又，該等化合物較佳為含有Ohi 〇 當量之不飽和基。 [化 12]162338.doc •21·201242931 [Chemical Formula] Compound A, A3 [Chemical Formula 11] Compound ΝαΑ4 Further, as the (B) polymerizable compound having an ethylenically unsaturated bond, a copolymer of acrylate, phenol and/or Cresol novolac epoxy resin, polyphenylmethane type epoxy resin having a polyfunctional epoxy group, epoxy acrylate resin, and epoxy compound represented by the following formula (3) = epoxy compound A resin obtained by the action of an unsaturated monobasic acid and further with a polybasic acid anhydride. Among these, a resin obtained by reacting an epoxy compound such as an epoxy compound represented by the following formula (3) with an unsaturated monobasic acid and further reacting with a polybasic acid anhydride is preferred. Further, these compounds are preferably unsaturated groups containing Ohi 当量 equivalents. [化 12]

(式中，X1表示直接鍵結、亞甲基、碳原子數為卜4之亞烷 基、碳原子數為3〜20之脂環式烴基、〇、s、s〇、ss、 so、co、oco或下述式（曱）、（乙）或（丙）所表示2之取代 I62338.doc -22- 201242931 基’上述亞烷基可經鹵素原子取代，R51、R52、尺53及R54 分別獨立表示氫原子、碳原子數為之烷基、碳原子數 為1〜8之烷氧基、碳原子數為2〜5之烯基或鹵素原子，上述 院基、烷氧基及烯基可經鹵素原子取代，m為〇〜1〇之整 數’ m不為〇時存在之光學異構物可為任意異構物）。 [化 13](wherein X1 represents a direct bond, a methylene group, an alkylene group having 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, hydrazine, s, s〇, ss, so, co , oco or a substitution of 2 represented by the following formula (曱), (b) or (c) I62338.doc -22- 201242931 base 'the above alkylene group may be substituted by a halogen atom, R51, R52, rule 53 and R54 respectively Independently, it represents a hydrogen atom, an alkyl group having a carbon number, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or a halogen atom, and the above-mentioned aristocracy, alkoxy group and alkenyl group may be used. Substituted by a halogen atom, m is an integer of 〇~1〇', and the optical isomer present when m is not ruthenium may be any isomer). [Chem. 13]

(甲） (式中，Z3表示氫原子、可經碳原子數為丨〜1〇之烷基或碳 原子數為1〜10之烷氧基取代之苯基、或者可經碳原子數為 1〜10之烷基或碳原子數為卜10之烷氧基取代之碳原子數為 3,之環烧基，Y丨表示碳原子數為卜1〇之烧基、碳原子數 為1〜10之烧氧基、碳原子數為2〜1G之稀基或齒素原子，上 述烧基、烧氧基及稀基可經自素原子取代，_〜5之整 數）。 [化 14] [化 15](A) (wherein Z3 represents a hydrogen atom, a phenyl group which may be substituted by an alkyl group having a carbon number of 丨~1〇 or an alkoxy group having 1 to 10 carbon atoms, or may have a carbon number of 1 The alkyl group of ～10 or the alkoxy group having a carbon number of 10 is substituted by a cycloalkyl group, and Y丨 represents a group having a carbon number of 1 10, and the number of carbon atoms is 1 to 10. The alkoxy group, a dilute group or a dentate atom having 2 to 1 G carbon atoms, and the above-mentioned alkyl group, alkoxy group and a dilute group may be substituted by a self-atomic atom, an integer of _5. [Chem. 14] [Chem. 15]

(丙） (式中’…分別獨立表示可_素原子取代之破原子 162338.doc •23- 201242931 數為1〜10之烧基、可經鹵素原子取代之碳原子數為6〜2〇之 芳基、可經鹵素原子取代之碳原子數為6〜20之芳氧基、可 經鹵素原子取代之碳原子數為6〜20之芳硫基、可經鹵素原 子取代之碳原子數為6〜20之芳基烯基、可經鹵素原子取代 之兔原子數為7〜20之芳基烧基、可經鹵素原子取代之碳原 子數為2〜20之雜環基、或鹵素原子，上述烷基及芳基烷基 中之伸烷基部分可經不飽和鍵、-〇_或_s•中斷，關於z4， 鄰接之Z4彼此可形成環’ p表示〇〜4之整數，q表示〇〜8之整 數，r表示0〜4之整數，s表示〇〜4之整數，1>與8之數之合計 為2〜4之整數）。 作為與上述環氧化合物作用之上述不飽和一元酸，可列 舉：丙烯酸、甲基丙烯酸、丁烯酸、肉桂酸、山梨酸、羥 基乙基甲基丙烯酸酯/順丁烯二酸酯、羥基乙基丙烯酸酯/ 順丁烯二酸酯、羥基丙基甲基丙烯酸酯/順丁烯二酸酯、 羥基丙基丙烯酸酯/順丁烯二酸酯、二環戊二烯順丁烯二 酸S旨等。 又，作為於上述不飽和一元酸產生作用後產生作用之上 述多元酸酐，可列舉：聯苯四羧酸二酐、四氫鄰苯二甲酸 酐、琥珀酸酐、聯苯四甲酸二酐、順丁烯二酸酐、偏苯三 甲酸酐、均苯四曱酸二酐、2,2，_3,3，_二苯甲酮四羧酸酐、 乙二醇雙偏笨三甲酸酐酯、甘油三偏苯三甲酸酐酯、六氫 鄰苯二曱酸酐、甲基四氫鄰苯二甲酸酐、耐地酸酐、曱基 耐地酸酐、三烷基四氫鄰苯二甲酸酐、六氫鄰苯二甲酸 酐、5-(2,5-二氧四氫呋喃基）_3_甲基環己烯_丨，2_二羧酸 162338.doc • 24· 201242931 肝、三烷基四氫鄰苯二甲酸酐 填丁稀.一酸肝加成物、 二烯基琥珀酸酐、甲基雙環庚烯二甲酸酐等。 元酸及上述多元酸酐之 上述環氧化合物、上述不飽和— 反應莫耳比較佳為如下所述。 即，於具有相對於上述環氧化合物之1個環氧基加成 o.w.o個上述不飽和—元酸之m基之結構的環氧加成物 中’較佳為上述多元酸軒之酸奸結構相對於該環氧加成物 之1個羥基成為0.1〜1.0個之比率。 元酸及上述多元酸酐之 上述環氧化合物、上述不飽和一 反應可依據常法進行。 於上述具有乙烯性不飽和鍵之聚合性化合物中於使用 具有酸值之化合物之情形時.，可賦^本發明之感光性組合 物鹼顯影性。於使用上述具有酸值之化合物之情形時，其 使用量較佳為於（Β)成分中成為50〜99質量〇/〇。 又，上述具有酸值之化合物亦可進而藉由與單官能或多 s忐環氧化合物反應而調整酸值後使用。藉由調整上述具 有酸值之化合物之酸值，可改良感光性樹脂之鹼顯影性。 上述具有酸值之化合物（即賦予鹼顯影性之具有乙烯性不 飽和鍵之聚合性化合物）較佳為固形物成分之酸值為5 mgKOH/g之範圍内，單官能或多官能環氧化合物之使用量 較佳為以滿足上述酸值之方式進行選擇。 作為上述單官能環氧化合物，可列舉：甲基丙烯酸縮水 甘油酿、曱基縮水甘油醚、乙基縮水甘油醚、丙基縮水甘 油_、異丙基縮水甘油謎、丁基縮水甘油蝴、異丁基縮水 162338.doc •25· 201242931 甘油醚、第三丁基縮水甘油醚、戊基縮水甘油醚、己基縮 水甘油醚、庚基縮水甘油醚、辛基縮水甘油醚、壬基縮水 甘油越、癸基縮水甘油喊、十一院基縮水甘油醚、十二院 基縮水甘油醚、十三烧基縮水甘油醚、十四烧基縮水甘油 醚、十五烷基縮水甘油醚、十六烷基縮水甘油醚、2-乙基 己基縮水甘油醚、烯丙基縮水甘油醚、炔丙基縮水甘油 醚、對甲氧基乙基縮水甘油醚、苯基縮水甘油醚、對甲氧 基縮水甘油醚、對丁基苯酚縮水甘油醚、曱酚基縮水甘油 _、2-曱基甲酚基縮水甘油謎、4-壬基苯基縮水甘油醚、 节基縮水甘油醚、對異丙苯基苯基縮水甘油謎、三苯甲基 縮水甘油醚、曱基丙烯酸2,3-環氧丙酯、環氧化大豆油、 環氧化亞麻仁油、丁酸縮水甘油酯、乙烯基環氧環己烷、 1’2-環氧-4-乙烯基環己烷、氧化苯匕烯、氧化蒎烯、曱基 苯乙烯氧化物、環氧環己烷、環氧丙烷、下述化合物 No.El、No.E2等。 [化 16] 化合物Νο.Ε1(C) (wherein '...individually represent the atomic atom substituted by the atomic atom 162338.doc •23- 201242931 The number of the alkyl group of 1 to 10, the number of carbon atoms which can be substituted by a halogen atom is 6~2〇 An aryl group, an aryloxy group having 6 to 20 carbon atoms which may be substituted by a halogen atom, an arylthio group having 6 to 20 carbon atoms which may be substituted by a halogen atom, and a carbon atom which may be substituted by a halogen atom are 6 An arylalkenyl group of -20, an arylalkyl group having a rabbit atomic number of 7 to 20 which may be substituted by a halogen atom, a heterocyclic group having 2 to 20 carbon atoms which may be substituted by a halogen atom, or a halogen atom, The alkyl group in the alkyl group and the arylalkyl group may be interrupted by an unsaturated bond, -〇_ or _s•, and with respect to z4, adjacent Z4 may form a ring with each other 'p' represents an integer of 〇~4, and q denotes 〇 An integer of ～8, r represents an integer of 0 to 4, s represents an integer of 〇~4, and 1> is an integer of 2 to 4 in total with 8). Examples of the unsaturated monobasic acid which acts on the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate/maleate, and hydroxyethyl b. Acrylate/maleate, hydroxypropyl methacrylate/maleate, hydroxypropyl acrylate/maleate, dicyclopentadiene maleic acid S Purpose. Further, examples of the polybasic acid anhydride which acts after the action of the unsaturated monobasic acid include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphenyltetracarboxylic dianhydride, and cis. Adipic anhydride, trimellitic anhydride, pyromellitic dianhydride, 2,2,_3,3,_benzophenonetetracarboxylic anhydride, ethylene glycol dip-trimethanol anhydride, glycerol trimellitic anhydride Ester, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, ceric anhydride, decyl benzoic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5 -(2,5-dioxotetrahydrofuranyl)_3_methylcyclohexene_丨,2_dicarboxylic acid 162338.doc • 24· 201242931 Liver, trialkyltetrahydrophthalic anhydride filled with dilute. Acid liver adduct, dienyl succinic anhydride, methyl bicycloheptene dicarboxylic anhydride, and the like. The above epoxy compound and the above-mentioned unsaturated-reactive moth of the above-mentioned polybasic acid anhydride are preferably as described below. That is, in the epoxy adduct having a structure in which an epoxy group of the above epoxy compound is added to owo of the above m-group of the unsaturated-acid acid, it is preferable that the above-mentioned polyacid acid yoke structure The ratio of one hydroxyl group to the epoxy adduct is 0.1 to 1.0. The above epoxy compound and the above-mentioned unsaturated one reaction of the monobasic acid and the above polybasic acid anhydride can be carried out according to a usual method. In the case where a compound having an acid value is used in the above polymerizable compound having an ethylenically unsaturated bond, the photosensitive composition of the present invention can be used for alkali developability. In the case of using the above-mentioned compound having an acid value, it is preferably used in an amount of 50 to 99% by mass in the (Β) component. Further, the above-mentioned compound having an acid value can be further used by adjusting the acid value by reacting with a monofunctional or polysulfonated epoxy compound. The alkali developability of the photosensitive resin can be improved by adjusting the acid value of the above compound having an acid value. The above-mentioned compound having an acid value (that is, a polymerizable compound having an ethylenically unsaturated bond imparting alkali developability) is preferably a solid component having an acid value of 5 mgKOH/g, and a monofunctional or polyfunctional epoxy compound. The amount of use is preferably selected so as to satisfy the above acid value. Examples of the monofunctional epoxy compound include glycidyl methacrylate, decyl glycidyl ether, ethyl glycidyl ether, propyl glycidol, isopropyl glycidol, butyl glycidyl, and Butyl shrinkage 162338.doc •25· 201242931 Glycerol ether, tert-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, decyl glycidol,癸-glycidol, 11-yard glycidyl ether, 12-yard glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, cetyl Glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether , p-butyl phenol glycidyl ether, nonylphenol glycidol _, 2-mercapto cresyl glycidyl riddle, 4-mercaptophenyl glycidyl ether, thioglycidyl ether, p-cumyl phenyl Glycerol mystery, triphenyl Glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinyl epoxy cyclohexane, 1'2-epoxy-4 - vinylcyclohexane, benzoquinone oxide, decene oxide, mercaptostyrene oxide, epoxycyclohexane, propylene oxide, the following compounds No. El, No. E2, and the like. [Chemistry 16] Compound Νο.Ε1

[化 17] 化合物No.E2 作為上述多官能環氧化合物，若使用選自雙酚型環氧化 合物及縮水甘油醚類所組成之群中之至少一種以上之化人 162338.doc -26· 201242931 物，則可制特性更加良好之（著色）驗顯影性感光性樹脂 組合物，故而較佳。 作為上述雙紛型環氧化合物，除可使用上述通式⑺所 表不之環氧化合物以外，例如亦可使用氫化雙酚型環氧化 合物等雙酚型環氧化合物。 又，作為上述縮水甘油醚類，可使用乙二醇二縮水甘油 醚、丙二醇二縮水甘油醚、丨，4_丁二醇二縮水甘油醚、 1 ’6己一醇一縮水甘油醚、丨，8-辛二醇二縮水甘油醚、 I，10-癸二醇二縮水甘油醚、2,2-二甲基·1，3-丙二醇二縮水 甘油醚、二乙二醇二縮水甘油醚、三乙二醇二縮水甘油 醚、四乙二醇二縮水甘油醚、六乙二醇二縮水甘油醚、 Μ-環己烷二曱醇二縮水甘油醚、Μ>1_三（縮水甘油氧基 甲基）丙烷、1，1，1-三（縮水甘油氧基甲基）乙院、 ’ 5 * ) _ 丨_ (縮水甘油氧基曱基）曱烷、1,1，1，1 -四（縮水甘油氧基曱基） 曱烷等。 此外’亦可使用笨酚酚醛清漆型環氧化合物、聯苯紛路 清漆型環氧化合物、甲酚酚醛清漆型環氧化合物、雙酚A 酚醛清漆型環氧化合物、二環戊二烯酚醛清漆型環氧化合 物等紛盤清漆型環氧化合物；3,4_環氧_6_甲基環己基甲 . 基-3,4_環氧-6-甲基環己烷羧酸酯、3,4-環氧環己基甲基· 3’4_環氧環己烷羧酸酯、1_環氧乙基_3,4·環氧環己烷等脂 環式環氧化合物；鄰笨二甲酸二縮水甘油酯、四氫鄰苯二 甲酸二縮水甘油酯、二聚酸縮水甘油酯等縮水甘油酯類； 四縮水甘油基二胺基二苯基甲烷、三縮水甘油基對胺基苯 162338.doc • 27- 201242931 酚、N，N•二縮水甘油基苯胺等縮纟甘油基胺冑；1，3_二縮 水甘油基-5,5·二甲基乙内酿腺、異氛尿酸三縮水甘油醋等 雜％式環氧化合物；二氧化二環戊二烯等二氧化物化合 物，萘型環氧化合物；三苯基甲炫型環氧化合物；二環戍 二烯型環氧化合物等。 作為可含有於本發明之感光性組合物中之上述（C)無機 化合物，例如可列舉：氧化錄、氧化鐵、氧化銀、氧化 鈦：氧化鋅、氧化鎂' 氧化鈣、氧化鉀、^氧化矽、氧化 銘等金屬氧化物；層狀黏土礦物、米洛麗藍、碳酸舞、碳 酸鎂、姑系、猛系、玻璃粉末（尤其是玻璃料）、雲母、滑 石、局嶺土、亞鐵氰化物、各種金屬硫酸鹽、硫化物、砸 化物、矽酸鋁、矽酸鈣、氫氧化鋁、链、金、銀、銅等。 於該等中，較佳為玻璃料、氧化欽、二氧切、層狀黏 土礦物、銀等。於本發明之感光性組合物中，（C)無機化 合物之含量相對於(Β)具有乙婦性不飽和鍵之聚合性化合 物⑽質量份，較佳為〇」〜_〇質量份，更佳為1〇〜_質 量伤。再者’該等無機化合物可使用一種或兩種以上。 該等無機化合物例如可用作填充劑、抗反射劑、導電 穩定劑阻燃劑、機械強度提昇劑、特殊波長吸收 劑、拒油墨劑等。 又，作為可含有於本發明之感光性組合物中之上述（D) 著色料，可列舉顏料、染料、天然色素等。該等著色料可 單獨或混合兩種以上而使用。 作為上述顏料，例如可使用：亞确基化合物；确基化合 162338.doc •28- 201242931 物；偶氣化合物；重氮化合物；㈣化合H琳化合 物；蒽酿化合物；香豆素化合物；醜菁化合物；異t朵琳 _化合物；異Μ琳化合物；^㈣化合物；蒽締葱晒 化合物，派瑞嗣化合物；花化合物；二綱基。比略幷料化 合物；硫散藍化合物；…化合物；三苯基甲统化合 物；姐酮化合物；蔡四缓酸；偶氮染料、花青染料之金 屬錯合物；色殿顏料；藉由爐法'槽法或熱法而獲得之碳 黑、或乙炔黑、科琴黑或燈黑等碳黑；利用環氧樹脂調整 或被覆上述碳黑而成者、預先於溶劑中利用樹脂對上述碳 黑進行分散處理而吸附2G〜綱mg/g之樹脂而成者、對上 述碳黑進行酸性或驗性表面處理而成者、平均粒徑為8⑽ 以上且DBP(DibUtyl phthalate，鄰苯二甲酸二丁醋）吸油量 為90 ml/100 g以下之碳黑、根據95〇β(：下之揮發成分中之 C〇及C〇2算出之總氧量相對於每10〇 ni2表面積為9 mg以上 ,石反黑，石墨、石墨化碳黑、活性碳、碳纖維、奈米碳 管、螺旋碳纖維、碳奈米角、碳氣凝膠、富勒烯丨苯胺 黑、顏料黑7、鈦黑；氧化鉻綠、米洛麗藍、#綠、鈷 藍、錳系、亞鐵氰化物、磷酸鹽群青、鐵藍、群青、天 藍、濃綠、翡翠綠、硫酸鉛、黃丹、鋅黃、鐵丹（紅色氧 ^鐵（ΙΠ))、鎘紅、合成鐵黑、棕土等有機或無機顏料。該 等顏料可單獨或混合複數種而使用。 作為上述顏料’亦可使用市售之顏料，例如可列舉：顏 料紅 1、2、3、9、10、14、17、22、23、31、38、41、 48 、 49 、 88 、 90 、 97 、 112 、 119 、 122 、 123 、 144 、 149 、 162338.doc -29- 201242931 166 、 168 、 169 、 170 、 171 、 177 、 179 、 180 、 184 、 185 、 192 、 200 、 202 、 209 、 215 、 216 、 217 、 220 、 223 、 224 、 226、227、228、240、254 ;顏料橙 13、31、34、36、 38、43、46、48、49、51、52、55、59、60、61、62、 64、65、71 ;顏料黃i、3、12、13、14、16、17、2〇、 24、55、60、73、81、83、86、93、95、97、98、1〇〇、 109、110、i13、114、117、12〇、125、126、127、129、 137 、 138 ' 139 、 147 、 148 、 150 、 151 、 152 、 153 、 154 、 166、168、175、18〇、185 ;顏料綠7、1〇、36 ;顏料藍 15、15 : 1、15 : 2、15 : 3、15 : 4、15 : 5、15 : 6、22、 24、56、60、61、62、64 ;顏料紫 1、19、23、27、29、 30、32 ' 37、40、50等。 作為上述染料’可列舉：偶氮染料、蒽醌染料、靛染 料、三芳基甲烷染料、咄p星染料、茜素染料、吖啶染料、 二苯乙烯染料、噻唑染料、萘酚染料、喹啉染料、硝基染 料、吲達胺染料、噚畊染料、酞菁染料、花青染料等染 料等，該等亦可混合複數種而使用。 於本發明之感光性組合物中含有（D)著色料之情形時， 其含量相對於（B)具有乙烯性不飽和鍵之聚合性化合物1〇〇 質量份較佳為5〇〜35〇質量份，更佳為1〇〇〜25〇質量份。 又，本發明之感光性組合物亦可不具有乙烯性不飽和鍵 而含有賦予鹼顯影性之化合物，作為此種化合物，只要為 八有酸值而可溶於鹼性水溶液之化合物則並無特別限定， 作為代表性者，可列舉鹼可溶性酚醛清漆樹脂（以下簡稱 162338.doc 201242931 為「盼搭清漆樹脂」）》盼搭清漆樹脂係於酸觸媒存在下 使酚類與醛類聚縮合而獲得。 作為上述酚類，例如可使用：苯酚、鄰甲酚、間曱紛、 對曱酚、鄰乙基苯酚、間乙基苯酚、對乙基苯酚、鄰丁基 苯酚、間丁基苯酚、對丁基苯酚、2,3-二甲苯酚、2,4_二 甲苯酚、2,5-二甲笨酚、3,4-二曱苯酚、3,5-二甲苯紛、 2,3,5 -三甲基苯盼、對苯基苯齡、氫酿、兒茶紛、間笨二 紛、2-甲基間苯二盼、鄰苯三紛、α_萘驗、雙紛a、二經 基本曱酸S旨、沒食子酸S旨等’該等盼類之中較佳為苯紛、 鄰曱酚、間甲酚、對甲酚、2,5-二甲苯酚、3,5_二甲苯 紛、2,3,5-二甲基苯紛、間苯二齡、2-甲基間笨二紛及雙 酚A。該等酚類可單獨或混合兩種以上而使用。 作為上述酿類’例如可使用：甲醛、三聚曱醛、乙路、 丙醛、苯甲醛、笨乙醛、α—苯丙醛、β_笨丙醛、鄰羥基苯 甲醛、間羥基苯曱醛、對羥基苯甲醛 '鄰氣苯甲醛、間氣 苯曱醛、對氣苯甲醛、鄰硝基苯甲醛、間硝基苯甲醛、對 硝基苯甲醛、鄰甲基笨甲醛、間甲基苯甲醛、對曱基笨甲 搭、對乙基苯曱酸、對正丁基苯甲駿等，該等化合物之中 較佳為甲醛、乙醛及笨甲醛。該等醛類可單獨或混合兩種 以上而使用，類相對於每以耳紛類，較佳為以〇7〜3莫 耳’尤佳為以0.7〜2莫耳之比例使用。 作為上述酸觸媒，例如可使用㈣、硝酸 '硫酸等無機 酸’或曱酸、草酸、乙酸等有機酸。該等酸觸媒之使用量 較佳為相對於每丨莫耳酚類為1χ1〇.4〜5χΐ(Γΐ莫耳。於縮合 162338.doc •31· 201242931 反應中通常使用水作為反應介質，於縮合反應所使用之紛 類不溶解於路類之水溶液而自反應初期起便成為不均勻系 統之情形時，亦可使用親水性溶劑作為反應介質。作為該 等親水性溶劑’例如可列舉曱醇、乙醇、丙醇、丁醇等醇 類’或四氫呋喃、二呤烷等環狀醚類。該等反應介質之使 用量通常相對於每100質量份反應原料為20〜1000質量份。 縮合反應之反應溫度可根據反應原料之反應性而適當調 整，通常為10〜200°C，較佳為70〜15(TC。縮合反應結束 後’為了去除存在於系統内之未反應原料、酸觸媒及反應 介質’ 一般而言使内溫上升至130〜23〇。(：，於減壓下蒸餾 除去揮發成分’繼而將熔融之酚醛清漆樹脂於鋼製傳送帶 專上流延而回收。 又’亦可於縮合反應結束後’藉由將反應混合物溶解於 上述親水性溶劑中並添加於水、正己烷、正庚烷等沈澱劑 中而使盼酸清漆樹脂析出，分離析出物並進行加熱乾燥， 藉此而回收。 作為上述酚醛清漆樹脂以外之例，可列舉聚羥基苯乙烯 或其衍生物、苯乙烯_順丁烯二酸酐共聚物、聚乙烯羥基 苯曱酸酯等。 於本發明之感光性組合物中可視需要進而添加溶劑。作 為°亥'合劑’通常可使用可溶解或分散上述各成分（(A)本發 月之光聚合起始劑及（B)具有乙烯性不飽和鍵之聚合性化 D物等）之溶劑，例如：甲基乙基酮、甲基戊基酮、二乙 丙網、曱基異丙基酮、甲基異丁基酮、環己酮、2-162338.doc -32- 201242931 庚酮等酮類；乙醚、二，号烷、四氫呋喃、1，2_二甲氧基乙 烷、1，2-二乙氧基乙烷、二丙二醇二甲醚等醚系溶劑；乙 酸曱酯、乙酸乙酯、乙酸正丙酯、乙酸異丙醋、乙酸正丁 酯、乙酸環己酯、乳酸乙酯、破珀酸二甲酯、 TEXANOL(2,2,4-三甲基-1,3戊二醇單異丁酸酯）等酯系溶 劑；乙二醇單曱醚、乙二醇單乙醚等溶纖劑系溶劑；甲 醇'乙醇、異丙醇或正丙醇、異丁醇或正丁醇、戊醇等醇 系溶劑；乙二醇單曱醚乙酸酯、乙二醇單乙醚乙酸酯、丙 二醇-1·單甲醚_2·乙酸酯、二丙二醇單甲醚乙酸酯、乙酸一 3 -甲氧基丁酯、丙酸乙氧基乙酯等謎酯系溶劑；苯、曱 笨、二甲苯等 BTX(Benzene Toluene Xylene，苯-甲苯·二 甲苯）系溶劑；己烷、庚烷、辛烷、環己烷等脂肪族烴系 溶劑；松節油、D-擰檬烯、蒎烯等萜烯系烴油；礦油精、 SwaZ〇l#310(Cosm〇 Matsuyama ⑻股份有限公司）、 S〇lvesso#i00(Exxon Chemkal股份有限公司）等烷烴系溶 劑；四氣化碳、氣仿、三氣乙烯、二氣曱烷、丨，2二氯乙 烧等11化脂肪族㈣溶劑；氯料_化料族烴系溶劑； 卡必醇系溶劑；苯胺；三乙基胺H乙酸；乙猜；二 硫化碳；Ν，Ν·二甲基甲醯胺；N，N•二曱基乙醯胺；n_甲基 比略烧酮’ 一甲基亞硬；水等，該等溶劑可使用一種，或 作為兩種以上之混合溶劑而使用。 該等之中，酮類、醚酯系溶劑等、尤其是丙二醇單 ^ 乙k S曰^衣己酮等於感光性組合物中可使光阻劑與 光聚合起始劑之相溶性變好，故而較佳。 162338.doc -33- 201242931 於本發明之感光性組合物中，溶劑之含量並無特別限 制，只要為使各成分均句分散或溶解、又，使本發明之感 先性組合物呈現㈣於各肖途之餘或糊狀之量即可通 常較佳為以本發明之感綠組合物中之固形物成分（溶劑 以外之全部成分）之量為10〜50質量％之範圍含有溶劑。 於本發明之感光性組合物中可添加使(c)無機化合物及/ 或（D)著色料分散之分散劑叫乍為該分散冑，只要為可使 (C)無機化合物或（D)著色料分散、穩定化者則並無限制， 可使用市售之分散劑，例如BYK Chemie公司製造之Βγκ 系列等。尤其是可較佳使用如下高分子分散劑，其包含具 有鹼性官能基之聚酯、聚醚、或聚胺基甲酸酯，具有氮原 子作為鹼性官能基，具有氮原子之官能基為胺及/或其四 級鹽’且胺值為1〜l〇〇mgK〇H/g。 又，本發明之感光性組合物中，亦可藉由將具有乙 烯性不飽和鍵之聚合性化合物與其他有機聚合物一併使用 而改善硬化物之特性。作為該有機聚合物，例如可列舉： 聚苯乙烯、聚甲基丙烯酸曱酯、甲基丙烯酸甲酯-丙烯酸 乙酯共聚物、聚（曱基）丙烯酸、苯乙烯甲基）丙烯酸共聚 物、（甲基）丙烯酸-甲基丙烯酸甲酯共聚物、乙烯·氣乙烯 共聚物、乙烯-乙烯基共聚物、聚氣乙稀樹脂、 ABS(Acrylonitrile Butadiene Styrene，丙稀腈丁二稀-苯 乙烯）樹脂、尼龍6、尼龍66、尼龍12、胺基甲酸酯樹脂、 聚碳酸酯、聚乙烯丁醛、纖維素酯、聚丙烯醯胺 '飽和聚 酯、酚樹脂、苯氧基樹脂、聚醯胺-醯亞胺樹脂、聚醯胺 162338.doc •34· 201242931 酸樹脂、環氧樹脂等，料之中，較佳為聚苯乙稀、（甲 基）丙稀酸·曱基丙烯酸甲酯共聚物、環氧樹脂。 於使用其他有機聚合物之情形時，其使用量相對於（b) 具有乙烯性不飽和鍵之上述聚合性化合物1〇〇質量份，較 佳為10〜500質量份。 於本發明之感光性組合物中可進而併用鏈轉移劑、增感 劑、界面活性劑、矽烷偶合劑、三聚氰胺化合物等。 作為上述鏈轉移劑或增感劑，一般而言使用含硫原子之 化合物。例如可列舉：硫代乙醇酸、硫代蘋果酸、硫代水 杨酸、2-巯基丙酸、3-疏基丙酸、3·疏基丁酸、N-(2-魏基 丙醯基）甘胺酸、2-疏基煙驗酸、3-[N-(2-魏基乙基）胺曱酿 基]丙酸、3-[N-(2-酼基乙基）胺基]丙酸、n-(3-疏基丙醢基） 丙胺酸、2-[基乙績酸、3-疏基丙續酸、4-巯基丁罐酸、 十二烧基（4-甲硫基）苯鍵、2-疏基乙醇、3-疏基-1，2-丙二 醇、1-巯基-2-丙醇、3-巯基-2·丁醇、酼基苯酚、2-酼基乙 基胺、2-酼基咪嗅、2-酼基笨并喷嗤、2-疏基-3-幾基。比 啶、2-巯基苯并噻唑、酼基乙酸、三羥甲基丙烷三（3-毓基 丙酸酯）' 季戊四醇四（3-酼基丙酸酯）等巯基化合物，氧化 該酼基化合物而獲得之二硫ϋ化合物，蛾乙酸、块丙酸、 2-碘乙醇、2-碘乙磺酸、3-碘丙磺酸等碘化烷基化合物， 三羥甲基丙烷三（3-巯基異丁酸酯）、丁二醇雙（3-酼基異丁 酸酯）、己二硫醇、秀二硫醇、1,4-二曱基疏基苯、丁二醇 雙硫代丙酸酯、丁二醇雙硫代乙醇酸酯、乙二醇雙硫代乙 醇酸酯、三羥甲基丙烷三硫代乙醇酸酯、丁二醇雙硫代丙 162338.doc •35- 201242931 酸酯、三羥甲基丙烷三硫代丙酸酯、三羥曱基丙烷三硫代 乙醇酸酯、季戊四醇四硫代丙酸酯、季戊四醇四硫代乙醇 酸酯、三羥基乙基三硫代丙酸酯、二乙基硫雜蒽酮、二異 丙基硫雜蒽酮、下述化合物No.Cl、三疏基丙酸三（2-經基 乙基）異氰尿酸酯等脂肪族多官能硫醇化合物，昭和電工 公司製造 Karenz MT BD1、PEI、NR1 等。 [化 18] 化合物No.ClIn the above-mentioned polyfunctional epoxy compound, at least one selected from the group consisting of bisphenol epoxy compounds and glycidyl ethers is used. 162338.doc -26· 201242931 Further, it is preferable to develop a photosensitive photosensitive resin composition which is more excellent in characteristics (coloring). In addition to the epoxy compound represented by the above formula (7), a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxide may be used. Further, as the glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hydrazine, 4-butanediol diglycidyl ether, 1 '6-hexanol monoglycidyl ether, hydrazine can be used. 8-octanediol diglycidyl ether, I, 10-nonanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, three Ethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, hydrazine-cyclohexane didecyl diglycidyl ether, hydrazine > 1_tris (glycidyloxymethyl) Base) propane, 1,1,1-tris(glycidoxymethyl)benzamine, '5*) _ 丨_(glycidoxycarbonyl) decane, 1,1,1,1 -tetra Glycidyloxy fluorenyl) decane and the like. In addition, 'phenol phenol varnish type epoxy compound, biphenyl varnish type epoxy compound, cresol novolak type epoxy compound, bisphenol A novolak type epoxy compound, dicyclopentadiene novolac varnish can also be used. a varnish-type epoxy compound such as an epoxy compound; 3,4_epoxy-6-methylcyclohexylmethyl.-3,4-epoxy-6-methylcyclohexanecarboxylate, 3, 4-epoxycyclohexylmethyl 3'4_epoxycyclohexane carboxylate, 1_epoxyethyl_3,4·epoxycyclohexane, etc.; alicyclic epoxy Glycidyl esters such as diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester; tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminobenzene 162338. Doc • 27- 201242931 Phenol, N,N• diglycidyl aniline and other glycosylamine oxime; 1,3_ diglycidyl-5,5·dimethylethene brewing gland, uric acid trihydrate a heteropolyoxy compound such as glycerin or the like; a dioxide compound such as dicyclopentadiene dioxide; a naphthalene type epoxy compound; a triphenylmethyl epoxide type epoxy compound; Diene type epoxy compounds. Examples of the (C) inorganic compound which may be contained in the photosensitive composition of the present invention include oxidation record, iron oxide, silver oxide, titanium oxide: zinc oxide, magnesium oxide 'calcium oxide, potassium oxide, and oxidation. Metal oxides such as bismuth and oxidized; layered clay minerals, milorie blue, carbonic acid dance, magnesium carbonate, phylum, ramets, glass powder (especially glass frit), mica, talc, slate, ferrous Cyanide, various metal sulfates, sulfides, tellurides, aluminum citrate, calcium citrate, aluminum hydroxide, chains, gold, silver, copper, and the like. Among these, glass frit, oxidized chin, dioxo prior, layered clay mineral, silver, and the like are preferable. In the photosensitive composition of the present invention, the content of the (C) inorganic compound is preferably 〇" to _ parts by mass, more preferably the mass of the polymerizable compound (10) having an ethylatrophic unsaturated bond. For 1〇~_ quality injury. Further, one or two or more kinds of these inorganic compounds may be used. These inorganic compounds can be used, for example, as a filler, an antireflection agent, a conductive stabilizer flame retardant, a mechanical strength enhancer, a special wavelength absorber, an ink repellent, and the like. Moreover, examples of the (D) coloring material which can be contained in the photosensitive composition of the present invention include pigments, dyes, natural colors, and the like. These coloring materials may be used singly or in combination of two or more. As the above pigment, for example, an α-based compound can be used; a compound of 162 338.doc • 28-201242931; an azo compound; a diazo compound; (4) a compound of H-lin; a brewing compound; a coumarin compound; Compound; iso-t-lin- _ compound; iso- lin-line compound; ^ (iv) compound; 葱 葱 化合物 化合物 ,, 派 嗣 嗣 compound; flower compound; Bismuth compound; sulphur blue compound; ... compound; triphenyl methamine compound; ketone compound; Tara tetrazoic acid; azo dye, metal complex of cyanine dye; color house pigment; by furnace method Carbon black obtained by the groove method or the thermal method, or carbon black such as acetylene black, ketjen black or lamp black; the carbon black obtained by adjusting or coating the carbon black with an epoxy resin, and the above-mentioned carbon black by using a resin in advance in a solvent A dispersion treatment is carried out to adsorb a resin of 2G to MPa/g, and the carbon black is subjected to an acidic or surface treatment. The average particle size is 8 (10) or more and DBP (DibUtyl phthalate) is dibutyl phthalate. Vinegar) carbon black with a water absorption of 90 ml/100 g or less, and a total oxygen amount calculated according to 95 〇β (the C 〇 and C 〇 2 in the volatile component below) is 9 mg or more per 10 〇 ni 2 surface area, Stone anti-black, graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, spiral carbon fiber, carbon nanohorn, carbon aerogel, fullerene aniline black, pigment black 7, titanium black; chromium oxide Green, Milorie Blue, #绿, cobalt blue, manganese, ferrocyanide, phosphoric acid Organic or inorganic pigments such as ultramarine blue, iron blue, ultramarine blue, sky blue, dark green, emerald green, lead sulfate, yellow dan, zinc yellow, iron dan (red oxygen ^ iron (ΙΠ)), cadmium red, synthetic iron black, brown earth These pigments may be used singly or in combination of a plurality of kinds. As the above pigments, commercially available pigments may also be used, and for example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31 may be mentioned. , 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 162338.doc -29- 201242931 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; pigment yellow i, 3, 12, 13, 14, 16, 17, 2, 24, 55, 60, 73 , 81, 83, 86, 93, 95, 97, 98, 1〇〇, 109, 110, i13, 114, 117, 12〇, 125, 126, 127, 129, 137, 138 '139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 18〇, 185; pigment green 7, 1, 〇, 36; pigment blue 15, 15 : 1, 15 : 2, 15 : 3, 15 : 4, 15 : 5, 15 : 6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32 '37, 40, 50, etc. Examples of the dyes mentioned above include azo dyes, anthraquinone dyes, anthraquinone dyes, triarylmethane dyes, anthraquinone dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, and quinolines. Dyes, nitro dyes, indamine dyes, sorghum dyes, phthalocyanine dyes, cyanine dyes, and the like, which may be mixed and used in plural. When the (D) coloring material is contained in the photosensitive composition of the present invention, the content thereof is preferably 5 〇 to 35 Å by mass based on 1 part by mass of the (B) polymerizable compound having an ethylenically unsaturated bond. More preferably, it is from 1 to 25 parts by mass. Further, the photosensitive composition of the present invention may contain a compound which imparts alkali developability without an ethylenically unsaturated bond, and as such a compound, there is no particular compound which is soluble in an alkaline aqueous solution as long as it has an acid value of eight. As a representative, an alkali-soluble novolak resin (hereinafter referred to as 162338.doc 201242931 is a "preserved varnish resin"), and it is expected that a varnish resin is obtained by polycondensing a phenol with an aldehyde in the presence of an acid catalyst. . As the phenols, for example, phenol, o-cresol, hydrazine, p-nonylphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butyl can be used. Phenolic, 2,3-xylenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-diphenylphenol, 3,5-xylene, 2,3,5 - Trimethylbenzene, p-phenylbenzene, hydrogen, catechu, stupid, 2-methylisophthalene, o-benzene, α-naphthalene, double a, two basic The meaning of citric acid S, gallic acid S, etc., among these, the preferred ones are benzophenone, o-nonylphenol, m-cresol, p-cresol, 2,5-xylenol, 3,5_two. Toluene, 2,3,5-dimethylbenzene, isophthalic acid, 2-methyl stupid and bisphenol A. These phenols may be used singly or in combination of two or more. As the above-mentioned brewing type, for example, formaldehyde, trimeric furfural, ethylbenzene, propionaldehyde, benzaldehyde, stupid acetaldehyde, α-phenylpropanal, β-stanopropanal, o-hydroxybenzaldehyde, m-hydroxyphenylhydrazine can be used. Aldehyde, p-hydroxybenzaldehyde, o-benzaldehyde, m-benzoic aldehyde, p-benzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methyl Benzoaldehyde, p-nonyl phenyl, p-ethyl benzoic acid, p-n-butyl benzophenone, etc., among these compounds are preferably formaldehyde, acetaldehyde and stupid formaldehyde. These aldehydes may be used singly or in combination of two or more kinds, and are preferably used in a ratio of 0.7 to 2 moles per ampere, preferably 〇7 to 3 moles. As the acid catalyst, for example, (IV), an inorganic acid such as nitric acid 'sulfuric acid' or an organic acid such as citric acid, oxalic acid or acetic acid can be used. The amount of the acid catalyst used is preferably 1χ1〇.4~5χΐ per mol of phenolic phenol. In the reaction of condensing 162338.doc •31·201242931, water is usually used as a reaction medium. In the case where the condensation reaction is not dissolved in the aqueous solution of the road and becomes an uneven system from the initial stage of the reaction, a hydrophilic solvent may be used as the reaction medium. As the hydrophilic solvent, for example, decyl alcohol may be mentioned. An alcohol such as ethanol, propanol or butanol or a cyclic ether such as tetrahydrofuran or dioxane. The reaction medium is usually used in an amount of 20 to 1000 parts by mass per 100 parts by mass of the reaction raw material. The reaction temperature can be appropriately adjusted depending on the reactivity of the reaction raw material, and is usually 10 to 200 ° C, preferably 70 to 15 (TC. After the end of the condensation reaction), in order to remove unreacted raw materials and acid catalysts present in the system. The reaction medium generally raises the internal temperature to 130 to 23 Torr. (:, the volatile component is distilled off under reduced pressure), and the molten novolac resin is continuously cast and recovered on a steel conveyor belt. After the condensation reaction is completed, the reaction mixture is dissolved in the hydrophilic solvent and added to a precipitating agent such as water, n-hexane or n-heptane to precipitate the acid varnish resin, and the precipitate is separated and heated and dried. In addition, examples of the novolak resin include polyhydroxystyrene or a derivative thereof, a styrene-maleic anhydride copolymer, a polyvinyl hydroxybenzoate, and the like. Further, a solvent may be added to the composition as needed. As the "Hay' mixture", a polymerization which can dissolve or disperse the above components ((A) a photopolymerization initiator of the present month and (B) an ethylenically unsaturated bond can be usually used. A solvent such as methyl ethyl ketone, methyl amyl ketone, diethyl propyl ketone, decyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-162338. Doc -32- 201242931 Ketones such as heptanone; ethers such as diethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether Solvent; decyl acetate, ethyl acetate, n-propyl acetate, acetic acid Propyl vinegar, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl chlorate, TEXANOL (2,2,4-trimethyl-1,3 pentanediol monoisobutyrate) Solvent; solvent of cellosolve such as ethylene glycol monoterpene ether or ethylene glycol monoethyl ether; alcoholic solvent such as methanol 'ethanol, isopropanol or n-propanol, isobutanol or n-butanol or pentanol; Glycol monoterpene ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1·monomethyl ether-2·acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate , a glycol ester such as ethoxyethyl propionate; BTX (Benzene Toluene Xylene) solvent such as benzene, hydrazine, xylene, etc.; hexane, heptane, octane, cyclohexane Aliphatic hydrocarbon solvent; terpene hydrocarbon oil such as turpentine, D-moneylene, terpene; mineral spirits, SwaZ〇l#310 (Cosm〇Matsuyama (8) Co., Ltd.), S〇lvesso#i00 (Exxon Chemkal Co., Ltd.) and other alkane-based solvents; tetra-carbonated carbon, gas-like, tri-ethylene, dioxane, hydrazine, 2 dichloroethene, etc. 11-acid aliphatic (tetra) solvent; chlorine material_chemical hydrocarbon system Dissolve ; carbene alcohol solvent; aniline; triethylamine H acetic acid; B guess; carbon disulfide; hydrazine, hydrazine dimethyl carbamide; N, N• dimercaptoacetamide; n_methyl ratio slightly burned The ketone is monomethyl hard; water, etc., and these solvents may be used alone or as a mixed solvent of two or more. Among these, ketones, ether ester solvents, and the like, especially propylene glycol monoethyl ketone ketone, are equivalent to the photosensitive composition, and the compatibility between the photoresist and the photopolymerization initiator can be improved. Therefore, it is better. 162338.doc -33- 201242931 In the photosensitive composition of the present invention, the content of the solvent is not particularly limited as long as the ingredients are dispersed or dissolved, and the composition of the present invention is rendered (4) It is preferable that the amount of the solid component or the amount of the paste in the green sensitive composition of the present invention is preferably from 10 to 50% by mass in the amount of the solid content component (all components other than the solvent). A dispersing agent which disperses (c) the inorganic compound and/or the (D) coloring material may be added to the photosensitive composition of the present invention as the dispersing enthalpy, as long as the (C) inorganic compound or (D) can be colored. There are no restrictions on the dispersion and stabilization of the materials, and commercially available dispersants such as the Βγκ series manufactured by BYK Chemie can be used. In particular, it is preferred to use a polymer dispersant comprising a polyester having a basic functional group, a polyether, or a polyurethane having a nitrogen atom as a basic functional group and a functional group having a nitrogen atom. The amine and/or its quaternary salt 'and the amine value is 1 to 1 〇〇 mg K 〇 H / g. Further, in the photosensitive composition of the present invention, the properties of the cured product can be improved by using a polymerizable compound having an ethylenically unsaturated bond together with another organic polymer. Examples of the organic polymer include polystyrene, poly(methacrylic acid methacrylate), methyl methacrylate-ethyl acrylate copolymer, poly(indenyl)acrylic acid, and styrenemethyl)acrylic acid copolymer. Methyl)acrylic acid-methyl methacrylate copolymer, ethylene/ethylene ethylene copolymer, ethylene-vinyl copolymer, polyethylene oxide resin, ABS (Acrylonitrile Butadiene Styrene) resin , nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate, polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenolic resin, phenoxy resin, polyamine - yttrium imide resin, polyamide 162338.doc • 34· 201242931 Acid resin, epoxy resin, etc. Among them, preferably polystyrene, (meth) acrylic acid, methyl methacrylate copolymerization Matter, epoxy resin. In the case of using other organic polymers, the amount thereof is preferably from 10 to 500 parts by mass based on 1 part by mass of the above polymerizable compound having an ethylenically unsaturated bond. Further, a chain transfer agent, a sensitizer, a surfactant, a decane coupling agent, a melamine compound or the like can be used in combination in the photosensitive composition of the present invention. As the above chain transfer agent or sensitizer, a compound containing a sulfur atom is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-cyanopropionic acid, 3, thioglycolic acid, N-(2-Williylpropyl fluorenyl) Glycine, 2-Sulfuric acid test, 3-[N-(2-Wylylethyl)amine aryl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid , n-(3-Silylpropyl) alanine, 2-[ylidene acid, 3-sulfopropionic acid, 4-mercaptobutyric acid, 12-alkyl (4-methylthio)benzene Bond, 2-mercaptoethanol, 3-sulfenyl-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, nonylphenol, 2-mercaptoethylamine, 2 - 酼基咪 sniffing, 2-mercapto is stupid and sneezing, 2-sulfo-3-yl. a mercapto compound such as pyridinium, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), oxidized the sulfhydryl compound The obtained dithizone compound, an alkyl iodide compound such as moth acetic acid, l-propionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid or 3-iodopropanesulfonic acid, trimethylolpropane tris(3-indenyl) Isobutyrate), butanediol bis(3-mercaptoisobutyrate), hexanedithiol, thiodithiol, 1,4-dimercaptophenylene, butanediol dithiopropionic acid Ester, butanediol dithioglycolate, ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, butanediol dithiopropyl 162338.doc •35- 201242931 acid ester , trimethylolpropane trithiopropionate, trihydrocarbyl propane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithiopropionic acid Aliphatic polyfunctionality such as ester, diethyl thiazolone, diisopropyl thioxanthone, the following compound No. Cl, tris(2-ylethyl)isocyanurate Mercaptan Compounds, manufactured by Showa Denko Karenz MT BD1, PEI, NR1 and so on. Compound No.Cl

作為上述界面活性劑’可使用全氟烷基磷酸酯、全氟烷 基羧酸鹽等氟界面活性劑；高級脂肪酸鹼鹽、烷基磺酸 鹽、烷基硫酸鹽等陰離子系界面活性劑；高級胺氫鹵酸 鹽、四級銨鹽等陽離子系界面活性劑；聚乙二醇烷基醚、 聚乙二醇脂肪酸酯、去水山梨醇脂肪酸酯、脂肪酸單甘油 酯等非離子界面活性劑；兩性界面活性劑，·聚矽氧系界面 活性劑等界面活性劑，該等亦可組合使用。 作為上述矽烷偶合劑，例如可使用信越化學公司製造之 石夕燒偶合劑’其中，可較佳地使用KBE-9007、KBM-502、KBE-4G3等具有異氰酸g旨基、甲基丙稀醯基或環氧 基之矽烷偶合劑。 作為上述三聚氰胺化合物，可列舉(聚)羥甲基三聚氰 胺（聚）細曱基甘腺、（聚）麵甲基苯并胍胺、⑻經曱基腺 I62338.doc • 36 - 201242931 等氮化合物中之活性羥曱基（CH2〇H*)之全部或一部分（至 少2個）經烷基醚化而成之化合物等。 此處，作為構成烷基醚之烧基，可列舉曱基、乙基或丁 基，該等相互可相同亦可不同。又，未經院基謎化之經甲 . &amp;可於-分子内進行自縮合，亦可於兩個分子間進行縮 合’其結果形成低聚物成分。 • 具體而言，可使用六甲氧基甲基三聚氰胺、六丁氧基甲 基一聚氰胺、四曱氧基甲基甘脲、四丁氧基曱基甘脲等。 於該等中’較佳為六曱氧基甲基三聚氰胺、六丁氧基甲 基三聚氰胺等經烷基醚化之三聚氰胺。 又，本發明之感光性組合物中亦可視需要添加對苯甲 謎氫酿、焦兒命盼、第二丁基兒茶紛、啡嘆〇井等熱聚合 抑制劑，塑化劑；接著促進劑；填充劑；消泡劑；均化 劑；表面調整劑；抗氧化劑；紫外線吸收劑；分散助劑； 抗凝聚劑；觸媒；效果促進劑；交聯劑；增黏劑等慣用之 添加物。 於本發明之感光性組合物中，（A)本發明之光聚合起始 劑及（B)具有乙婦性不飽和鍵之聚合性化合物以外之任竟 成分（其中，（C)無機化合物、（D)著色料、及溶劑除外）之 . 使用量可根據其使用目的而適當選擇，並無特別限制，較 佳為相對於（B)具有乙烯性不飽和鍵之聚合性化合物丨〇〇質 量份合計為50質量份以下。 本發明之感光性組合物可照射能量射線而製成硬化物。 該硬化物可形成為適應於用途之適當之形狀。例如於形成 162338.doc 37· 201242931 膜狀之硬化物之情形時’本發明之感光性組合物可利用旋 轉式塗佈機、輥式塗佈機、棒式塗佈機、模塗佈機、簾幕 式塗佈機、各種印刷、浸潰等公知之手段而應用於鈉玻 璃、石英玻璃、半導體基板、金屬、紙'塑膠等支持基體 上。又’亦可暫時施加於膜等支持基體上之後，再轉印至 其他支持基體上，其應用方法並無限制。 作為使本發明之感光性組合物硬化時所使用之能量射線 之光源，可利用由超高壓水銀燈、高壓水銀燈、中壓水銀 燈、低壓水銀燈、水銀蒸汽弧燈、氙弧燈、碳弧燈、金屬 i化物燈、螢光燈、鎢絲燈、準分子燈、殺菌燈、發光二 極體、CRT(Cathode Ray Tube ’陰極射線管）光源等所獲得 之具有自2000埃至7000埃之波長之電磁波能或電子束、X 射線、放射線等高能量射線，較佳為使用發出波長為 300〜450 nm之光之超高壓水銀燈、水銀蒸汽弧燈、碳弧 燈、氙弧燈等。 進而’藉由於曝光光源中使用雷射光，從而不使用遮罩 而根據電腦等之數位資訊直接形成圖像的雷射直接繪圖法 不僅可謀求生產性之提高，亦可謀求解像性或位置精度等 之提高故而較為有用’作為該雷射光，可較佳地使用 340〜430 nm之波長之光，亦可使用準分子雷射 '氮雷射、 氬離子雷射、氦鎘雷射、氦氖雷射、氪離子雷射、各種半 導體雷射及YAG(yttrium aluminum garnet，紀銘石梅石）雷 射等發出自可見光至紅外區域之光者。於使用該等雷射光 之情形時，較佳為添加吸收自可見至紅外光之該區域之增 162338.doc -38 - 201242931 感色素。 本發明之感光性組合物可用於：光硬化性塗料或清漆； 光硬化性接著劑；印刷基板；彩色電視、pC(pers〇nal Computer，個人電腦）監視器、個人數位助理、數位相機 等彩色顯示裝置之液晶顯示元件中之彩色濾光片； CCD(Charge Coupled Device，電荷耦合元件）影像感測器 之彩色濾光片；電漿顯示面板用之電極材料；粉末塗覆； 印刷油墨；印刷版；接著劑；牙科用組合物；凝膠塗覆； 電子工程學用之光阻劑；電鍍阻劑；蝕刻阻劑；乾膜；焊 接阻劑，用以製造各種顯示用途用之彩色濾光片或於電漿 顯不面板、電氣發光顯示裝置、及LCD(Liquid crystal Display，液晶顯示器）之製造步驟中用以形成該等之結構 的抗蝕劑；用以封裝電氣及電子零件之組合物；阻焊劑； 磁記錄材料；微機械零件；波導；光開關；鍍敷用遮罩； 蝕刻遮罩；彩色試驗系統；玻璃纖維電纜塗敷；網版印刷 用模板，用於藉由立體光刻製造立體物體之材料；全像記 錄用材料；圖像記錄材料；微細電子電路；脫色材料；用 於圖像記錄材料之脫色材料；使用微膠囊之圖像記錄材料 用之脫色材料；印刷配線板用光阻材料；uv(Ultra Violet，备、外線）及可見光雷射直接圖像系統用之光阻材 料，形成印刷電路基板之逐次積層中之介電質層所使用之 光阻材料或保護膜等各種用途，其用途並無特別限制。 本發明之感光性組合物亦可以形成液晶顯示面板用間隔 件為目的及形成垂直定向型液晶顯示元件用突起為目的而 162338.doc •39- 201242931 使用。尤其可用作用以同時形成垂直配向型液晶顯示元件 用之突起與間隔件的感光性組合物。 上述液晶顯示面板用間隔件可藉由如下步驟較佳地形 成：（1)於基板上形成本發明之感光性組合物之塗膜之步 驟’ (2)經由具有特定圖案形狀之遮罩對該塗膜照射能量射 線（光）之步驟，（3)曝光後之供烤步驟，⑷使曝光後之覆膜 顯影之步驟、（5)加熱顯影後之該覆膜之步驟。 添加有（D)著色料之本發明之感光性組合物可較佳地用 作構成彩色據光片中之RGB(RedGreenBlue，紅綠藍）等各 像素之光阻劑、或形成各像素之間隔壁之黑矩陣用光阻 劑。進而於添加拒油墨劑之黑矩陣用光阻劑之情形時，可 較佳地用於分佈角為5 〇。以上之喷墨方式彩色據光片用間 隔壁。作為該拒油墨劑’可較佳地使用氟系界面活性劑及 含有氟系界面活性劑之組合物。 於用於上述喷墨方式彩色濾光片用間隔壁之情形時，利 用使由本發明之感光性組合物所形成之間隔壁劃分被轉印 體，並藉由噴墨法對經劃分之被轉印體上之凹部賦予液滴 而形成圖像區域的方法製造光學元件。此時，較佳為上述 液滴含有著色劑而將上述圖像區域著色，於該情形時，藉 由上述製造方法所製作之光學元件於基板上至少具有包含 複數之著色區域之像素群與隔離該像素群之各著色區域之 間隔壁。 本發明之感光性組合物亦可用作保護膜或絕緣膜用組合 物。於該情形時’可含有紫外線吸收劑、院基化改性三聚 162338.doc 201242931 氰胺及/或丙烯酸改性三聚氰胺、於分子_含有醇性羥基 之1或2官能之（甲基）丙烯酸酯單體及/或石夕溶膝。 上述保護膜、絕緣膜用之感光性組合物係以如下成分為 主成分之樹脂組合物： (A) 本發明之光聚合起始劑、 (B) 具有乙烯性不飽和鍵之聚合性化合物（較佳為包含重 量平均分子量為2,0〇〇〜40,0〇〇、酸值為5〇〜2〇〇11^〖(；^/§之 含羧基之聚合性化合物）、及 (X)環氧化合物，並且 相對於（B)成分100重量份，較佳為（A)成分換算成本發 明之肟酯化合物量為0.01〜2.0重量份、（χ)成分為1〇〜4〇重 量份。 上述絕緣膜可用於在可剝離之支持基材上設置有絕緣樹 脂層之積層體中之該絕緣樹脂層，該積層體可藉由鹼性水 溶液而顯影，絕緣樹脂層之膜厚較佳為10〜100 μιηβ 本發明之感光性組合物可藉由含有（c)無機化合物而用 作感光性糊劑組合物。該感光性糊劑組合物可用於形成電 漿顯不器面板之間隔壁圖案、介電質圖案、電極圖案及黑 矩陣圖案等煅燒物圖案。 實施例 以下，列舉實施例及比較例對本發明進而詳細地進行說 明’但本發明並不限定於該等實施例等。 [實施例1]化合物No. 1之製造 〈步驟1&gt;甲基丙烯酸酯化 162338.doc 201242931 將包含1-(4-(4-(2-羥基乙氧基）苯硫基）苯基）丙烷-丨_酮 (以下亦稱作酮體a)19_8 g(65 mmol)、曱基丙烯酸56.2 g(653 mmol)、對曱本續酸一水合物 5.0 g(26 mmol)、BHT (butylated hydroxytoluene，二丁 基羥基甲苯）i 2 g(5 6 mmol)及二氯乙烷121 g之溶液攪拌回流ι〇 5小時。冷卻 後，添加乙酸乙酯與水進行油水分離。以水、碳酸氫鈉水 溶液、水之順序清洗有機層。利用無水硫酸鎂乾燥有機層 後，進行脫溶劑，獲得26.3 g下述甲基丙烯酸酯體a。 [化 19] 甲基两烯酸酯Aa ★〜。χχσ1&quot; &lt;步驟2&gt;肟化 將包含26.0 g(70 mmol)步驟1所獲得之甲基丙烯酸酯體 a、濃鹽酸7.3 g(70 mmol)及二甲基曱醯胺70 g的溶液冷卻 至5 C ’添加亞補酸異丁醋10.8 g(l〇5 mmol)，並於室溫下 攪拌3小時。添加乙酸乙酯與水進行油水分離，以水、碳 酸氫鈉水溶液、水之順序清洗有機層。利用無水硫酸鎂乾 燥有機層後’進行脫溶劑，獲得23.8 g下述肟體a。 [化 20] «體a &lt;步驟3&gt;肟酯化 於7〇°C下將包含23.8 g(60 mmol)步驟2所獲得之肟體a、 162338.doc •42- 201242931 乙酸酐9.1 g(90 mmol)及乙酸乙酯79 g的溶液攪拌4小時。 冷卻後，添加水進行油水分離。以水、碳酸氫納水溶液、 水之順序清洗有機層。利用無水硫酸鎂乾燥有機層後，進 行脫溶劑。將所獲得之粗產物27.2 g藉由管柱層析圖 (Column Chromatogram)進行純化，獲得2.3 g化合物 No. 1。藉由分析確認所獲得之化合物為目標物。將分析結 果示於[表1]〜[表3]。 [實施例2〜4]化合物No.2、化合物No.3、化合物Νο·4之製造 除使用對應之酮體代替酮體a(且關於化合物Νο·3，使用 丙烯酸代替曱基丙烯酸）以外，依照實施例1所記載之方法 分別製造化合物No.2、化合物No.3及化合物Νο.4。將分析 結果不於[表1]~[表3]。 [表1] 肟酯化合物 XmaxM(nm) 熔點 實施例1 化合物No. 1 336 76 實施例2 化合物No.2 336 非晶體 實施例3 化合物No.3 334 非晶體 實施例4 化合物Νο.4 - 室溫下為液體 *1 :溶劑1 卜使用CHC13作溶劑。 [表2] 肟酯化合物 IR吸收光譜(cnf1) 實施例1 化合物No.l 2965, 1776, 1717, 1658, 1584, 1495, 1460, 1400, 1365, 1321， 1252,1202, 1180,1081，1040, 993, 939, 884, 828, 746, 645 實施例3 化合物No.3 2957, 1778, 1726, 1715, 1666, 1585, 1439, 1402, 1365, 1271, 1178, 1122, 1107, 1082, 1045, 1012, 991, 943, 903, 885, 845, 810, 758, 692 實施例4 化合物Νο.4 3360, 2954, 1775, 1712, 1660, 1584, 1529, 1493, 1454, 1402, 1365, 1297, 1232, 1203, 1168, 1081, 992, 939, 902, 880, 829, 775, 747, 686, 627, 591, 536,485,436 162338.doc •43- 201242931 [表3] 肟酯化合物 ,H-NMR(ppm):CDCl3 實施例1 化合物No. 1 1.97 (s, 3H), 2.25 (s, 3H), 2.26 (s, 3H), 4.27 (t, 2H), 4.53 (t, 2H), 5.60 - 5.62 (m, 1H), 6.16 (s, 1H), 6.97 (d, 2H), 7.08 (d, 2H), 7.47 (d5 2H), 7.94 (d. 2H) 實施例2 化合物No.2 1.95 (s, 3H), 2.27 (s, 3H)S 2.29 (s, 3H), 4.48 (t, 2H), 4.57 (t, 2H), 5.59 (m, 1H), 6.14 (s, 1H), 7.35 (d, 2H)S 7.45 (d, 2H), 8.00 (d, 2H), 8.04 (d, 2H) 實施例3 化合物No.3 2.27 (s, 3H), 2.29(s,3H), 4.50 (t, 2H), 4.56 (t, 2H), 5.87 (d, 1H), 6.12 - 6.19 (m9 1H), 6.45 (d, 1H), 7.35 (d, 2H), 7.45 (d, 2H), 8.00 (d, 2H), 8.04 (d, 2H) 實施例4 化合物No.4 1.96 (s, 3H), 2.27 (s, 6H), 3.54 (m, 2H), 4.20 - 4.27 (m, 4H), 4.47 (t, 2H), 5.14 (br, 1H), 5.60 (s, 1H), 6.13 (s, 1H), 6.98 (d, 2H), 7.09 (d, 2H) ,7.49 (d, 2H), 7.95 (d, 2H) [實施例5]鹼顯影性感光性樹脂組合物No. 1之製造 &lt;步驟1&gt;鹼顯影性樹脂[賦予鹼顯影性之（B)成分]之製備 於反應容器中添加雙酚薙型環氧樹脂（環氧當量為23 i， 上述通式（3)所表示之環氧化合物）184 g、丙稀酸58 g、 2,6-二第三丁基對甲酚〇.26@、四正丁基溴化錄〇.118及丙 二醇-1-單甲醚·2_乙酸酯23 g，於12〇。(：下攪拌16小時。將 反應液冷卻至室溫為止’添加丙二醇·1_單甲喊·2_乙酸醋 35 g、聯苯四曱酸二酐59 g及四正丁基溴化銨〇.24 g，於 120°C下搜拌4小時。進而添加四氫苯二甲酸酐2〇 g ,於 12 0 C下授拌4小時’於1 〇 〇。〇下揽拌3小時，於8 〇 °c下授拌 4小時’於60°C下攪拌6小時，於40°C下攪拌11小時後，添 加丙二醇-1-單曱謎-2-乙酸醋90 g，以丙二醇_ι_單甲謎_2_ 乙酸醋溶液之形式獲得目標物驗顯影性樹脂N〇丨（mw= 5000、Mn=2100、酸值（固形物成分）為 92 7 mgK〇H/g)。 &lt;步驟2&gt;鹼顯影性感光性樹脂組合物N〇. 1之製備 混合作為賦予驗顯影性之（B)成分之14.7 g&lt;步驟ι&gt;所獲 162338.doc -44 - 201242931 得之鹼顯影性樹脂、作為（B)成分之二季戊四醇五丙 烯酸酯及二季戊四醇六丙烯酸酯（AR〇NIX M_4〇2，東亞合 成股份有限公司製造）3.〇 g'界面活性劑FZ 2122(Nipp〇n Unicar股份有限公司製造）之環己酮1%溶液丨8 g、丙二醇· 1-單甲醚-2-乙酸酯10.0 g、以及環己酮2〇2 g，添加作為 (A)成分之0.3 g實施例i所得之化合*N〇丨並充分攪拌，獲 得作為本發明之感光性組合物的鹼顯影性感光性樹脂組合 物 Ν ο · 1。 [實施例6]驗顯影性感光性樹脂組合物ν〇·2之製造 除將貫施例1所獲得之化合物Ν〇丨替換為實施例2所獲得 之化合物No.2以外，以與實施例5之&lt;步驟2&gt;相同之方法獲 得作為本發明之感光性組合物的鹼顯影性感光性樹脂組合 物 Νο·2。 [實施例7]鹼顯影性感光性樹脂組合物Νο.3之製造 除將實施例1所獲得之化合物N〇. 1替換為實施例3所獲得 之化合物No.3以外’以與實施例5之〈步驟2&gt;相同之方法獲 得作為本發明之感光性組合物的鹼顯影性感光性樹脂組合 物 Ν 〇 · 3。 [比較例1 ]鹼顯影性感光性樹脂組合物No.4之製造 除將實施例1所獲得之化合物No.l替換為2·苄基-2-二曱 基胺基-1-(4-咪啉基苯基）-i_ 丁酮以外，以與實施例5之&lt;步 驟2&gt;相同之方法獲得作為比較品之鹼顯影性感光性樹脂組 合物No.4。 [比較例2]鹼顯影性感光性樹脂組合物n〇.5之製造 162338.doc -45- 201242931 除將實施例1所得之化合物No.l替換為乙基_6_(2_甲 基苯曱醯基）-9H-咔唑-3-基]乙酮}_(〇_乙醯肟）以外，以與 實施例5之&lt;步驟2&gt;相同之方法獲得作為比較品之鹼顯影性 感光性樹脂組合物No.5。 &lt;穿透性&gt; 以如下所述之方式進行所獲得之鹼顯影性感光性樹脂組 合物No.l〜No.5之穿透性試驗。 即’於玻璃基板上旋塗（500 rpm下2秒，800 rpm下6秒） 鹼顯影性感光性樹脂組合物’使用熱板於9〇它下進行預供 烤90秒。繼而，使用高壓水銀燈作為光源以15〇 mJ/cm2進 行曝光後’使用烘箱於230°C下進行後烘烤30分鐘，獲得 硬化膜。對所獲得之硬化膜使用吸光光度計測定於38〇 nm 下之穿透率。將結果示於[表4]。 [表4] 驗顯影性感光性樹脂組合物 穿透率(％) No. 1(實施例5) 88 Νο·2(實施例6) 86 Νο·3(實施例7) 86 Νο.4(比較例1) 82 Νο.5(比較例2) 80 — 如表4所記載般，與使用比較化合物之比較例1及2之感 光性組合物相比，將本發明之肟酯化合物用作光聚合起始 劑之本發明之感光性組合物之穿透率較高。 [實施例8]導電性組合物No. 1之製造 將作為賦予鹼顯影性之（B)成分之14.1 g實施例5之&lt;步驟 1&gt;所獲得之鹼顯影性樹脂No.l、作為（B)成分之二季戊四 162338.doc • 46 · 201242931 醇五丙烤S文S曰及一季戊四醇六丙稀酸醋（ar〇nix M-402， 東亞合成股份有限公司製造）7· 1 g、界面活性劑Βγκ_323 (BYK Chemie·Japan股份有限公司製造）〇 〇5 g、texan〇l (2,2,4-三甲基-1,3-戊二醇單異丁酸酯）u 3 g、作為（A)成分 之0.7 g實施例1所得之化合物No.l、以及作為（c)成分之玻 璃料3.1 g及銀粉63.7 g混合並攪拌後，利用三輥混練機進 行混練’獲得作為本發明之感光性組合物的導電性組合物 Νο·1。 [實施例9]著色鹼顯影性感光性樹脂組合物Ν〇丨之製造 &lt;步驟1&gt;藍色分散液之製造 將57.6 g簟色顏料顏料藍丨5 : 6、分散劑Ajisper PB821(Ajinomoto Fine-Techno 股份有限公司製造）20.0 g、 分散助劑Solsperse 500〇(Avecia股份有限公司製造）2.4 g、 及丙二醇-1-單甲醚_2-乙酸酯320.0 g放入500 ml聚乙烯製 容器中’使用粒徑為0.5 mm之氧化錄珠350 g，利用塗料 調節器振盪10小時後，過濾分離氧化锆珠，獲得藍色分散 液。 〈步驟2&gt;著色驗顯影性感光性樹脂組合物No. 1之製造 混合作為（D)成分之 &lt;步驟1&gt;所獲得之藍色分散液10.63 g、作為賦予驗顯影性之（B)成分之2.98 g實施例5之〈步驟 1&gt;所獲得之鹼顯影性樹脂No.l、作為（B)成分之二季戊四 醇五丙烯酸酯及二季戊四醇六丙烯酸酯（ARONIX M-402， 東亞合成股份有限公司製造）〇.3 1 g、作為（B)成分之丙烯 酸胺基曱酸酯UN3320HS(根上工業股份有限公司製造）〇.31 162338.doc -47- 201242931 g界面活性劑BYK-323(BYK Chemie.Japan股份有限公司 製造）之環己酮1%溶液0.30 g、丙二醇單曱醚·2-乙酸酯 4.70 g、以及環己酮10.36 g，添加作為（Α)成分之〇41 g實 施例1所得之化合物No. 1並攪拌，獲得作為本發明之感光 性組合物的著色鹼顯影性感光性樹脂組合*N〇 1。 [比較例3]著色鹼顯影性感光性樹脂組合物ν〇·2之製造 除將實施例1所得之化合物No.l替換為ι_[9_乙基-6-(2-曱 基苯甲醯基）-9H-咔唑-3-基]乙酮1_(〇_乙醯肟）以外，以與 實施例9之 &lt;步驟2&gt;相同之方法獲得作為比較品之著色鹼顯 影性感光性樹脂組合物N 〇. 2。 [比較例4]著色鹼顯影性感光性樹脂組合物N〇 3之製造 除將實施例1所獲得之化合物No丨替換為2甲基_ 1-(4-甲 硫基苯基）-2-咪啉基丙烷·丨_酮以外，以與實施例9之&lt;步驟 2相同之方法獲得作為比較品之著色驗顯影性感光性樹脂 組合物No.3。 [比較例5]著色鹼顯影性感光性樹脂組合物N〇 4之製造 除將實施例1所獲得之化合物N〇」替㈣i _[4_(苯硫基） 苯基]·1，2-辛二酮2-(〇_苯甲醯肟）以外’以與實施例9之〈步 驟2相同之方法獲知作為比較品之著色驗顯影性感光性樹 脂組合物Ν 〇. 4。 [比較例6]著色鹼顯影性感光性樹脂組合物ν〇 5之製造 除將實施例1所得之化合物No.l替換為2-苄基·2·二甲基 胺基-1-(4-味琳基苯基·丁嗣以外，以與實施例9之〈步驟 2相同之方法獲得作為比較品之著色鹼顯影性感光性樹脂 ]62338.doc -48- 201242931 組合物Ν ο. 5。 &lt;穿透性&gt; 以如下所述之方式進行所獲得之著色鹼顯影性感光性樹 脂組合物No.1〜No.3之穿透性試驗。 於玻璃基板上旋塗（500 rpm、7秒）著色鹼顯影性感光性 樹脂組合物，並使用熱板於90°C下進行預烘烤90秒。繼 而，使用高壓水銀燈作為光源，以150 mJ/cm2進行曝光 後，使用烘箱於230°C下進行後烘烤30分鐘，獲得硬化 膜。作為耐熱性試驗，將所獲得之硬化膜進而於260°C下 加熱1小時。對耐熱性試驗後之硬化膜使用吸光光度計測 定於420 nm下之穿透率。將結果示於[表5]。 [表5] 著色鹼顯影性感光性樹脂組合物 穿透率(％) No.l(實施例9) 61 No.2(比較例3) 55 No.3(比較例4) 28 如表5所記載般，與使用比較化合物之比較例3及4之著 色驗性顯影性感光性樹脂組合物相比，將本發明之躬酯化 合物用作光聚合起始劑之本發明之著色鹼性顯影性感光性 樹脂組合物之穿透率較高。 &lt;逸氣性&gt; 作為所獲得之著色鹼顯影性感光性樹脂組合物No. 1、 No.3〜Νο·5之逸氣性試驗，以如下所述之方式測定硬化物 之重量減少率。 即，於玻璃基板上旋塗（500 rpm、7秒）著色鹼顯影性感 162338.doc -49- 201242931 光性樹脂組合物，並使用熱板於90°C下預烘烤9〇秒。繼 而，使用高壓水銀燈作為光源，以100 mJ/cm2進行曝光， 獲得硬化膜。將該硬化膜削取約3 mg，將削取之硬化膜用 作試樣，並藉由 TG-DTA(Thermogravimetric-Differential Thermal Analyzer，熱重-示差熱分析儀）（Seiko Instruments 股份有限公司製造）測定於230°C下保持30分鐘時之重量減 少率。將將結果示於[表6]。 [表6] 著色鹼顯影性感光性樹脂組合物 重量減少率(％) No. 1(實施例9) -4.3 No.3(比較例4) -15.6 Νο·4(比較例5) -11.9 No.5(比較例6) -11.9 根據表6可知，與使用比較化合物之比較例4〜6之著色驗 性顯影性感光性樹脂組合物相比，將本發明之肟酯化合物 用作光聚合起始劑之作為本發明之感光性組合物的著色驗 性顯影性感光性樹脂組合物之耐熱性優異，且逸氣較少。 再者，根據該結果可推測：作為光聚合起始劑之本發明之 肟酯化合物與樹脂成分進行反應，藉此，本發明之肟酯化 合物及/或樹脂成分之昇華性變低。As the surfactant, a fluorosurfactant such as a perfluoroalkyl phosphate or a perfluoroalkyl carboxylate; an anionic surfactant such as a higher fatty acid alkali salt, an alkyl sulfonate or an alkyl sulfate; a cationic surfactant such as a higher amine hydrohalide or a quaternary ammonium salt; a nonionic such as a polyethylene glycol alkyl ether, a polyethylene glycol fatty acid ester, a sorbitan fatty acid ester, or a fatty acid monoglyceride; Surfactant; an amphoteric surfactant; a surfactant such as a polyoxyn surfactant; these may also be used in combination. As the decane coupling agent, for example, a sulphur coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, KBE-9007, KBM-502, KBE-4G3, etc. having an isocyanate group, methyl propyl group can be preferably used. A decane- or epoxy-based decane coupling agent. Examples of the melamine compound include (poly)methylol melamine (poly) fine mercapto gland, (poly) face methyl benzoguanamine, and (8) sulfhydryl gland I62338.doc • 36 - 201242931 A compound obtained by alkylating all or a part (at least 2) of an active hydroxymethyl group (CH2〇H*) with an alkyl group. Here, examples of the alkyl group constituting the alkyl ether include a mercapto group, an ethyl group or a butyl group, and these may be the same or different. Further, the meridian which has not been clarified by the faculty can be self-condensed in the molecule, or can be condensed between two molecules, and as a result, an oligomer component is formed. • Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetradecyloxymethyl glycoluril, tetrabutoxy guanyl glycoluril or the like can be used. Among these, melamine which is alkyl etherified, such as hexamethyleneoxymethyl melamine or hexabutoxymethyl melamine, is preferred. Further, in the photosensitive composition of the present invention, a thermal polymerization inhibitor such as a benzil hydrogen brewing, a pyrophoric expectant, a second butyl tea, a sigh, and a plasticizer may be added as needed; Agent; filler; defoamer; leveling agent; surface conditioner; antioxidant; ultraviolet absorber; dispersing aid; anti-agglomerating agent; catalyst; effect promoter; cross-linking agent; tackifier Things. In the photosensitive composition of the present invention, (A) a photopolymerization initiator of the present invention and (B) a component other than a polymerizable compound having an ethylavalent unsaturated bond (wherein (C) an inorganic compound, (D) In addition to the coloring material and the solvent, the amount to be used may be appropriately selected depending on the purpose of use, and is not particularly limited, and is preferably a mass of the polymerizable compound having an ethylenically unsaturated bond with respect to (B). The total amount is 50 parts by mass or less. The photosensitive composition of the present invention can be irradiated with energy rays to form a cured product. The cured product can be formed into a suitable shape for use. For example, in the case of forming a film-like cured product of 162338.doc 37·201242931, the photosensitive composition of the present invention can utilize a spin coater, a roll coater, a bar coater, a die coater, It is applied to a support substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper plastic or the like by a curtain coating machine, various printing, and impregnation. Further, it may be temporarily applied to a support substrate such as a film and then transferred to another support substrate, and the application method is not limited. As a light source for the energy ray used in curing the photosensitive composition of the present invention, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp, a xenon arc lamp, a carbon arc lamp, a metal can be used. Electromagnetic waves having a wavelength of from 2000 Å to 7000 Å obtained by i-lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light-emitting diodes, CRT (Cathode Ray Tube 'cathode ray tube) light sources, etc. High-energy ray, such as electron beam, X-ray, or radiation, is preferably an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, or the like that emits light having a wavelength of 300 to 450 nm. Furthermore, by using laser light in an exposure light source, a laser direct mapping method that directly forms an image based on digital information such as a computer without using a mask can not only improve productivity, but also solve image quality or positional accuracy. It is useful to increase the brightness. As the laser light, light of a wavelength of 340 to 430 nm can be preferably used, and an excimer laser 'nitrogen laser, argon ion laser, cadmium cadmium laser, or germanium can also be used. Laser, cesium ion laser, various semiconductor lasers and YAG (yttrium aluminum garnet) lasers emitted from the visible to the infrared region. In the case of using such laser light, it is preferred to add an increase in 162338.doc -38 - 201242931 sensitizing dye which absorbs the region from visible to infrared light. The photosensitive composition of the present invention can be used for: photocurable paints or varnishes; photocurable adhesives; printed substrates; color televisions, pC (persinnal computer, personal computer) monitors, personal digital assistants, digital cameras, etc. Color filter in liquid crystal display device of display device; color filter of CCD (Charge Coupled Device) image sensor; electrode material for plasma display panel; powder coating; printing ink; Edition; adhesive; dental composition; gel coating; photoresist for electronic engineering; plating resist; etching resist; dry film; solder resist for color filter for various display purposes a resist for forming such a structure in a manufacturing step of a plasma display panel, an electroluminescent display device, and an LCD (Liquid Crystal Display); a composition for packaging electrical and electronic parts Solder resist; magnetic recording material; micromechanical part; waveguide; optical switch; mask for plating; etching mask; color test system; Template for screen printing, material for manufacturing solid objects by stereolithography; material for hologram recording; image recording material; fine electronic circuit; decolorizing material; decolorizing material for image recording material; use of microcapsule Decolorizing material for image recording material; photoresist material for printed wiring board; UV (Ultra Violet, standby, external line) and photoresist material for visible light laser direct image system, forming successive layers of printed circuit board The use of the photoresist material or the protective film used for the dielectric layer is not particularly limited. The photosensitive composition of the present invention can also be used for the purpose of forming a spacer for a liquid crystal display panel and for forming a projection for a vertical alignment type liquid crystal display element. 162338.doc • 39-201242931 is used. In particular, it can be used as a photosensitive composition for simultaneously forming protrusions and spacers for a vertical alignment type liquid crystal display element. The spacer for a liquid crystal display panel can be preferably formed by the following steps: (1) a step of forming a coating film of the photosensitive composition of the present invention on a substrate ' (2) via a mask having a specific pattern shape The step of irradiating the energy ray (light) by the coating film, (3) the baking step after the exposure, (4) the step of developing the film after the exposure, and (5) the step of heating the film after the development. The photosensitive composition of the present invention to which the (D) coloring material is added can be preferably used as a photoresist for RGB (Red Green Blue, red green blue) or the like in a color light film, or between pixels. A photoresist for the black matrix of the next wall. Further, in the case of adding a photoresist for a black matrix of an ink repellent, it can be preferably used for a distribution angle of 5 Å. The above ink jet method is used as a color partitioning spacer. As the ink repellent agent, a fluorine-based surfactant and a composition containing a fluorine-based surfactant can be preferably used. In the case of the above-described partition wall for a color filter for an ink jet method, the partitioned body formed by the photosensitive composition of the present invention is divided into a transfer body, and the divided portion is transferred by an inkjet method. An optical element is produced by a method in which a concave portion on a printed body imparts a droplet to form an image region. In this case, it is preferable that the droplet contains a coloring agent to color the image region. In this case, the optical element produced by the above-described manufacturing method has at least a pixel group including a plurality of colored regions on the substrate and isolation. a partition wall of each colored region of the pixel group. The photosensitive composition of the present invention can also be used as a composition for a protective film or an insulating film. In this case, 'may contain UV absorbers, deuterated modified trimer 162338.doc 201242931 cyanamide and / or acrylic modified melamine, in the molecule - 1 or 2 functional (meth)acrylic acid containing alcoholic hydroxyl groups Ester monomer and / or Shi Xi dissolve knee. The photosensitive composition for the protective film or the insulating film is a resin composition containing the following components as a main component: (A) a photopolymerization initiator of the present invention, and (B) a polymerizable compound having an ethylenically unsaturated bond ( Preferably, it comprises a weight average molecular weight of 2,0 〇〇 to 40,0 〇〇, an acid value of 5 〇2 to 2 〇〇11^, (^^/§ of a carboxyl group-containing polymerizable compound), and (X) The epoxy compound is preferably used in an amount of 0.01 to 2.0 parts by weight based on 100 parts by weight of the component (B), and the amount of the oxime ester compound in the invention is from 0.01 to 2.0 parts by weight, and the (χ) component is from 1 to 4 parts by weight. The insulating film can be used for the insulating resin layer in the laminated body provided with the insulating resin layer on the peelable supporting substrate, and the laminated body can be developed by an alkaline aqueous solution, and the insulating resin layer preferably has a film thickness of 10 ～100 μηβ The photosensitive composition of the present invention can be used as a photosensitive paste composition by containing (c) an inorganic compound. The photosensitive paste composition can be used to form a partition wall pattern of a plasma display panel, Calcined matter pattern such as dielectric pattern, electrode pattern, and black matrix pattern EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. However, the present invention is not limited to the examples and the like. [Example 1] Production of Compound No. 1 <Step 1> Methyl Acrylate 162338.doc 201242931 will contain 1-(4-(4-(2-hydroxyethoxy)phenylthio)phenyl)propane-indole-ketone (hereinafter also referred to as ketone body a) 19_8 g (65 Ment), 56.2 g (653 mmol) of methacrylic acid, 5.0 g (26 mmol) of hydrazine monobasic acid monohydrate, BHT (butylated hydroxytoluene, dibutylhydroxytoluene) i 2 g (5 6 mmol) and dichloro The solution of 121 g of hexane was stirred and refluxed for 5 hours. After cooling, ethyl acetate and water were added to carry out oil-water separation. The organic layer was washed with water, aqueous sodium hydrogen carbonate and water. Desolvation was carried out to obtain 26.3 g of the following methacrylate body a. [Chem. 19] Methyldienoate Aa ★~.χχσ1&quot;&lt;Step2&gt; Deuteration would contain 26.0 g (70 mmol) of step 1 The obtained methacrylate body a, concentrated hydrochloric acid 7.3 g (70 mmol) and dimethyl decylamine 70 g solution were cooled to 5 C 'Add subglycolic acid isobutyl vinegar 10.8 g (10 〇 5 mmol), and stir at room temperature for 3 hours. Add ethyl acetate and water for oil-water separation, wash with water, sodium bicarbonate solution, water. Organic layer. After drying the organic layer with anhydrous magnesium sulfate, the solvent was removed to obtain 23.8 g of the following steroid a. [Chemical 20] «Body a &lt;Step 3&gt; The esterification at 2 ° C will contain 23.8 g. (60 mmol) The solution of steroid a, 162338.doc • 42-201242931 acetic anhydride 9.1 g (90 mmol) and ethyl acetate 79 g obtained in step 2 was stirred for 4 hours. After cooling, water was added for oil-water separation. The organic layer was washed in the order of water, aqueous sodium hydrogencarbonate, and water. After drying the organic layer with anhydrous magnesium sulfate, the solvent was removed. The crude product obtained was purified by column chromatography (Column Chromatogram) to obtain 2.3 g of Compound No. 1. The compound obtained was confirmed to be a target by analysis. The analysis results are shown in [Table 1] to [Table 3]. [Examples 2 to 4] The production of the compound No. 2, the compound No. 3, and the compound Νο·4 was carried out except that the corresponding ketone body was used instead of the ketone body a (and the compound Νο. 3 was used instead of methacrylic acid). Compound No. 2, Compound No. 3, and Compound Νο. 4 were separately produced according to the method described in Example 1. The analysis results are not in [Table 1]~[Table 3]. [Table 1] oxime ester compound XmaxM (nm) Melting point Example 1 Compound No. 1 336 76 Example 2 Compound No. 2 336 Amorphous Example 3 Compound No. 3 334 Amorphous Example 4 Compound Νο. 4 - Room The temperature is liquid*1: Solvent 1 uses CHC13 as a solvent. [Table 2] Oxime ester compound IR absorption spectrum (cnf1) Example 1 Compound No. 1 2965, 1776, 1717, 1658, 1584, 1495, 1460, 1400, 1365, 1321, 1252, 1202, 1180, 1081, 1040, 993, 939, 884, 828, 746, 645 Example 3 Compound No. 3 2957, 1778, 1726, 1715, 1666, 1585, 1439, 1402, 1365, 1271, 1178, 1122, 1107, 1082, 1045, 1012, 991, 943, 903, 885, 845, 810, 758, 692 Example 4 Compound Νο.4 3360, 2954, 1775, 1712, 1660, 1584, 1529, 1493, 1454, 1402, 1365, 1297, 1232, 1203, 1168, 1081, 992, 939, 902, 880, 829, 775, 747, 686, 627, 591, 536, 485, 436 162338.doc • 43- 201242931 [Table 3] oxime ester compound, H-NMR (ppm): CDCl3 Example 1 Compound No. 1 1.97 (s, 3H), 2.25 (s, 3H), 2.26 (s, 3H), 4.27 (t, 2H), 4.53 (t, 2H), 5.60 - 5.62 (m, 1H), 6.16 (s, 1H), 6.97 (d, 2H), 7.08 (d, 2H), 7.47 (d5 2H), 7.94 (d. 2H) Example 2 Compound No. 2 1.95 (s, 3H), 2.27 (s, 3H)S 2.29 (s, 3H), 4.48 (t, 2H), 4.57 (t, 2H), 5.59 (m, 1H), 6.14 (s, 1H), 7.35 (d, 2H)S 7.45 (d, 2H ), 8.00 (d, 2H), 8.04 (d, 2H) Example 3 Compound No. 3 2. 27 (s, 3H), 2.29(s,3H), 4.50 (t, 2H), 4.56 (t, 2H), 5.87 (d, 1H), 6.12 - 6.19 (m9 1H), 6.45 (d, 1H), 7.35 (d, 2H), 7.45 (d, 2H), 8.00 (d, 2H), 8.04 (d, 2H) Example 4 Compound No. 4 1.96 (s, 3H), 2.27 (s, 6H), 3.54 ( m, 2H), 4.20 - 4.27 (m, 4H), 4.47 (t, 2H), 5.14 (br, 1H), 5.60 (s, 1H), 6.13 (s, 1H), 6.98 (d, 2H), 7.09 (d, 2H), 7.49 (d, 2H), 7.95 (d, 2H) [Example 5] Production of alkali-developable photosensitive resin composition No. 1 &lt;Step 1&gt; Alkali-developable resin [Alkaline development Preparation of the component (B)] bisphenolphthalein type epoxy resin (epoxy equivalent of 23 i, epoxy compound represented by the above formula (3)) 184 g, acrylic acid 58 g was added to the reaction vessel. 2,6-di-t-butyl-p-cresol oxime.26@, tetra-n-butyl bromide. 118 and propylene glycol-1-monomethyl ether·2_acetate 23 g, at 12 〇. (: stirring for 16 hours. Cooling the reaction solution to room temperature] Adding propylene glycol·1_monomethyl shingle 2_acetic acid vinegar 35 g, biphenyl tetraphthalic acid dianhydride 59 g and tetra-n-butylammonium bromide .24 g, mix for 4 hours at 120 ° C. Add 4 〇g of tetrahydrophthalic anhydride, and mix for 4 hours at 12 ° C '1 〇〇. Mix for 3 hours, at 8 〇°c under mixing for 4 hours', stirring at 60 ° C for 6 hours, stirring at 40 ° C for 11 hours, adding propylene glycol-1-monosaccharide-2-acetic acid vinegar 90 g to propylene glycol_ι_单In the form of a solution of acetic acid acetic acid _2_acetic acid vinegar, the target resin (Nw=5000, Mn=2100, and acid value (solid content) was 92 7 mgK〇H/g) was obtained. &lt;Step 2&gt; The alkali-developable photosensitive resin composition N〇. 1 is prepared by mixing 14.7 g of the component (B) imparting developability, and the alkali-developing resin obtained as 162338.doc-44 - 201242931 B) Dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (AR〇NIX M_4〇2, manufactured by Toagosei Co., Ltd.) 3. 〇g' surfactant FZ 2122 (Nipp〇n Unicar) Cyclohexanone 1% solution 丨 8 g, propylene glycol 1- 1-methyl ether-2-acetate 10.0 g, and cyclohexanone 2 〇 2 g, added as 0.3 g of (A) component The compound obtained in Example i was sufficiently stirred to obtain an alkali-developable photosensitive resin composition Ν · 1 which is a photosensitive composition of the present invention. [Example 6] Development of a photosensitive photosensitive resin composition The production of ν〇·2 was carried out in the same manner as in Example 2 &lt;Step 2&gt; except that the compound obtained in Example 1 was replaced with Compound No. 2 obtained in Example 2. The alkali-developable photosensitive resin composition of the photosensitive composition of the invention Νο. 2 [Example 7] Production of alkali-developable photosensitive resin composition Νο. 3 In addition to the compound obtained in Example 1, N〇. In the same manner as in the step 2 of Example 5, the alkali-developable photosensitive resin composition Ν 〇 3 which is the photosensitive composition of the present invention was obtained in the same manner as the compound No. 3 obtained in the third embodiment. [Comparative Example 1] Production of alkali-developable photosensitive resin composition No. 4 except for Example The compound No. 1 obtained in 1 was replaced with 2·benzyl-2-didecylamino-1-(4-morpholinylphenyl)-i-butanone, and the &lt;Step 2&gt; of Example 5 In the same manner, an alkali-developable photosensitive resin composition No. 4 as a comparative product was obtained. [Comparative Example 2] Production of an alkali-developable photosensitive resin composition n〇.5 162338.doc -45-201242931 The compound No. 1 obtained in Example 1 was replaced with ethyl-6-(2-methylphenylhydrazino)-9H-indazol-3-yl]ethanone}_(〇_乙醯肟), and In the same manner as in &lt;Step 2&gt; of Example 5, an alkali-developable photosensitive resin composition No. 5 as a comparative product was obtained. &lt;Permeability&gt; The penetration test of the obtained alkali-developable photosensitive resin compositions No. 1 to No. 5 was carried out in the following manner. Namely, the base-developed photosensitive resin composition was spin-coated on a glass substrate (2 seconds at 500 rpm and 6 seconds at 800 rpm), and prebaked for 90 seconds using a hot plate under 9 Torr. Then, after exposure using a high-pressure mercury lamp as a light source at 15 〇 mJ/cm 2 , post-baking was carried out at 230 ° C for 30 minutes using an oven to obtain a cured film. The obtained cured film was measured for its transmittance at 38 〇 nm using an absorptiometer. The results are shown in [Table 4]. [Table 4] Development Photosensitive Resin Composition Permeability (%) No. 1 (Example 5) 88 Νο·2 (Example 6) 86 Νο·3 (Example 7) 86 Νο. 4 (Comparative Example 1) 82 Νο. 5 (Comparative Example 2) 80 - As described in Table 4, the oxime ester compound of the present invention was used as a photopolymerization as compared with the photosensitive compositions of Comparative Examples 1 and 2 using comparative compounds. The photosensitive composition of the present invention having a starter has a high transmittance. [Example 8] The production of the conductive composition No. 1 was as follows (14.1 g of the alkali developability-imparting component (B), and the alkali-developable resin No. 1 obtained in &lt;Step 1&gt; B) Ingredients: Dipentaquat 162338.doc • 46 · 201242931 Alcoholic propylene sorghum S 曰 and one pentaerythritol hexaacetic acid vinegar (ar〇nix M-402, manufactured by Toagosei Co., Ltd.) 7·1 g, Surfactant Βγκ_323 (manufactured by BYK Chemie·Japan Co., Ltd.) 〇〇 5 g, texan〇l (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate) u 3 g, 0.7 g of the compound (I) obtained in Example 1 and the glass frit 3.1 g as the component (c) and 63.7 g of the silver powder were mixed and stirred, and then kneaded by a three-roll kneader to obtain the present invention. The conductive composition of the photosensitive composition is Νο·1. [Example 9] Production of colored alkali-developable photosensitive resin composition &&lt;Step1&gt; Production of blue dispersion 57.6 g of ochre pigment Pigment Blue 丨 5 : 6, Dispersant Ajisper PB821 (Ajinomoto Fine -Techno Co., Ltd.) 20.0 g, dispersing aid Solsperse 500〇 (manufactured by Avecia Co., Ltd.) 2.4 g, and propylene glycol-1-monomethyl ether-2-acetate 320.0 g in 500 ml polyethylene container In the middle of the experiment, 350 g of an oxidized recording bead having a particle diameter of 0.5 mm was used, and after shaking for 10 hours with a paint regulator, the zirconia beads were separated by filtration to obtain a blue dispersion. <Step 2> Coloring Inspection Development Photosensitive Resin Composition No. 1 was produced by mixing (D) as a component (D), 10.63 g of the blue dispersion obtained, and (B) as a component for imparting developability. 2.98 g of the alkali-developable resin No. 1 obtained in Example 5 of Example 5, dipentaerythritol pentaacrylate as the component (B), and dipentaerythritol hexaacrylate (ARONIX M-402, East Asia Synthetic Co., Ltd.) Manufactured 〇.3 1 g, amide amide phthalate UN3320HS (manufactured by Gensei Kogyo Co., Ltd.) as a component (B) 31.31 162338.doc -47- 201242931 g Surfactant BYK-323 (BYK Chemie. 0.30 g of a 1% solution of cyclohexanone manufactured by Japan Co., Ltd., 4.70 g of propylene glycol monodecyl ether·2-acetate, and 10.36 g of cyclohexanone, and added as a (Α) component, 41 g of the obtained Example 1 The compound No. 1 was stirred and the coloring alkali-developing photosensitive resin composition *N〇1 which is a photosensitive composition of the present invention was obtained. [Comparative Example 3] Production of colored alkali-developable photosensitive resin composition ν〇·2 In addition to the compound No. 1 obtained in Example 1, replaced with ι_[9-ethyl-6-(2-mercaptobenzamide) A color-base-developing photosensitive resin which is a comparative product is obtained in the same manner as in the &lt;Step 2&gt; of Example 9 except for -9H-carbazol-3-yl]ethanone 1_(〇_acetamidine). Composition N 〇. 2. [Comparative Example 4] Production of colored alkali-developable photosensitive resin composition N〇3, except that the compound No. obtained in Example 1 was replaced with 2 methyl-1-(4-methylthiophenyl)-2- A color-developing photosensitive photo-resin composition No. 3 as a comparative product was obtained in the same manner as in the step 2 of Example 9 except for the morpholinopropane oxime-ketone. [Comparative Example 5] Production of colored alkali-developable photosensitive resin composition N〇4 except that the compound obtained in Example 1 was N(")i_[4_(phenylthio)phenyl]·1,2-octyl In the same manner as in the step 2 of Example 9, the same procedure as in the step 2 of Example 9 was carried out to obtain a color-developing photosensitive photosensitive resin composition Ν 4. [Comparative Example 6] Production of a colored alkali-developable photosensitive resin composition ν 5 except that the compound No. 1 obtained in Example 1 was replaced with 2-benzyl·2·dimethylamino-1-(4- In the same manner as in Step 2 of Example 9, a color base-developing photosensitive resin was obtained in the same manner as in Step 2 of Example 9 in the same manner as in the case of the above-mentioned Step 2 of the present invention. 62338.doc -48 - 201242931 Composition Ν ο. 5. &lt;Penetration&gt; The penetrability test of the obtained alkali-developing photosensitive resin composition No. 1 to No. 3 was carried out as follows. Spin coating on a glass substrate (500 rpm, 7 seconds) The colored alkali-developed photosensitive resin composition was prebaked at 90 ° C for 90 seconds using a hot plate. Then, using a high pressure mercury lamp as a light source, after exposure at 150 mJ/cm 2 , an oven was used at 230 ° C. After baking for 30 minutes, a cured film was obtained. As a heat resistance test, the obtained cured film was further heated at 260 ° C for 1 hour. The cured film after the heat resistance test was measured at 420 nm using an absorptiometer. The penetration rate is shown in [Table 5]. [Table 5] Colored alkali-developable photosensitive resin combination Transmittance (%) No. 1 (Example 9) 61 No. 2 (Comparative Example 3) 55 No. 3 (Comparative Example 4) 28 As shown in Table 5, Comparative Examples 3 and 4 using comparative compounds The colored alkaline-developable photosensitive resin composition of the present invention using the oxime ester compound of the present invention as a photopolymerization initiator has a higher transmittance than the color-developable photosensitive resin composition. Outgassing property As an outgassing test of the obtained coloring base-developing photosensitive resin composition No. 1, No. 3 to Νο. 5, the weight reduction rate of the cured product was measured as follows. That is, a photosensitive resin developed 162338.doc -49 - 201242931 optical resin composition was spin-coated (500 rpm, 7 seconds) on a glass substrate, and prebaked at 90 ° C for 9 seconds using a hot plate. Using a high-pressure mercury lamp as a light source, exposure was performed at 100 mJ/cm2 to obtain a cured film. The cured film was cut to about 3 mg, and the cured film was used as a sample, and TG-DTA (Thermogravimetric-Differential Thermal) was used. Analyzer, Thermogravimetric-Differential Thermal Analyzer (manufactured by Seiko Instruments Co., Ltd.) The weight reduction rate at 30 ° C for 30 minutes. The results are shown in [Table 6]. [Table 6] Color-base-developable photosensitive resin composition weight reduction rate (%) No. 1 (Example 9) -4.3 No. 3 (Comparative Example 4) -15.6 Νο·4 (Comparative Example 5) -11.9 No. 5 (Comparative Example 6) -11.9 According to Table 6, the coloring of Comparative Examples 4 to 6 using comparative compounds was observed. The color-developing photosensitive photosensitive resin composition which is the photosensitive composition of the present invention which uses the oxime ester compound of the present invention as a photopolymerization initiator is excellent in heat resistance as compared with the photographic ester-developing photosensitive resin composition. And less gas. In addition, it is estimated that the oxime ester compound of the present invention as a photopolymerization initiator reacts with the resin component, whereby the sublimation property of the oxime ester compound and/or the resin component of the present invention becomes low.

[實施例10]著色鹼顯影性感光性樹脂組合物No.6之製造 混合作為（D)成分之實施例9之〈步驟1&gt;所得之藍色分散 液10.63 g、作為賦予鹼顯影性之（B)成分之2.93 g實施例5 之〈步驟1&gt;所獲得之鹼顯影性樹脂No.1、作為（B)成分之二 季戊四醇五丙烯酸酯及二季戊四醇六丙烯酸酯（ARONIX 162338.doc -50- 201242931 M-402 ’東亞合成股份有限公司製造）〇.3〇 g、作為（B)成分 之丙烯酸胺基甲酸酯UN3320HS(根上工業股份有限公司製 造）0.30 g、增感劑DETX-S(日本化藥股份有限公司製造） 0.05 g、界面活性劑BYK-323(BYK Chemie.Japan股份有限 公司製造）之環己酮10/〇溶液〇_30 g、丙二醇-1-單曱ϋ·2-乙 酸酯4.72 g、以及環己酮10.36 g，添加作為（Α)成分之0.41 g實施例1所獲得之化合物No_ 1並充分攪拌，獲得作為本發 明之感光性組合物的著色驗顯影性感光性樹脂組合物 Νο·6 〇 [比較例7]著色鹼顯影性感光性樹脂組合物Ν〇 7之製造 除將貫施例1所得之化合物No.l替換為ι_[9·乙基-6-(2-曱 基苯甲醯基）-9H-咔唑-3-基]乙酮1-(0_乙醯肟）以外，以與 實施例1 0相同之方法獲得作為比較品之著色鹼顯影性感光 性樹脂組合物No.7。 [比較例8]著色鹼顯影性感光性樹脂組合物N〇 8之製造 除將實施例1所獲得之化合物N〇 1替換為2_甲基_ 1 _(4_甲 硫基笨基）-2-咪淋基丙烷_丨_酮以外，以與實施例1〇相同之 方法獲得作為比較品之著色鹼顯影性感光性樹脂組合物 Νο·8。 [比較例9]著色驗顯影性感光性樹脂組合物Ν。.9之製造 除將實施例1所獲得之化合物Ν〇丨替換為(苯硫基） 苯土] 1 ’2辛—酮2_(〇_苯曱醯肟）以外，以與實施例丄〇相同 方法獲得作為比較品之著色驗顯影性感光性樹脂組合物 Νο·9。 162338.doc -51 - 201242931 [比較例10]著色驗顯影性感光性樹脂組合物No· 1 〇之製造 除將實施例1所獲得之化合物No.l替換為2-节基_2_二甲 基胺基-1-(4-味嚇·基苯基）-1 - 丁酮以外，以與實施例1 〇相同 之方法獲得作為比較品之著色驗顯影性感光性樹脂組合物 No.10。 &lt;光微影性&gt; 作為所獲得之著色鹼顯影性感光性樹脂組合物N〇 6〜J 〇 之光微影性之3平價’分別藉由以下之方法對按照以下之順 序之感光度、密接性及殘渣進行評價。將結果示於[表7]。 於玻璃基板上旋塗（500 rpm、7秒）著色鹼顯影性感光性 樹脂組合物，並使用熱板於9〇r下進行預烘烤90秒。繼 而，使用高壓水銀燈作為光源，經由遮罩以特定量（5〇、 100或150 mJ/cm2)進行曝光。使用2 5質量％碳酸鈉水溶液 作為顯影液，並利用旋轉顯影機顯影45秒後，充分水洗， 接著使用烘箱於230°C下進行後烘烤3〇分鐘，使圖案固 定。 (感光度） 以下述四個等級評價著色驗顯影性感光性樹脂組合物之 感光度。 即，將所形成之圖案之線寬超過遮罩開口線寬時之曝光 量為50 mjW之情形設為a，將為⑽之情形設為 b ’將為150 mJW之情形設為c，將即便為15〇 亦 未形成圖案之情形設為de (密接性） 162338.doc •52· 201242931 以下述四個等級評價著色鹼顯影性感光性樹脂組合物之 密接性。 即，將以100 rnJ/cm2進行曝光、顯影後所殘留之圖案之 最細之遮罩線寬為3 μηι以下之情形設為A，將超過3 μπι且 為10 μιη以下之情形設為Β，將超過1〇 μηι且為15 μιη以下 之情形§史為C，將超過15 pm之情形設為d。 (殘渣） 將顯影後，於非曝光部之玻璃面上完全未觀察到殘渣之 情形設為〇，將於一面上觀察到殘渣之情形設為 [表7] 著色鹼顯影性感光性樹脂組合物 感光度 密接性 殘渣 Νο.6(實施例10) a A 〇 Νο.7(比較例7) a A X Νο.8(比較例8) d D o Νο.9(比較例9) b B o Νο·10(比較例1〇) d D 〇 根據表7可知，本發明之肟酯化合物與比較例7所使用之 化合物相比未確認到殘渣，故而顯影性優異。又，若使用 本發明之聘酯化合物，則與比較例8〜1 〇所使用之化合物相 比感光度、密接性優異。 [貫施例11 ]著色驗顯影性感光性樹脂組合物No · 11之製造 混合作為（D)成分之將實施例9之 &lt; 步驟丨 &gt; 中之顏料藍 15 : 6變更為碳黑而製備之碳黑分散液7〇6 g、作為賦予驗 顯影性之（B)成分之3 ·〇7 g實施例5之 &lt;步驟丨 &gt;所獲得之鹼顯 影性樹脂Νο·1、作為（B)成分之二季戊四醇五丙烯酸酯及 162338.doc -53- 201242931 二季戊四醇六丙烯酸酯（ARONIX Μ·4〇2，東亞合成股份有 限公司製造）0.53 g、界面活性劑BYK-323(BYK Chemie.[Example 10] Production of the coloring alkali-developing photosensitive resin composition No. 6 The "blue dispersion" obtained in the <Step 1> of Example 9 as the component (D) was mixed with 10.63 g as an alkali-developing property ( B) 2.93 g of the component of Example 5 <Step 1> The alkali-developable resin No. 1, the dipentaerythritol pentaacrylate as the component (B), and dipentaerythritol hexaacrylate (ARONIX 162338.doc -50- 201242931 M-402 'Made in East Asia Synthetic Co., Ltd.' 〇.3〇g, acrylamide urethane UN3320HS (manufactured by Gensei Kogyo Co., Ltd.) 0.30 g, sensitizer DETX-S (Japan) Chemical Co., Ltd.) 0.05 g, surfactant BYK-323 (BYK Chemie. Japan Co., Ltd.) cyclohexanone 10 / hydrazine solution 〇 _30 g, propylene glycol - -1- 曱ϋ · 2- 4.72 g of an acid ester and 10.36 g of cyclohexanone, and 0.41 g of the compound No. 1 obtained in Example 1 as a (Α) component was added and stirred sufficiently to obtain a color-developing photosensitive light property as a photosensitive composition of the present invention. Resin composition Νο·6 〇 [Comparative Example 7] colored alkali Production of the photosensitive photosensitive resin composition Ν〇7 except that the compound No. 1 obtained in Example 1 was replaced with ι_[9·ethyl-6-(2-mercaptobenzylidene)-9H-carbazole A color base-developing photosensitive resin composition No. 7 as a comparative product was obtained in the same manner as in Example 10 except that -3-yl]ethanone 1-(0-acetamidine). [Comparative Example 8] Production of the colored alkali-developable photosensitive resin composition N〇8, except that the compound N〇1 obtained in Example 1 was replaced by 2-methyl-1_(4-methylthiophenyl)- A color-base-developing photosensitive resin composition Νο·8 as a comparative product was obtained in the same manner as in Example 1 except that 2-dimethylidenepropane-oxime-ketone was used. [Comparative Example 9] Coloring test development of photosensitive photosensitive resin composition Ν. The production of .9 was the same as in Example 以外 except that the compound obtained in Example 1 was replaced by (phenylthio)benzophenone] 1 '2 octyl ketone 2 _(〇_benzoquinone). The method was carried out to obtain a color-developing photosensitive photosensitive resin composition 比较ο·9 as a comparative product. 162338.doc -51 - 201242931 [Comparative Example 10] Coloring inspection development of photosensitive photosensitive resin composition No. 1 制造 Manufacture of 〇 除 将 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物A color-developing photosensitive photo-resin composition No. 10 as a comparative product was obtained in the same manner as in Example 1 except that the amino-amino-1-(4-pyroxyphenyl)-1-butanone was used. &lt;Photopictability&gt; As the obtained photo-alkali-developable photosensitive resin composition N〇6~J 〇3 valence of light opacity' respectively, the sensitivity in the following order was respectively obtained by the following method , adhesion and residue were evaluated. The results are shown in [Table 7]. The photosensitive alkali-developable photosensitive resin composition was spin-coated (500 rpm, 7 seconds) on a glass substrate, and prebaked at 90 Torr for 90 seconds using a hot plate. Then, using a high pressure mercury lamp as a light source, exposure is performed by a mask in a specific amount (5 〇, 100 or 150 mJ/cm 2 ). Using a 25 mass% aqueous solution of sodium carbonate as a developing solution, and developing by a rotary developing machine for 45 seconds, the mixture was sufficiently washed with water, and then post-baked at 230 ° C for 3 minutes in an oven to fix the pattern. (Sensitivity) The sensitivity of the coloring and developing photosensitive resin composition was evaluated in the following four grades. In other words, the case where the line width of the formed pattern exceeds the opening width of the mask is 50 mjW is set to a, the case where (10) is set to b', and the case where 150 mJW is set to c, even if In the case where the pattern was not formed, it was set to de (adhesiveness). 162338.doc • 52·201242931 The adhesion of the colored alkali-developable photosensitive resin composition was evaluated in the following four grades. In other words, the case where the minimum mask width of the pattern remaining after exposure and development at 100 rnJ/cm 2 is 3 μηι or less is A, and when it is more than 3 μπι and 10 μιη or less, it is set to Β, The case where the value exceeds 1 〇μηι and is 15 μιη or less is §, and the case where it exceeds 15 pm is set to d. (Residue) After the development, the residue was not observed at all on the glass surface of the non-exposed portion, and the residue was observed on one side. [Table 7] Colored alkali-developable photosensitive resin composition Sensitivity adhesion residue Νο.6 (Example 10) a A 〇Νο. 7 (Comparative Example 7) a AX Νο. 8 (Comparative Example 8) d D o Νο. 9 (Comparative Example 9) b B o Νο· (Comparative Example 1) d D 〇 According to Table 7, the oxime ester compound of the present invention has no residue as compared with the compound used in Comparative Example 7, and therefore has excellent developability. Further, when the ester compound of the present invention is used, it is superior in sensitivity and adhesion to the compound used in Comparative Example 8 to #1. [Example 11] Coloring test development photosensitive photosensitive resin composition No. 11 was produced as the component (D), and the pigment blue 15: 6 in Example 9 was changed to carbon black. 7 〇 6 g of the prepared carbon black dispersion, 3 〇 7 g of the component (B) which imparts developability, and the alkali-developable resin Νο·1 obtained in the &lt;Step 丨&gt; B) Dipentaerythritol pentaacrylate and 162338.doc -53- 201242931 Dipentaerythritol hexaacrylate (ARONIX Μ·4〇2, manufactured by Toagosei Co., Ltd.) 0.53 g, surfactant BYK-323 (BYK Chemie.

Japan股份有限公司製造）之環己酮1%溶液〇 3〇 g、丙二醇_ 卜單甲醚-2-乙酸酯8.16 g、以及環己酮10.69g，添加作為 (A)成分之〇.19 g實施例1所獲得之化合物No· 1並充分攪 拌，獲得作為本發明之感光性組合物的著色鹼顯影性感光 性樹脂組合物No.l 1。 [實施例12]著色鹼顯影性感光性樹脂組合物N〇. 12之製造 除將實施例1所獲得之化合物N 0.丨替換為實施例2所獲得 之化合物Νο·2以外，以與實施例丨丨相同之方法獲得作為本 發明之感光性組合物的著色鹼顯影性感光性樹脂組合物 No.12。 [貫施例13 ]著色驗顯影性感光性樹脂組合物N〇 13之製造 除將實施例1所獲得之化合物No.丨替換為實施例3所獲得 之化合物Νο·3以外，以與實施例〗丨相同之方法獲得作為本 發明之感光性組合物的著色鹼顯影性感光性樹脂組合物 No.13。 [比較例11]著色鹼顯影性感光性樹脂組合物N〇14之製造 除將實施例1所獲得之化合物No.i替換為1[9乙基_6_(2_ 甲基苯甲醯基）-9H-咔唑-3-基]乙酮乙醯肟）以外，以 與實施例11相同之方法獲得作為比較品之著色鹼顯影性感 光性樹脂組合物No. 14。 [比較例12]著色鹼顯影性感光性樹脂組合物N〇 l5之製造 除將實施例1所獲得之化合物No.l替換為^[4^苯硫基） 162338.doc •54- 201242931 笨基]-1，2-辛二酮2-(〇_苯甲酿 之肪）以外，以與實施例11相同 N〇 15。 者色鹼顯衫性感光性樹脂組合物 &lt;光微影性&gt; 作為所獲得之著色驗顯影性感光性樹脂組合物版心^ 之：微影性之評價，分別藉由以下之方法對按照以下順序 度、密接性及顯影性進行評價。將結㈣於[表8]。 於玻璃基板上旋塗（_ rpm、7秒）著色驗顯影性感光性 樹脂組合物’使用熱板於90t下進行預烘烤9〇秒。繼而， 使用高壓水銀燈作為井调，Μ +、ώ 巧尤源經由遮罩以特定量（100或120 mJ/cm2)進行曝光。使紅5質量％碳_水隸作為顯影 液’利用旋轉顯影機顯影45秒後，充分水洗，接著使用姆 箱於230°C下進行後烘烤30分鐘使圖案固定。 (感光度） 以下述三個等級評價著色驗顯影性感光性樹脂組合物之 感光度。 即’將所形成之圖案之線寬超過遮罩開口線寬時之曝光 量為100 mJ/cm2之情形設為a，將為12〇 mj/cm2之情形設為 b，將即便為120mJ/cm2亦未形成圖案之情形設為c。 (密接性） 以下述二個等級s平價著色鹼顯影性感光性樹脂組合物之 密接性。 即，將以100 mJ/cm2進行曝光、顯影後所殘留之圖案之 最細之遮罩線寬為3 μηι以下之情形設為A ’將超過3 μηι且 162338.doc -55- 201242931 為5 μπι以下之情形設為B，將超過5 μιη之情形設為C。 (顯影性） 將顯影後，於非曝光部之玻璃面上完全未觀察到殘渣之 情形設為〇，將於一面上觀察到殘渣之情形設為X。 [表8] 著色鹼顯影性感光性樹脂組合物 感光度 密接性 顯影性 Νο·11(實施例11) b B 〇 Νο·12(實施例12) a A 〇 No. 13 (實施例13) a A 〇 Νο·14(比較例11) a A X Νο·15(比較例12) c C 〇 根據表8可知，若使用本發明之肟酯化合物，則與比較 例12所使用之化合物相比感光度及密接性良好。又，可知 與感光度及密接性良好之比較例11相比，若使用本發明之 將酯化合物，則顯影性優異。 根據以上之結果，可知以下之情況。 若使用本發明之肟酯化合物，則與比較例2、3、7及11 所使用之化合物相比，可見光區域之穿透性及顯影性優 異。 又，若使用本發明之肟酯化合物，則與比較例4及8所使 用之化合物相比，可見光區域之穿透性、耐熱性、感光度 及密接性優異。 又，若使用本發明之肟酯化合物，則與比較例5、9及12 所使用之化合物相比，耐熱性、感光度及密接性優異。 又，若使用本發明之肟酯化合物，則與比較例1、6及10 所使用之化合物相比，可見光區域之穿透性、而ί熱性、感 162338.doc -56- 201242931 光度及密接性優異。 如上所述，若使用本發明之肟酯化合物，則可見光區域 之穿透性較高，耐熱性優異，光微影性優異，本發明之肟 酯化合物可用作光聚合起始劑。 162338.doc •57-Japan's cyclohexanone 1% solution 〇 3〇g, propylene glycol _ monomethyl ether-2-acetate 8.16 g, and cyclohexanone 10.69 g, added as a component (A). g The compound No. 1 obtained in Example 1 was sufficiently stirred to obtain a colored base-developable photosensitive resin composition No. l1 as a photosensitive composition of the present invention. [Example 12] The production of the colored alkali-developable photosensitive resin composition N〇. 12 was carried out except that the compound N 0.丨 obtained in Example 1 was replaced with the compound Νο·2 obtained in Example 2, and The colored alkali-developable photosensitive resin composition No. 12 as the photosensitive composition of the present invention was obtained by the same method. [Example 13] Coloring test development Photosensitive resin composition N〇13 was produced except that the compound No. 获得 obtained in Example 1 was replaced with the compound Νο·3 obtained in Example 3, and Examples In the same manner, a colored alkali-developable photosensitive resin composition No. 13 as a photosensitive composition of the present invention was obtained. [Comparative Example 11] Production of the colored alkali-developable photosensitive resin composition N〇14 except that the compound No. i obtained in Example 1 was replaced with 1 [9 ethyl-6-(2-methylbenzylidene)- A color base-developable photosensitive resin composition No. 14 as a comparative product was obtained in the same manner as in Example 11 except that 9H-carbazol-3-yl]ethanone. [Comparative Example 12] Production of the colored alkali-developable photosensitive resin composition N〇l5, except that the compound No. 1 obtained in Example 1 was replaced with ^[4^phenylthio) 162338.doc •54-201242931 In the same manner as in Example 11, except that -1,2-octanedione 2-(indole_benzaldehyde) was used. The base color-sensitive photosensitive resin composition &lt;photo-pictability&gt; As the obtained color-developed photosensitive photosensitive resin composition core: the evaluation of lithography, respectively, by the following method The evaluation was carried out in accordance with the following order, adhesion, and developability. Will be knotted (four) in [Table 8]. The photosensitive photosensitive resin composition was spin-coated (_ rpm, 7 seconds) on a glass substrate, and prebaked at 90 t for 9 seconds using a hot plate. Then, using a high-pressure mercury lamp as a well-adjusted, Μ+, ώ 尤 source is exposed to a specific amount (100 or 120 mJ/cm 2 ) via a mask. The red 5% by mass of carbon_water was used as a developing solution. After developing for 45 seconds by a rotary developing machine, it was sufficiently washed with water, and then post-baked at 230 ° C for 30 minutes using a case to fix the pattern. (Sensitivity) The sensitivity of the coloring and developing photosensitive resin composition was evaluated in the following three levels. That is, 'the case where the line width of the formed pattern exceeds the opening width of the mask is 100 mJ/cm 2 is a, and the case where 12 〇mj/cm 2 is 12 is set to b, even if it is 120 mJ/cm 2 The case where no pattern is also formed is c. (Adhesiveness) The adhesion of the base-developable photosensitive resin composition was evaluated by the following two grades of the sizable base. That is, the case where the minimum mask width of the pattern remaining after exposure and development at 100 mJ/cm 2 is 3 μηι or less is set as A 'will exceed 3 μηι and 162338.doc -55 - 201242931 is 5 μπι The following case is set to B, and the case where it exceeds 5 μm is set to C. (Developability) After the development, the residue was not observed at all on the glass surface of the non-exposed portion, and the residue was observed on one side as X. [Table 8] Colored alkali-developable photosensitive resin composition sensitivity-adhesive developability 实施ο·11 (Example 11) b B 〇Νο·12 (Example 12) a A 〇 No. 13 (Example 13) a A 〇Νο·14 (Comparative Example 11) a AX Νο·15 (Comparative Example 12) c C 〇 According to Table 8, it is understood that the sensitivity of the compound used in Comparative Example 12 is used when the oxime ester compound of the present invention is used. And the adhesion is good. In addition, it is found that the ester compound is excellent in developability when the ester compound of the present invention is used as compared with Comparative Example 11 in which the sensitivity and the adhesion are good. Based on the above results, the following cases are known. When the oxime ester compound of the present invention is used, the penetrability and developability in the visible light region are superior to those of the compounds used in Comparative Examples 2, 3, 7, and 11. Further, when the oxime ester compound of the present invention is used, the light-transmitting region, the heat resistance, the sensitivity, and the adhesion are excellent as compared with the compounds used in Comparative Examples 4 and 8. Moreover, when the oxime ester compound of the present invention is used, it is superior in heat resistance, sensitivity, and adhesion to the compounds used in Comparative Examples 5, 9, and 12. Further, when the oxime ester compound of the present invention is used, the transmittance in the visible light region is higher than that of the compounds used in Comparative Examples 1, 6, and 10, and the heat sensitivity and feeling are 162,338.doc -56 - 201242931 luminosity and adhesion. Excellent. As described above, when the oxime ester compound of the present invention is used, the transmittance in the visible light region is high, the heat resistance is excellent, and the photo-pictability is excellent, and the oxime ester compound of the present invention can be used as a photopolymerization initiator. 162338.doc •57-

Claims (1)

201242931 七、申請專利範圍： 1. 一種肟酯化合物，其係由下述通式（1)所表示： [化1]201242931 VII. Patent application scope: 1. An oxime ester compound represented by the following general formula (1): [Chemical Formula 1] (1) O^^R2 (式中，R1、R2、汉3及R4分別獨立表示Rll、、 COOR ' SR ' S02Ru &gt; C〇NR12R13^ CN &gt; Rn、R12及R13分別獨立表示氫原子、或作為碳原子數 為1〜20之烷基、碳原子數為6〜3〇之芳基、碳原子數為 7〜30之芳基烷基或碳原子數為2〜2〇雜環基的取代基， 及R13所表示之取代基之氫原子可進而經 OR21、COR21、SR2〗、NR22r23、c〇nr22r23、nr22 〇r23 ' -NR22CO-OCOR23 . -C(=N-〇R2,).r22 . -C(=N-〇COR21). R22、CN、自素原子、_c〇〇r21、-cr21=(：r22r23、⑺ CR^cm〇-co_CR21=CR22R23、养c=〇或環氧基 等取代， R21、R22及R23分別獨立表示氫原子、或作為碳原子數 為1〜20之烷基、碳原子數為6〜3〇之芳基、碳原子數為 7〜30之芳基烷基或碳原子數為2〜2〇雜環基的取代基， R21、R22及R23所表示之取代基之氫原子可進而經CN、 鹵素原子、羥基或羧基取代， R&quot;、f、^以^及…所表示之取代基之伸 烷基部分可藉由-0-、-S-、_coo_、_〇〇：()、_NR24 、 162338.doc 201242931 C〇、-COS-、-OCS-或-cs。. -NR24COO- X -OCONR24 中斷1~5次， r表示氫原子、碳原子數為uo之烧其、 6〜3〇之芳基、碳原子數 2广之以碳原子數為 2〜2〇之雜環基， 為7〜3〇之芳基烧基或碳原子數為 Rn、R12、R〗3 ' R2丨、R22s 〇23 κ及汉23所表示之取代基之烧其 部分可具有分支側鏈，亦 凡基 ” j 了為環狀院基，又，R/2與R 13 及R22與R23亦可分別一起形成環， 料 X表不氧原子、硫原子、硒原子、cr31r32、、服33 或 PR34， R R、R及尺34分別獨立表示氫原子、或作為碳原 子數為1〜20之烧基、碳原子數為6〜3G之芳基或碳原子數 為7〜30之方基烧基的取代基， R 、R 'R及R34所表示之取代基之烷基部分可具有 分支側鏈，亦可為環狀烷基，、R32、尺33及尺34所表示 之取代基之烷基末端可為不飽和鍵，rH'r32、r33&amp;r34 亦可各自獨立地與鄰接之任意苯環一起形成環， a表不0〜4之整數， b表示1〜5之整數， R4之至少一者為具有-CR2丨=CR22R23、-CO-CR21=CR22R23 、-0-C0-CR21=CR22R23、·Ν=(：=0或環氧基之基）。 2. 一種光聚合起始劑，其係含有如請求項1之肟酯化合物 而成。 3. —種感光性組合物，其係含有（A)如請求項2之光聚合起 162338.doc 201242931 4. 始劑、及（B)具有乙烯性不飽和鍵之聚合性化合物而成。 如請求項3之感光性組合物’其申上述（Β)具有乙稀性不 飽和鍵之聚合性化合物之至少一者為賦予鹼顯影性之化 合物。 5. 如請求項3或4之感光性組合物，其係進而含有無機化合 物而成。 • 6. 如請求項3之感光性組合物’其係進而含有（d)著色料而 成。 7. 一種硬化物，其係對如諸求瑁3夕成， ， 明水項j之感光性組合物照射能 量射線而成。 8. -種彩色遽光片，其使用如請求項7之硬化物。 162338.doc 201242931 四、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明： 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：(1) O^^R2 (wherein R1, R2, han3, and R4 independently represent Rll, COOR 'SR ' S02Ru &gt; C 〇 NR12R13^ CN &gt; Rn, R12, and R13 each independently represent a hydrogen atom, Or as an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 3 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 2 carbon atoms. The substituent, and the hydrogen atom of the substituent represented by R13 may further be OR21, COR21, SR2, NR22r23, c〇nr22r23, nr22 〇r23 '-NR22CO-OCOR23 . -C(=N-〇R2,).r22 -C(=N-〇COR21). R22, CN, self-primary atom, _c〇〇r21, -cr21=(:r22r23, (7) CR^cm〇-co_CR21=CR22R23, raise c=〇 or epoxy, etc. R21, R22 and R23 each independently represent a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 3 carbon atoms, and an arylalkyl group having 7 to 30 carbon atoms. Or a substituent having 2 to 2 ring carbon atoms; the hydrogen atom of the substituent represented by R21, R22 and R23 may be further substituted by CN, a halogen atom, a hydroxyl group or a carboxyl group, and R&quot;, f, ^^ And the alkyl group of the substituent represented by The fraction can be interrupted by -0-, -S-, _coo_, _〇〇:(), _NR24, 162338.doc 201242931 C〇, -COS-, -OCS- or -cs.. -NR24COO- X -OCONR24 ~5 times, r represents a hydrogen atom, an aryl group having a carbon atom number of uo, an aryl group of 6 to 3 fluorene, a heterocyclic group having a carbon number of 2 to 2 Å, and having a carbon number of 2 to 2 Å, which is 7 to 3 The aryl group or the number of carbon atoms Rn, R12, R 3 ' R2 丨, R22s 〇 23 κ and the substituent represented by Han 23 may have a branched side chain, and the In the case of a ring-shaped base, R/2 and R 13 and R22 and R23 may also form a ring together, and the material X is a non-oxygen atom, a sulfur atom, a selenium atom, a cr31r32, a service 33 or a PR34, RR, R and The ruler 34 independently represents a hydrogen atom, or a substituent having a carbon number of 1 to 20, an aryl group having 6 to 3 carbon atoms or a group having 7 to 30 carbon atoms, R, The alkyl moiety of the substituent represented by R 'R and R34 may have a branched side chain or a cyclic alkyl group, and the alkyl terminal of the substituent represented by R32, the ruler 33 and the rule 34 may be an unsaturated bond. ,rH'r32, r33&amp;r34 Each of them may independently form a ring together with any adjacent benzene ring, a represents an integer of 0 to 4, b represents an integer of 1 to 5, and at least one of R4 has -CR2丨=CR22R23, -CO-CR21=CR22R23 , -0-C0-CR21=CR22R23, ·Ν=(:=0 or the base of an epoxy group). A photopolymerization initiator comprising the oxime ester compound of claim 1. A photosensitive composition comprising (A) a photopolymerizable compound according to claim 2, 162, 338.doc 201242931, a starting agent, and (B) a polymerizable compound having an ethylenically unsaturated bond. The photosensitive composition of claim 3, wherein at least one of the above-mentioned (Β) polymerizable compounds having an ethylenically unsaturated bond is a compound which imparts alkali developability. 5. The photosensitive composition of claim 3 or 4, which further comprises an inorganic compound. 6. The photosensitive composition of claim 3, which further comprises (d) a coloring matter. A cured product obtained by irradiating an energy ray to a photosensitive composition such as 瑁 瑁 , ,, and Mingshui j. 8. A colored calender using a hardened material as claimed in claim 7. 162338.doc 201242931 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: 162338.doc162338.doc
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