TWI411599B - Oxime ester compounds and photopolymerization initiators containing the same - Google Patents

Oxime ester compounds and photopolymerization initiators containing the same Download PDF

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TWI411599B
TWI411599B TW97100056A TW97100056A TWI411599B TW I411599 B TWI411599 B TW I411599B TW 97100056 A TW97100056 A TW 97100056A TW 97100056 A TW97100056 A TW 97100056A TW I411599 B TWI411599 B TW I411599B
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TW200930694A (en
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Daisuke Sawamoto
Nobuhide Tominaga
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Adeka Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly sensitive photopolymerization initiator that is activated by efficiently absorbing a long wavelength light such as a light with a wavelength of 405 nm or 365 nm. <P>SOLUTION: The oxime ester compound is represented by general formula (I) (wherein R<SP>1</SP>and R<SP>2</SP>represent R, OR, COR, SR, CONR'R" or CN; R, R' and R" represent an alkyl group or the like; R<SP>3</SP>and R<SP>4</SP>each independently represent R, OR, SR, a cyano group, a halogen atom or a hydroxyl group; a and b each independently are 0 to 4; X represents an oxygen atom, a sulfur atom, a selenium atom, a carbon atom, N-R<SP>5</SP>or P-R<SP>12</SP>; and R<SP>5</SP>and R<SP>12</SP>represent an alkyl group). <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

肟酯化合物及含有該化合物之光聚合起始劑Oxime ester compound and photopolymerization initiator containing the same

本發明係關於一種作為感光性組合物中所使用之光聚合起始劑而有用之新穎肟酯化合物、以該肟酯化合物為有效成分之光聚合起始劑、以及使具有乙烯性不飽和鍵之聚合性化合物中含有該光聚合起始劑而成之感光性組合物。The present invention relates to a novel oxime ester compound useful as a photopolymerization initiator used in a photosensitive composition, a photopolymerization initiator having the oxime ester compound as an active ingredient, and an ethylenically unsaturated bond A photosensitive composition comprising the photopolymerization initiator in the polymerizable compound.

感光性組合物係將光聚合起始劑加入具有乙烯性不飽和鍵之聚合性化合物中者；可藉由對該感光性組合物照射405 nm或365 nm之光而使其聚合硬化，因而該感光性組合物可應用於光硬化性油墨、感光性印刷版、各種光阻劑等中。The photosensitive composition is a photopolymerization initiator added to a polymerizable compound having an ethylenically unsaturated bond; the photosensitive composition can be polymerized and cured by irradiating light of 405 nm or 365 nm, and thus The photosensitive composition can be applied to a photocurable ink, a photosensitive printing plate, various photoresists, and the like.

作為上述感光性組合物中所使用之光聚合起始劑，於下述專利文獻1~8中提出有具有咔唑基結構之O－醯基肟化合物。但是，該等公知的O－醯基肟化合物尤其是在感度方面無法充分滿足要求。As the photopolymerization initiator used in the above-mentioned photosensitive composition, an O-indenyl ruthenium compound having a carbazole group structure is proposed in Patent Documents 1 to 8 below. However, these well-known O-indenyl ruthenium compounds do not sufficiently satisfy the requirements particularly in terms of sensitivity.

[專利文獻1]日本專利特開2001－302871號公報 [專利文獻2]日本專利特表2004－534797號公報 [專利文獻3]日本專利特開2005－25169號公報 [專利文獻4]日本專利特開2005－128483號公報 [專利文獻5]日本專利特開2005－242279號公報 [專利文獻6]日本專利特開2005－242280號公報 [專利文獻7]日本專利特開2006－16545號公報 [專利文獻8]日本專利第3754065號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-302871 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-534797 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-25169 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2005-128483 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2005-242279 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2005-242280 [Patent Document 7] Japanese Patent Laid-Open Publication No. 2006-16545 [Patent Document 8] Japanese Patent No. 3754065

本發明所欲解決之問題係，到目前為止尚無具有滿足要求之感度之光聚合起始劑。The problem to be solved by the present invention is that there has been no photopolymerization initiator having a sensitivity that satisfies the requirements so far.

因此，本發明之目的在於提供一種有效吸收405 nm或365 nm等長波長之光而活化之具有高感度之光聚合起始劑。Accordingly, it is an object of the present invention to provide a photopolymerization initiator which is highly responsive to efficiently absorbing light of a long wavelength of 405 nm or 365 nm.

本發明藉由提供以下述通式(I)所表示之肟酯化合物、及以該肟酯化合物為有效成分之光聚合起始劑，而達成上述目的。The present invention achieves the above object by providing an oxime ester compound represented by the following formula (I) and a photopolymerization initiator containing the oxime ester compound as an active ingredient.

(式中，R1 及R2 分別獨立表示R11 、OR11 、COR11 、SR11 、CONR12 R13 或者CN；R11 、R12 及R13 分別獨立表示氫原子、碳原子數1~20之烷基、碳原子數6~30之芳基、碳原子數7~30之芳基烷基或者碳原子數2~20之雜環基，該等烷基、芳基、芳基烷基及雜環基之氫原子，亦可進一步由OR21 、COR21 、SR21 、NR22 R23 、CONR22 R23 、－NR22 －OR23 、－NCOR22 －OCOR23 、－C(＝N－OR21 )－R22 、－C(＝N－OCOR21 )－R22 、CN、鹵素原子、－CR21 ＝CR22 R23 、－CO－CR21 ＝CR22 R23 、羧基、或者環氧基取 代，R21 、R22 及R23 分別獨立表示氫原子、碳原子數1~20之烷基、碳原子數6~30之芳基、碳原子數7~30之芳基烷基、或者碳原子數2~20之雜環基；上述以R11 、R12 、R13 、R21 、R22 及R23 所表示之取代基的亞烷基部分之亞甲基，亦可由不飽和鍵、醚鍵、硫醚鍵、酯鍵、硫酯鍵、醯胺鍵或者胺甲酸酯鍵中斷1~5次，上述取代基之烷基部分既可具分支側鏈，亦可為環狀烷基，上述取代基之烷基末端亦可為不飽和鍵，又，R12 與R13 以及R22 與R23 亦可分別結合而形成環。 (wherein R 1 and R 2 each independently represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN; and R 11 , R 12 and R 13 each independently represent a hydrogen atom and a carbon number of 1~ An alkyl group of 20, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, such an alkyl group, an aryl group or an arylalkyl group And the hydrogen atom of the heterocyclic group may further be OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -NCOR 22 -OCOR 23 , -C(=N -OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 , CN, halogen atom, -CR 21 =CR 22 R 23 , -CO-CR 21 =CR 22 R 23 , carboxyl group, or ring The oxy group is substituted, and R 21 , R 22 and R 23 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, Or a heterocyclic group having 2 to 20 carbon atoms; the methylene group of the alkylene moiety of the substituent represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 may also be unsaturated Bond, ether bond, thioether bond, ester bond, thioester bond, guanamine bond or urethane Key interrupt 1 to 5 times, the alkyl portion of the substituents of both groups with branched side chains, may also be cyclic alkyl terminal group of the above substituent may also be an unsaturated bond, and, R 12 and R 13 And R 22 and R 23 may also be combined to form a ring.

R3 及R4 分別獨立表示R11 、OR11 、SR11 、COR11 、CONR12 R13 、NR12 COR11 、OCOR11 、COOR11 、SCOR11 、OCSR11 、COSR11 、CSOR11 、CN、鹵素原子或者羥基，a及b分別獨立為0~4。R 3 and R 4 each independently represent R 11 , OR 11 , SR 11 , COR 11 , CONR 12 R 13 , NR 12 COR 11 , OCOR 11 , COOR 11 , SCOR 11 , OCSR 11 , COSR 11 , CSOR 11 , CN, A halogen atom or a hydroxyl group, a and b are each independently 0 to 4.

X表示氧原子、硫原子、硒原子、CR31 R32 、CO、NR33 或者PR34 ，R31 、R32 、R33 及R34 分別獨立表示R11 、OR11 、COR11 、SR11 、CONR12 R13 或者CN；X為CR31 R32 時，R3 與R4 亦可結合而形成環，或者R3 亦可介隔－X－而與相鄰苯環的1個碳原子鍵結而形成環結構；X為氧原子、硫原子、硒原子或PR34 時，R3 亦可介隔－X－而與相鄰苯環的1個碳原子鍵結而形成環結構，或者R3 與R4 亦可結合而形成環，R31 、R32 、R33 及R34 亦可分別獨立與相鄰的任一苯環結合而形成環)。X represents an oxygen atom, a sulfur atom, a selenium atom, CR 31 R 32 , CO, NR 33 or PR 34 , and R 31 , R 32 , R 33 and R 34 each independently represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN; when X is CR 31 R 32 , R 3 and R 4 may also combine to form a ring, or R 3 may also bond to 1 carbon atom of an adjacent benzene ring via -X- And forming a ring structure; when X is an oxygen atom, a sulfur atom, a selenium atom or PR 34 , R 3 may also be bonded to one carbon atom of an adjacent benzene ring via -X- to form a ring structure, or R 3 R 4 may also be bonded to form a ring, and R 31 , R 32 , R 33 and R 34 may be independently bonded to any adjacent benzene ring to form a ring).

又，本發明提供上述光聚合起始劑以及含有具有乙烯性不飽和鍵的聚合性化合物而成之感光性組合物。Moreover, the present invention provides the photopolymerization initiator and a photosensitive composition comprising a polymerizable compound having an ethylenically unsaturated bond.

又，本發明提供上述光聚合起始劑以及含有具有乙烯性不飽和鍵的鹼性顯影性化合物而成之鹼性顯影性感光性樹脂組合物。Moreover, the present invention provides the above-mentioned photopolymerization initiator and an alkali-developable photosensitive resin composition containing an alkali-developable compound having an ethylenically unsaturated bond.

又，本發明提供使上述鹼性顯影性感光性樹脂組合物進而含有色材而成之著色鹼性顯影性感光性樹脂組合物。Moreover, the present invention provides a colored alkali-developable photosensitive resin composition in which the above-described alkali-developable photosensitive resin composition further contains a color material.

以下，就本發明之肟酯化合物以及以該化合物為有效成分之光聚合起始劑加以詳細說明。Hereinafter, the oxime ester compound of the present invention and a photopolymerization initiator containing the compound as an active ingredient will be described in detail.

至於上述通式(I)中，以R11 、R12 、R13 、R21 、R22 、R23 、R31 、R32 、R33 及R34 所表示之烷基，例如可舉出：甲基、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、乙烯基、烯丙基、丁烯基、乙炔基、丙炔基、甲氧基乙基、乙氧基乙基、丙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙氧基乙氧基乙基、甲氧基丙基、2－(苯并噁唑－2'－基)乙烯基等，其中較好的是碳原子數1~8之烷基。In the above formula (I), the alkyl group represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 31 , R 32 , R 33 and R 34 may, for example, be: Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, Isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, decyl, isodecyl, undecyl, vinyl, allyl, butenyl, ethynyl, propyne , methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, methoxy A propyl group, a 2-(benzoxazole-2'-yl)vinyl group or the like, and among them, an alkyl group having 1 to 8 carbon atoms is preferred.

至於以R11 、R12 、R13 、R21 、R22 、R23 、R31 、R32 、R33 及R34 所表示之芳基，例如可舉出：苯基、甲苯基、二甲苯基、乙基苯基、氯苯基、萘基、蒽基、菲基(phenanthryl)等，其中較好的是碳原子數6~12之芳基。The aryl group represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 31 , R 32 , R 33 and R 34 may, for example, be a phenyl group, a tolyl group or a xylene group. A group, an ethylphenyl group, a chlorophenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, etc., of which an aryl group having 6 to 12 carbon atoms is preferred.

至於以R11 、R12 、R13 、R21 、R22 、R23 、R31 、R32 、R33 及R34 所表示之芳基烷基，例如較好地舉出：苄基、氯苄 基、α－甲基苄基、α,α－二甲基苄基、苯基乙基、苯基乙烯基等碳原子數7~13之芳基烷基。As the arylalkyl group represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 31 , R 32 , R 33 and R 34 , for example, a benzyl group or a chlorine is preferably mentioned. An arylalkyl group having 7 to 13 carbon atoms such as a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group or a phenylvinyl group.

至於以R11 、R12 、R13 、R21 、R22 、R23 、R31 、R32 、R33 及R34 所表示之雜環基，例如較好地舉出：吡啶基、嘧啶基、呋喃基、噻吩基、四氫呋喃基、二氧戊環基等5~7員雜環。As the heterocyclic group represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 31 , R 32 , R 33 and R 34 , for example, a pyridyl group or a pyrimidinyl group is preferably mentioned. a 5- to 5-membered heterocyclic ring such as a furyl group, a thienyl group, a tetrahydrofuranyl group or a dioxolane group.

又，至於R12 與R13 可結合而形成之環、R22 與R23 可結合而形成之環、R3 與R4 可結合而形成之環、R3 介隔－X－而與相鄰苯環的1個碳原子鍵結而形成之環結構、以及R31 、R32 、R33 與相鄰的苯環可結合而形成之環，例如較好地舉出：環戊烷環、環己烷環、環戊烯環、苯環、哌啶環、嗎啉環、內酯環、內醯胺環等5~7員環。And, as for ring R 12 and R 13 may combine to form it, R 22 and R 23 may be bonded together to form the ring, R 3 R 4 may be bonded to the ring is formed of, R 3 -X- and the adjacent interposed A ring structure formed by bonding one carbon atom of a benzene ring, and a ring formed by combining R 31 , R 32 and R 33 with an adjacent benzene ring, for example, preferably a cyclopentane ring or a ring 5~7 member rings such as hexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring and indoleamine ring.

又，至於亦可取代R11 、R12 、R13 、R21 、R22 、R23 、R31 、R32 、R33 及R34 之鹵素原子，可舉出：氟、氯、溴、碘。又，至於亦可取代R11 、R12 、R13 、R21 、R22 、R23 、R31 、R32 、R33 及R34 之雜環基，例如可舉出：吡啶基、嘧啶基、呋喃基、苯并噁唑－2－基、四氫哌喃基、吡咯啶基、咪唑啶基、吡唑啶基、四氫噻唑基、異四氫噻唑基、噁唑啶基、異噁唑啶基、哌啶基、哌嗪基、嗎啉基等5~7員雜環基。Further, the halogen atom of R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 31 , R 32 , R 33 and R 34 may be substituted, and fluorine, chlorine, bromine or iodine may be mentioned. . Further, the heterocyclic group of R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 31 , R 32 , R 33 and R 34 may be substituted, and examples thereof include a pyridyl group and a pyrimidinyl group. , furyl, benzoxazol-2-yl, tetrahydropentanyl, pyrrolidinyl, imidazolidinyl, pyrazolyl, tetrahydrothiazolyl, isotetrahydrothiazolyl, oxazolidinyl, isomer A 5-7 membered heterocyclic group such as an oxazolidinyl group, a piperidinyl group, a piperazinyl group or a morpholinyl group.

又，至於以R3 及R4 所表示之鹵素原子，可舉出：氟、氯、溴、碘。Further, examples of the halogen atom represented by R 3 and R 4 include fluorine, chlorine, bromine and iodine.

上述以R11 、R12 、R13 、R21 、R22 及R23 所表示之取代基之伸烷基部分之亞甲基，亦可由不飽和鍵、醚鍵、硫醚鍵、 酯鍵、硫酯鍵、醯胺鍵或胺甲酸酯鍵中斷1~5次，此時，進行中斷之鍵結基，既可為1種亦可為2種以上，於可進行連續中斷之基之情形時，2個以上鍵結基亦可進行連續中斷。The methylene group of the alkyl group of the substituent represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 may be an unsaturated bond, an ether bond, a thioether bond or an ester bond. The thioester bond, the guanamine bond, or the urethane bond is interrupted 1 to 5 times. In this case, the interrupted bond group may be one type or two or more types, and the case may be used for continuous interruption. At the same time, more than two bonding groups can also be continuously interrupted.

又，上述取代基之烷基部分既可具分支側鏈，亦可為環狀烷基；上述取代基之烷基末端亦可為不飽和鍵。Further, the alkyl moiety of the substituent may have a branched side chain or a cyclic alkyl group; and the alkyl terminal of the substituent may be an unsaturated bond.

本發明之肟酯化合物中，於上述通式(I)中X為硫原子者之溶解性優異，故較好。又，滿足下述條件之肟酯化合物之溶解性亦優異，故較好：於上述通式(I)中，R1 及R2 既可具分支側鏈，亦可為環狀烷基，係亦可由選自鹵素原子、OR21 及COR21 中之1種以上取代的碳原子數1~20之烷基；亦可由選自鹵素原子、OR21 及COR21 中之1種以上取代的碳原子數6~30之芳基；或者亦可由選自鹵素原子、OR21 及COR21 中之1種以上取代的碳原子數7~30之芳基烷基。In the oxime ester compound of the present invention, X is a sulfur atom in the above formula (I), and is excellent in solubility. Further, since the solubility of the oxime ester compound which satisfies the following conditions is also excellent, in the above formula (I), R 1 and R 2 may have a branched side chain or a cyclic alkyl group. may also be selected from halogen atoms, OR 21, and 21 or more carbon atoms in the alkyl group COR 1 sUBSTITUTED of 1 to 20; also, OR 21 and 21 above the COR sUBSTITUTED 1 halogen atom selected from a carbon atom An aryl group having 6 to 30 carbon atoms; or an arylalkyl group having 7 to 30 carbon atoms which may be substituted with one or more selected from the group consisting of a halogen atom, OR 21 and COR 21 .

該等之中，X為硫原子者；或者R1 及R2 既可具分支側鏈亦可為環狀烷基，為可由鹵素原子取代的碳原子數1~20之烷基、可由鹵素原子取代的碳原子數6~30之芳基、或可由鹵素原子取代的碳原子數7~30之芳基烷基者，其合成容易且感度亦較高，因而較好。尤其好的肟酯化合物，可舉出R1 為甲基或十一烷基者、R2 為甲基或苯基者。Among these, X is a sulfur atom; or R 1 and R 2 may have a branched side chain or a cyclic alkyl group, and may be an alkyl group having 1 to 20 carbon atoms which may be substituted by a halogen atom, and may be a halogen atom. The substituted aryl group having 6 to 30 carbon atoms or the arylalkyl group having 7 to 30 carbon atoms which may be substituted by a halogen atom is preferred because it is easy to synthesize and has high sensitivity. Particularly preferred oxime ester compounds include those in which R 1 is a methyl group or an undecyl group, and R 2 is a methyl group or a phenyl group.

因此，至於以上述通式(I)所表示之本發明之肟酯化合物之較佳具體例，可舉出以下化合物No.1~No.25之化合物。 但是，本發明並不受以下化合物任何限制。Therefore, as a preferable specific example of the oxime ester compound of the present invention represented by the above formula (I), the following compounds No. 1 to No. 25 can be mentioned. However, the present invention is not limited by any of the following compounds.

[化2] [Chemical 2]

對於以上述通式(I)表示之本發明之肟酯化合物之合成方法並無特限定，例如X為硫原子者，可根據下述[化24]之反應式、且藉由以下方法而製造。首先，於氫氧化鈉存在下使對氯硝基苯1與硫酚2反應而獲得硫化物化合物3，繼而於氯化鋁存在下使硫化物化合物3與醯氯4反應而獲得醯基化合物5。繼而，使醯基化合物5與鹽酸羥胺反應，而獲得肟化合物6。進而，使肟化合物6與酸酐7或醯氯7'反應，而獲得上述通式(I)中之X為硫原子之本發明之肟酯化合物。又，X為氧原子、硒原子、碳原子、N－R5 及P－R12 者，亦可根據上述方法製造。The method for synthesizing the oxime ester compound of the present invention represented by the above formula (I) is not particularly limited. For example, if X is a sulfur atom, it can be produced by the following method according to the reaction formula of the following [Chem. 24]. . First, p-chloronitrobenzene 1 is reacted with thiophenol 2 in the presence of sodium hydroxide to obtain sulfide compound 3, and then sulfide compound 3 is reacted with ruthenium chloride 4 in the presence of aluminum chloride to obtain mercapto compound 5. . Then, the mercapto compound 5 is reacted with hydroxylamine hydrochloride to obtain the indole compound 6. Further, the hydrazine compound 6 is reacted with the acid anhydride 7 or the hydrazine chloride 7' to obtain the oxime ester compound of the present invention wherein X in the above formula (I) is a sulfur atom. Further, X is an oxygen atom, a selenium atom, a carbon atom, N-R 5 or P-R 12 , and can be produced by the above method.

本發明之肟酯化合物，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。The oxime ester compound of the present invention can be used as a photopolymerization initiator for a polymerizable compound having an ethylenically unsaturated bond.

以下，就本發明之感光性組合物加以說明。Hereinafter, the photosensitive composition of the present invention will be described.

本發明之感光性組合物，係含有以上述本發明之肟酯化合物為有效成分之光聚合起始劑及具有乙烯性不飽和鍵之聚合性化合物、以及根據需要含有無機填充機及/或色材、進而含有溶劑等任意成分者。The photosensitive composition of the present invention contains a photopolymerization initiator containing the above-described oxime ester compound of the present invention as an active ingredient, a polymerizable compound having an ethylenically unsaturated bond, and, if necessary, an inorganic filling machine and/or color. The material further contains any component such as a solvent.

上述具有乙烯性不飽和鍵之聚合性化合物並無特別限定，可使用先前感光性組合物中所使用者，例如可舉出：乙烯、丙烯、丁烯、異丁烯、氯乙烯、偏二氯乙烯、偏二氟乙烯、四氟乙烯等不飽和脂肪族烴；(甲基)丙烯酸、α－ 氯丙烯酸、亞甲基丁二酸、順丁烯二酸、檸康酸、反丁烯二酸、雙環庚烯二甲酸(himic acid)、丁烯酸(crotonic acid)、異丁烯酸、乙烯基乙酸、烯丙基乙酸、桂皮酸、己二烯酸、甲基反丁烯二酸、偏苯三甲酸、均苯四甲酸、2,2'－3,3'－二苯甲酮四甲酸、3,3'－4,4'－二苯甲酮四甲酸、丁二酸單[2－(甲基)丙烯醯氧基乙酯]、鄰苯二甲酸單[2－(甲基)丙烯醯氧基乙酯]、ω－羧基聚己內酯單(甲基)丙烯酸酯等兩末端具有羧基及羥基之聚合物之單(甲基)丙烯酸酯、(甲基)丙烯酸羥乙酯－順丁烯二酸酯、(甲基)丙烯酸羥丙酯－順丁烯二酸酯、二環戊二烯－順丁烯二酸酯或者具有1個羧基及2個以上(甲基)丙烯醯基之多官能(甲基)丙烯酸酯等不飽和多元酸；(甲基)丙烯酸2－羥乙酯、(甲基)丙烯酸2－羥丙酯、(甲基)丙烯酸縮水甘油酯、下述化合物No.26~No.29、(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)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、(甲基)丙烯酸異壬酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸二甲胺基甲酯、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸胺基丙酯、(甲基)丙烯酸二甲胺基丙酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸聚(乙氧基)乙酯、(甲基)丙烯酸丁氧基乙氧基乙酯、(甲基)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)丙烯酸乙烯酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸苄酯、乙二醇二(甲基) 丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4－丁二醇二(甲基)丙烯酸酯、1,6－己二醇二(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、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、三環癸烷二羥甲基二(甲基)丙烯酸酯、三((甲基)丙烯醯基乙基)異氰脲酸酯、聚酯(甲基)丙烯酸酯寡聚物等不飽和一元酸與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、亞甲基丁二酸酐、檸康酸酐、甲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－(2,5－二氧四氫呋喃基)－3－甲基－3－環己烯－1,2－二甲酸酐、三烷基四氫鄰苯二甲酸酐－順丁烯二酸酐加成物、十二烷烯基丁二酸酐、甲基雙環庚烯二甲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、二伸乙三胺三(甲基)丙烯醯胺、苯二甲基雙(甲基)丙烯醯胺、α－氯丙烯醯胺、N－2－羥基乙基(甲基)丙烯醯胺等不飽和一元酸與多元胺之醯胺；丙烯醛等不飽和醛；(甲基)丙烯腈、α－氯丙烯腈、二氰亞乙烯(vinylidene cyanide)、烯丙基氰(allyl cyanide)等不飽和腈；苯乙烯、4－甲基苯乙烯、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 酚、乙烯基磺酸、4－乙烯基苯磺酸、乙烯基苄基甲醚、乙烯基苄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；乙烯胺、丙烯胺、N－乙烯基吡咯啶酮、乙烯基哌啶等不飽和胺化合物；烯丙醇、巴豆醇等乙烯基醇；乙烯基甲醚、乙烯基***、N－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－苯基順丁烯二醯亞胺、N－環己基順丁烯二醯亞胺等不飽和醯亞胺類；茚、1－甲基茚等茚類；1,3－丁二烯、異戊二烯、氯丁二烯(chloroprene)等脂肪族共軛二烯類；聚苯乙烯、聚(甲基)丙烯酸甲酯、聚(甲基)丙烯酸正丁酯、聚矽氧烷等聚合物分子鏈之末端上具有單(甲基)丙烯醯基之巨單體(macromonomer)類；氯乙烯、偏二氯乙烯、丁二酸雙乙烯酯、鄰苯二甲酸二烯丙酯、磷酸三烯丙酯、異氰脲酸三烯丙酯、乙烯基硫醚、乙烯基咪唑、乙烯基噁唑啉、乙烯基咔唑、乙烯基吡咯啶酮、乙烯基吡啶、含羥基之乙烯基單體與聚異氰酸酯化合物所形成之乙烯基胺甲酸酯化合物、含羥基之乙烯基單體與聚環氧化合物形成之乙烯基環氧化合物等。以本發明之肟酯化合物為有效成分之光聚合起始劑適用於該等之中的以下化合物：於兩末端具有羧基及羥基之聚合物之單(甲基)丙烯酸酯、具有1個羧基及2個以上(甲基)丙烯醯基之多官能(甲基)丙烯酸酯、不飽和一元酸與多元醇或多元酚之酯。The polymerizable compound having an ethylenically unsaturated bond is not particularly limited, and those used in the conventional photosensitive composition may, for example, be ethylene, propylene, butylene, isobutylene, vinyl chloride or vinylidene chloride. Unsaturated aliphatic hydrocarbon such as vinylidene fluoride or tetrafluoroethylene; (meth)acrylic acid, α- Chloroacrylic acid, methylene succinic acid, maleic acid, citraconic acid, fumaric acid, himic acid, crotonic acid, methacrylic acid, vinyl acetate , allyl acetic acid, cinnamic acid, hexadienoic acid, methyl fumaric acid, trimellitic acid, pyromellitic acid, 2,2'-3,3'-benzophenonetetracarboxylic acid, 3,3' -4,4'-benzophenonetetracarboxylic acid, succinic acid mono [2-(methyl) propylene methoxyethyl ester], phthalic acid mono [2-(methyl) propylene methoxyethyl ester Mono-(meth) acrylate, hydroxyethyl (meth) acrylate-maleate, a polymer having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate , (meth) hydroxypropyl acrylate-maleate, dicyclopentadiene-maleate or polyfunctional having one carboxyl group and two or more (meth) acrylonitrile groups (A) Unsaturated polybasic acid such as acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, the following compound No. 26~No. 29, methyl (meth) acrylate, (methyl) Butyl olefinate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , isodecyl (meth)acrylate, octadecyl (meth)acrylate, dodecyl (meth)acrylate, methoxyethyl (meth)acrylate, dimethyl (meth)acrylate Aminomethyl ester, dimethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, Poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, ( Tetrahydrofuranyl methacrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di(methyl) Acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1, 4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tris(A) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate Unsaturated ester, tricyclodecane dimethylol di(meth) acrylate, tris((meth) propylene decyl ethyl) isocyanurate, polyester (meth) acrylate oligomer An ester of a monobasic acid with a polyhydric alcohol or a polyhydric phenol; a metal salt of an unsaturated polybasic acid such as zinc (meth)acrylate or magnesium (meth)acrylate; maleic anhydride, methylene succinic anhydride, citraconic anhydride, Methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl 3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecyl aldol succinic anhydride, methyl bicycloheptene dimethyl An anhydride of an unsaturated polybasic acid such as an acid anhydride; (meth) acrylamide, methylene bis(meth) acrylamide, diethylenetriamine tris(meth) acrylamide, benzodimethyl bis (A) Base) an unsaturated monobasic acid such as acrylamide, α-chloropropenylamine or N-2-hydroxyethyl(meth)acrylamide or a polyamine; an unsaturated aldehyde such as acrolein; (methyl) Unsaturated nitrile such as acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, allyl cyanide, styrene, 4-methylstyrene, 4-ethylstyrene, 4- Methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyl toluene, vinylbenzoic acid, vinylbenzene Unsaturated aromatic compounds such as phenol, vinyl sulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinylamine, propylene An unsaturated amine compound such as an amine, N-vinylpyrrolidone or vinylpiperidine; a vinyl alcohol such as allyl alcohol or crotyl alcohol; vinyl methyl ether, vinyl ether, N-butyl vinyl ether, isobutyl Vinyl ether such as vinyl ether or allyl glycidyl ether; unsaturated quinone imine such as maleimide, N-phenyl maleimide, N-cyclohexyl maleimide Anthraquinones such as hydrazine and 1-methylhydrazine; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene and poly(methyl) a macromonomer having a mono(meth)acrylonitrile group at the end of a polymer molecular chain such as methyl acrylate, n-butyl poly(meth)acrylate or polyoxyalkylene; vinyl chloride, partial Vinyl chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl sulfide, ethylene Imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compound formed by a hydroxyl group-containing vinyl monomer and a polyisocyanate compound, a hydroxyl group-containing vinyl group A vinyl epoxy compound or the like formed of a monomer and a polyepoxide. A photopolymerization initiator containing the oxime ester compound of the present invention as an active ingredient is suitable for the following compounds: a mono(meth)acrylate having a carboxyl group and a hydroxyl group at both terminals, having one carboxyl group and A polyfunctional (meth) acrylate of two or more (meth) acrylonitrile groups, an ester of an unsaturated monobasic acid and a polyhydric alcohol or a polyhydric phenol.

該等聚合性化合物，可單獨使用，或者可將2種以上混合使用，又，於將2種以上混合使用之情形時，亦可預先 使彼等共聚合而作為共聚物使用。These polymerizable compounds may be used singly or in combination of two or more kinds. When two or more kinds are used in combination, they may be used in advance. They are copolymerized and used as a copolymer.

又，作為上述具有乙烯性不飽和鍵之聚合性化合物，亦可使用具有乙烯性不飽和鍵之鹼性顯影性化合物，而將本發明之感光性組合物製成鹼性顯影性感光性樹脂組合物。作為該具有乙烯性不飽和鍵之鹼性顯影性化合物，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、使不飽和一元酸與以下述通式(II)表示的環氧化合物等環氧化合物作用進而再使多元酸酐發揮作用而獲得之樹脂。該等之中，較好的是使不飽和一元酸與以下述通式(II)表示的環氧化合物等環氧化合物作用，進而再使多元酸酐發揮作 用而形成之樹脂。Further, as the polymerizable compound having an ethylenically unsaturated bond, an alkali-developable compound having an ethylenically unsaturated bond may be used, and the photosensitive composition of the present invention may be made into an alkali-developable photosensitive resin composition. Things. As the alkali-developable compound having an ethylenically unsaturated bond, a copolymer of acrylate, a phenol and/or a cresol novolac epoxy resin, and a polyphenylmethane ring having a polyfunctional epoxy group can be used. An oxygen resin, a resin obtained by reacting an unsaturated monobasic acid with an epoxy compound such as an epoxy compound represented by the following formula (II), and further causing a polybasic acid anhydride to function. Among these, it is preferred to act on an unsaturated monobasic acid and an epoxy compound such as an epoxy compound represented by the following formula (II), and further to make the polybasic acid anhydride work. A resin formed by use.

又，上述具有乙烯性不飽和鍵之鹼性顯影性化合物，較好的是含有0.2~1.0當量之不飽和基。Further, the alkali-developable compound having an ethylenically unsaturated bond preferably contains 0.2 to 1.0 equivalent of an unsaturated group.

(式中，X1 表示直接鍵結、亞甲基、碳原子數1~4之亞烷基、碳原子數3~20之脂環式烴基、O、S、SO2 、SS、SO、CO、OCO或者以下述[化30]或[化31]所表示之取代基，該亞烷基亦可由鹵素原子取代，R41 、R42 、R43 及R44 分別獨立表示氫原子、碳原子數1~5之烷基、碳原子數1~8之烷氧基、碳原子數2~5之烯基或者鹵素原子，烷基、烷氧基及烯基亦可由鹵素原子取代，m為0~10之整數)。 (wherein X 1 represents a direct bond, a methylene group, an alkylene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, O, S, SO 2 , SS, SO, CO , OCO or a substituent represented by the following [Chem. 30] or [Chem. 31], the alkylene group may also be substituted by a halogen atom, and R 41 , R 42 , R 43 and R 44 each independently represent a hydrogen atom and a carbon atom. An alkyl group of 1 to 5, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or a halogen atom, and an alkyl group, an alkoxy group and an alkenyl group may be substituted by a halogen atom, and m is 0~ An integer of 10).

(式中，Y1 表示氫原子、或者碳原子數1~10之烷基或亦可由烷氧基取代之苯基或碳原子數3~10之環烷基，Z1 表示碳原子數1~10之烷基、碳原子數1~10之烷氧基、碳原子數2~10之烯基或者鹵素原子，烷基、烷氧基及烯基亦可由鹵素原子取代，d為0~5之數)。 (wherein Y 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms or a phenyl group which may be substituted by an alkoxy group or a cycloalkyl group having 3 to 10 carbon atoms, and Z 1 represents a carbon number of 1~ An alkyl group of 10, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, an alkyl group, an alkoxy group and an alkenyl group may be substituted by a halogen atom, and d is 0 to 5 number).

至於作用於上述環氧化合物之上述不飽和一元酸，可舉出：丙烯酸、甲基丙烯酸、丁烯酸、桂皮酸、己二烯酸、甲基丙烯酸羥乙酯－順丁烯二酸酯、丙烯酸羥乙酯－順丁烯二酸酯、甲基丙烯酸羥丙酯－順丁烯二酸酯、丙烯酸羥丙酯/順丁烯二酸酯、二環戊二烯－順丁烯二酸酯等。As the unsaturated monobasic acid which acts on the above epoxy compound, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, hexadienoic acid, hydroxyethyl methacrylate-maleate, and hydroxyethyl acrylate may be mentioned. Ester-maleate, hydroxypropyl methacrylate-maleate, hydroxypropyl acrylate/maleate, dicyclopentadiene-maleate, and the like.

又，至於使上述不飽和一元酸作用後再作用之上述多元酸酐，可舉出：聯苯四甲酸二酐、四氫鄰苯二甲酸酐、丁二酸酐、聯苯二甲酸酐(biphthalic acid anhydride)、順丁烯二酸酐、偏苯三甲酸酐、均苯四甲酸酐、2,2'－3,3'－二苯甲酮四甲酸酐、乙二醇雙偏苯三甲酸酯、甘油三偏苯三甲酸酯、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、耐地酸酐、甲基耐地酸酐、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－3－環己烯－1,2－二甲酸酐、三烷基四氫鄰苯二甲酸酐－順丁烯二酸酐加成物、十二烯基丁二酸酐、甲基雙環庚烯二甲酸酐等。Further, examples of the polybasic acid anhydride which acts after the action of the unsaturated monobasic acid include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, and biphthalic acid anhydride. ), maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol trimellitate, glycerol trim Benzoic acid ester, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, acid anhydride, methylic acid anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic acid Anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride An adduct, dodecenyl succinic anhydride, methyl bicycloheptylene anhydride, and the like.

上述環氧化合物、上述不飽和一元酸及上述多元酸酐之反應莫耳比，較好的是如下所示。即，於具有在上述環氧化合物的1個環氧基上加成有0.1~1.0個上述不飽和一元酸的羧基之結構之環氧加成物中，較好的是，相對於該環氧加成物的1個羥基，上述多元酸酐之酸酐結構為0.1~1.0個 之比率。The reaction molar ratio of the above epoxy compound, the above unsaturated monobasic acid and the above polybasic acid anhydride is preferably as follows. That is, in the epoxy adduct having a structure in which a carboxyl group having 0.1 to 1.0 of the above unsaturated monobasic acid is added to one epoxy group of the epoxy compound, it is preferred to be relative to the epoxy. One hydroxyl group of the adduct, the acid anhydride structure of the above polybasic acid anhydride is 0.1 to 1.0 The ratio.

上述環氧化合物、上述不飽和一元酸及上述多元酸酐之反應，可根據常規方法進行。The reaction of the above epoxy compound, the above unsaturated monobasic acid and the above polybasic acid anhydride can be carried out according to a conventional method.

為了調整酸價以改良本發明之(著色)鹼性顯影性感光性樹脂組合物之顯影性，可在使用上述具有乙烯性不飽和鍵之鹼性顯影性化合物之同時，進一步併用單官能或多官能環氧化合物。上述具有乙烯性不飽和鍵之鹼性顯影性化合物，其固形分之酸價較好的是5~120 mgKOH/g之範圍，單官能或多官能環氧化合物之使用量，較好的是以滿足上述酸價之方式進行選擇。In order to adjust the acid value to improve the developability of the (colored) alkali-developable photosensitive resin composition of the present invention, it is possible to further use a monofunctional or multi-functional compound while using the above-mentioned alkali-developable compound having an ethylenically unsaturated bond. Functional epoxy compound. The alkali-developable compound having an ethylenically unsaturated bond has a solid acid value of preferably from 5 to 120 mgKOH/g, and a monofunctional or polyfunctional epoxy compound is preferably used. The method of satisfying the above acid value is selected.

至於上述單官能環氧化合物，可舉出：甲基丙烯酸縮水甘油酯、甲基縮水甘油醚、乙基縮水甘油醚、丙基縮水甘油醚、異丙基縮水甘油醚、丁基縮水甘油醚、異丁基縮水甘油醚、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、壬基縮水甘油醚、癸基縮水甘油醚、十一烷基縮水甘油醚、十二烷基縮水甘油醚、十三烷基縮水甘油醚、十四烷基縮水甘油醚、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、甲苯基縮水甘油醚、2－甲基甲苯基縮水甘油醚、4－壬基苯基縮水甘油醚、苄基縮水甘油醚、對異丙苯基苯基縮水甘油醚、三苯甲基縮水甘油醚、甲基丙烯酸2,3－環氧丙酯、環氧化大豆油、 環氧化亞麻籽油、丁酸縮水甘油酯、乙烯基環己烷單氧化物、1,2－環氧基－4－乙烯基環己烷、氧化苯乙烯、氧化蒎烯、氧化甲基苯乙烯、氧化環己烯、氧化丙烯、下述化合物No.30、No.31等。Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, and butyl glycidyl ether. Isobutyl glycidyl ether, tert-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, decyl glycidyl ether, Undecyl glycidyl ether, lauryl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2- Ethylhexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxyglycidyl ether, p-butyl phenol shrinkage Glycerol ether, cresyl glycidyl ether, 2-methyltolyl glycidyl ether, 4-mercaptophenyl glycidyl ether, benzyl glycidyl ether, p-cumyl phenyl glycidyl ether, trityl Glycidyl ether, methyl propyl Acid 2,3-epoxy ester, epoxidized soybean oil, Epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, decene oxide, oxidized methyl styrene And cyclohexene oxide, propylene oxide, the following compound No. 30, No. 31, and the like.

作為上述多官能環氧化合物，若使用選自由雙酚型環氧化合物及縮水甘油醚類所組成之群中之一種以上化合物，則可獲得特性更好之(著色)鹼性顯影性感光性樹脂組合物，因而較好。作為該雙酚型環氧化合物，除了以上述通式(II)所表示之環氧化合物，其他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，至於該縮水甘油醚類，可舉出：乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、1,4－丁二醇二縮水甘油醚、1,6－己二醇二縮水甘油醚、1,8－辛二醇二縮水甘油醚、1,10－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、1,4－環己烷二甲醇二縮水甘油醚、1,1,1－三(縮水甘油氧基甲基)丙烷、1,1,1－三(縮水甘 油氧基甲基)乙烷、1,1,1－三(縮水甘油氧基甲基)甲烷、1,1,1,1－四(縮水甘油氧基甲基)甲烷等。When one or more compounds selected from the group consisting of a bisphenol epoxy compound and a glycidyl ether are used as the polyfunctional epoxy compound, a (colored) alkali-developable photosensitive resin having better properties can be obtained. The composition is therefore preferred. As the bisphenol type epoxy compound, in addition to the epoxy compound represented by the above formula (II), for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound may be used. Further, examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,6-hexanediol diglycidyl ether. 1,8-octanediol diglycidyl ether, 1,10-nonanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl Ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexane dimethanol diglycidyl ether, 1,1,1-three (glycidoxymethyl)propane, 1,1,1-tris (reducing Oloxymethyl)ethane, 1,1,1-tris(glycidoxymethyl)methane, 1,1,1,1-tetrakis(glycidoxymethyl)methane, and the like.

此外亦可使用：苯酚酚醛清漆型環氧化合物、聯苯酚醛清漆型環氧化合物、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酚醛清漆型環氧化合物；3,4－環氧基－6－甲基環己基甲基－3,4－環氧基－6－甲基環己烷甲酸酯、3,4－環氧環己基甲基－3,4－環氧環己烷甲酸酯、1－環氧乙基－3,4－環氧環己烷等脂環式環氧化合物；鄰苯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酚、N,N－二縮水甘油基苯胺等縮水甘油胺類；1,3－二縮水甘油基－5,5－二甲基乙內醯脲、異氰脲酸三縮水甘油酯等雜環式環氧化合物；二環戊二烯二氧化物等二氧化化合物；萘型環氧化合物、三苯基甲烷型環氧化合物、二環戊二烯型環氧化合物等。In addition, a phenol novolak type epoxy compound, a biphenol novolak type epoxy compound, a cresol novolak type epoxy compound, a bisphenol A novolak type epoxy compound, a dicyclopentadiene novolac type ring can also be used. a novolac type epoxy compound such as an oxygen compound; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexane formate, 3,4- An alicyclic epoxy compound such as epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or 1-epoxyethyl-3,4-epoxycyclohexane; phthalic acid condensed water Glycidyl esters such as glyceride, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester; tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, N, N a glycidylamine such as diglycidylaniline; a heterocyclic epoxy compound such as 1,3-diglycidyl-5,5-dimethylhydantoin or triglycidyl isocyanurate; Dioxide compound such as cyclopentadiene dioxide; naphthalene type epoxy compound, triphenylmethane type epoxy compound, dicyclopentadiene type epoxy Compounds, etc.

於本發明之感光性組合物中，對於光聚合起始劑之添加量並無特別限定，但本發明之肟酯化合物之添加量，相對於具有乙烯性不飽和鍵之上述聚合性化合物100質量份，較好的是1~70質量份，更好的是1~50質量份，最好的是5~30質量份。In the photosensitive composition of the present invention, the amount of the photopolymerization initiator to be added is not particularly limited, but the amount of the oxime ester compound of the present invention is 100% based on the mass of the above polymerizable compound having an ethylenically unsaturated bond. The portion is preferably from 1 to 70 parts by mass, more preferably from 1 to 50 parts by mass, most preferably from 5 to 30 parts by mass.

特別是於將本發明之感光性組合物製成(著色)鹼性顯影性感光性樹脂組合物之情形時，上述具有乙烯性不飽和鍵之鹼性顯影性化合物之含量，於本發明之(著色)鹼性顯影 型感光性樹脂組合物中，較好的是1~20質量%，尤其好的是3~12質量。In particular, in the case where the photosensitive composition of the present invention is formed into a (colored) alkali-developable photosensitive resin composition, the content of the above-mentioned alkali-developable compound having an ethylenically unsaturated bond is in the present invention ( Coloring) alkaline development The photosensitive resin composition is preferably from 1 to 20% by mass, particularly preferably from 3 to 12% by mass.

於本發明之感光性組合物中可進一步加入溶劑。至於該溶劑，通常為根據需要可將上述各成分(本發明之肟酯化合物及具有乙烯性不飽和鍵之聚合性化合物等)溶解或分散之溶劑，例如可舉出：甲基乙基酮、甲基戊基酮、二乙基酮、丙酮、甲基異丙基酮、甲基異丁基酮、環己酮等酮類；***、二噁烷、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；乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯等酯系溶劑；乙二醇單甲醚、乙烯醇單***、丙二醇單甲醚乙酸酯等溶纖劑系溶劑；甲醇、乙醇、異或正丙醇、異或正丁醇、戊醇等醇系溶劑；乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、丙二醇甲醚乙酸酯等醚酯系溶劑；苯、甲苯、二甲苯等BTX系溶劑；己烷、庚烷、辛烷、環己烷等脂肪族烴系溶劑；松節油、D－檸檬烯、蒎烯等萜烯系烴油；礦油精、Swasol # 310(Cosmo Matsuyama Oil股份有限公司)、Solvesso # 100(Exxon化學股份有限公司)等石蠟系溶劑；四氯化碳、氯仿、三氯乙烯、二氯甲烷、1,2－二氯乙烷等鹵化脂肪族烴系溶劑；氯苯等鹵化芳香族烴系溶劑；卡必醇系溶劑、苯胺、三乙胺、吡啶、乙酸、乙腈、二硫化碳、N,N－二甲基甲醯胺、N－甲基吡咯啶酮、二甲基亞碸、水等；該等溶劑，可使用1種或者製成2種以上之混合溶劑而使用。Further, a solvent can be added to the photosensitive composition of the present invention. The solvent is usually a solvent which dissolves or disperses each of the above components (the oxime ester compound of the present invention and a polymerizable compound having an ethylenically unsaturated bond), and, for example, methyl ethyl ketone, Ketones such as methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone; diethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxy An ether solvent such as ethane, 1,2-diethoxyethane or dipropylene glycol dimethyl ether; an ester solvent such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate or n-butyl acetate; a cellosolve solvent such as ethylene glycol monomethyl ether, vinyl alcohol monoethyl ether or propylene glycol monomethyl ether acetate; an alcohol solvent such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol or pentanol; Ether ester solvent such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate or propylene glycol methyl ether acetate; BTX solvent such as benzene, toluene or xylene; hexane, heptane, octane An aliphatic hydrocarbon solvent such as cyclohexane; a terpene hydrocarbon oil such as turpentine, D-limonene or decene; mineral spirits, Swasol #310 ( Cosmo Matsuyama Oil Co., Ltd., Solvesso # 100 (Exxon Chemical Co., Ltd.) and other paraffinic solvents; halogenated aliphatics such as carbon tetrachloride, chloroform, trichloroethylene, dichloromethane, 1,2-dichloroethane Hydrocarbon solvent; halogenated aromatic hydrocarbon solvent such as chlorobenzene; carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N-methylpyrrole The ketone, dimethyl hydrazine, water, and the like can be used, and one type of the solvent or a mixture of two or more types can be used.

該等之中，酮類、溶纖劑系溶劑等，特別是丙二醇－1－單甲醚－2－乙酸酯、環己酮等，於感光性組合物中使光阻劑與光聚合起始劑的相溶性變佳，因而較好。Among these, a ketone or a cellosolve-based solvent, particularly propylene glycol-1-monomethyl ether-2-acetate or cyclohexanone, is used to form a photoresist in a photosensitive composition. It is preferred that the compatibility of the starting agent is improved.

本發明之感光性組合物中，可進一步含有無機化合物。至於該無機化合物，例如可舉出：氧化鎳、氧化鐵、氧化銥、氧化鈦、氧化鋅、氧化鎂、氧化鈣、氧化鉀、氧化矽、氧化鋁等金屬氧化物；層狀黏土礦物、米洛麗藍(Milori blue)、碳酸鈣、碳酸鎂、鈷系、錳系、玻璃粉末、雲母、滑石、高嶺土、亞鐵氰化物、各種金屬硫酸鹽、硫化物、硒化物、矽酸鋁、矽酸鈣、氫氧化鋁、鉑、金、銀、銅等，該等之中，較好的是氧化鈦、氧化矽、層狀黏土礦物、銀等。於本發明之感光性組合物中，無機化合物之含量，相對於具有乙烯性不飽和鍵之上述聚合性化合物100質量份，較好的是0.1~50質量份，更好的是0.5~20質量份。該等無機化合物，可使用1種或者2種以上。The photosensitive composition of the present invention may further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, cerium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, cerium oxide, and aluminum oxide; layered clay minerals and rice. Milori blue, calcium carbonate, magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum citrate, antimony Calcium acid, aluminum hydroxide, platinum, gold, silver, copper, etc., among these, titanium oxide, cerium oxide, layered clay mineral, silver, etc. are preferable. In the photosensitive composition of the present invention, the content of the inorganic compound is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass based on 100 parts by mass of the above polymerizable compound having an ethylenically unsaturated bond. Share. These inorganic compounds may be used alone or in combination of two or more.

該等無機化合物，例如可作為填充機、抗反射劑、導電劑、穩定劑、阻燃劑、機械強度增強劑、特殊波長吸收劑、拒油墨劑等而使用。These inorganic compounds can be used, for example, as a filling machine, an antireflection agent, a conductive agent, a stabilizer, a flame retardant, a mechanical strength enhancer, a special wavelength absorber, an ink repellent, and the like.

又，本發明之感光性組合物(特別是鹼性顯影性感光性樹脂組合物)，亦可進一步含有色材而形成著色感光性組合物。至於該色材，可舉出：顏料、染料、天然色素等。該等色材，可單獨使用或者將2種以上混合使用。Further, the photosensitive composition of the present invention (particularly, an alkali-developable photosensitive resin composition) may further contain a color material to form a colored photosensitive composition. As the color material, a pigment, a dye, a natural pigment, or the like can be given. These color materials may be used singly or in combination of two or more.

至於上述顏料，例如可使用：亞硝基合物、硝基化合物、偶氮化合物、二偶氮化合物、二苯并哌喃(xanthene) 化合物、喹啉化合物、蒽醌化合物、香豆素化合物、酞菁化合物、異吲哚啉酮化合物、異吲哚啉化合物、喹吖啶酮化合物、蒽締蒽酮(anthanthrone)化合物、哌瑞酮(perinone)化合物、苝(perylene)化合物、二酮吡咯并吡咯(diketopyrrolopyrrole)化合物、硫代靛藍化合物、二噁嗪化合物、三苯基甲烷化合物、喹酞酮(quinophthalone)化合物、萘四甲酸；偶氮染料、花青染料之金屬錯合物；色澱顏料(lake pigment)；藉由爐法、槽法、熱法而獲得之碳黑，或者乙炔黑，柯琴黑或燈黑等碳黑；將上述碳黑進行酸性或者鹼性表面處理者；石墨、石墨化碳黑、活性炭、碳纖維、碳奈米管、微螺旋碳纖維(carbon microcoil)、碳奈米角(carbon nanohorn)、碳氣凝膠(earbon aerogel)、富勒烯；苯胺黑、顏料黑7、鈦黑；疏水性樹脂、氧化鉻綠、米洛麗藍、鈷綠、鈷青、錳系、亞鐵氰化物、磷酸鹽群青、紺青、群青、天藍色顏料、濃綠色顏料(viridian)、翠綠色顏料、硫酸鉛、黃色鉛、鋅黃、鐵丹(紅色氧化鐵(III))、鎘紅、合成鐵黑、赭色等有機或無機顏料。該等顏料可單獨使用，或者將複數種混合使用。As the above pigment, for example, a nitroso compound, a nitro compound, an azo compound, a diazo compound, or xanthene can be used. a compound, a quinoline compound, an anthraquinone compound, a coumarin compound, a phthalocyanine compound, an isoindolinone compound, an isoporphyrin compound, a quinacridone compound, an anthanthrone compound, piperidone (perinone) compound, perylene compound, diketopyrrolopyrrole compound, thioindigo compound, dioxazine compound, triphenylmethane compound, quinophthalone compound, naphthalenetetracarboxylic acid; a nitrogen complex, a metal complex of a cyanine dye; a lake pigment; a carbon black obtained by a furnace method, a tank method, a thermal method, or a carbon black such as acetylene black, keeqin black or lamp black; The above carbon black is subjected to acidic or alkaline surface treatment; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel ( Earbon aerogel), fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin, chrome oxide green, milorie blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate green, indigo Ultramarine, sky blue pigment, strong green pigment (viridian), emerald green pigment, lead sulfate, yellow lead, zinc yellow, iron (red iron oxide (III)), cadmium red, synthetic iron black, ochre, etc. pigment. These pigments may be used singly or in combination of plural kinds.

作為上述顏料，可使用市售之顏料，例如可舉出：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、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1、3、12、13、14、16、17、20、24、55、60、73、81、83、86、93、95、97、98、100、109、110、113、114、117、120、125、126、127、129、137、138、139、147、148、150、151、152、153、154、166、168、175、180、185；顏料綠7、10、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。As the pigment, commercially available pigments can be used, and examples thereof include pigment red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90. 97, 112, 119, 122, 123, 144, 149, 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 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; pigment green 7, 10, 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, and the like.

至於上述染料，可舉出：偶氮染料、蒽醌染料、靛藍染料、三芳基甲烷染料、二苯并哌喃染料、茜素染料、吖啶染料、芪染料、噻唑染料、萘酚染料、喹啉染料、硝基染料、吲達胺染料、噁嗪染料、酞青素染料、花青染料等染料等；該等亦可將複數種混合使用。As the above dyes, there may be mentioned azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, dibenzopyran dyes, alizarin dyes, acridine dyes, anthraquinone dyes, thiazole dyes, naphthol dyes, and quinoxanes. Dyestuff dyes, nitro dyes, indamine dyes, oxazine dyes, anthraquinone dyes, cyanine dyes, and the like; these may also be used in combination.

於本發明之感光性組合物中，上述色材之添加量，相對於具有乙烯性不飽和鍵之上述聚合性化合物100質量份，較好的是50~350質量份，更好的是100~250質量份。In the photosensitive composition of the present invention, the amount of the color material added is preferably from 50 to 350 parts by mass, more preferably from 100 to 100 parts by mass, based on 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. 250 parts by mass.

又，亦可藉由與使用具有乙烯性不飽和鍵之上述聚合性化合物之同時使用其他有機聚合物，而改善硬化物之特性。至於該有機聚合物，例如可舉出：聚苯乙烯、聚甲基丙烯酸甲酯、甲基丙烯酸甲酯－丙烯酸乙酯共聚物、聚(甲基)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－氯乙烯共聚物、乙烯－乙烯基共聚物、聚氯乙烯樹脂、ABS樹脂、尼龍6、尼龍66、 尼龍12、胺甲酸酯樹脂、聚碳酸酯聚乙烯基丁醛、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、聚醯胺酸樹脂、環氧樹脂等；該等之中，較好的是聚苯乙烯、(甲基)丙烯酸－甲基丙烯酸甲酯共聚物、環氧樹脂。Further, the properties of the cured product can be improved by using other organic polymers simultaneously with the use of the above polymerizable compound having an ethylenically unsaturated bond. As the organic polymer, for example, polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymerization may be mentioned. , (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, Nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polypropylene decylamine, saturated polyester, phenol resin, phenoxy resin, polyamidoximine resin, polyamine An acid resin, an epoxy resin or the like; among these, polystyrene, a (meth)acrylic acid-methyl methacrylate copolymer, and an epoxy resin are preferable.

於使用其他有機聚合物之情形時，其使用量，相對於具有乙烯性不飽和鍵之述聚合性化合物100質量份，較好的是10~500質量份。In the case of using other organic polymers, the amount thereof is preferably from 10 to 500 parts by mass based on 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond.

本發明之感光性組合物中，進而可併用具有不飽和鍵之單體、鏈轉移劑、界面活性劑等。Further, in the photosensitive composition of the present invention, a monomer having an unsaturated bond, a chain transfer agent, a surfactant, or the like may be used in combination.

至於上述具有不飽和鍵之單體，可舉出：丙烯酸－2－羥乙酯、丙烯酸－2－羥丙酯、丙烯酸異丁酯、丙烯酸正辛酯、丙烯酸異辛酯、丙烯酸異壬酯、丙烯酸十八烷基酯、丙烯酸甲氧基乙酯、丙烯酸二甲胺基乙酯、丙烯酸鋅、1,6－己二醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、甲基丙烯酸－2－羥乙酯、甲基丙烯酸－2－羥丙酯、甲基丙烯酸丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸環己酯、三羥甲基丙烷三甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇三丙烯酸酯、雙酚A二縮水甘油醚(甲基)丙烯酸酯、雙酚F二縮水甘油醚(甲基)丙烯酸酯、雙酚Z二縮水甘油醚(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯等。Examples of the monomer having an unsaturated bond include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isodecyl acrylate, and the like. Octadecyl acrylate, methoxyethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, methacrylic acid-2 -Hydroxyethyl ester, 2-hydroxypropyl methacrylate, butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol Acrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, bisphenol A diglycidyl ether (meth) acrylate, bisphenol F diglycidyl ether (meth) acrylate, bisphenol Z Diglycidyl ether (meth) acrylate, tripropylene glycol di (meth) acrylate, and the like.

至於上述鏈轉移劑，可舉出：硫代乙醇酸、硫代蘋果酸、硫代水楊酸、2－巰基丙酸、3－巰基丙酸、3－巰基丁 酸、N－(2－巰基丙醯基)甘胺酸、2－巰基菸鹼酸、3－[N－(2－巰基乙基)胺甲醯基]丙酸、3－[N－(2－巰基乙基)胺基]丙酸、N－(3－巰基丙醯基)丙胺酸、2－巰基乙磺酸、3－巰基丙磺酸、4－巰基丁磺酸、十二烷基(4－甲硫基)苯醚、2－巰基乙醇、3－巰基－1,2－丙二醇、1－巰基－2－丙醇、3－巰基－2－丁醇、巰基苯酚、2－巰基乙胺、2－巰基咪唑、2－巰基－3－羥基吡啶、2－巰基苯并噻唑、巰基乙酸、三羥甲基丙烷三(3－巰基丙酸酯)、季戊四醇四(3－巰基丙酸酯)等巰基化合物、將該巰基化合物氧化而獲得之二硫化物化合物、碘乙酸、碘丙酸、2－碘乙醇、2－碘乙磺酸、3－碘丙磺酸等碘代烷基化合物。As the chain transfer agent, there may be mentioned: thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutylene Acid, N-(2-amidinopropyl)glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)amine-methylmethyl]propionic acid, 3-[N-(2 -mercaptoethyl)amino]propionic acid, N-(3-mercaptopropyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl ( 4-methylthio)phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, nonylphenol, 2-mercaptoethylamine , 2-mercaptoimidazole, 2-mercapto-3-hydroxypyridine, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate) An oxime-based compound, a disulfide compound obtained by oxidizing the mercapto compound, an iodoalkyl compound such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid or 3-iodopropanesulfonic acid.

至於上述界面活性劑，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、山梨糖醇酐脂肪酸酯、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。As the above surfactant, a fluorosurfactant such as a perfluoroalkyl phosphate or a perfluoroalkyl carboxylate, an anionic interfacial activity such as a higher fatty acid alkali salt, an alkyl sulfonate or an alkyl sulfate can be used. Agent, cationic surfactant such as higher amine halide or quaternary ammonium salt, nonionic such as polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, fatty acid monoglyceride Surfactants, amphoteric surfactants, surfactants such as polyoxo-based surfactants; these may also be used in combination.

又，本發明之感光性組合物中，除了作為光聚合起始劑之本發明之肟酯化合物以外，根據需要亦可併用其他光聚合起始劑或者增感劑，有時亦藉由併用其他光聚合起始劑而發揮顯著之加乘效果。Further, in the photosensitive composition of the present invention, in addition to the oxime ester compound of the present invention as a photopolymerization initiator, other photopolymerization initiators or sensitizers may be used in combination as needed, and sometimes other combinations may be used. A photopolymerization initiator exhibits a remarkable additive effect.

作為可與本發明之肟酯化合物併用之光聚合起始劑，可使用習知之化合物，例如可舉出：二苯甲酮、苯基聯苯基酮、1－羥基－1－苯甲醯基環己烷、安息香、苄基二甲基縮 酮、1－苄基－1－二甲胺基－1－(4'－嗎啉基苯甲醯基)丙烷、2－嗎啉基－2－(4'－甲基巰基)苯甲醯基丙烷、噻噸酮、1－氯－4－丙氧基噻噸酮、異丙基噻噸酮、二乙基噻噸酮、乙基蒽醌、4－苯甲醯基－4'－甲基二苯硫醚、安息香丁醚、2－羥基－2－苯甲醯基丙烷、2－羥基－2－(4'－異丙基)苯甲醯基丙烷、4－丁基苯甲醯基三氯甲烷、4－苯氧基苯甲醯基二氯甲烷、苯甲醯基甲酸甲酯、1,7－雙(9'－吖啶基)庚烷、9－正丁基－3,6－雙(2'－嗎啉基異丁醯基)咔唑、2－甲基－4,6－雙(三氯甲基)均三嗪、2－苯基－4,6－雙(三氯甲基)均三嗪、2－萘基－4,6－雙(三氯甲基)均三嗪、2,2－雙(2－氯苯基)－4,5,4',5'－四苯基－1－2'－聯咪唑、4,4－偶氮二異丁腈、三苯基膦、樟腦醌、N－1414、N－1717、N－1919、PZ－408(ADEKA股份有限公司製)、IRGACURE369、IRGACURE907、IRGACUREOXE01、IRGACUREOXE02(汽巴精化股份有限公司製)、過氧化苯甲醯、以下述通式(III)~(V)表示之化合物等；該等光聚合起始劑，可使用1種或者將2種以上組合使用。於使用該等其他光聚合起始劑之情形時，其使用量，較好的是設為本發明之肟酯化合物的使用量之等量以下。As a photopolymerization initiator which can be used in combination with the oxime ester compound of the present invention, a conventional compound can be used, and examples thereof include benzophenone, phenylbiphenyl ketone, and 1-hydroxy-1-benzhydryl group. Cyclohexane, benzoin, benzyldimethyl Ketone, 1-benzyl-1-dimethylamino-1-(4'-morpholinylbenzylidene)propane, 2-morpholinyl-2-(4'-methylindenyl) benzhydryl Propane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl hydrazine, 4-benzylidene-4'-methyl Diphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzhydrylpropane, 2-hydroxy-2-(4'-isopropyl)benzimidyl propane, 4-butylbenzylidene-based Methyl chloride, 4-phenoxybenzhydryl dichloromethane, methyl benzomethionate, 1,7-bis(9'-acridinyl)heptane, 9-n-butyl-3,6- Bis(2'-morpholinylisobutyl) carbazole, 2-methyl-4,6-bis(trichloromethyl)s-triazine, 2-phenyl-4,6-bis(trichloromethyl) Triazine, 2-naphthyl-4,6-bis(trichloromethyl)s-triazine, 2,2-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl -1-2'-biimidazole, 4,4-azobisisobutyronitrile, triphenylphosphine, camphorquinone, N-1414, N-1717, N-1919, PZ-408 (made by ADEKA CORPORATION) , IRGACURE369, IRGACURE907, IRGACUREOXE01, IRGACUREOXE02 ( a product of the following formula (III) to (V); and the photopolymerization initiator may be used alone or in combination of two or more. . In the case of using these other photopolymerization initiators, the amount thereof to be used is preferably equal to or less than the equivalent amount of the oxime ester compound of the present invention.

(式中，R1 及R2 與上述通式(I)相同，R6 與R1 相同，Y2 表示 鹵素原子或者烷基，n為0~5)。 (wherein R 1 and R 2 are the same as those of the above formula (I), R 6 is the same as R 1 , Y 2 represents a halogen atom or an alkyl group, and n is 0 to 5).

(式中，R1 及R2 與上述通式(I)相同，R6 、Y2 及n與上述通式(III)相同，R'1 、R'2 及R'6 與R1 相同，Y'2 與Y2 相同，R7 表示二醇殘基或二硫醇殘基，Z2 表示氧原子或硫原子)。 (wherein R 1 and R 2 are the same as the above formula (I), R 6 , Y 2 and n are the same as the above formula (III), and R' 1 , R' 2 and R' 6 are the same as R 1 , Y' 2 is the same as Y 2 , R 7 represents a diol residue or a dithiol residue, and Z 2 represents an oxygen atom or a sulfur atom).

(式中，R1 及R2 與上述通式(I)相同，R6 、Y2 及n與上述通式(III)相同，Z3 表示氧原子、硫原子或硒原子，A表示雜環基，p為0~5之整數，q為0或1)。 (wherein R 1 and R 2 are the same as the above formula (I), R 6 , Y 2 and n are the same as the above formula (III), Z 3 represents an oxygen atom, a sulfur atom or a selenium atom, and A represents a heterocyclic ring. Base, p is an integer from 0 to 5, and q is 0 or 1).

又，本發明之感光性組合物中，根據需要可加入對苯甲醚、對苯二酚、鄰苯二酚、第三丁基鄰苯二酚、硫代二苯胺(phenothiazine)等熱聚合抑制劑；塑化劑；黏著促進劑；填充機；消泡劑；均染劑；表面調整劑；抗氧化劑；紫外線吸收劑；分散助劑；抗凝集劑；觸媒；效果促進劑；增感劑；交聯劑；增黏劑等慣用之添加物。Further, in the photosensitive composition of the present invention, thermal polymerization inhibition such as p-anisole, hydroquinone, catechol, tert-butyl catechol, phenothiazine or the like may be added as needed. Agent; plasticizer; adhesion promoter; filling machine; defoamer; leveling agent; surface conditioner; antioxidant; ultraviolet absorber; dispersing aid; anti-aggregating agent; catalyst; effect promoter; Additives such as crosslinkers; crosslinkers; tackifiers.

於本發明之感光性組合物中，具有乙烯性不飽和鍵之上述聚合性化合物及本發明之肟酯化合物以外之任意成分(其中，上述其他光聚合起始劑、無機填充機、色材及溶劑除外)之使用量，係根據其使用目的而適當地選擇，並無特別限制，較好的是相對於具有乙烯性不飽和鍵之上述聚合性化合物100質量份，合計為50質量份以下。In the photosensitive composition of the present invention, the polymerizable compound having an ethylenically unsaturated bond and any component other than the oxime ester compound of the present invention (wherein the other photopolymerization initiator, the inorganic filler, the color material, and the like) The amount of the solvent to be used is appropriately selected depending on the purpose of use, and is not particularly limited, and is preferably 50 parts by mass or less based on 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond.

本發明之感光性組合物，可藉由旋轉塗佈機、輥塗機、棒式塗佈機、模塗佈機、淋幕式塗佈機、各種印刷、浸漬等公知之手段，而應用於碳酸鈉玻璃、石英玻璃、半導體基板、金屬、紙、塑膠等支持基體上。又，亦可於暫時塗佈於薄膜等支持基體上之後，轉印至其他支持基體上，對其應用方法並無限制。The photosensitive composition of the present invention can be applied by a known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing, and dipping. Sodium carbonate glass, quartz glass, semiconductor substrate, metal, paper, plastic and other supporting substrates. Further, it may be applied to a support substrate such as a film temporarily, and then transferred to another support substrate, and the application method thereof is not limited.

本發明之感光性組合物，可使用於以下各種用途：光硬化性塗料或清漆、光硬化性黏著劑、印刷基板、或者彩色電視、PC顯示器、個人數位助理、數位相機等之彩色顯示之液晶顯示元件中之彩色濾光器、電漿顯示面板用電極材料、粉末塗層、印刷油墨、印刷版、黏著劑、牙科用組合物、膠衣、電子工程用光阻劑、抗電鍍劑、抗蝕刻劑、液狀及乾燥膜兩者、阻焊劑、用以製造各種顯示用途用彩色濾光器之顯示面板或者電漿顯示面板、於電發光顯示裝置及LCD之製程中用以形成構造之抗蝕劑、用以將電氣及電子零件加以封裝之組合物、磁記錄材料、微小機械零件、光波導、光開關、電鍍用遮罩、蝕刻遮罩、顏色試驗系、玻璃纖維纜線塗層、網版印刷用模版、用以藉由雷射光合 高分子成型(stereolithography)而製造三維物體之材料、全像記錄用材料、圖像記錄材料、微電子電路、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脫色材料、印刷配線板用光阻材料、UV及可見雷射直接圖像系用光阻材料、印刷電路基板之逐次積層中的介電體層形成時所使用之光阻材料或保護膜等，對其用途並無特別限制。The photosensitive composition of the present invention can be used for various applications such as photocurable paints or varnishes, photocurable adhesives, printed substrates, or color display liquid crystals such as color televisions, PC monitors, personal digital assistants, and digital cameras. Color filter in display element, electrode material for plasma display panel, powder coating, printing ink, printing plate, adhesive, dental composition, gel coat, photoresist for electronic engineering, anti-electroplating agent, anti-resistance An etchant, a liquid and a dry film, a solder resist, a display panel or a plasma display panel for manufacturing various color filters for display purposes, and a structure for forming a structure in an electroluminescent display device and an LCD process Etch, composition for encapsulating electrical and electronic parts, magnetic recording materials, micro mechanical parts, optical waveguides, optical switches, plating masks, etch masks, color test systems, fiberglass cable coatings, Screen printing stencil for laser photolithography A material for producing a three-dimensional object, a material for hologram recording, an image recording material, a microelectronic circuit, a decoloring material, a decoloring material for an image recording material, and an image recording material using a microcapsule for polymer molding (stereolithography) a decolorizing material, a photoresist material for a printed wiring board, a photoresist material for a UV and visible laser direct image, a photoresist material or a protective film used for forming a dielectric layer in a successive layer of a printed circuit board, etc. Its use is not particularly limited.

又，作為使含有本發明之肟酯化合物之感光性組合物產生硬化時所使用之活性光的光源，可使用發出波長為300~450 nm之光者，例如可使用超高壓水銀燈、水銀蒸氣弧燈、碳弧燈、氙弧燈等。Further, as a light source for causing the photosensitive composition containing the oxime ester compound of the present invention to be cured, it is possible to use a light having a wavelength of 300 to 450 nm, for example, an ultrahigh pressure mercury lamp or a mercury vapor arc can be used. Lights, carbon arc lamps, xenon arc lamps, etc.

[實施例][Examples]

以下，舉出實施例等更詳細地說明本發明，但本發明並非限定於該等實施例者。Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto.

[實施例1－1]化合物No.1之製造[Example 1-1] Production of Compound No. 1

<步驟1>硫化物化合物之製造<Step 1> Manufacture of sulfide compound

於氮氣環境中，加入對氯硝基苯15.8 g(100毫莫耳)、硫酚12.1 g(110毫莫耳)及二甲基乙醯胺69.4 g，再加入氫氧化鈉12.5 g(150毫莫耳)，於50℃下攪拌1小時。冷卻至室溫，於乙酸乙酯/水系中進行油水分離。蒸餾除去溶劑，獲得作為黃色結晶之目的物即硫化物化合物23.1 g(收率99%，HPLC純度為99%)。In a nitrogen atmosphere, add 15.8 g (100 mmol) of p-chloronitrobenzene, 12.1 g (110 mmol) of thiophenol and 69.4 g of dimethylacetamide, and then add 12.5 g of sodium hydroxide (150 m). Mohr), stirred at 50 ° C for 1 hour. The mixture was cooled to room temperature and subjected to oil-water separation in ethyl acetate/water. The solvent was distilled off to obtain 23.1 g of a sulfide compound as an object of a yellow crystal (yield: 99%, HPLC purity: 99%).

<步驟2>醯基體之製造<Step 2> Manufacture of 醯 base

於氮氣環境中，加入氯化鋁12.0 g(90毫莫耳)及二氯乙 烷27.0 g，於冰浴冷卻下，緩慢滴加乙醯氯3.56 g(45毫莫耳)，繼而緩慢滴加步驟1中獲得之硫化物化合物5.78 g(25毫莫耳)及二氯乙烷27.0 g，於5℃下攪拌30分鐘。將反應液置於冰水中，進行油水分離。經由脫溶劑、自乙酸乙酯中之再結晶，而獲得作為淡黃色結晶之目的物即醯基體2.94 g(收率43%，HPLC純度96%)。Add 10.5 g (90 mmol) of aluminum chloride and dichloroethane in a nitrogen atmosphere. 27.0 g of alkane, under ice-cooling, slowly add 3.56 g (45 mmol) of acetamidine chloride, and then slowly add the sulfide compound obtained in step 1 to 5.78 g (25 mmol) and dichloroethane. 27.0 g, stirred at 5 ° C for 30 minutes. The reaction solution was placed in ice water to separate oil and water. By re-solvent and recrystallization from ethyl acetate, 2.94 g (yield: 43%, HPLC purity: 96%) of the oxime substrate which is the object of pale yellow crystals was obtained.

<步驟3>化合物No.1之製造<Step 3> Production of Compound No. 1

於氮氣流中，加入步驟2中獲得之醯基體2.73 g(10毫莫耳)、鹽酸羥胺1.04 g(15毫莫耳)、及二甲基乙醯胺5.8 g，於80℃下攪拌1小時。冷卻至室溫，進行油水分離。蒸餾除去溶劑，於殘留物中加入乙酸丁酯10.0 g，繼而加入乙酸酐1.23 g(12毫莫耳)，於90℃下攪拌1小時，冷卻至室溫。以5%氫氧化鈉水溶液進行中和，經由油水分離、脫溶劑、自乙酸乙酯中之再結晶，而獲得淡黃色結晶2.41 g(收率73%，HPLC純度99%)。對該淡黃色結晶進行各種分析，確認該淡黃色結晶為目標物即化合物No.1。分析結果示於如下。To the nitrogen stream, 2.73 g (10 mmol) of the hydrazine substrate obtained in Step 2, 1.04 g (15 mmol) of hydroxylamine hydrochloride, and 5.8 g of dimethylacetamide were added, and the mixture was stirred at 80 ° C for 1 hour. . Cool to room temperature and perform oil-water separation. The solvent was distilled off, and 10.0 g of butyl acetate was added to the residue, followed by the addition of 1.23 g (12 mmol) of acetic anhydride, and the mixture was stirred at 90 ° C for 1 hour, and cooled to room temperature. The mixture was neutralized with a 5% aqueous sodium hydroxide solution, and the mixture was separated from ethyl acetate (yield: ethyl acetate) (yield: 73%, HPLC purity: 99%). Each of the pale yellow crystals was analyzed, and it was confirmed that the pale yellow crystal was the target compound No. 1. The results of the analysis are shown below.

(分析結果)(analysis results)

(1)熔點：91.9℃(1) Melting point: 91.9 ° C

(2)1 H－NMR測定：(ppm)2.29(s：3H),2.42(s：3H),7.28(d：2H),7.53(d：2H),7.81(d：2H),8.10(d：2H)(2) 1 H-NMR measurement: (ppm) 2.29 (s: 3H), 2.42 (s: 3H), 7.28 (d: 2H), 7.53 (d: 2H), 7.81 (d: 2H), 8.10 (d) :2H)

(3)IR測定：(cm－1 )1775、1592、1576、1519、1477、1393、1368、1342、 1316、1203、1115、1085、1009、993、939、902、853、846、836、741、682、639(3) IR measurement: (cm -1 ) 1775, 1592, 1576, 1519, 1477, 1393, 1368, 1342, 1316, 1203, 1115, 1085, 1009, 993, 939, 902, 853, 846, 836, 741 682,639

(4)UV光譜測定(氯仿)λmax＝346 nm(4) UV spectroscopy (chloroform) λmax = 346 nm

(5)分解溫度測定(氮氣環境中，升溫速度10℃/分鐘，5%質量減少溫度)270℃(5) Decomposition temperature measurement (in a nitrogen atmosphere, the heating rate is 10 ° C / min, 5% mass reduction temperature) 270 ° C

[實施例1－2]化合物No.23之製造[Example 1-2] Production of Compound No. 23

除使用十二醯氯來代替實施例1－1之步驟2中所使用之乙醯氯以外，其餘均以與實施例1－1同樣之步驟，製造化合物No.23。作為中間體之醯基體之收率為30%，HPLC純度為99%。所獲得化合物No.23之收率為66%，HPLC純度為99%。所獲得化合物No.23之分析結果示於如下。Compound No. 23 was produced in the same manner as in Example 1-1, except that twelcium chloride was used instead of the ethyl chlorobenzene used in the step 2 of Example 1-1. The yield of the ruthenium substrate as an intermediate was 30%, and the HPLC purity was 99%. The yield of the obtained Compound No. 23 was 66%, and the HPLC purity was 99%. The analysis results of the obtained Compound No. 23 are shown below.

(1)熔點：73.9℃(1) Melting point: 73.9 ° C

(2)1 H－NMR測定：(ppm)0.88(t：3H),1.20~1.49(m：16H),1.58(tt：2H),2.28(s：3H),2.86(t：2H),7.25(d：2H),7.54(d：2H),7.77(d：2H),8.10(d：2H)(2) 1 H-NMR measurement: (ppm) 0.88 (t: 3H), 1.20 to 1.49 (m: 16H), 1.58 (tt: 2H), 2.28 (s: 3H), 2.86 (t: 2H), 7.25 (d: 2H), 7.54 (d: 2H), 7.77 (d: 2H), 8.10 (d: 2H)

(3)IR測定：(cm－1 )3095、2917、2851、1766、1598、1517、1471、1397、1365、1348、1284、1204、1083、1000、946、895、853、837、745、720、686(3) IR measurement: (cm -1 ) 3095, 2917, 2851, 1766, 1598, 1517, 1471, 1397, 1365, 1348, 1284, 1204, 1083, 1000, 946, 895, 853, 837, 745, 720 686

(4)UV光譜測定(氯仿)λmax＝341 nm(4) UV spectroscopy (chloroform) λmax = 341 nm

(5)分解溫度測定(氮氣環境中，升溫速度10℃/分鐘，5%質量減少溫度)255℃(5) Decomposition temperature measurement (in a nitrogen atmosphere, the heating rate is 10 ° C / min, 5% mass reduction temperature) 255 ° C

[實施例1－3]化合物No.24之製造[Example 1-3] Production of Compound No. 24

除使用十二醯氯來代替實施例1－1之步驟2中所使用之乙醯氯、使用苯甲醯氯及三乙胺來代替實施例1－1之步驟3中所使用之乙酸酐以外，其餘均以與實施例1－1同樣之步驟，製造化合物No.24。作為中間體之醯基體之收率為30%，HPLC純度為99%。所獲得化合物No.24之收率為64%，HPLC純度為99%。所獲得化合物No.24之分析結果示於如下。In place of the acetic anhydride used in the second step of Example 1-1, instead of the ethyl hydrazine chloride used in the second step of Example 1-1, using benzamidine chloride and triethylamine. The same procedure as in Example 1-1 was carried out to produce Compound No. 24. The yield of the ruthenium substrate as an intermediate was 30%, and the HPLC purity was 99%. The yield of the obtained Compound No. 24 was 64%, and the HPLC purity was 99%. The analysis results of the obtained Compound No. 24 are shown below.

(1)熔點：92.0℃(1) Melting point: 92.0 ° C

(2)1 H－NMR測定：(ppm)0.87(t：3H),1.20~1.49(m：16H),1.69(tt：2H),2.99(t：2H),7.27(ddd：2H),7.52(dd：2H),7.57(ddd：2H),7.64(tt：1H),7.86(ddd：2H),8.11(ddd：2H),8.13(d：2H)(2) 1 H-NMR measurement: (ppm) 0.87 (t: 3H), 1.20 to 1.49 (m: 16H), 1.69 (tt: 2H), 2.99 (t: 2H), 7.27 (ddd: 2H), 7.52 (dd: 2H), 7.57 (ddd: 2H), 7.64 (tt: 1H), 7.86 (ddd: 2H), 8.11 (ddd: 2H), 8.13 (d: 2H)

(3)IR測定：(cm－1 )2952、2918、2849、1749、1593、1575、1509、1470、1449、1340、1243、1177、1110、1082、1065、1022、919、884、846、784、744、722、707、680(3) IR measurement: (cm -1 ) 2952, 2918, 2849, 1749, 1593, 1575, 1509, 1470, 1449, 1340, 1243, 1177, 1110, 1082, 1065, 1022, 919, 884, 846, 784 , 744, 722, 707, 680

(4)UV光譜測定(氯仿)λmax＝341 nm(4) UV spectroscopy (chloroform) λmax = 341 nm

(5)分解溫度測定(氮氣環境中，升溫速度10℃/分鐘，5%質量減少溫度) 245℃(5) Decomposition temperature measurement (in a nitrogen atmosphere, the heating rate is 10 ° C / min, 5% mass reduction temperature) 245 ° C

[實施例2]感光性組合物No.1之製備[Example 2] Preparation of photosensitive composition No. 1

向丙烯酸系共聚物14.0 g中，加入三羥甲基丙烷三丙烯酸酯5.90 g、實施例1－1中獲得之化合物No.1(2.70 g)及乙基溶纖劑79.0 g，充分攪拌，獲得感光性組合物No.1。To 14.0 g of the acrylic copolymer, 5.90 g of trimethylolpropane triacrylate, Compound No. 1 (2.70 g) obtained in Example 1-1, and 79.0 g of ethyl cellosolve were added, and the mixture was sufficiently stirred. Photosensitive composition No. 1.

再者，上述丙烯酸系共聚物，係藉由將甲基丙烯酸20質量份、甲基丙烯酸羥乙酯15質量份、甲基丙烯酸甲酯10質量份及甲基丙烯酸丁酯55質量份溶解於乙基溶纖劑300質量份中，於氮氣環境中加入偶氮二異丁腈0.75質量份，於70℃下使其反應5小時而獲得者。Further, the acrylic copolymer is prepared by dissolving 20 parts by mass of methacrylic acid, 15 parts by mass of hydroxyethyl methacrylate, 10 parts by mass of methyl methacrylate and 55 parts by mass of butyl methacrylate in B. In 300 parts by mass of the base cellosolve, 0.75 parts by mass of azobisisobutyronitrile was added to a nitrogen atmosphere, and the mixture was reacted at 70 ° C for 5 hours.

[實施例3－1~3－3]感光性組合物No.2－1~No.2－3之製備[Examples 3-1 to 3-3] Preparation of photosensitive composition No. 2-1 to No. 2-3

將二季戊四醇五丙烯酸酯15.0 g、1,4－丁二醇二縮水甘油醚3.74 g加以混合，添加實施例1－1~1－3中獲得之化合物No.1、化合物No.23及化合物No.24(均為3.30 g)、以及乙基溶纖劑78 g，充分攪拌，分別獲得感光性組合物No.2－1~2－3。15.0 g of dipentaerythritol pentaacrylate and 3.74 g of 1,4-butanediol diglycidyl ether were mixed, and Compound No. 1, Compound No. 23 and Compound No. obtained in Examples 1-1 to 1-3 were added. .24 (both 3.30 g) and 78 g of ethyl cellosolve were thoroughly stirred to obtain photosensitive compositions No. 2-1 to 2-3, respectively.

[實施例4－1~4－3]作為鹼性顯影性感光性樹脂組合物之感光性組合物No.3－1~No.3－3之製備[Examples 4-1 to 4-3] Preparation of photosensitive composition No. 3-1 to No. 3-3 as an alkali-developable photosensitive resin composition

<步驟1>鹼性顯影性樹脂組合物No.1之製備<Step 1> Preparation of Alkaline Developing Resin Composition No. 1

加入1,1－雙(4'－環氧基丙氧基苯基)－1－(1"－聯苯基)－1－環己基甲烷17.0 g、丙烯酸4.43 g、2,6－二第三丁基－對甲基苯酚0.06 g、四丁基乙酸銨0.11 g及丙二醇－1－單甲醚－2－乙酸酯14.3 g，於120℃下攪拌16小時。冷卻至室溫，添加丙二醇－1－單甲醚－2－乙酸酯7.18 g、丁二酸酐4.82 g及四丁基乙 酸銨0.25 g，於100℃下攪拌5小時。進而，添加1,1－雙(4'－環氧基丙氧基苯基)－1－(1"－聯苯基)－1－環己基甲烷5.08 g及丙二醇－1－單甲醚－2－乙酸酯2.18 g，於120℃下攪拌12小時，於80℃下攪拌2小時，於40℃下攪拌2小時後，添加丙二醇－1－單甲醚－2－乙酸酯13.1 g，而獲得作為丙二醇－1－單甲醚－2－乙酸酯溶液之目標物即顯影性樹脂組合物No.1(Mw＝4200，Mn＝2100，酸價(固形分)55 mgKOH/g)。Add 1,1-bis(4'-epoxypropoxyphenyl)-1-(1"-biphenyl)-1-cyclohexylmethane 17.0 g, 4.43 g of acrylic acid, 2,6-di third 0.06 g of butyl-p-methylphenol, 0.11 g of tetrabutylammonium acetate and 14.3 g of propylene glycol-1-monomethyl ether-2-acetate were stirred at 120 ° C for 16 hours, cooled to room temperature, and propylene glycol was added. 1-monomethyl ether-2-acetate 7.18 g, succinic anhydride 4.82 g and tetrabutyl B Ammonium 0.25 g was stirred at 100 ° C for 5 hours. Further, 1,1-bis(4'-epoxypropoxyphenyl)-1-(1"-biphenyl)-1-cyclohexylmethane 5.08 g and propylene glycol-1-monomethyl ether-2 were added. - 2.18 g of acetate, stirred at 120 ° C for 12 hours, stirred at 80 ° C for 2 hours, and stirred at 40 ° C for 2 hours, then added propylene glycol-1-monomethyl ether-2-acetate 13.1 g, The developing resin composition No. 1 (Mw = 4200, Mn = 2100, acid value (solid content) 55 mgKOH/g) which is a target of a propylene glycol-1-monomethyl ether-2-acetate solution was obtained.

<步驟2>感光性組合物No.3－1~No.3－3之製備<Step 2> Preparation of Photosensitive Composition No. 3-1 to No. 3-3

將步驟1中獲得之鹼性顯影性樹脂組合物No.1(2.68 g)、三羥甲基丙烷三丙烯酸酯0.73 g、丙二醇－1－單甲醚－2－乙酸酯7.91 g及環己酮5.18 g加以混合，添加實施例1－1~1－3中獲得之化合物No.1、化合物No.23及化合物No.24(均為1.58 g)，充分攪拌，分別獲得作為鹼性顯影性感光性樹脂組合物之感光性組合物No.3－1~3－3。The alkali-developable resin composition No. 1 (2.68 g) obtained in the step 1, 0.73 g of trimethylolpropane triacrylate, 7.91 g of propylene glycol-1-monomethyl ether-2-acetate, and cyclohexene The ketone 5.18 g was mixed, and the compound No. 1, the compound No. 23, and the compound No. 24 (both 1.58 g) obtained in Examples 1-1 to 1-3 were added, and the mixture was thoroughly stirred to obtain an alkaline development. Photosensitive composition No. 3-1 to 3-3 of the photosensitive resin composition.

[實施例5]作為鹼性顯影性感光性樹脂組合物之感光性組合物No.4之製備[Example 5] Preparation of photosensitive composition No. 4 as an alkali-developable photosensitive resin composition

<步驟1>鹼性顯影性樹脂組合物No.2之製備<Step 1> Preparation of Alkaline Developing Resin Composition No. 2

加入雙酚芴(bisphenol fluorene)型環氧樹脂(環氧當量231)184 g、丙烯酸58.0 g、2,6－二第三丁基－對甲基苯酚0.26 g、四丁基乙酸銨0.11 g及丙二醇－1－單甲醚－2－乙酸酯23.0 g，於120℃下攪拌16小時，冷卻至室溫，加入丙二醇－1－單甲醚－2－乙酸酯35.0 g、聯苯二甲酸酐59.0 g及四正丁基溴化銨0.24 g，於120℃下攪拌4小時。進而，添加四氫鄰苯二甲酸酐20 g，於120℃下攪拌4小時，於100℃下攪 拌3小時，於80℃下攪拌4小時，於60℃下攪拌6小時，於40℃下攪拌11小時後，添加丙二醇－1－單甲醚－2－乙酸酯90.0 g，而獲得作為丙二醇－1－單甲醚－2－乙酸酯溶液之目標物即鹼性顯影性樹脂組合物No.2(Mw＝5000，Mn＝2100，酸價(固形分)92.7 mgKOH/g)。Bisphenol fluorene type epoxy resin (epoxy equivalent 231) 184 g, acrylic acid 58.0 g, 2,6-di-t-butyl-p-methylphenol 0.26 g, tetrabutylammonium acetate 0.11 g and 23.0 g of propylene glycol-1-monomethyl ether-2-acetate, stirred at 120 ° C for 16 hours, cooled to room temperature, added propylene glycol-1-monomethyl ether-2-acetate 35.0 g, biphenyl An acid anhydride of 59.0 g and 0.24 g of tetra-n-butylammonium bromide was stirred at 120 ° C for 4 hours. Further, 20 g of tetrahydrophthalic anhydride was added, and the mixture was stirred at 120 ° C for 4 hours, and stirred at 100 ° C. After mixing for 3 hours, stirring at 80 ° C for 4 hours, stirring at 60 ° C for 6 hours, and stirring at 40 ° C for 11 hours, adding propylene glycol-1-monomethyl ether-2-acetate 90.0 g to obtain propylene glycol The target of the 1-monomethyl ether-2-acetate solution was an alkali-developable resin composition No. 2 (Mw = 5000, Mn = 2100, acid value (solid content) 92.7 mgKOH/g).

<步驟2>感光性組合物No.4之製備<Step 2> Preparation of Photosensitive Composition No. 4

將步驟1中獲得之鹼性顯影性樹脂組合物No.2(2.68 g)、三羥甲基丙烷三甲基丙烯酸酯0.73 g、丙二醇－1－單甲醚－2－乙酸酯7.91 g及環己酮5.18 g加以混合，添加實施例1－1中獲得之化合物No.1(1.58 g)，充分攪拌，獲得作為鹼性顯影性感光性樹脂組合物之感光性組合物No.4。The alkali-developable resin composition No. 2 (2.68 g) obtained in the step 1, 0.73 g of trimethylolpropane trimethacrylate, and 7.91 g of propylene glycol-1-monomethyl ether-2-acetate and To the cyclopentanone 5.18 g, the compound No. 1 (1.58 g) obtained in Example 1-1 was added, and the mixture was stirred well to obtain a photosensitive composition No. 4 as an alkali-developable photosensitive resin composition.

[實施例6]作為著色鹼性顯影性感光性樹脂組合物之感光性組合物No.5之製備[Example 6] Preparation of photosensitive composition No. 5 as a colored alkali-developable photosensitive resin composition

進而除添加顏料藍15(2.00 g)以外，其餘以與實施例4－1~4－3同樣之方式，獲得作為著色鹼性顯影性感光性樹脂組合物之感光性組合物No.5－1~5－3。Further, in the same manner as in Examples 4-1 to 4-3, a photosensitive composition No. 5-1 as a colored alkali-developable photosensitive resin composition was obtained, except that Pigment Blue 15 (2.00 g) was added. ~5-3.

[實施例7]作為著色鹼性顯影性感光性樹脂組合物之感光性組合物No.6之製備[Example 7] Preparation of photosensitive composition No. 6 as colored alkali-developable photosensitive resin composition

進而除加入碳黑3.00 g以外，其餘以與實施例5同樣之方式，獲得作為著色鹼性顯影性感光性樹脂組合物之感光性組合物No.6。In the same manner as in Example 5, a photosensitive composition No. 6 as a colored alkali-developable photosensitive resin composition was obtained in the same manner as in Example 5 except that the carbon black was added in an amount of 3.00 g.

[比較例1]感光性組合物No.7之製備[Comparative Example 1] Preparation of photosensitive composition No. 7

除使用下述[化37]中所示之比較化合物1(3.30 g)來代替實施例1－1中獲得之化合物No.1(3.30 g)以外，其餘以與實 施例3－1同樣之方式，獲得比較用感光性組合物No.7。In addition to the comparative compound 1 (3.30 g) shown in the following [Chem. 37], instead of the compound No. 1 (3.30 g) obtained in Example 1-1, In the same manner as in Example 3-1, a photosensitive composition No. 7 for comparison was obtained.

[比較例2]感光性組合物No.8之製備[Comparative Example 2] Preparation of photosensitive composition No. 8

除使用下述[化38]所表示之比較化合物2(1.58 g)來代替實施例1－1中獲得之化合物No.1(3.30 g)以外，其餘以與實施例3－1同樣之方式，獲得比較用感光性組合物No.8。The same procedure as in Example 3-1 was carried out except that Comparative Compound 2 (1.58 g) represented by the following [Chem. 38] was used instead of Compound No. 1 (3.30 g) obtained in Example 1-1. Photosensitive composition No. 8 for comparison was obtained.

[比較例3]作為鹼性顯影性感光性樹脂組合物之感光性組合物No.9之製備[Comparative Example 3] Preparation of photosensitive composition No. 9 as an alkali-developable photosensitive resin composition

除使用比較化合物1(1.58 g)來代替實施例1－1中獲得之化合物No.1(1.58 g)以外，其餘以與實施例4－1同樣之方式，獲得作為比較用鹼性顯影性感光性樹脂組合物之感光性組合物No.9。An alkaline development photosensitive light for comparison was obtained in the same manner as in Example 4-1 except that Comparative Compound 1 (1.58 g) was used instead of Compound No. 1 (1.58 g) obtained in Example 1-1. Photosensitive composition No. 9 of the resin composition.

[比較例4]作為鹼性顯影性感光性樹脂組合物之感光性組合物No.10之製備[Comparative Example 4] Preparation of photosensitive composition No. 10 as an alkali-developable photosensitive resin composition

除使用比較化合物2(1.58 g)來代替實施例1－1中獲得之化合物No.1(1.58 g)以外，其餘以與實施例4－1同樣之方式， 獲得作為比較用鹼性顯影性感光性樹脂組合物之感光性組合物No.10。The same procedure as in Example 4-1 was carried out except that Comparative Compound 2 (1.58 g) was used instead of Compound No. 1 (1.58 g) obtained in Example 1-1. Photosensitive composition No. 10 which is an alkaline developing photosensitive resin composition for comparison was obtained.

[實施例8]感光性組合物No.11之製備[Example 8] Preparation of photosensitive composition No. 11

進而除添加氧化鈦4.52 g以外，其餘以與實施例2同樣之方式，獲得感光性組合物No.11。Further, photosensitive composition No. 11 was obtained in the same manner as in Example 2 except that 4.52 g of titanium oxide was added.

對於所獲得之感光性組合物No.2－1~No.2－3以及比較用感光性組合物No.7、No.8，以如下方式進行硬度試驗。試驗結果示於表1。The obtained photosensitive compositions No. 2-1 to No. 2-3 and comparative photosensitive compositions No. 7 and No. 8 were subjected to a hardness test as follows. The test results are shown in Table 1.

又，對於作為鹼性顯影性感光性樹脂組合物之感光性組合物No.3－1~No.3－3以及比較用感光性組合物No.9、No.10，以如下方式進行感度之評價。評價結果示於表2。Further, photosensitive compositions No. 3-1 to No. 3-3 and comparative photosensitive compositions No. 9 and No. 10, which are alkaline-developable photosensitive resin compositions, were subjected to sensitivity as follows. Evaluation. The evaluation results are shown in Table 2.

<硬度試驗><hardness test>

以# 3棒式塗佈機將感光性組合物塗佈於厚度50 μm之聚對苯二甲酸乙二醇酯薄膜上。使用附有帶式輸送機之光照射裝置，對其照射80 W/cm的高壓水銀燈之光而使其硬化。將燈至帶式輸送機之距離設為10 cm，將帶式輸送機之線速度設為8 cm/分鐘。硬化後於室溫下放置24小時後，之後使用鉛筆硬度試驗機，以1 kg荷重測定鉛筆硬度。The photosensitive composition was applied onto a polyethylene terephthalate film having a thickness of 50 μm by a #3 bar coater. Using a light irradiation device with a belt conveyor, it was irradiated with light of a high-pressure mercury lamp of 80 W/cm to be hardened. Set the distance from the lamp to the belt conveyor to 10 cm and the line speed of the belt conveyor to 8 cm/min. After hardening, it was allowed to stand at room temperature for 24 hours, and then the pencil hardness was measured using a pencil hardness tester at a load of 1 kg.

<感度><sensitivity>

以# 3棒式塗佈機，以約1 μm之厚度將鹼性顯影性感光性樹脂組合物塗佈於鋁基板上。於60℃下進行15分鐘預烤後，藉由日本分光股份有限公司製造之分光照射裝置CT－25CP，使用超高壓水銀燈作為光源進行曝光，繼而於25℃ 下浸漬於2.5質量%碳酸鈉溶液中進行顯影，充分水洗，分別測定於365 nm及405 nm處之分光感度。關於感度之測定，係根據殘留於鋁基板上之硬化膜段數及在365 nm及405 nm各處之射出光量，而求出在365 nm及405 nm波長之光下硬化所需之最小硬化能量。The alkali-developable photosensitive resin composition was applied onto an aluminum substrate at a thickness of about 1 μm using a #3 bar coater. After pre-baking at 60 ° C for 15 minutes, the ultra-high pressure mercury lamp was used as a light source for exposure by a spectroscopic irradiation device CT-25CP manufactured by JASCO Corporation, and then at 25 ° C. The solution was immersed in a 2.5% by mass sodium carbonate solution for development, and sufficiently washed with water to measure the spectral sensitivity at 365 nm and 405 nm, respectively. For the determination of sensitivity, the minimum hardening energy required for hardening at 365 nm and 405 nm is determined based on the number of hardened film segments remaining on the aluminum substrate and the amount of light emitted at 365 nm and 405 nm. .

由表1可知，實施例3－1~3－3之感光性組合物No.2－1~No.2－3之硬度較高，但比較例1之感光性組合物No.7以及比較例2之感光性組合物No.8並不具有充分之硬度。As is clear from Table 1, the photosensitive compositions No. 2-1 to No. 2-3 of Examples 3-1 to 3-3 had higher hardness, but the photosensitive composition No. 7 of Comparative Example 1 and Comparative Example The photosensitive composition No. 8 of 2 did not have sufficient hardness.

又，由表2可知，作為鹼性顯影性感光性樹脂組合物之實施例4－1~4－3之感光性組合物No.3－1~No.3－3，對於長波長即365 nm及405 nm之任一波長之光之感度皆優異。相對於此，比較例3之感光性組合物No.9對於365 nm之光之感度較低，因此不得不增加曝光量，對於405 nm之光並不產生硬化。又，比較例4之感光性組合物No.10，對於365 nm 之光具有充分之感度，但對於405 nm之光之感度較低，因此不得不增加曝光量。Further, as is clear from Table 2, photosensitive compositions No. 3-1 to No. 3-3 of Examples 4-1 to 4-3 which are alkali-developable photosensitive resin compositions, for long wavelengths, that is, 365 nm And the sensitivity of light of any wavelength of 405 nm is excellent. On the other hand, the photosensitive composition No. 9 of Comparative Example 3 had a low sensitivity to light of 365 nm, so that the exposure amount had to be increased, and hardening was not caused for light of 405 nm. Further, photosensitive composition No. 10 of Comparative Example 4, for 365 nm The light has sufficient sensitivity, but the sensitivity to light at 405 nm is low, so the exposure has to be increased.

產業上之可利用性Industrial availability

本發明之肟酯化合物之感光性優異，特別是對長波長即365 nm(i線)及405 nm(h線)之明線的感度優異，因此係作為光聚合起始劑有用者。The oxime ester compound of the present invention is excellent in photosensitivity, and is particularly excellent in sensitivity to long wavelengths of 365 nm (i-line) and 405 nm (h line), and is therefore useful as a photopolymerization initiator.

Claims (8)

一種肟酯化合物，其係以下述通式(I)表示： (式中，R1 及R2 分別獨立表示R11 、OR11 、COR11 、SR11 、CONR12 R13 或CN；R11 、R12 及R13 分別獨立表示氫原子、碳原子數1~20之烷基、碳原子數6~30之芳基、碳原子數7~30之芳基烷基或碳原子數2~20之雜環基，該等烷基、芳基、芳基烷基及雜環基之氫原子亦可進一步由OR21 、COR21 、SR21 、NR22 R23 、CONR22 R23 、-NR22 -OR23 、-NCOR22 -OCOR23 、-C(=N-OR21 )-R22 、-C(=N-OCOR21 )-R22 、CN、鹵素原子、-CR21 =CR22 R23 、-CO-CR21 =CR22 R23 、羧基或環氧基所取代，R21 、R22 及R23 分別獨立表示氫原子、碳原子數1~20之烷基、碳原子數6~30之芳基、碳原子數7~30之芳基烷基或碳原子數2~20之雜環基；上述以R11 、R12 、R13 、R21 、R22 及R23 所示取代基之伸烷基部分之亞甲基亦可由不飽和鍵、醚鍵、硫醚鍵、酯鍵、硫酯鍵、醯胺鍵或者胺甲酸酯鍵中斷1~5次，上述取代基之烷基部分既可具分支側鏈，亦可為環狀烷基，上述取代基之烷基末端亦可為不飽和鍵，又，R12 與R13 以及R22 與R23 亦可分別結合而形成環； R3 及R4 分別獨立表示R11 、OR11 、SR11 、COR11 、CONR12 R13 、NR12 COR11 、OCOR11 、COOR11 、SCOR11 、OCSR11 、COSR11 、CSOR11 、CN、鹵素原子或羥基，a及b分別獨立為0~4；X表示氧原子、硫原子、硒原子、CR31 R32 、CO、NR33 或PR34 ，R31 、R32 、R33 及R34 分別獨立表示R11 、OR11 、COR11 、SR11 、CONR12 R13 或CN：X為CR31 R32 時，R3 與R4 亦可結合而形成環，或者R3 亦可介隔-X-而與相鄰苯環的1個碳原子鍵結而形成環結構；X為氧原子、硫原子、硒原子或者PR34 時，R3 亦可介隔-X-而與相鄰苯環的1個碳原子鍵結而形成環結構，或者R3 與R4 亦可結合而形成環，R31 、R32 、R33 及R34 亦可分別獨立與相鄰之任一苯環結合而形成環)。An oxime ester compound represented by the following formula (I): (wherein R 1 and R 2 each independently represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN; and R 11 , R 12 and R 13 each independently represent a hydrogen atom and a carbon number of 1~ An alkyl group of 20, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, such an alkyl group, an aryl group or an arylalkyl group And the hydrogen atom of the heterocyclic group may further be OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -NCOR 22 -OCOR 23 , -C(=N- OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 , CN, halogen atom, -CR 21 =CR 22 R 23 , -CO-CR 21 =CR 22 R 23 , carboxy or epoxy group Substituted, R 21 , R 22 and R 23 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or carbon. a heterocyclic group having 2 to 20 atoms; the methylene group of the alkyl group having a substituent represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 may be an unsaturated bond or an ether bond. The thioether bond, the ester bond, the thioester bond, the guanamine bond or the urethane bond is interrupted 1 to 5 times, and the alkyl moiety of the above substituent may be divided into The side chain may also be a cyclic alkyl group, and the alkyl terminal of the above substituent may also be an unsaturated bond, and R 12 and R 13 and R 22 and R 23 may be bonded to each other to form a ring; R 3 and R 4 independently represents R 11 , OR 11 , SR 11 , COR 11 , CONR 12 R 13 , NR 12 COR 11 , OCOR 11 , COOR 11 , SCOR 11 , OCSR 11 , COSR 11 , CSOR 11 , CN, a halogen atom or The hydroxyl group, a and b are each independently 0 to 4; X represents an oxygen atom, a sulfur atom, a selenium atom, CR 31 R 32 , CO, NR 33 or PR 34 , and R 31 , R 32 , R 33 and R 34 are independently represented. When R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN: X is CR 31 R 32 , R 3 and R 4 may be combined to form a ring, or R 3 may be separated by -X- It is bonded to one carbon atom of an adjacent benzene ring to form a ring structure; when X is an oxygen atom, a sulfur atom, a selenium atom or PR 34 , R 3 may also be separated from -X- and one of the adjacent benzene rings. a carbon atom is bonded to form a ring structure, or R 3 and R 4 may be bonded to form a ring, and R 31 , R 32 , R 33 and R 34 may be independently bonded to any adjacent benzene ring to form a ring) . 如請求項1之肟酯化合物，其中上述通式(I)中之X為硫原子。 The oxime ester compound of claim 1, wherein X in the above formula (I) is a sulfur atom. 如請求項1或2之肟酯化合物，其中上述通式(I)中之R1 及R2 可具分支側鏈，亦可為環狀烷基，為可由鹵素原子取代的碳原子數1~20之烷基、可由鹵素原子取代的碳原子數6~30之芳基、或可由鹵素原子取代的碳原子數7~30之芳基烷基。The oxime ester compound of claim 1 or 2, wherein R 1 and R 2 in the above formula (I) may have a branched side chain or a cyclic alkyl group, and the number of carbon atoms which may be substituted by a halogen atom is 1~ An alkyl group of 20, an aryl group having 6 to 30 carbon atoms which may be substituted by a halogen atom, or an arylalkyl group having 7 to 30 carbon atoms which may be substituted by a halogen atom. 一種光聚合起始劑，其係以如請求項1至3中任一項之肟酯化合物為有效成分者。 A photopolymerization initiator which is an active ingredient of the oxime ester compound according to any one of claims 1 to 3. 一種感光性組合物，其係含有如請求項4之光聚合起始 劑及具有乙烯性不飽和鍵之聚合性化合物而成者。 A photosensitive composition comprising the photopolymerization initiation as claimed in claim 4 A compound and a polymerizable compound having an ethylenically unsaturated bond. 如請求項5之感光性組合物，其係進一步含有氧化鎳、氧化鐵、氧化銥、氧化鈦、氧化鋅、氧化鎂、氧化鈣、氧化鉀、氧化矽、氧化鋁等金屬氧化物；層狀黏土礦物、米洛麗藍(Milori blue)、碳酸鈣、碳酸鎂、鈷系、錳系、玻璃粉末、雲母、滑石、高嶺土、亞鐵氰化物、各種金屬硫酸鹽、硫化物、硒化物、矽酸鋁、矽酸鈣、氫氧化鋁、鉑、金、銀、銅等無機化合物而成者。 The photosensitive composition of claim 5, further comprising a metal oxide such as nickel oxide, iron oxide, cerium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, cerium oxide or aluminum oxide; Clay minerals, Milori blue, calcium carbonate, magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, antimony It is an inorganic compound such as aluminum acid, calcium citrate, aluminum hydroxide, platinum, gold, silver or copper. 一種鹼性顯影性感光性樹脂組合物，其係含有如請求項4之光聚合起始劑及具有乙烯性不飽和鍵之鹼性顯影性化合物而成者。 An alkali-developable photosensitive resin composition containing the photopolymerization initiator of claim 4 and an alkali-developable compound having an ethylenically unsaturated bond. 一種著色鹼性顯影性感光性樹脂組合物，其係使如請求項7之鹼性顯影性感光性樹脂組合物進一步含有色材而成者。 A colored alkali-developable photosensitive resin composition obtained by further comprising a color material as the alkali-developable photosensitive resin composition of claim 7.
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EP2223910B1 (en) * 2007-12-25 2012-11-07 Adeka Corporation Oxime esters and photopolymerization initiators containing the same
JP5336274B2 (en) 2008-07-09 2013-11-06 東京応化工業株式会社 Colored photosensitive resin composition and oxime photopolymerization initiator
JP5441369B2 (en) * 2008-07-16 2014-03-12 富士フイルム株式会社 Photocurable composition, ink composition, and ink jet recording method using the same
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CN107266334B (en) 2012-09-28 2020-04-24 大东凯米克斯株式会社 Fluorene compound, photopolymerization initiator containing the fluorene compound, and photosensitive composition containing the photopolymerization initiator
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JP6375236B2 (en) 2014-02-04 2018-08-15 新日鉄住金化学株式会社 Photosensitive composition for light shielding film and cured product thereof
US10539872B2 (en) * 2014-07-15 2020-01-21 Tokyo Ohka Kogyo Co., Ltd. Photosensitive composition and compound
KR102189685B1 (en) * 2015-10-08 2020-12-14 샹조우 트론리 뉴 일렉트로닉 머티리얼즈 컴퍼니 리미티드 Fluorene-containing oxime ester photoinitiator, its synthesis, photosensitive resin composition containing the same, and its application

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001233842A (en) * 1999-12-15 2001-08-28 Ciba Specialty Chem Holding Inc Photoinitiator of oxime ester
US20040072101A1 (en) * 2002-09-30 2004-04-15 Fuji Photo Film Co., Ltd. Polymerizable composition and planographic printing plate precursor

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG77689A1 (en) * 1998-06-26 2001-01-16 Ciba Sc Holding Ag New o-acyloxime photoinitiators
JP2002107926A (en) * 2000-09-29 2002-04-10 Taiyo Ink Mfg Ltd Photosensitive resin composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001233842A (en) * 1999-12-15 2001-08-28 Ciba Specialty Chem Holding Inc Photoinitiator of oxime ester
US20040072101A1 (en) * 2002-09-30 2004-04-15 Fuji Photo Film Co., Ltd. Polymerizable composition and planographic printing plate precursor

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