TWI495631B - Asymmetric dioxime ester and corresponding intermediate, manufacturing method and applications. - Google Patents

Asymmetric dioxime ester and corresponding intermediate, manufacturing method and applications. Download PDF

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TWI495631B
TWI495631B TW103130220A TW103130220A TWI495631B TW I495631 B TWI495631 B TW I495631B TW 103130220 A TW103130220 A TW 103130220A TW 103130220 A TW103130220 A TW 103130220A TW I495631 B TWI495631 B TW I495631B
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alkyl
substituted
phenyl
cycloalkyl
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TW201546034A (en
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Wenchao Zhao
Yonglin Wang
Chenlong Wang
Zhongli Ma
Lixiu Yao
Weijing Hu
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Insight High Technology Co Ltd
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    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
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    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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Description

不對稱二肟酯化合物及其中間體與其製造方法及應用Asymmetric diterpene ester compound and intermediate thereof and manufacturing method and application thereof

本發明涉及不對稱二肟酯化合物，其特徵是分子中亞芳基並環狀酮肟和鏈狀酮肟同時存在的酯化衍生物，酯化的肟基處於羰基α-位，其具有在光固化組合物中作為光引發劑的用途。The present invention relates to an asymmetric diterpene ester compound characterized by an esterified derivative of an arylene group and a cyclic ketoxime in a molecule, and an esterified fluorenyl group at the α-position of the carbonyl group, which has Use as a photoinitiator in photocurable compositions.

肟酯化合物作為光引發劑很早就被發現，美國專利US3558309、US4255513兩份專利中都公開了肟酯化合物作為光引發劑，但是，一些結構的肟酯熱穩定性不佳或感亮度低，難以在熱穩定性、感亮度等性能方面滿足現代電子工業的使用要求。中國專利CN1514845A公開了一系列肟酯化合物，並有兩個品種OXE01和OXE02上市銷售，性能相近的產品還有中國專利CN101565472B和CN101508744B公開的肟酯305和304。The oxime ester compound has been discovered as a photoinitiator. The oxime ester compound is disclosed as a photoinitiator in both of the patents of US Pat. No. 3,558,309 and US Pat. No. 4,255,513. However, some structures of oxime esters have poor thermal stability or low brightness. It is difficult to meet the requirements of the modern electronic industry in terms of thermal stability, brightness, and the like. Chinese patent CN1514845A discloses a series of oxime ester compounds, and two varieties of OXE01 and OXE02 are marketed, and similar products include oxime esters 305 and 304 disclosed in Chinese patents CN101565472B and CN101508744B.

中國專利CN102046667B描述的取代咔唑並氧雜環酮肟酯具有長達405nm的吸收波長，有利於使用LED燈固化、可見光固化，但因其分子量的加大而減少了單位重量的引發活性；專利WO2008138732中公開的以苯基咔唑為母體的各種二肟酯衍生物在一個分子中有了兩個肟酯基團，其中一個肟酯處於N取代位置上的苯基對位，實驗證明，這樣的肟酯活性很低，不能給該分子的光引發活性帶來額外的貢獻，不具有實用性。The substituted oxazolooxacyclohexanone ester described in Chinese patent CN102046667B has an absorption wavelength of up to 405 nm, which is advantageous for curing with LED lamps and visible light curing, but reduces the activity per unit weight due to the increase of molecular weight; The various diterpene ester derivatives of phenyl carbazole as disclosed in WO2008138732 have two oxime ester groups in one molecule, wherein one oxime ester is in the phenyl position of the N-substituted position, and experiments have proved that The oxime ester activity is very low, and it cannot give an additional contribution to the photoinitiating activity of the molecule, and is not practical.

除此之外也有不少其他肟酯類光引發劑的專利，如：WO2006018973、WO2007071497、CN1805955B、CN1922142B、CN1928715A、CN101508744B、CN102020727，但他們都是在咔唑的3、6、9位置的側鏈上進行各種修飾，有的分子量增大，對感光性能沒有任何提高。In addition, there are many other patents for oxime ester photoinitiators, such as: WO2006018973, WO2007071497, CN1805955B, CN1922142B, CN1928715A, CN101508744B, CN102020727, but they are all side chains at the 3, 6, and 9 positions of carbazole. Various modifications were made, and some molecular weights increased without any improvement in photosensitivity.

本發明提出一種不對稱二肟酯化合物，具有非常優良的光引發活性，包含以下結構通式I化合物： 其中，Ar1 選自被X1 所取代的C6 -C20 鄰亞芳基或C3 -C20 鄰亞雜芳基，C6 -C20 鄰亞芳基或C3 -C20 鄰亞雜芳基以相鄰的兩個原子與Y1 和羰基相連構 成併環結構，其餘原子上的取代基各自由下列所構成的群組選出：氫原子、鹵素原子、C1 -C12 烷基、C5 -C7 環烷基、C5 -C7 環烷基所取代的C1 -C4 烷基、C1- C12 烷氧基、C1 -C4 烷基苄氧基、C1 -C3 亞烷基二氧基、R2 C(O)O、C1 -C12 烷基硫基、C1 -C4 烷基苯硫基、CN、羧基、C1 -C12 烷氧基羰基、芳基羰基、雜芳基羰基、X3 R18 、C1 -C4 烷基苯氧基、C1-C8烷基醯基苯氧基、C5 -C6 環烷基醯基苯氧基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯氧基、芳基醯基苯氧基、雜芳基醯基苯氧基、R2 C(O)O取代的C1 -C4 烷基硫基、C1 -C4 烷基苯硫基、C1 -C8 烷基醯基苯硫基、C5 -C6 環烷基醯基苯硫基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯硫基、芳基醯基苯硫基、雜芳基醯基苯硫基；被一個或多個C1 -C12 烷氧基、C1 -C4 烷基苄氧基、R2 C(O)O取代的C1 -C4 烷氧基；苯基及任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、芳基醯基、雜芳基醯基、X3 R17 、苯基、鹵素原子、CN取代的苯基；及環氧丙基，其中環氧基任意地與C1 -C4 烷基醛、酮縮合；X3 選自O、S或NR22 ；Ar2 選自：通過X1 與Ar1 相連接的C6 -C20 亞芳基，或通過X1 與Ar1 相連接的C3 -C20 亞雜芳基；或通過X1 與Ar1 相連接時，與X1 鄰位的Ar2 碳原子以直鍵、碳原子、羰基、O、S、NR18 與Ar1 相連接構成環狀結構；n為0或1； X1 選自：O、S、NR18 或Y2 -Z1 -Y2 ；Y1 選自：(CH2 )m CR15 R16 、NR19 、O(CR15 R16 )m 、S(CR15 R16 )m 、(CR15 R16 )m C=O或S=O，m為0或1；Z1 選自：C1 -C10 直鏈亞烷基、C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 支鏈亞烷基、無取代基的C6 -C20 亞芳基、或有取代基的C6 -C20 亞芳基；Y2 選自：O、S、NR18 或O-C(O)；R1 選自：氫原子、C1 -C18 烷基、二苯基膦醯基，二(C1 -C4 烷氧基)膦醯基；或任意被一個或多個C3 -C7 環烷基、苯基、OR20 、SR21 、NR22 R23 所取代的C2 -C18 烷基，其中，C2 -C18 烷基的苯基被任意一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代；或被C3 -C7 亞環烷基、亞苯基、O、S、NR22 所***的C2 -C18 烷基；C3 -C8 環烷基、CN、NO2 、苯基；或被任意一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代的苯 基；或C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或多個鹵素原子、C1 -C4 烷基、C5 環烷基、C6 環烷基、苯基、CN、OH、X3 R20 所取代；或C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或多個的亞苯基、X3 ***；或苯基未被取代的苯甲醯基、苯氧基羰基；或苯基被任意一個或多個鹵素原子、C1 -C4 烷基、C5 環烷基、C6 環烷基、苯基、CN、OH、X2 R20 所取代的苯甲醯基、苯氧基羰基；R2 、R3 各自獨立地選自：氫原子、C1 -C18 烷基、C1 -C18 烷氧基、C2 -C18 烯基、苯基、萘基、C5 -C7 環烷基其中之一；或任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C2 -C18 烯基；或被C5 -C7 環亞烷基、亞苯基、O、S、NR17 所***的C2 -C18 烯基；或任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代且被C5 -C7 環亞烷基、亞苯基、O、S、NR17 所***的C2 -C18 烯基；或任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；或苯基未被取代的苯甲醯基、苯氧基羰基； 或苯基被任意一個或多個鹵素原子R17- 、C5 環烷基、C6 環烷基、CN、OH、XR17 取代的苯甲醯基、苯氧基羰基；苯基或萘基；或任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、苯基、鹵素原子、CN所取代的苯基；或任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、苯基、鹵素原子、CN所取代的萘基；R15 、R16 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、羧基所取代的C1 -C5 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基其中之一；或任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C2 -C18 烷基；或被C5 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；或任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；或任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基取代的C2 -C4 烷基醯基、苯甲醯基、XR17 、苯基、鹵素原子、CN所取代的苯基；或R15 、R16 與其共同所連的碳原子一起構成環狀且成環的原子數為4-7； 或R15 、R16 分別與相鄰的取代基一起構成環狀且成環的原子數為4-7；R17 為C1 -C4 烷基；R18 、R19 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基其中之一；或任意被一個或多個鹵素原子、C1 -C4 烷基、C3 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C1 -C18 烷基；或任意被一個或多個C3 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；或任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；或任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基所取代的C2 -C4 烷基醯基、芳基醯基、XR17 、苯基、鹵素原子、CN所取代的苯基；或R18 通過直鍵、碳原子、羰基與Ar1 或Ar2 其中之一中的芳環相連構成新的環；或R19 通過直鍵、碳原子、羰基與Ar1 中的芳環相連構成新的環；R20 、R21 、R22 、R23 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C3 -C7 環烷基其中之一；或被鹵素、CN、C1 -C4 烷氧基所取代的C1 -C18 烷基； 或被一個或多個氧原子、C5 -C7 亞環烷基、亞苯基所***的C2 -C18 烷基；或被苯基、C3 -C7 環烷基所取代的C1 -C3 烷基；或苯基、萘基未被取代的苯基、萘基、苯甲醯基；或任意被鹵素、C1 -C4 烷基、C1 -C4 烷氧基、C1 -C4 烷基硫基、苯氧基、苯硫基、NR24 R25 、C1 -C12 烷基醯基、苯甲醯基所取代的苯基、萘基、苯甲醯基；R24 、R25 各自為C1 -C4 烷基，或NR24 R25 一起為嗎福林(morpholine)，哌啶(piperidine)，哌啶(piperazine)，N-甲基哌啶(N-methyl piperazine)，吡咯(pyrrole)。The present invention provides an asymmetric diterpene ester compound having very excellent photoinitiating activity, comprising the following compound of the formula I: Wherein Ar 1 is selected from a C 6 -C 20 o-arylene or C 3 -C 20 o-heteroaryl group substituted by X 1 , a C 6 -C 20 o-arylene group or a C 3 -C 20 sub- The heteroaryl group is bonded to Y 1 and a carbonyl group by two adjacent atoms to form a ring structure, and the substituents on the remaining atoms are each selected from the group consisting of a hydrogen atom, a halogen atom, and a C 1 -C 12 alkyl group. , C 5 -C 7 cycloalkyl, C 5 -C 7 cycloalkyl substituted C 1 -C 4 alkyl, C 1- C 12 alkoxy, C 1 -C 4 alkylbenzyl group, C 1- C 3 alkylenedioxy, R 2 C(O)O, C 1 -C 12 alkylthio, C 1 -C 4 alkylphenylthio, CN, carboxyl, C 1 -C 12 alkane Oxycarbonyl, arylcarbonyl, heteroarylcarbonyl, X 3 R 18 , C 1 -C 4 alkylphenoxy, C1-C8 alkylnonylphenoxy, C 5 -C 6 cycloalkylindolyl Phenoxy, C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkyl nonylphenoxy, aryl nonylphenoxy, heteroarylnonylphenoxy, R 2 C(O) O-substituted C 1 -C 4 alkylthio, C 1 -C 4 alkylphenylthio, C 1 -C 8 alkylmercaptophenylthio, C 5 -C 6 cycloalkylnonylphenylthio , C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkylmercaptophenylthio, aromatic a fluorenyl phenylthio group, a heteroarylmercaptophenylthio group; substituted by one or more C 1 -C 12 alkoxy groups, C 1 -C 4 alkylbenzyloxy groups, R 2 C(O)O C 1 -C 4 alkoxy; phenyl and optionally by one or more C 1 -C 4 alkyl, carboxy, C 1 -C 12 alkyl fluorenyl, aryl fluorenyl, heteroaryl fluorenyl, X 3 R 17 , phenyl, halogen atom, CN substituted phenyl; and epoxy propyl group, wherein the epoxy group is arbitrarily condensed with a C 1 -C 4 alkyl aldehyde, a ketone; X 3 is selected from O, S or NR 22; Ar 2 is selected from: and X 1 through Ar 1 C connected 6 -C 20 arylene group, or by X 1 and Ar 1 C 3 -C 20 connected heteroarylene group; or X 1 and by When Ar 1 is bonded, the Ar 2 carbon atom ortho to X 1 is bonded to a straight bond, a carbon atom, a carbonyl group, O, S, NR 18 and Ar 1 to form a cyclic structure; n is 0 or 1; X 1 is selected From: O, S, NR 18 or Y 2 -Z 1 -Y 2 ; Y 1 is selected from: (CH 2 ) m CR 15 R 16 , NR 19 , O(CR 15 R 16 ) m , S(CR 15 R 16 ) m , (CR 15 R 16 ) m C=O or S=O, m is 0 or 1; Z 1 is selected from: C 1 -C 10 linear alkylene, C 1 -C 10 branched alkylene a C 1 -C 10 attached to a terminal group by one or more oxygen or sulfur atoms a linear alkylene group, a C 1 -C 10 branched alkylene group bonded to a terminal group by one or more oxygen atoms or a sulfur atom, and a C 2 -C 10 inserted by one or more oxygen atoms or sulfur atoms a linear alkylene group, a C 2 -C 10 branched alkylene group inserted by one or more oxygen atoms or sulfur atoms, an unsubstituted C 6 -C 20 arylene group, or a substituted C 6 -C 20 arylene; Y 2 is selected from: O, S, NR 18 or OC(O); R 1 is selected from the group consisting of: a hydrogen atom, a C 1 -C 18 alkyl group, a diphenylphosphinium group, a di(C) 1 -C 4 alkoxy)phosphonium; or any C 2 -C 18 alkane substituted by one or more C 3 -C 7 cycloalkyl, phenyl, OR 20 , SR 21 , NR 22 R 23 a phenyl group of a C 2 -C 18 alkyl group which is optionally substituted with one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl Substituted by CN, C 1 -C 4 alkyl alkoxy, aryloxy; or C 2 -C 18 inserted by C 3 -C 7 cycloalkylene, phenylene, O, S, NR 22 Alkyl; C 3 -C 8 cycloalkyl, CN, NO 2 , phenyl; or by any one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkane Base, phenyl, a heteroaryl group, a CN, a C 1 -C 4 alkyl alkoxy group, an aryloxy group-substituted phenyl group; or a C 1 -C 12 alkylfluorenyl group, a C 1 -C 12 alkoxycarbonyl group, wherein the alkyl group is optionally Substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 cycloalkyl, C 6 cycloalkyl, phenyl, CN, OH, X 3 R 20 ; or C 1 -C 12 alkyl Mercapto, C 1 -C 12 alkoxycarbonyl, wherein alkyl is optionally substituted with one or more phenylene groups, X 3 ; or phenyl unsubstituted benzylidene, phenoxycarbonyl; or benzene a benzylidene group or a benzene substituted with any one or more halogen atoms, C 1 -C 4 alkyl, C 5 cycloalkyl, C 6 cycloalkyl, phenyl, CN, OH, X 2 R 20 Oxycarbonyl; R 2 and R 3 are each independently selected from the group consisting of: hydrogen atom, C 1 -C 18 alkyl group, C 1 -C 18 alkoxy group, C 2 -C 18 alkenyl group, phenyl group, naphthyl group, C One of 5- C 7 cycloalkyl groups; or optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkyl alkoxy, aryloxy substituted C 2 -C 18 alkenyl; or C 5 -C 7 cycloalkylene, phenylene, O, S, NR 17 Insert C 2 -C 18 alkenyl; or optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN a C 2 -C 18 alkenyl group substituted with a C 1 -C 4 alkyl alkoxy group, an aryloxy group, and a C 5 -C 7 cycloalkylene group, a phenylene group, an O, S, NR 17 ; Or any C 5 -C 7 cycloalkyl group substituted by one or more C 1 -C 4 alkyl groups, a phenyl group, a halogen atom, CN; or a phenyl unsubstituted benzylidene group or a phenoxycarbonyl group Or a phenyl fluorenyl group or a phenoxycarbonyl group in which a phenyl group is substituted by any one or more halogen atoms R 17- , C 5 cycloalkyl, C 6 cycloalkyl, CN, OH, XR 17 ; phenyl or naphthalene; Or any phenyl group substituted by one or more C 1 -C 4 alkyl groups, C 1 -C 4 alkoxy groups, phenyl groups, halogen atoms, CN; or optionally by one or more C 1 -C a 4- alkyl group, a C 1 -C 4 alkoxy group, a phenyl group, a halogen atom, a CN-substituted naphthyl group; and R 15 and R 16 are each independently selected from the group consisting of hydrogen atoms, C 1 -C C18 alkyl, carboxy substituted C 1 -C 5 alkyl, C 1 -C 4 alkoxy substituted acyl C 1 -C 5 alkyl group, R 2 C (O Any one of C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, phenyl substituted by O; or optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C a 7- cycloalkyl group, a heterocycloalkyl group, a phenyl group, a heteroaryl group, a CN, a C 1 -C 4 alkyl alkoxy group, a C 2 -C 18 alkyl group substituted with an aryloxy group; or a C 5 -C 7 -cycloalkylene, phenylene, O, S, NR 17 inserted C 2 -C 18 alkyl; or optionally by one or more C 1 -C 4 alkyl, phenyl, halogen atom, CN Substituted C 5 -C 7 cycloalkyl; or optionally by one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy, C 1 -C 12 alkyl fluorenyl, C 5 - C 6 cycloalkylcarbinyl, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkylfluorenyl, benzamidine, XR 17 , phenyl, halogen atom, phenyl substituted by CN; Or R 15 and R 16 together with the carbon atom to which they are attached form a cyclic ring and the number of atoms formed is 4-7; or R 15 and R 16 together with adjacent substituents form a cyclic and ring-shaped atom. number of 4-7; R 17 is C 1 -C 4 alkyl; R 18, R 19 are each independently selected from the group consisting of the following: a hydrogen atom, C 1 -C 18 alkyl, C 1 -C 4 Substituted acyl group C 1 -C 5 alkyl group, R 2 C (O) O substituted C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, phenyl wherein one; or any By one or more halogen atoms, C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkoxy, aryl a C 1 -C 18 alkyl group substituted with a methoxy group; or any C 2 -C 18 alkane inserted by one or more C 3 -C 7 cycloalkylene groups, phenylene groups, O, S, NR 17 Or any C 5 -C 7 cycloalkyl substituted by one or more C 1 -C 4 alkyl, phenyl, halogen atom, CN; or optionally C 1 -C 4 alkyl , carboxy, C 1 -C 12 alkyl acyl, C 5 -C 6 cycloalkyl methyl acyl, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkyl acyl, aryl acyl , XR 17 , phenyl, a halogen atom, a phenyl group substituted by CN; or R 18 is bonded to an aromatic ring in one of Ar 1 or Ar 2 by a straight bond, a carbon atom, a carbonyl group, or a new ring; or R 19 A new ring is formed by a straight bond, a carbon atom, a carbonyl group and an aromatic ring in Ar 1 ; R 20 , R 21 , R 22 and R 23 are each independently selected from the group consisting of the following: And one of a hydrogen atom, a C 1 -C 18 alkyl group, a C 3 -C 7 cycloalkyl group; or a C 1 -C 18 alkyl group substituted by a halogen, CN, a C 1 -C 4 alkoxy group; Or a C 2 -C 18 alkyl group inserted by one or more oxygen atoms, a C 5 -C 7 cycloalkylene group, a phenylene group; or a C substituted by a phenyl group, a C 3 -C 7 cycloalkyl group 1 -C 3 alkyl; or phenyl, naphthyl unsubstituted phenyl, naphthyl, benzhydryl; or optionally halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenoxy, phenylthio, NR 24 R 25 , C 1 -C 12 alkyl fluorenyl, phenyl substituted with phenyl fluorenyl, naphthyl, benzhydryl ; R 24 and R 25 are each C 1 -C 4 alkyl, or NR 24 R 25 together is morpholine, piperididine, piperazine, N-methylpiperidine (N -methyl piperazine), pyrrole.

再者，本發明再提出一種結構通式I不對稱二肟酯化合物的製造方法，包含以下步驟：(1)步驟1：將下列結構通式Ⅳ化合物中環戊酮羰基的鄰位亞甲基上進行選擇性肟化，肟化的方法是將結構通式Ⅳ化合物與亞硝酸烷基酯在酸性溶液中發生肟化反應，得到對應的中間體為一種酮肟化合物，如下列結構通式V化合物； (2)步驟2：將結構通式V化合物繼續進行第二肟化，第二肟化方法為下列兩者其中之一： 方法A：將結構通式V化合物與亞硝酸烷基酯在酸性溶液中發生肟化反應，得到對應的第二肟化中間體結構通式Ⅵ化合物；方法B：將結構通式V化合物在羥胺溶液中發生側鏈R1 CH2 CO中羰基的肟化反應，得到對應的第二肟化中間體結構通式Ⅶ化合物； (3)步驟3：將上述第二肟化中間體Ⅵ或Ⅶ化合物其中之一與下列醯化試劑： 或其等價醯化試劑發生酯化反應得到對應結構通式I化合物。Furthermore, the present invention further provides a process for producing an asymmetric dioxime ester compound of the formula I, which comprises the following steps: (1) Step 1: The ortho-methylene group of the cyclopentanone carbonyl group in the following compound of the formula IV is The selective deuteration is carried out by deuteration of a compound of the formula IV and an alkyl nitrite in an acidic solution to obtain a corresponding intermediate as a ketoxime compound, such as the following compound of the formula V. ; (2) Step 2: The compound of the formula V is further subjected to a second deuteration method, and the second deuteration method is one of the following: Method A: the compound of the formula V and the alkyl nitrite are in an acidic solution. The deuteration reaction occurs to obtain the corresponding second deuterated intermediate structure of the compound of formula VI; Method B: the deuteration reaction of the carbonyl group in the side chain R 1 CH 2 CO is carried out in the hydroxylamine solution of the compound of the formula V. Corresponding second deuterated intermediate structure of the compound of formula VII; (3) Step 3: One of the above second deuterated intermediates VI or VII compounds and the following deuteration reagents: Or an esterification reaction of its equivalent deuteration reagent to give a corresponding structural formula I compound.

本發明再提出一種不對稱二酮化合物，如結構通式Ⅳ所示： 其中，Ar1 選自被X1 所取代的C6 -C20 鄰亞芳基或C3 -C20 鄰亞雜芳基，C6 -C20 鄰亞芳基或C3 -C20 鄰亞雜芳基以相鄰的兩個原子與Y1 和羰基相連構成並環結構，其餘原子上的取代基各自由下列所構成的群組選出：氫原子、鹵素原子、C1 -C12 烷基、C5 -C7 環烷基、C5 -C7 環烷基所取代的C1 -C4 烷基、C1- C12 烷氧基、C1 -C4 烷基苄氧基、C1 -C3 亞烷基 二氧基、R2 C(O)O、C1 -C12 烷基硫基、C1 -C4 烷基苯硫基、CN、羧基、C1 -C12 烷氧基羰基、芳基羰基、雜芳基羰基、X3 R18 、C1 -C4 烷基苯氧基、C1-C8烷基醯基苯氧基、C5 -C6 環烷基醯基苯氧基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯氧基、芳基醯基苯氧基、雜芳基醯基苯氧基、R2 C(O)O取代的C1 -C4 烷基硫基、C1 -C4 烷基苯硫基、C1 -C8 烷基醯基苯硫基、C5 -C6 環烷基醯基苯硫基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯硫基、芳基醯基苯硫基、雜芳基醯基苯硫基；或被一個或多個C1 -C12 烷氧基、C1 -C4 烷基苄氧基、R2 C(O)O取代的C1 -C4 烷氧基；或為苯基，或任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、芳基醯基、雜芳基醯基、X3 R17 、苯基、鹵素原子、CN取代的苯基；或為环氧丙基，其中环氧基任意地与C1 -C4 烷基醛、酮缩合；X3 選自O、S或NR22 ；Ar2 選自：通過X1 與Ar1 相連接的C6 -C20 亞芳基、通過X1 與Ar1 相連接的C3 -C20 亞雜芳基；或通過X1 與Ar1 相連接時，與X1 鄰位的Ar2 碳原子以直鍵、碳原子、羰基、O、S、NR18 與Ar1 相連接構成環狀結構；X1 由下列所構成的群組選出：O、S、NR18 或Y2 -Z1 -Y2 ；Y1由下列所構成的群組選出： (CH2 )m CR15 R16 、NR19 、O(CR15 R16 )m 、S(CR15 R16 )m 、(CR15 R16 )m C=O及S=O，m為0或1；Z1 由下列所構成的群組選出：C1 -C10 直鏈亞烷基、C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 支鏈亞烷基、無取代基的C6 -C20 亞芳基、及有取代基的C6 -C20 亞芳基；Y2 由下列所構成的群組選出：O、S、NR18 及O-C(O)；R1 由下列所構成的群組選出：氫原子、C1 -C18 烷基、二苯基膦醯基，二(C1 -C4 烷氧基)膦醯基；或任意被一個或多個C3 -C7 環烷基、苯基、OR20 、SR21 、NR22 R23 所取代的C2 -C18 烷基，其中，C2 -C18 烷基的苯基被任意一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代；或被C3 -C7 亞環烷基、亞苯基、O、S、NR22 所***的C2 -C18 烷基；C3 -C8 環烷基、CN、NO2 、苯基；或任意一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代的苯基；或C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或多個鹵素原子、C1 -C4 烷基、C5 環烷基、C6 環烷基、苯基、CN、 OH、X3 R20 所取代；或C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或多個的亞苯基、X3 ***；或苯基未被取代的苯甲醯基、苯氧基羰基；或苯基被任意一個或多個鹵素原子、C1 -C4 烷基、C5 環烷基、C6 環烷基、苯基、CN、OH、X2 R20 所取代的苯甲醯基、苯氧基羰基；R15 、R16 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、羧基所取代的C1 -C5 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基其中之一；或任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C2 -C18 烷基；或被C5 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；或任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基取代的C2 -C4 烷基醯基、苯甲醯基、XR17 、鹵素原子、CN所取代的苯基；R17 為C1 -C4 烷基；R18 、R19 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、 R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基其中之一；或任意被一個或多個鹵素原子、C1 -C4 烷基、C3 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C1 -C18 烷基；或任意被一個或多個C3 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；或任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；或任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基所取代的C2 -C4 烷基醯基、芳基醯基、XR17 、苯基、鹵素原子、CN所取代的苯基；R20 、R21 、R22 、R23 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C3 -C7 環烷基其中之一；或被鹵素、CN、C1 -C4 烷氧基所取代的C1 -C18 烷基；或被一個或多個氧原子、C5 -C7 亞環烷基、亞苯基所***的C2 -C18 烷基；或被苯基、C3 -C7 環烷基所取代的C1 -C3 烷基；或苯基、萘基、苯甲醯基；或任意被鹵素、C1 -C4 烷基、C1 -C4 烷氧基、C1 -C4 烷基硫基、苯氧基、苯硫基、NR24 R25 、C1 -C12 烷基醯基、苯甲醯基所取代的苯基、萘基、苯甲醯基；R24 、R25 各自為C1 -C4 烷基；或NR24 R25 一起为嗎福林(morpholine)， 哌啶(piperidine)，哌啶(piperazine)，N-甲基哌啶(N-methyl piperazine)，吡咯(pyrrole)。The invention further proposes an asymmetric diketone compound, as shown in the structural formula IV: Wherein Ar 1 is selected from a C 6 -C 20 o-arylene or C 3 -C 20 o-heteroaryl group substituted by X 1 , a C 6 -C 20 o-arylene group or a C 3 -C 20 sub- The heteroaryl group is bonded to Y 1 and a carbonyl group by two adjacent atoms to form a ring structure, and the substituents on the remaining atoms are each selected from the group consisting of a hydrogen atom, a halogen atom, and a C 1 -C 12 alkyl group. , C 5 -C 7 cycloalkyl, C 5 -C 7 cycloalkyl substituted C 1 -C 4 alkyl, C 1- C 12 alkoxy, C 1 -C 4 alkylbenzyl group, C 1- C 3 alkylenedioxy, R 2 C(O)O, C 1 -C 12 alkylthio, C 1 -C 4 alkylphenylthio, CN, carboxyl, C 1 -C 12 alkane Oxycarbonyl, arylcarbonyl, heteroarylcarbonyl, X 3 R 18 , C 1 -C 4 alkylphenoxy, C1-C8 alkylnonylphenoxy, C 5 -C 6 cycloalkylindolyl Phenoxy, C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkyl nonylphenoxy, aryl nonylphenoxy, heteroarylnonylphenoxy, R 2 C(O) O-substituted C 1 -C 4 alkylthio, C 1 -C 4 alkylphenylthio, C 1 -C 8 alkylmercaptophenylthio, C 5 -C 6 cycloalkylnonylphenylthio , C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkylmercaptophenylthio, aromatic a fluorenyl phenylthio group, a heteroaryl fluorenyl phenylthio group; or substituted by one or more C 1 -C 12 alkoxy groups, C 1 -C 4 alkylbenzyloxy groups, R 2 C(O)O C 1 -C 4 alkoxy; or phenyl, or optionally substituted by one or more C 1 -C 4 alkyl, carboxyl, C 1 -C 12 alkyl fluorenyl, aryl fluorenyl, heteroaryl An fluorenyl group, X 3 R 17 , a phenyl group, a halogen atom, a CN-substituted phenyl group; or a glycidyl group in which an epoxy group is arbitrarily condensed with a C 1 -C 4 alkyl aldehyde, a ketone; X 3 is selected from O, S or NR 22; Ar 2 is selected from: and X 1 through Ar 1 C connected 6 -C 20 arylene group, and X 1 through Ar C 3 -C 20 heteroarylene group 1 is connected; or When X 1 is bonded to Ar 1 , the Ar 2 carbon atom ortho to X 1 is bonded to a straight bond, a carbon atom, a carbonyl group, O, S, NR 18 and Ar 1 to form a cyclic structure; X 1 is as follows: The group formed consists of: O, S, NR 18 or Y 2 -Z 1 -Y 2 ; Y1 is selected from the group consisting of: (CH 2 ) m CR 15 R 16 , NR 19 , O (CR 15 R 16 ) m , S(CR 15 R 16 ) m , (CR 15 R 16 ) m C=O and S=O, m is 0 or 1; Z 1 is selected from the group consisting of C 1 -C 10 linear alkylene, C 1 -C 10 Alkylene group, substituted with one or more oxygen atom or sulfur atom attached to the end groups C 1 -C 10 straight chain alkylene group, an oxygen atom or a sulfur atom attached to a terminal group or a C 1 -C more a 10- branched alkylene group, a C 2 -C 10 linear alkylene group inserted by one or more oxygen atoms or sulfur atoms, a C 2 -C 10 branch inserted by one or more oxygen atoms or sulfur atoms a chain alkylene group, an unsubstituted C 6 -C 20 arylene group, and a substituted C 6 -C 20 arylene group; Y 2 is selected from the group consisting of O, S, NR 18 and OC(O); R 1 is selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a diphenylphosphinofluorenyl group, a di(C 1 -C 4 alkoxy)phosphonium group; Any C 2 -C 18 alkyl group substituted by one or more C 3 -C 7 cycloalkyl, phenyl, OR 20 , SR 21 , NR 22 R 23 wherein C 2 -C 18 alkyl benzene Any one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkoxy , aryloxy substituted; or C 2 -C 18 alkyl inserted by C 3 -C 7 cycloalkylene, phenylene, O, S, NR 22 ; C 3 -C 8 ring Alkyl, CN, NO 2 , phenyl; or any one or more of halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN a C 1 -C 4 alkyl alkoxy group, an aryloxy group-substituted phenyl group; or a C 1 -C 12 alkyl group, a C 1 -C 12 alkoxycarbonyl group, wherein the alkyl group is optionally one or more Halogen atom, C 1 -C 4 alkyl group, C 5 cycloalkyl group, C 6 cycloalkyl group, phenyl group, CN, OH, X 3 R 20 substituted; or C 1 -C 12 alkyl fluorenyl group, C 1 a -C 12 alkoxycarbonyl group, wherein the alkyl group is optionally interrupted by one or more phenylene groups, X 3 ; or a phenyl unsubstituted benzylidene group, a phenoxycarbonyl group; or a phenyl group is optionally a plurality of halogen atoms, C 1 -C 4 alkyl group, C 5 cycloalkyl group, C 6 cycloalkyl group, phenyl group, CN, OH, X 2 R 20 substituted benzamyl group, phenoxycarbonyl group; R 15 and R 16 are each independently selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a C 1 -C 5 alkyl group substituted by a carboxyl group, and a C 1 -C 4 alkoxyfluorenyl group. substituted C 1 -C 5 alkyl group, R 2 C (O) O substituted C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, phenyl wherein one; or any Substituted with one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyl group, an aryl a C 2 -C 18 alkyl group substituted by a methoxy group; or a C 2 -C 18 alkyl group inserted by a C 5 -C 7 cycloalkylene group, a phenylene group, O, S, NR 17 ; Or a plurality of C 1 -C 4 alkyl groups, a phenyl group, a halogen atom, a C 5 -C 7 cycloalkyl group substituted by CN; or optionally one or more C 1 -C 4 alkyl groups, C 1 -C 4 Alkoxy, carboxy, C 1 -C 12 alkyl fluorenyl, C 5 -C 6 cycloalkylcarbenyl, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkyl fluorenyl, benzo a thiol group, XR 17 , a halogen atom, a phenyl group substituted by CN; R 17 is a C 1 -C 4 alkyl group; and R 18 and R 19 are each independently selected from the group consisting of a hydrogen atom, C 1 - C 18 alkyl, C 1 -C 4 alkoxy substituted acyl C 1 -C 5 alkyl group, R 2 C (O) O substituted C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl One of an alkyl group and a phenyl group; or any one or more halogen atoms, a C 1 -C 4 alkyl group, a C 3 -C 7 cycloalkyl group, a heterocycloalkyl group, a phenyl group, a heteroaryl group, CN, C 1 -C 4 alkanoyl group, an aryl acyl oxygen Substituted C 1 -C 18 alkyl; or optionally substituted with one or more C 3 -C 7 cycloalkylene, phenylene, O, S, NR 17 inserted C 2 -C 18 alkyl; or Any C 5 -C 7 cycloalkyl group substituted by one or more C 1 -C 4 alkyl groups, phenyl groups, halogen atoms, CN; or optionally by one or more C 1 -C 4 alkyl groups, carboxyl groups, alkyl C 1 -C 12 acyl, C 5 -C 6 cycloalkyl methyl acyl, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkyl acyl, aryl acyl, XR 17 a phenyl group, a halogen atom, a phenyl group substituted by CN; R 20 , R 21 , R 22 and R 23 are each independently selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a C 3 group ; One of -C 7 cycloalkyl groups; or a C 1 -C 18 alkyl group substituted by halogen, CN, C 1 -C 4 alkoxy; or by one or more oxygen atoms, C 5 -C 7 a C 2 -C 18 alkyl group in which a cycloalkyl group or a phenylene group is inserted; or a C 1 -C 3 alkyl group substituted by a phenyl group or a C 3 -C 7 cycloalkyl group; or a phenyl group, a naphthyl group, or a benzene group; Mercapto; or optionally halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenoxy, phenylthio, NR 24 R 25 , C 1 -C 12 alkoxy Acyl, benzoyl substituted phenyl group, a naphthyl group, a benzoyl group; R 24, R 25 are each C 1 -C 4 alkyl; or NR 24 R 25 together are you phenylephrine (morpholine), Piperidine, piperazine, N-methyl piperazine, pyrrole.

一種酮肟化合物，如結構通式V化合物： 其中，Ar1 選自被X1 所取代的C6 -C20 鄰亞芳基或C3 -C20 鄰亞雜芳基，C6 -C20 鄰亞芳基或C3 -C20 鄰亞雜芳基以相鄰的兩個原子與Y1 和羰基相連構成並環結構，其餘原子上的取代基各自由下列所構成的群組選出：氫原子、鹵素原子、C1 -C12 烷基、C5 -C7 環烷基、C5 -C7 環烷基所取代的C1 -C4 烷基、C1- C12 烷氧基、C1 -C4 烷基苄氧基、C1 -C3 亞烷基二氧基、R2 C(O)O、C1 -C12 烷基硫基、C1 -C4 烷基苯硫基、CN、羧基、C1 -C12 烷氧基羰基、芳基羰基、雜芳基羰基、X3 R18 、C1 -C4 烷基苯氧基、C1-C8烷基醯基苯氧基、C5 -C6 環烷基醯基苯氧基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯氧基、芳基醯基苯氧基、雜芳基醯基苯氧基、R2 C(O)O取代的C1 -C4 烷基硫基、C1 -C4 烷基苯硫基、C1 -C8 烷基醯基苯硫基、C5 -C6 環烷基醯基苯硫基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯硫基、芳基醯基苯硫基、雜芳基醯基苯硫基；或被一個或多個C1 -C12 烷氧基、C1 -C4 烷基苄氧基、R2 C(O)O取代的C1 -C4 烷氧基； 或為苯基，或任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、芳基醯基、雜芳基醯基、X3 R17 、苯基、鹵素原子、CN取代的苯基；環氧丙基，其中環氧基任意地與C1 -C4 烷基醛、酮縮合；X3 選自下列所構成的群組O、S或NR22 ；Ar2 選自：通過X1 與Ar1 相連接的C6 -C20 亞芳基、通過X1 與Ar1 相連接的C3 -C20 亞雜芳基；或通過X1 與Ar1 相連接時，與X1 鄰位的Ar2 碳原子以直鍵、碳原子、羰基、O、S、NR18 與Ar1 相連接構成環狀結構；X1 由下列所構成的群組選出：O、S、NR18 或Y2 -Z1 -Y2 ；Y1由下列所構成的群組選出：(CH2 )m CR15 R16 、NR19 、O(CR15 R16 )m 、S(CR15 R16 )m 、(CR15 R16 )m C=O及S=O，m為0或1；Z1 由下列所構成的群組選出：C1 -C10 直鏈亞烷基、C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 支鏈亞烷基、無取代基的C6 -C20 亞芳基、或有取代基的C6 -C20 亞芳基；Y2 由下列所構成的群組選出：O、S、NR18 或O-C(O)； R1 由下列所構成的群組選出：氫原子、C1 -C18 烷基、二苯基膦醯基，二(C1 -C4 烷氧基)膦醯基；或任意被一個或多個C3 -C7 環烷基、苯基、OR20 、SR21 、NR22 R23 所取代的C2 -C18 烷基，其中，C2 -C18 烷基的苯基被任意一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代；或被C3 -C7 亞環烷基、亞苯基、O、S、NR22 所***的C2 -C18 烷基；C3 -C8 環烷基、CN、NO2 、苯基；或任意一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代的苯基；或C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或多個鹵素原子、C1 -C4 烷基、C5 環烷基、C6 環烷基、苯基、CN、OH、X3 R20 所取代；或C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或多個的亞苯基、X3 ***；或苯基未被取代的苯甲醯基、苯氧基羰基；或苯基被任意一個或多個鹵素原子、C1 -C4 烷基、C5 環烷基、C6 環烷基、苯基、CN、OH、X2 R20 所取代的苯甲醯基、苯氧基羰基；R15 、R16 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、羧基所取代的C1 -C5 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基其中之一； 或任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C2 -C18 烷基；或被C5 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；或任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；或任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基取代的C2 -C4 烷基醯基、苯甲醯基、XR17 、鹵素原子、CN所取代的苯基；R17 為C1 -C4 烷基；R18 、R19 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基其中之一；或任意被一個或多個鹵素原子、C1 -C4 烷基、C3 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C1 -C18 烷基；或任意被一個或多個C3 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；或任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；或任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基所取代的C2 -C4 烷基醯基、芳基醯基、 XR17 、苯基、鹵素原子、CN所取代的苯基；R20 、R21 、R22 、R23 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C3 -C7 環烷基其中之一；或被鹵素、CN、C1 -C4 烷氧基所取代的C1 -C18 烷基；或被一個或多個氧原子、C5 -C7 亞環烷基、亞苯基所***的C2 -C18 烷基；或被苯基、C3 -C7 環烷基所取代的C1 -C3 烷基；或苯基、萘基、苯甲醯基；或任意被鹵素、C1 -C4 烷基、C1 -C4 烷氧基、C1 -C4 烷基硫基、苯氧基、苯硫基、NR24 R25 、C1 -C12 烷基醯基、苯甲醯基所取代的苯基、萘基、苯甲醯基；R24 、R25 各自為C1 -C4 烷基；或NR24 R25 一起为嗎福林(morpholine)，哌啶(piperidine)，哌啶(piperazine)，N-甲基哌啶(N-methyl piperazine)，吡咯(pyrrole)。A ketoxime compound, such as a compound of formula V: Wherein Ar 1 is selected from a C 6 -C 20 o-arylene or C 3 -C 20 o-heteroaryl group substituted by X 1 , a C 6 -C 20 o-arylene group or a C 3 -C 20 sub- The heteroaryl group is bonded to Y 1 and a carbonyl group by two adjacent atoms to form a ring structure, and the substituents on the remaining atoms are each selected from the group consisting of a hydrogen atom, a halogen atom, and a C 1 -C 12 alkyl group. , C 5 -C 7 cycloalkyl, C 5 -C 7 cycloalkyl substituted C 1 -C 4 alkyl, C 1- C 12 alkoxy, C 1 -C 4 alkylbenzyl group, C 1- C 3 alkylenedioxy, R 2 C(O)O, C 1 -C 12 alkylthio, C 1 -C 4 alkylphenylthio, CN, carboxyl, C 1 -C 12 alkane Oxycarbonyl, arylcarbonyl, heteroarylcarbonyl, X 3 R 18 , C 1 -C 4 alkylphenoxy, C1-C8 alkylnonylphenoxy, C 5 -C 6 cycloalkylindolyl Phenoxy, C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkyl nonylphenoxy, aryl nonylphenoxy, heteroarylnonylphenoxy, R 2 C(O) O-substituted C 1 -C 4 alkylthio, C 1 -C 4 alkylphenylthio, C 1 -C 8 alkylmercaptophenylthio, C 5 -C 6 cycloalkylnonylphenylthio , C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkylmercaptophenylthio, aromatic a fluorenyl phenylthio group, a heteroaryl fluorenyl phenylthio group; or substituted by one or more C 1 -C 12 alkoxy groups, C 1 -C 4 alkylbenzyloxy groups, R 2 C(O)O C 1 -C 4 alkoxy; or a phenyl group, or optionally substituted by one or more C 1 -C 4 alkyl groups, carboxyl groups, C 1 -C 12 alkyl fluorenyl groups, aryl fluorenyl groups, heteroaryl groups Anthracenyl, X 3 R 17 , phenyl, halogen atom, CN substituted phenyl; epoxy propyl group, wherein the epoxy group is arbitrarily condensed with a C 1 -C 4 alkyl aldehyde, a ketone; X 3 is selected from the following the group consisting of O, S or NR 22; Ar 2 is selected from: and X 1 through Ar 1 C connected 6 -C 20 arylene group, and X 1 through Ar C 3 -C 20 heteroarylene 1 connected An aryl group; or when X 1 is bonded to Ar 1 , an Ar 2 carbon atom ortho to X 1 is bonded to a straight bond, a carbon atom, a carbonyl group, O, S, NR 18 and Ar 1 to form a cyclic structure; 1 is selected from the group consisting of: O, S, NR 18 or Y 2 -Z 1 -Y 2 ; Y1 is selected from the group consisting of: (CH 2 ) m CR 15 R 16 , NR 19 , O (CR 15 R 16 ) m , S(CR 15 R 16 ) m , (CR 15 R 16 ) m C=O and S=O, m is 0 or 1; Z 1 is selected from the group consisting of: C 1 -C 10 straight chain alkylene Group, C 1 -C 10 branched alkylene, substituted by one or more oxygen atom or sulfur atom attached to the end groups C 1 -C 10 straight chain alkylene group, are connected one or more oxygen atom or sulfur atom, the end groups C 1 -C 10 branched alkylene, substituted by one or more oxygen atoms or sulfur atom inserted straight chain C 2 -C 10 alkylene group, substituted with one or more oxygen atom or a sulfur atom An inserted C 2 -C 10 branched alkylene group, an unsubstituted C 6 -C 20 arylene group, or a substituted C 6 -C 20 arylene group; Y 2 is selected from the group consisting of :O, S, NR 18 or OC(O); R 1 is selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a diphenylphosphinium group, and a di(C 1 -C 4 alkane). An oxy)phosphonium group; or any C 2 -C 18 alkyl group substituted by one or more C 3 -C 7 cycloalkyl groups, phenyl, OR 20 , SR 21 , NR 22 R 23 , wherein C A 2- C 18 alkyl phenyl group is optionally substituted with one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyl group, an aryloxy group, a substituted acyl; or C 3 -C 7 inserted cycloalkylene, phenylene, O, S, NR 22 C 2 -C 18 Group; C 3 -C 8 cycloalkyl, CN, NO 2, phenyl; or any one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, a phenyl group, a heteroaryl group, a CN, a C 1 -C 4 alkyl alkoxy group, an aryloxy group-substituted phenyl group; or a C 1 -C 12 alkyl group, a C 1 -C 12 alkoxycarbonyl group, wherein The alkyl group is optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 cycloalkyl, C 6 cycloalkyl, phenyl, CN, OH, X 3 R 20 ; or C 1 -C a 12 alkyl fluorenyl group, a C 1 -C 12 alkoxycarbonyl group, wherein the alkyl group is optionally interrupted by one or more phenylene groups, X 3 ; or a phenyl unsubstituted benzylidene group, a phenoxycarbonyl group Or a benzamidine in which a phenyl group is substituted with any one or more halogen atoms, C 1 -C 4 alkyl, C 5 cycloalkyl, C 6 cycloalkyl, phenyl, CN, OH, X 2 R 20 And phenoxycarbonyl; R 15 and R 16 are each independently selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a C 1 -C 5 alkyl group substituted by a carboxyl group, and C 1 - acyl C 4 alkoxy substituted C 1 -C 5 alkyl group, R 2 C (O) O substituted C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, phenyl which One; or optionally substituted with one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkoxy a C 2 -C 18 alkyl group substituted with a decyloxy group or an aryloxy group; or a C 2 -C 18 alkane inserted by a C 5 -C 7 cycloalkylene group, a phenylene group, an O, S, or NR 17 Or any C 5 -C 7 cycloalkyl substituted by one or more C 1 -C 4 alkyl, phenyl, halogen atom, CN; or optionally C 1 -C 4 alkyl , C 1 -C 4 alkoxy, carboxy, C 1 -C 12 alkylfluorenyl, C 5 -C 6 cycloalkylcarbenyl, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkane A phenyl group substituted with a fluorenyl group, a benzamidine group, an XR 17 group, a halogen atom, or a CN; R 17 is a C 1 -C 4 alkyl group; and R 18 and R 19 are each independently selected from the group consisting of: a hydrogen atom, C 1 -C 18 alkyl, C 1 -C 4 alkoxy substituted acyl C 1 -C 5 alkyl group, R 2 C (O) O substituted C 1 -C 4 alkyl, One of C 5 -C 7 cycloalkyl, phenyl; or optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkoxy Group, aryloxy group, acyl substituted C 1 -C 18 alkyl; or optionally substituted with one or more C 3 -C 7 cycloalkylene, phenylene, O, S, NR 17 C 2 inserted -C 18 alkyl; or any C 5 -C 7 cycloalkyl substituted by one or more C 1 -C 4 alkyl, phenyl, halogen atom, CN; or optionally by one or more C 1 - C 4 alkyl group, carboxyl group, C 1 -C 12 alkyl fluorenyl group, C 5 -C 6 cycloalkylcarbenyl group, C 2 -C 4 alkyl fluorenyl group substituted by C 5 -C 6 cycloalkyl group, An arylsulfonyl group, XR 17 , a phenyl group, a halogen atom, a phenyl group substituted by CN; R 20 , R 21 , R 22 and R 23 are each independently selected from the group consisting of hydrogen atom, C 1 - One of C 18 alkyl, C 3 -C 7 cycloalkyl; or C 1 -C 18 alkyl substituted by halogen, CN, C 1 -C 4 alkoxy; or by one or more oxygen atoms a C 5 -C 7 cycloalkylene group, a C 2 -C 18 alkyl group in which a phenylene group is inserted; or a C 1 -C 3 alkyl group substituted by a phenyl group or a C 3 -C 7 cycloalkyl group; Phenyl, naphthyl, benzhydryl; or optionally halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenoxy, phenylthio NR 24 R 25 , C 1 -C 12 alkyl fluorenyl, phenyl, naphthyl, benzhydryl substituted with benzylidene; R 24 and R 25 are each C 1 -C 4 alkyl; or NR 24 R 25 together is morpholine, piperididine, piperazine, N-methyl piperazine, pyrrole.

本發明再提出一種不對稱二肟酯化合物的中間體，為二酮肟化合物，包含下列結構式Ⅵ及Ⅶ化合物所構成群組之其中之一： 其中，Ar1 選自被X1 所取代的C6 -C20 鄰亞芳基或C3 -C20 鄰亞雜芳基，C6 -C20 鄰亞芳基或C3 -C20 鄰亞雜芳基以相鄰的兩個原子與Y1 和羰基相連構 成並環結構，其餘原子上的取代基各自由下列所構成的群組選出：氫原子、鹵素原子、C1 -C12 烷基、C5 -C7 環烷基、C5 -C7 環烷基所取代的C1 -C4 烷基、C1- C12 烷氧基、C1 -C4 烷基苄氧基、C1 -C3 亞烷基二氧基、R2 C(O)O、C1 -C12 烷基硫基、C1 -C4 烷基苯硫基、CN、羧基、C1 -C12 烷氧基羰基、芳基羰基、雜芳基羰基、X3 R18 、C1 -C4 烷基苯氧基、C1-C8烷基醯基苯氧基、C5 -C6 環烷基醯基苯氧基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯氧基、芳基醯基苯氧基、雜芳基醯基苯氧基、R2 C(O)O取代的C1 -C4 烷基硫基、C1 -C4 烷基苯硫基、C1 -C8 烷基醯基苯硫基、C5 -C6 環烷基醯基苯硫基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯硫基、芳基醯基苯硫基、雜芳基醯基苯硫基；或被一個或多個C1 -C12 烷氧基、C1 -C4 烷基苄氧基、R2 C(O)O取代的C1 -C4 烷氧基；或苯基及任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、芳基醯基、雜芳基醯基、X3 R17 、苯基、鹵素原子、CN取代的苯基；或環氧丙基，其中環氧基任意地與C1 -C4 烷基醛、酮縮合；X3 選自O、S或NR22 ；Ar2 選自：通過X1 與Ar1 相連接的C6 -C20 亞芳基、通過X1 與Ar1 相連接的C3 -C20 亞雜芳基；或通過X1 與Ar1 相連接時，與X1 鄰位的Ar2 碳原子以直鍵、碳 原子、羰基、O、S、NR18 與Ar1 相連接構成環狀結構；X1 由下列所構成的群組選出：O、S、NR18 或Y2 -Z1 -Y2 ；Y1由下列所構成的群組選出：(CH2 )m CR15 R16 、NR19 、O(CR15 R16 )m 、S(CR15 R16 )m 、(CR15 R16 )m C=O及S=O，m為0或1；Z1 由下列所構成的群組選出：C1 -C10 直鏈亞烷基、C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 支鏈亞烷基、無取代基的C6 -C20 亞芳基、或有取代基的C6 -C20 亞芳基；Y2 由下列所構成的群組選出：O、S、NR18 或O-C(O)；R1 由下列所構成的群組選出：氫原子、C1 -C18 烷基、二苯基膦醯基，二(C1 -C4 烷氧基)膦醯基；或任意被一個或多個C3 -C7 環烷基、苯基、OR20 、SR21 、NR22 R23 所取代的C2 -C18 烷基，其中，C2 -C18 烷基的苯基被任意一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代；或被C3 -C7 亞環烷基、亞苯基、O、S、NR22 所***的C2 -C18 烷基；C3 -C8 環烷基、CN、NO2 、苯基；或任意一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷 基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代的苯基；或C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或多個鹵素原子、C1 -C4 烷基、C5 環烷基、C6 環烷基、苯基、CN、OH、X3 R20 所取代；或C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或多個的亞苯基、X3 ***；或苯基未被取代的苯甲醯基、苯氧基羰基；或苯基被任意一個或多個鹵素原子、C1 -C4 烷基、C5 環烷基、C6 環烷基、苯基、CN、OH、X2 R20 所取代的苯甲醯基、苯氧基羰基；R15 、R16 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、羧基所取代的C1 -C5 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基其中之一；或任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C2 -C18 烷基；或被C5 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；或任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基取代的C2 -C4 烷基醯基、苯甲醯基、XR17 、鹵素原子、CN所取代的苯基； R17 為C1 -C4 烷基；R18 、R19 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基其中之一；或任意被一個或多個鹵素原子、C1 -C4 烷基、C3 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C1 -C18 烷基；或任意被一個或多個C3 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；或任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；或任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基所取代的C2 -C4 烷基醯基、芳基醯基、XR17 、苯基、鹵素原子、CN所取代的苯基；R20 、R21 、R22 、R23 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C3 -C7 環烷基其中之一；或被鹵素、CN、C1 -C4 烷氧基所取代的C1 -C18 烷基；或被一個或多個氧原子、C5 -C7 亞環烷基、亞苯基所***的C2 -C18 烷基；或被苯基、C3 -C7 環烷基所取代的C1 -C3 烷基；或苯基、萘基、苯甲醯基；或任意被鹵素、C1 -C4 烷基、C1 -C4 烷氧基、C1 -C4 烷基硫基、苯 氧基、苯硫基、NR24 R25 、C1 -C12 烷基醯基、苯甲醯基所取代的苯基、萘基、苯甲醯基；R24 、R25 各自為C1 -C4 烷基；或NR24 R25 一起为嗎福林(morpholine)，哌啶(piperidine)，哌啶(piperazine)，N-甲基哌啶(N-methyl piperazine)，吡咯(pyrrole)。The invention further provides an intermediate of an asymmetric diterpene ester compound, which is a diketone oxime compound, comprising one of the group consisting of the following compounds of the formula VI and VII: Wherein Ar 1 is selected from a C 6 -C 20 o-arylene or C 3 -C 20 o-heteroaryl group substituted by X 1 , a C 6 -C 20 o-arylene group or a C 3 -C 20 sub- The heteroaryl group is bonded to Y 1 and a carbonyl group by two adjacent atoms to form a ring structure, and the substituents on the remaining atoms are each selected from the group consisting of a hydrogen atom, a halogen atom, and a C 1 -C 12 alkyl group. , C 5 -C 7 cycloalkyl, C 5 -C 7 cycloalkyl substituted C 1 -C 4 alkyl, C 1- C 12 alkoxy, C 1 -C 4 alkylbenzyl group, C 1- C 3 alkylenedioxy, R 2 C(O)O, C 1 -C 12 alkylthio, C 1 -C 4 alkylphenylthio, CN, carboxyl, C 1 -C 12 alkane Oxycarbonyl, arylcarbonyl, heteroarylcarbonyl, X 3 R 18 , C 1 -C 4 alkylphenoxy, C1-C8 alkylnonylphenoxy, C 5 -C 6 cycloalkylindolyl Phenoxy, C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkyl nonylphenoxy, aryl nonylphenoxy, heteroarylnonylphenoxy, R 2 C(O) O-substituted C 1 -C 4 alkylthio, C 1 -C 4 alkylphenylthio, C 1 -C 8 alkylmercaptophenylthio, C 5 -C 6 cycloalkylnonylphenylthio , C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkylmercaptophenylthio, aromatic a fluorenyl phenylthio group, a heteroaryl fluorenyl phenylthio group; or substituted by one or more C 1 -C 12 alkoxy groups, C 1 -C 4 alkylbenzyloxy groups, R 2 C(O)O C 1 -C 4 alkoxy; or phenyl and optionally by one or more C 1 -C 4 alkyl, carboxy, C 1 -C 12 alkyl fluorenyl, aryl fluorenyl, heteroaryl fluorenyl , X 3 R 17 , phenyl, halogen atom, CN substituted phenyl; or epoxy propyl group, wherein the epoxy group is arbitrarily condensed with a C 1 -C 4 alkyl aldehyde, a ketone; X 3 is selected from O, S or NR 22; Ar 2 is selected from: and X 1 through Ar 1 C connected 6 -C 20 arylene group, and X 1 through Ar C 3 -C 20 heteroarylene group 1 is connected; or by X 1 When it is bonded to Ar 1 , the Ar 2 carbon atom ortho to X 1 is bonded to a straight bond, a carbon atom, a carbonyl group, O, S, NR 18 and Ar 1 to form a cyclic structure; X 1 is composed of the following group; The group is selected: O, S, NR 18 or Y 2 -Z 1 -Y 2 ; Y1 is selected from the group consisting of: (CH 2 ) m CR 15 R 16 , NR 19 , O(CR 15 R 16 ) m , S(CR 15 R 16 ) m , (CR 15 R 16 ) m C=O and S=O, m is 0 or 1; Z 1 is selected from the group consisting of C 1 -C 10 straight chain alkyl group, C 1 -C 10 branched alkylene Group, with one or more oxygen atom or sulfur atom attached to the end groups C 1 -C 10 straight chain alkylene group, are connected in end groups one or more oxygen atom or a sulfur atom, C 1 -C 10 branched alkylene group, substituted with one or more oxygen atoms or sulfur atom inserted C 2 -C 10 linear alkylene, the alkylene is one or more oxygen atom or sulfur atom inserted branched C 2 -C 10 group, a group of unsubstituted C 6 -C 20 arylene group, or an optionally substituted C 6 -C 20 arylene group; Y 2 by the group selected consisting of the following: O, S, NR 18, or OC (O R 1 is selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a diphenylphosphinofluorenyl group, a di(C 1 -C 4 alkoxy)phosphonium group; or any one Or a C 2 -C 18 alkyl group substituted by a C 3 -C 7 cycloalkyl group, a phenyl group, OR 20 , SR 21 , NR 22 R 23 , wherein the phenyl group of the C 2 -C 18 alkyl group is optionally One or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkoxy, aryl Oxy-substituted; or C 2 -C 18 alkyl group inserted by C 3 -C 7 cycloalkylene, phenylene, O, S, NR 22 ; C 3 -C 8 cycloalkyl, C N, NO 2 , phenyl; or any one or more of halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 a -C 4 alkyl alkoxy group, an aryloxy group-substituted phenyl group; or a C 1 -C 12 alkylfluorenyl group, a C 1 -C 12 alkoxycarbonyl group, wherein the alkyl group is optionally subjected to one or more halogen atoms, C 1 -C 4 alkyl, C 5 cycloalkyl, C 6 cycloalkyl, phenyl, CN, OH, X 3 R 20 substituted; or C 1 -C 12 alkyl fluorenyl, C 1 -C 12 An alkoxycarbonyl group wherein the alkyl group is optionally interrupted by one or more phenylene groups, X 3 ; or a phenyl unsubstituted benzylidene group, a phenoxycarbonyl group; or a phenyl group by any one or more halogens Atom, C 1 -C 4 alkyl, C 5 cycloalkyl, C 6 cycloalkyl, phenyl, CN, OH, X 2 R 20 substituted benzinyl, phenoxycarbonyl; R 15 , R 16 are each independently selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a C 1 -C 5 alkyl group substituted by a carboxyl group, and a C 1 -C 4 alkoxyfluorenyl group substituted by C 1 -C 5 alkyl, R 2 C(O)O substituted C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, phenyl one; or optionally Or a plurality of halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkoxy, aryloxy a C 2 -C 18 alkyl group substituted by a group; or a C 2 -C 18 alkyl group inserted by a C 5 -C 7 cycloalkylene group, a phenylene group, O, S, NR 17 ; optionally one or more a C 1 -C 4 alkyl group, a phenyl group, a halogen atom, a C 5 -C 7 cycloalkyl group substituted by CN; or optionally one or more C 1 -C 4 alkyl groups, C 1 -C 4 alkoxy Base, carboxyl group, C 1 -C 12 alkyl fluorenyl group, C 5 -C 6 cycloalkylcarbenyl group, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkyl fluorenyl group, benzamyl group , XR 17 , a halogen atom, a phenyl group substituted by CN; R 17 is a C 1 -C 4 alkyl group; and R 18 and R 19 are each independently selected from the group consisting of hydrogen atom, C 1 -C 18 Alkyl, C 1 -C 4 alkoxyfluorenyl substituted C 1 -C 5 alkyl, R 2 C(O)O substituted C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl One of the phenyl groups; or optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkyl alkoxy, aryloxy substituted C 1 -C 18 alkyl; or any C 2 -C 18 alkyl group inserted by one or more C 3 -C 7 cycloalkylene, phenylene, O, S, NR 17 ; or optionally One or more C 1 -C 4 alkyl groups, a phenyl group, a halogen atom, a C 5 -C 7 cycloalkyl group substituted by CN; or optionally one or more C 1 -C 4 alkyl groups, a carboxyl group, C 1 -C 12 alkyl fluorenyl, C 5 -C 6 cycloalkylcarbenyl, C 2 -C 4 alkyl fluorenyl substituted by C 5 -C 6 cycloalkyl, aryl fluorenyl, XR 17 , benzene a phenyl group substituted with a halogen atom and a CN; R 20 , R 21 , R 22 and R 23 are each independently selected from the group consisting of hydrogen atom, C 1 -C 18 alkyl group, C 3 -C One of 7 cycloalkyl groups; or a C 1 -C 18 alkyl group substituted by halogen, CN, C 1 -C 4 alkoxy group; or one or more oxygen atoms, C 5 -C 7 hypocycloalkane a C 2 -C 18 alkyl group in which a phenylene group is inserted; or a C 1 -C 3 alkyl group substituted by a phenyl group or a C 3 -C 7 cycloalkyl group; or a phenyl group, a naphthyl group, a benzamidine group Or any halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenoxy, phenylthio, NR 24 R 25 , C 1 - C 12 alkyl fluorenyl, a phenyl, naphthyl, benzhydryl group substituted with a benzamidine group; each of R 24 and R 25 is a C 1 -C 4 alkyl group; or NR 24 R 25 together is a morpholine, piperidine ( Piperidine), piperazine, N-methyl piperazine, pyrrole.

本發明再提出一種光固化組合物，含有光引發劑和至少一種可進行自由基聚合的碳碳雙鍵化合物，光引發劑包含至少一種前述的不對稱二肟酯化合物。The invention further provides a photocurable composition comprising a photoinitiator and at least one carbon-carbon double bond compound which is capable of undergoing free radical polymerization, the photoinitiator comprising at least one of the foregoing asymmetric diterpene ester compounds.

本發明再提出一種光固化組合物的應用，先將前述的光固化組合物用於製造帶有顏色的或透明的下列製品之一：塗料、油墨、粘合劑、光致抗蝕劑或光阻劑；再將製品用於印刷、3D列印、顯示器件中彩色濾光片的生產、電子器件封裝、印刷電路板介質層。The invention further proposes the use of a photocurable composition for first producing one of the following colored or transparent articles: a coating, an ink, a binder, a photoresist or light. The resist is used for printing, 3D printing, color filter production in display devices, electronic device packaging, and printed circuit board dielectric layers.

本發明再提出一種光固化組合物的固化方法，將前述的光固化組合物塗布於基材上，用波長為190-600nm的光線照射使塗布層固化。The present invention further provides a method for curing a photocurable composition, which comprises applying the photocurable composition described above to a substrate, and curing the coating layer by irradiation with light having a wavelength of from 190 to 600 nm.

本發明再提出一種以光固化組合物製作凸起圖案的方法，先將前述的光固化組合物用溶劑稀釋；再將稀釋後的光固化組合物塗布於基材上，經烘乾、曝光、顯影方法除去未曝光部分得到凸起圖案。The invention further provides a method for preparing a convex pattern by using a photocurable composition, which first dilutes the photocurable composition with a solvent; then applies the diluted photocurable composition to a substrate, and is dried, exposed, The developing method removes the unexposed portion to obtain a raised pattern.

本發明再提出一種彩色濾光片，包含黑色、紅色、綠色、藍色圖元，由包含前述不對稱二肟酯化合物、光固化單體、鹼溶性樹脂、顏料及添加劑構成的組合物，依序經過塗布、曝光、顯影、熱處理過程而得到。The invention further provides a color filter comprising black, red, green and blue primitives, comprising a composition comprising the asymmetric diterpene ester compound, a photocurable monomer, an alkali soluble resin, a pigment and an additive, The order is obtained by coating, exposure, development, and heat treatment.

本發明再提出一種彩色濾光片的製造方法，包含黑色、紅 色、綠色、藍色圖元，是將含有至少一種前述不對稱二肟酯化合物、光固化單體、鹼溶性樹脂、顏料及添加劑構成的組合物依序進行塗布、曝光、顯影、熱處理，最後得到該彩色濾光片。The invention further provides a method for manufacturing a color filter, which comprises black and red. The color, green, and blue primitives are sequentially coated, exposed, developed, and heat-treated with a composition comprising at least one of the aforementioned asymmetric diterpene ester compound, photocurable monomer, alkali-soluble resin, pigment, and additive. The color filter is obtained.

因此，本發明的主要目的在於提出包含結構通式I的不對稱二肟酯化合物，具有非常優良的光引發活性。Accordingly, it is a primary object of the present invention to provide an asymmetric diterpene ester compound comprising the structural formula I which has very excellent photoinitiating activity.

本發明的又一目的在於提出一種包含由結構通式I的不對稱二肟酯化合物所製成的光固化組合物及其製造方法與相關應用，由於有良好的光引發活性，因此具有很好的感光性能。A further object of the present invention is to provide a photocurable composition comprising the asymmetric diterpene ester compound of the formula I, a method for its production and related applications, which have good photoinitiating activity and therefore have good Photographic performance.

本發明的再一目的在於提出包含結構通式I的不對稱二肟酯化合物所製成的彩色濾光片及製造方法，以結構通式I化合物所製造的彩色濾光片具有非常良好的光學特性。A further object of the present invention is to provide a color filter and a method for producing the asymmetric diterpene ester compound of the formula I having a color filter having a very good optical structure. characteristic.

系列1：結構通式I化合物，表示如下： 其中，Ar1 為被X1 取代的C6 -C20 鄰亞芳基或C3 -C20 鄰亞雜芳基，C6 -C20 鄰亞芳 基或C3 -C20 鄰亞雜芳基以相鄰的兩個原子與Y1 和羰基相連構成並環結構，其餘原子上的取代基各自為：氫原子、鹵素原子、C1 -C12 烷基、C5 -C7 環烷基、C5 -C7 環烷基取代的C1 -C4 烷基、C1 -C12 烷氧基其中之一；或被一個或多個C1 -C12 烷氧基、C1 -C4 烷基苄氧基、R2 C(O)O取代的C1 -C4 烷氧基；或為苯基；或任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、芳基醯基、雜芳基醯基、X3 R17 、苯基、鹵素原子、CN取代的苯基；C1 -C4 烷基苄氧基、R2 C(O)O取代的C1 -C4 烷氧基、C1 -C3 亞烷基二氧基、R2 C(O)O、C1 -C12 烷基硫基、C1 -C4 烷基苯硫基、CN、羧基、C1 -C12 烷氧基羰基、芳基羰基、雜芳基羰基、X3 R18 、C1 -C4 烷基苯氧基、C1 -C8 烷基醯基苯氧基、C5 -C6 環烷基醯基苯氧基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯氧基、C1 -C3 亞烷基二氧基、芳基醯基苯氧基、雜芳基醯基苯氧基、R2 C(O)O取代的C1 -C4 烷基硫基、R2 C(O)O取代的C1 -C4 烷基苯硫基、C1 -C8 烷基醯基苯硫基、C5 -C6 環烷基醯基苯硫基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯硫基、芳基醯基苯硫基、雜芳基醯基苯硫基；或為環氧丙基，其中環氧基任意地與C1 -C4 烷基醛、酮縮合；X3 為O、S或NR22 ；Ar2 為C6 -C20 亞芳基、C3 -C20 亞雜芳基，通過X1 與Ar1 相連接；或通過X1 與Ar1 相連接同時，其取代基X1 鄰位的Ar2 碳原子通過直鍵、碳原子、羰基、O、S、NR18 再與Ar1 相連接構成環狀結構；n為0或1； X1 為O、S、NR18 或Y2 -Z1 -Y2 ；Y1 為(CH2 )m CR15 R16 、NR19 、O(CR15 R16 )m 、S(CR15 R16 )m 、(CR15 R16 )m C=O、S=O；m為0或1；Z1 為C1 -C10 直鏈亞烷基或C1 -C10 支鏈亞烷基；或被一個或多個氧、硫原子連在端基的C1 -C10 直鏈亞烷基；或被一個或多個氧、硫原子連在端基的C1 -C10 支鏈亞烷基；或被一個或多個氧、硫原子***的C1 -C10 直鏈亞烷基；或被一個或多個氧、硫原子***的C1 -C10 支鏈亞烷基；無取代基或有取代基的C6 -C20 亞芳基；Y2 為O、S、NR18 或O-C(O)；R1 由下列所構成的群組選出：氫原子、C2 -C18 烷基；或任意被一個或多個C3 -C7 環烷基、苯基、OR20 、SR21 、NR22 R23 取代的C2 -C18 烷基，其中，C2 -C18 烷基的苯基被任意一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代；或被C3 -C7 亞環烷基、亞苯基、O、S、NR22 ***的C2 -C18 烷基；或C3 -C8 環烷基、CN、NO2 、苯基；或任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代的苯基；或R1 為C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或兩個以上鹵素原子、C1 -C4 烷基、C5 或C6 環烷基、苯基、CN、 OH、X3 R20 取代；或R1 為C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或兩個以上亞苯基、X3 ***；或R1 為苯基未被取代的苯甲醯基、苯氧基羰基；或R1 為任意被一個或兩個以上鹵素原子、C1 -C4 烷基、C5 環烷基或C6 環烷基、苯基、CN、OH、X2 R20 取代取代的苯甲醯基、苯氧基羰基；或R1 為二苯基膦醯基，二(C1 -C4 烷氧基)膦醯基；或R1 為二苯基膦醯基，二(C1 -C4 烷氧基)膦醯基；R2 、R3 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C1 -C18 烷氧基、C5 -C7 環烷基、苯基其中之一；或R2 、R3 各自獨立地任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代和/或被C5 -C7 環亞烷基、亞苯基、O、S、NR17 ***C2 -C18 烯基；或R2 、R3 各自獨立地為任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代的C2 -C18 烷基；或R2 、R3 各自獨立地被C5 -C7 環亞烷基、亞苯基、O、S、NR17 ***的C2 -C18 烷基；或任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代且被 C5 -C7 環亞烷基、亞苯基、O、S、NR17 所***的C2 -C18 烯基；或前述C2 -C18 烷基被取代或被***的狀況同時存在；或R2 、R3 各自獨立地任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN取代的C5 -C7 環烷基；或R2 、R3 各自獨立地為苯基或任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、苯基、鹵素原子、CN取代的苯基；或R2 、R3 各自獨立地為萘基或任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、苯基、鹵素原子、CN取代的萘基；或R2 、R3 各自獨立地為苯基未被取代的苯甲醯基、苯氧基羰基；或R2 、R3 各自獨立地為被任意一個或兩個以上鹵素原子、R17 、C5 環烷基、C6 環烷基、CN、OH、XR17 取代的苯甲醯基或苯氧基羰基；R15 、R16 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、羧基取代的C1 -C5 烷基、C1 -C4 烷氧基醯基取代的C1 -C5 烷基、R2 C(O)O取代的C1 -C4 烷基其中之一；或任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代的C2 -C18 烷基；或被C5 -C7 亞環烷基、亞苯基、O、S、NR17 ***的C2 -C18 烷基；或前述C2 -C18 烷基被取代或被***的狀況同時存在；或R15 、R16 各自獨立地為C5 -C7 環烷基；或任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN取代的C5 -C7 環烷基； 或R15 、R16 各自獨立地為苯基；或任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基取代的C2 -C4 烷基醯基、苯甲醯基、XR17 、苯基、鹵素原子、CN取代的苯基；或R15 、R16 與其共同所連的碳原子或矽原子一起構成環狀且成環的原子數為4-7；或R15 、R16 分別與相鄰的取代基一起構成環狀且成環的原子數為4-7；R17 為C1 -C4 烷基；R18 、R19 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C1 -C4 烷氧基醯基取代的C1 -C5 烷基、R2 C(O)O取代的C1 -C4 烷基其中之一；或任意被一個或多個鹵素原子、C1 -C4 烷基、C3 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代的C1 -C18 烷基；或被任意被一個或多個C3 -C7 亞環烷基、亞苯基、O、S、NR17 ***的C2 -C18 烷基；或R18 、R19 各自獨立地為C5 -C7 環烷基；或任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN取代的C5 -C7 環烷基；或R18 、R19 各自獨立地為苯基；或任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基取代的C2 -C4 烷基醯基、芳基醯基、XR17 、苯基、鹵素原子、CN取代的苯 基；或上述R18 通過直鍵、碳原子、羰基與Ar1 或Ar2 中的芳環相連構成新的環；或上述R19 通過直鍵、碳原子、羰基與Ar1 中的芳環相連構成新的環；R20、 R21 、R22 、R23 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、被鹵素、CN、C1 -C4 烷氧基取代的C1 -C18 烷基、C3 -C7 環烷基其中之一；或被一個或多個氧原子、C5 -C7 亞環烷基、亞苯基***的C2 -C18 烷基；或被苯基、C3 -C7 環烷基取代的C1 -C3 烷基；或R20 、R21 、R22 、R23 各自獨立地為苯基、萘基未被取代的苯基、萘基、苯甲醯基；或R20 、R21 、R22 、R23 各自獨立地為任意地被鹵素、C1 -C4 烷基、C1 -C4 烷氧基、C1 -C4 烷基硫基、苯氧基、苯硫基、NR24 R25 、C1 -C12 烷基醯基、苯甲醯基取代的苯基、萘基、苯甲醯基；R24 、R25 各自為C1 -C4 烷基；或NR24 R25 為嗎福林(morpholine)，哌啶(piperidine)，哌啶(piperazine)，N-甲基哌啶(N-methyl piperazine)，吡咯(pyrrole)。Series 1: Structure of a compound of formula I, expressed as follows: Wherein, Ar 1 is substituted with X 1 being C 6 -C 20 arylene group or o-C 3 -C 20 heteroarylene group ortho, ortho-C 6 -C 20 arylene or C 3 -C 20 heteroarylene o The two adjacent atoms are bonded to Y 1 and a carbonyl group to form a ring structure, and the substituents on the remaining atoms are each: a hydrogen atom, a halogen atom, a C 1 -C 12 alkyl group, a C 5 -C 7 cycloalkyl group. One of a C 5 -C 7 cycloalkyl substituted C 1 -C 4 alkyl group, a C 1 -C 12 alkoxy group; or one or more C 1 -C 12 alkoxy groups, C 1 -C a 4 -alkylbenzyloxy group, a R 2 C(O)O substituted C 1 -C 4 alkoxy group; or a phenyl group; or optionally exemplified by one or more C 1 -C 4 alkyl groups, a carboxyl group, C 1 - C 12 alkyl fluorenyl, aryl fluorenyl, heteroaryl fluorenyl, X 3 R 17 , phenyl, halogen atom, CN substituted phenyl; C 1 -C 4 alkylbenzyloxy, R 2 C ( O) O-substituted C 1 -C 4 alkoxy, C 1 -C 3 alkylenedioxy, R 2 C(O)O, C 1 -C 12 alkylthio, C 1 -C 4 alkane Benzothio group, CN, carboxyl group, C 1 -C 12 alkoxycarbonyl group, arylcarbonyl group, heteroarylcarbonyl group, X 3 R 18 , C 1 -C 4 alkylphenoxy group, C 1 -C 8 alkane Phenyl phenoxy, C 5 -C 6 cycloalkylnonylphenoxy, C 5 -C 6 cycloalkyl-substituted C 1 -C 4 alkylnonylphenoxy, C 1 -C 3 alkylenedioxy, arylnonylphenoxy, heteroarylnonylphenoxy, R 2 C(O)O substituted C 1 -C 4 alkylthio group, R 2 C(O)O substituted C 1 -C 4 alkylphenylthio group, C 1 -C 8 alkylmercaptobenzene sulfur , C 5 -C 6 cycloalkylnonylphenylthio, C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkylmercaptophenylthio, arylmercaptophenylthio, heteroaryl a mercaptophenylthio group; or a glycidyl group in which an epoxy group is arbitrarily condensed with a C 1 -C 4 alkyl aldehyde or a ketone; X 3 is O, S or NR 22 ; Ar 2 is a C 6 -C 20 arylene, C 3 -C 20 heteroarylene group, X 1 and connected by Ar 1; or 1 simultaneously connected, the substituent X 1 Ar 2 vicinal carbon atoms by a direct bond and X 1 through Ar, The carbon atom, carbonyl group, O, S, NR 18 are further connected to Ar 1 to form a cyclic structure; n is 0 or 1; X 1 is O, S, NR 18 or Y 2 -Z 1 -Y 2 ; Y 1 is (CH 2 ) m CR 15 R 16 , NR 19 , O(CR 15 R 16 ) m , S(CR 15 R 16 ) m , (CR 15 R 16 ) m C=O, S=O; m is 0 or 1; Z 1 is a C 1 -C 10 linear alkylene group or a C 1 -C 10 branched alkylene group; or by one or more oxygen, a C 1 -C 10 linear alkylene group having a sulfur atom attached to the terminal group; or a C 1 -C 10 branched alkylene group bonded to the terminal group by one or more oxygen or sulfur atoms; or by one or more a C 1 -C 10 linear alkylene group in which oxygen or a sulfur atom is inserted; or a C 1 -C 10 branched alkylene group inserted by one or more oxygen or sulfur atoms; an unsubstituted or substituted C 6 -C 20 arylene; Y 2 is O, S, NR 18 or OC(O); R 1 is selected from the group consisting of: a hydrogen atom, a C 2 -C 18 alkyl group; or any one or more C 3 -C 7 cycloalkyl, phenyl, OR 20 , SR 21 , NR 22 R 23 substituted C 2 -C 18 alkyl, wherein the C 2 -C 18 alkyl phenyl group is any one or more Halogen atom, C 1 -C 4 alkyl group, C 5 -C 7 cycloalkyl group, heterocycloalkyl group, phenyl group, heteroaryl group, CN, C 1 -C 4 alkoxy group, aryloxy group Or a C 2 -C 18 alkyl group inserted by a C 3 -C 7 cycloalkylene group, a phenylene group, an O, S, NR 22 ; or a C 3 -C 8 cycloalkyl group, CN, NO 2 , a phenyl group; Or optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkoxy Base, Fang a methoxy-substituted phenyl group; or R 1 is a C 1 -C 12 alkyl fluorenyl group, a C 1 -C 12 alkoxycarbonyl group, wherein the alkyl group is optionally substituted by one or two or more halogen atoms, C 1 -C 4 Alkenyl, C 5 or C 6 cycloalkyl, phenyl, CN, OH, X 3 R 20 substituted; or R 1 is C 1 -C 12 alkyl fluorenyl, C 1 -C 12 alkoxycarbonyl, wherein An alkyl group is optionally substituted by one or two or more phenylene groups, X 3 ; or R 1 is a phenyl fluorenyl group or a phenoxycarbonyl group which is unsubstituted by a phenyl group; or R 1 is optionally any one or two or more halogen atoms , C 1 -C 4 alkyl, C 5 cycloalkyl or C 6 cycloalkyl, phenyl, CN, OH, X 2 R 20 substituted substituted benzinyl, phenoxycarbonyl; or R 1 is two Phenylphosphonium fluorenyl, bis(C 1 -C 4 alkoxy)phosphonium fluorenyl; or R 1 is diphenylphosphinofluorenyl, di(C 1 -C 4 alkoxy)phosphonium; R 2 , R 3 is each independently selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a C 1 -C 18 alkoxy group, a C 5 -C 7 cycloalkyl group, or a phenyl group; R 2, R 3 are each independently optionally substituted with one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl , CN, C 1 -C 4 alkanoyl group, an acyl group, a substituted aryloxy and / or C 5 -C 7 cycloalkylene, phenylene, O, S, NR 17 inserted C 2 -C 18 alkenyl Or R 2 and R 3 are each independently one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN , C 1 -C 4 alkyl alkoxy, aryloxy substituted C 2 -C 18 alkyl; or R 2 , R 3 are each independently C 5 -C 7 cycloalkylene, phenylene, O , S, NR 17 inserted C 2 -C 18 alkyl; or optionally by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyl group, aryloxy group, acyl and substituted by C 5 -C 7 cycloalkylene, phenylene, O, S, NR 17 inserted C 2 - a C 18 alkenyl group; or a condition in which the aforementioned C 2 -C 18 alkyl group is substituted or inserted; or R 2 and R 3 are each independently optionally substituted by one or more C 1 -C 4 alkyl groups, phenyl groups, a halogen atom, a CN-substituted C 5 -C 7 cycloalkyl group; or R 2 and R 3 are each independently a phenyl group or optionally one or more C 1 -C 4 alkyl groups, C 1 -C 4 alkoxy groups Phenyl, a halogen atom, a CN-substituted phenyl group; or R 2 and R 3 are each independently a naphthyl group or optionally substituted by one or more C 1 -C 4 alkyl groups, C 1 -C 4 alkoxy groups, phenyl groups, halogen atoms a CN substituted naphthyl group; or R 2 and R 3 are each independently a phenyl unsubstituted benzylidene group or a phenoxycarbonyl group; or R 2 and R 3 are each independently one or more of two or more a halogen atom, a R 17 , a C 5 cycloalkyl group, a C 6 cycloalkyl group, a CN, OH, an XR 17 substituted benzhydryl group or a phenoxycarbonyl group; and R 15 and R 16 are each independently a group consisting of the following: Group selected: hydrogen atom, C 1 -C 18 alkyl group, carboxyl substituted C 1 -C 5 alkyl group, C 1 -C 4 alkoxyfluorenyl substituted C 1 -C 5 alkyl group, R 2 C(O Any one of O-substituted C 1 -C 4 alkyl groups; or optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl group, C 5 -C 7 cycloalkyl group, heterocycloalkyl group, phenyl group, Heteroaryl, CN, C 1 -C 4 alkyl alkoxy, aryloxy substituted C 2 -C 18 alkyl; or C 5 -C 7 cycloalkylene, phenylene, O, S, a C 2 -C 18 alkyl group in which NR 17 is inserted; or a condition in which the aforementioned C 2 -C 18 alkyl group is substituted or inserted; or R 15 , R 16 are each independently a C 5 -C 7 cycloalkyl; or optionally substituted with one or more C 1 -C 4 alkyl group, a phenyl group, a halogen atom, CN substituted C 5 -C 7 cycloalkyl; or R 15 , R 16 are each independently phenyl; or optionally by one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy, C 1 -C 12 alkyl fluorenyl, C 5 - C 6 cycloalkylcarbinyl, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkyl fluorenyl, benzhydryl, XR 17 , phenyl, halogen atom, CN substituted phenyl; R 15 and R 16 together with the carbon atom or a ruthenium atom to which they are attached form a cyclic ring and the number of atoms formed is 4-7; or R 15 and R 16 together with adjacent substituents form a ring and form a ring. The atomic number is 4-7; R 17 is a C 1 -C 4 alkyl group; and R 18 and R 19 are each independently selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, and C 1 - C 4 alkoxy substituted with acyl C 1 -C 5 alkyl group, R 2 C (O) O-substituted C 1 -C 4 alkyl wherein one; or optionally substituted with one or more halogen atoms, C 1 - C 4 alkyl, C 3 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkoxy, aryloxy substituted C 1 -C 18 alkyl; or optionally substituted with one or more C 3 -C 7 cycloalkylene, phenylene, O, S, NR 17 inserted into the C 2 -C 18 alkyl; or R 18, R are each independently a C 5 -C 7 cycloalkyl, 19; or optionally substituted with one or more C 1 -C 4 alkyl group, a phenyl group, a halogen atom, CN substituted C 5 -C 7 cycloalkyl; or R 18 And R 19 are each independently phenyl; or optionally substituted by one or more C 1 -C 4 alkyl groups, carboxyl groups, C 1 -C 12 alkyl fluorenyl groups, C 5 -C 6 cycloalkylcarbenyl groups, C a 5- C 6 cycloalkyl-substituted C 2 -C 4 alkylfluorenyl group, an arylsulfonyl group, an XR 17 group, a phenyl group, a halogen atom, a CN-substituted phenyl group; or the above R 18 through a direct bond, a carbon atom, a carbonyl group is bonded to an aromatic ring in Ar 1 or Ar 2 to form a new ring; or R 19 is bonded to an aromatic ring in Ar 1 through a straight bond, a carbon atom or a carbonyl group to form a new ring; R 20 , R 21 , R 22 And R 23 are each independently selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a C 1 -C 18 alkyl group substituted by a halogen, CN, a C 1 -C 4 alkoxy group, C One of 3- C 7 cycloalkyl groups; or inserted by one or more oxygen atoms, C 5 -C 7 cycloalkylene groups, phenylene groups C 2 -C 18 alkyl; or C 1 -C 3 alkyl substituted by phenyl, C 3 -C 7 cycloalkyl; or R 20 , R 21 , R 22 , R 23 are each independently phenyl, a naphthyl unsubstituted phenyl, naphthyl, benzhydryl group; or R 20 , R 21 , R 22 , R 23 are each independently halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenoxy, phenylthio, NR 24 R 25, C 1 -C 12 alkyl acyl, benzoyl substituted phenyl group, a naphthyl group, Benzopyridinyl; R 24 and R 25 are each C 1 -C 4 alkyl; or NR 24 R 25 is morpholine, piperididine, piperazine, N-methylpiperidine N-methyl piperazine, pyrrole.

系列2：結構通式Ⅱ化合物，如下列所示： 其中，R4 、R5 、R6 、R7 、R8 、R9 、R10 各自獨立地為：氫原子、鹵素原子、C1 -C12 烷基、C5 -C7 環烷基、C5 -C7 環烷基取代的C1 -C4 烷基、C1 -C12 烷氧基、苯基、C1 -C4 烷基苄氧基其中之一；或任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、芳基醯基、雜芳基醯基、X3 R17 、苯基、鹵素原子、CN取代的苯基；或被一個或多個C1 -C12 烷氧基、C1 -C4 烷基苄氧基、R2 C(O)O取代的C1 -C4 烷氧基；或R2 C(O)O、CN、羧基、C1 -C12 烷氧基羰基、芳基羰基、雜芳基羰基、X3 R18 ；或為C1 -C4 烷基苯氧基、C1 -C4 烷基苯硫基、C1 -C8 烷基醯基苯氧基、芳基醯基苯氧基、雜芳基醯基苯氧基、C5 -C6 環烷基醯基苯氧基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯氧基、C1 -C3 亞烷基二氧基、C1 -C12 烷基硫基、R2 C(O)O取代的C1 -C4 烷基硫基、R2 C(O)O取代的C1 -C4 烷基苯硫基、C1 -C8 烷基醯基苯硫基、芳基醯基苯硫基、雜芳基醯基苯硫基、C5 -C6 環烷基醯基苯硫基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯硫基； 或R4 、R5 、R6 、R7 、R8 、R9 、R10 、R11 、R12 、R13 、R14 各自獨立地為環氧丙基，其中環氧基任意地與C1 -C4 烷基醛、酮縮合；X1 為O，S或NR18 ；Y1 為O、S或CR15 R16 ；其他取代基定義同系列1。Series 2: Compounds of the formula II, as shown below: Wherein R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each independently: a hydrogen atom, a halogen atom, a C 1 -C 12 alkyl group, a C 5 -C 7 cycloalkyl group, One of C 5 -C 7 cycloalkyl substituted C 1 -C 4 alkyl, C 1 -C 12 alkoxy, phenyl, C 1 -C 4 alkylbenzyloxy; or optionally by one or more a C 1 -C 4 alkyl group, a carboxyl group, a C 1 -C 12 alkyl fluorenyl group, an aryl fluorenyl group, a heteroaryl fluorenyl group, a X 3 R 17 group, a phenyl group, a halogen atom, a CN substituted phenyl group; with one or more C 1 -C 12 alkoxy, C 1 -C 4 alkylbenzyl group, R 2 C (O) O-substituted C 1 -C 4 alkoxy; or R 2 C (O) O, CN, carboxyl, C 1 -C 12 alkoxycarbonyl, arylcarbonyl, heteroarylcarbonyl, X 3 R 18 ; or C 1 -C 4 alkylphenoxy, C 1 -C 4 alkyl Phenylthio, C 1 -C 8 alkyl nonylphenoxy, aryl nonylphenoxy, heteroaryl nonylphenoxy, C 5 -C 6 cycloalkylnonylphenoxy, C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkyl nonylphenoxy, C 1 -C 3 alkylenedioxy, C 1 -C 12 alkylthio, R 2 C(O)O Substituted C 1 -C 4 alkylthio, R 2 C(O)O substituted C 1 -C 4 alkylphenylthio, C 1 -C 8 alkyl nonylphenylthio, aryl nonylphenylthio, heteroaryl nonylphenylthio, C 5 -C 6 cycloalkylnonylphenylthio, C 5 -C 6 cycloalkyl Substituted C 1 -C 4 alkylmercaptophenylthio; or R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 are each independently Is a glycidyl group in which an epoxy group is arbitrarily condensed with a C 1 -C 4 alkyl aldehyde, a ketone; X 1 is O, S or NR 18 ; Y 1 is O, S or CR 15 R 16 ; The base definition is the same as series 1.

系列3：在結構通式Ⅱ化合物中：R4 、R5 、R6 、R7 、R8 、R9 、R10 均為氫原子；X1 為O或S；Y1 為CH2 、CHCH3 或C(CH3 )2 ；n=1；R1 為C1 -C12 烷基或任意被一個或多個C3 -C7 環烷基、苯基、OR20 、SR21 、NR22 R23 取代的C1 -C12 烷基；R2 、R3 各自獨立地為甲基、乙基、苯基、2-甲基苯基、3-甲基苯基、2,4,6-三甲基苯基或2,6-二甲氧基苯基其中之一；其他基團定義同系列2中通式Ⅱ相應基團定義。Series 3: In the compound of the formula II: R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are all hydrogen atoms; X 1 is O or S; Y 1 is CH 2 , CHCH 3 or C(CH 3 ) 2 ; n=1; R 1 is C 1 -C 12 alkyl or optionally substituted by one or more C 3 -C 7 cycloalkyl, phenyl, OR 20 , SR 21 , NR 22 R 23 -substituted C 1 -C 12 alkyl; R 2 and R 3 are each independently methyl, ethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 2,4,6- One of trimethylphenyl or 2,6-dimethoxyphenyl; the other groups are defined as the corresponding groups of formula II in series 2.

上述結構通式I化合物中，R2 C(O)或R3 C(O)還可以被(R2 )2 P或R2 S(O2 )代替生成對應的亞磷(膦)酸酯或磺酸酯，也具有光致自由基或光致陽離子引發作用。In the above compound of formula I, R 2 C(O) or R 3 C(O) may also be replaced by (R 2 ) 2 P or R 2 S(O 2 ) to form the corresponding phosphorous (phosphonate) or Sulfonates also have photoinduced free radical or photocationic cations.

系列6：上述系列1-5中的各自的結構通式I、Ⅱ化合物，其具體結構有： Series 6: The respective structural formula I, II compounds of the above series 1-5, the specific structures of which are:

本發明還提供所述的系列1中結構通式I化合物的製造方法，包含以下步驟：(1)步驟1：在下列結構通式Ⅳ化合物中環戊酮羰基的鄰位亞甲基上進行選擇性肟化，肟化的方法是將結構通式Ⅳ化合物與亞硝酸烷基酯在酸性溶液中發生肟化反應，得到對應的中間體，為一種酮肟化合物，如下列結構通式V化合物； The present invention also provides a process for the preparation of the compound of the formula I in the series 1, comprising the steps of: (1) Step 1: Selecting on the ortho-methylene group of the cyclopentanone carbonyl group in the following compound of the formula IV; The method of deuteration and deuteration is to carry out a oximation reaction of a compound of the formula IV with an alkyl nitrite in an acidic solution to obtain a corresponding intermediate, which is a ketone oxime compound, such as the following compound of the formula V;

(V)(2)第二步：將中間體結構通式V化合物繼續進行第二肟化，有下列兩種方法：方法A：結構通式V化合物與亞硝酸烷基酯在酸性溶液中發生肟化反應，得到對應第二中間體結構通式Ⅵ化合物；方法B：結構通式V化合物在羥胺溶液中發生側鏈R1 CH2 CO中羰基的肟化反應，得到對應的第二中間體結構通式Ⅶ化合物；當肟基存在順反異構體時，得到的結構通式Ⅵ、Ⅶ化合物是其各自異構體的混合物； (V) (2) Step 2: The intermediate structure of the compound of the formula V is continued to be subjected to the second deuteration by the following two methods: Process A: the compound of the formula V and the alkyl nitrite are produced in an acidic solution. The oximation reaction gives a compound of the formula VI corresponding to the second intermediate structure; Method B: the thiolation reaction of the carbonyl group in the side chain R 1 CH 2 CO occurs in the hydroxylamine solution in the hydroxylamine solution to obtain the corresponding second intermediate a compound of the formula VII; when a cis-trans isomer is present in the thiol group, the resulting compound of the formula VI, VII is a mixture of its respective isomers;

(3)第三步：將上述第二肟化中間體結構通式Ⅵ或Ⅶ化合物與下列醯化試劑： 或其等價醯化試劑發生酯化反應得到對應前述結構通式I化合物；當中間體結構通式Ⅵ或Ⅶ化合物的肟基存在順反異構體時，得到的結構通式I化合物是其異構體的混合物，或經過提純得到其各個異構體，上述反 應過程中所涉及結構的所有基團定義同系列1中相應結構基團定義。 (3) The third step: the above-mentioned second deuterated intermediate structure of the compound of the formula VI or VII with the following deuteration reagent: Or an equivalent esterification reagent is esterified to obtain a compound of the above formula I; when the intermediate structure of the compound of formula VI or VII is present in the cis-trans isomer, the obtained compound of formula I is Mixtures of isomers, or after purification to obtain individual isomers, all groups of the structures involved in the above reaction are defined in the same way as the corresponding structural groups in series 1.

本發明還提供一種不對稱二酮化合物，包含結構通式Ⅳ化合物，如下所示： 其中，基團Ar1 、Ar2 、X1 、Y1 、R1 的定義同系列1中結構通式I化合物相應基團定義；另外，X3 為O、S或NR22 ；Z1 為下列群組的其中之一：C1 -C10 直鏈亞烷基、C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 支鏈亞烷基、無取代基的C6 -C20 亞芳基、或有取代基的C6 -C20 亞芳基；Y2 為O、S、NR18 或O-C(O)；R15 、R16 各自獨立地為下列群組的其中之一：氫原子、C1 -C18 烷基、羧基所取代的C1 -C5 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基；或任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環 烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C2 -C18 烷基；或被C5 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；或任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；或任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基取代的C2 -C4 烷基醯基、苯甲醯基、XR17 、鹵素原子、CN所取代的苯基；R17 為C1 -C4 烷基；R18 、R19 各自獨立地為下列群組的其中之一：氫原子、C1 -C18 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基；或任意被一個或多個鹵素原子、C1 -C4 烷基、C3 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C1 -C18 烷基；或任意被一個或多個C3 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；或任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；或任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基所取代的C2 -C4 烷基醯基、芳基醯基、XR17 、苯基、鹵素原子、CN所取代的苯基； R20 、R21 、R22 、R23 各自獨立地由為下列群組的其中之一：氫原子、C1 -C18 烷基、C3 -C7 環烷基；或被鹵素、CN、C1 -C4 烷氧基所取代的C1 -C18 烷基；或被一個或多個氧原子、C5 -C7 亞環烷基、亞苯基所***的C2 -C18 烷基；或被苯基、C3 -C7 環烷基所取代的C1 -C3 烷基；或苯基、萘基、苯甲醯基；或任意被鹵素、C1 -C4 烷基、C1 -C4 烷氧基、C1 -C4 烷基硫基、苯氧基、苯硫基、NR24 R25 、C1 -C12 烷基醯基、苯甲醯基所取代的苯基、萘基、苯甲醯基；R24 、R25 各自為C1 -C4 烷基；或NR24 R25 一起為嗎福林(morpholine)，哌啶(piperidine)，哌啶(piperazine)，N-甲基哌啶(N-methyl piperazine)，吡咯(pyrrole)。The invention also provides an asymmetric diketone compound comprising a compound of the formula IV, as shown below: Wherein the radicals Ar 1, Ar 2, X 1 , defined Y 1, R 1 of the same series in a compound of Formula I structure corresponding groups defined above; further, X 3 is O, S or NR 22; Z 1 is the following One of the group: C 1 -C 10 linear alkylene, C 1 -C 10 branched alkylene, C 1 -C 10 straight bonded to the end group by one or more oxygen or sulfur atoms a chain alkylene group, a C 1 -C 10 branched alkylene group bonded to a terminal group by one or more oxygen atoms or a sulfur atom, and a C 2 -C 10 straight inserted by one or more oxygen atoms or sulfur atoms a chain alkylene group, a C 2 -C 10 branched alkylene group inserted by one or more oxygen atoms or sulfur atoms, an unsubstituted C 6 -C 20 arylene group, or a substituted C 6 - C 20 arylene; Y 2 is O, S, NR 18 or OC(O); R 15 and R 16 are each independently one of the following groups: a hydrogen atom, a C 1 -C 18 alkyl group, a carboxyl group substituted C 1 -C 5 alkyl, C 1 -C 4 alkoxy substituted acyl C 1 -C 5 alkyl group, R 2 C (O) O substituted C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, phenyl; or any one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl , Heteroaryl, CN, C 1 -C 4 alkanoyl group, aryloxy group, acyl substituted C 2 -C 18 alkyl; or C 5 -C 7 cycloalkylene, phenylene, O, a C 2 -C 18 alkyl group to which S, NR 17 is inserted; or a C 5 -C 7 cycloalkyl group optionally substituted by one or more C 1 -C 4 alkyl groups, a phenyl group, a halogen atom, or CN; Any one or more of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy, C 1 -C 12 alkyl fluorenyl, C 5 -C 6 cycloalkylcarbenyl, C 5 - C 6 cycloalkyl-substituted C 2 -C 4 alkylfluorenyl, benzhydryl, XR 17 , halogen atom, CN substituted phenyl; R 17 is C 1 -C 4 alkyl; R 18 , R 19 are each independently one of the following groups: a hydrogen atom, C 1 -C 18 alkyl, C 1 -C 4 alkoxy substituted acyl C 1 -C 5 alkyl group, R 2 C (O a C 1 -C 4 alkyl group, a C 5 -C 7 cycloalkyl group, a phenyl group substituted by O; or optionally substituted by one or more halogen atoms, a C 1 -C 4 alkyl group, a C 3 -C 7 naphthenic ring a C 1 -C 18 alkyl group substituted with a heterocycloalkyl group, a phenyl group, a heteroaryl group, a CN, a C 1 -C 4 alkyl alkoxy group, an aryloxy group; or optionally one or more C 3 -C 7 cycloalkylene, phenylene, O, S, NR 17 inserted C 2 -C 18 alkyl; or any C 5 -C 7 cycloalkyl substituted by one or more C 1 -C 4 alkyl, phenyl, halogen atom, CN; or optionally Or C 2 -C substituted by a plurality of C 1 -C 4 alkyl groups, carboxyl groups, C 1 -C 12 alkyl fluorenyl groups, C 5 -C 6 cycloalkylcarbenyl groups, C 5 -C 6 cycloalkyl groups a 4- alkyl fluorenyl group, an aryl fluorenyl group, an XR 17 group, a phenyl group, a halogen atom, a phenyl group substituted by CN; R 20 , R 21 , R 22 , and R 23 are each independently one of the following groups; a hydrogen atom, a C 1 -C 18 alkyl group, a C 3 -C 7 cycloalkyl group; or a C 1 -C 18 alkyl group substituted by a halogen, CN, a C 1 -C 4 alkoxy group; a plurality of oxygen atoms, a C 5 -C 7 cycloalkylene group, a C 2 -C 18 alkyl group in which a phenylene group is inserted; or a C 1 -C 3 substituted by a phenyl group or a C 3 -C 7 cycloalkyl group ; Alkyl; or phenyl, naphthyl, benzhydryl; or optionally halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenoxy , phenylthio, NR 24 R 25 , C 1 -C 12 alkyl fluorenyl, phenyl, naphthyl, benzhydryl substituted by benzylidene; R 24 and R 25 are each C 1 -C 4 Alkyl; or NR 24 R 25 together is morpholine, piperididine, piperazine, N-methyl piperazine, pyrrole.

本發明還提供一種不對稱二酮化合物的中間體，為一種酮肟化合物，如下列結構通式V化合物所示： 其中，基團Ar1 、Ar2 、X1 、Y1 、R1 的定義同系列1中通式I化合物相應基團定義；另外，X3 為O、S或NR22 ；Z1 為下列群組的其中之一： C1 -C10 直鏈亞烷基、C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 支鏈亞烷基、無取代基的C6 -C20 亞芳基、或有取代基的C6 -C20 亞芳基；Y2 為O、S、NR18 或O-C(O)；R15 、R16 各自獨立地為下列群組的其中之一：氫原子、C1 -C18 烷基、羧基所取代的C1 -C5 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基；或任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C2 -C18 烷基；或被C5 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；或任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；或任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基取代的C2 -C4 烷基醯基、苯甲醯基、XR17 、鹵素原子、CN所取代的苯基；R17 為C1 -C4 烷基；R18 、R19 各自獨立地為下列群組的其中之一： 或氫原子、C1 -C18 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基；或任意被一個或多個鹵素原子、C1 -C4 烷基、C3 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C1 -C18 烷基；或任意被一個或多個C3 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；或任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；或任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基所取代的C2 -C4 烷基醯基、芳基醯基、XR17 、苯基、鹵素原子、CN所取代的苯基；R20 、R21 、R22 、R23 各自獨立地由為下列群組的其中之一：氫原子、C1 -C18 烷基、C3 -C7 環烷基；或被鹵素、CN、C1 -C4 烷氧基所取代的C1 -C18 烷基；或被一個或多個氧原子、C5 -C7 亞環烷基、亞苯基所***的C2 -C18 烷基；或被苯基、C3 -C7 環烷基所取代的C1 -C3 烷基；或苯基、萘基、苯甲醯基；或任意被鹵素、C1 -C4 烷基、C1 -C4 烷氧基、C1 -C4 烷基硫基、苯氧基、苯硫基、NR24 R25 、C1 -C12 烷基醯基、苯甲醯基所取代的苯基、萘基、苯甲醯基； R24 、R25 各自為C1 -C4 烷基；或NR24 R25 一起為嗎福林(morpholine)，哌啶(piperidine)，哌啶(piperazine)，N-甲基哌啶(N-methyl piperazine)，吡咯(pyrrole)。The present invention also provides an intermediate of an asymmetric diketone compound, which is a ketone oxime compound, as shown by the following compound of the formula V: Wherein the definition of the groups Ar 1 , Ar 2 , X 1 , Y 1 , R 1 is the same as the corresponding group of the compound of the formula I in the series 1; in addition, X 3 is O, S or NR 22 ; Z 1 is the following group One of the group: a C 1 -C 10 linear alkylene group, a C 1 -C 10 branched alkylene group, a C 1 -C 10 linear chain attached to the terminal group by one or more oxygen or sulfur atoms An alkylene group, a C 1 -C 10 branched alkylene group bonded to a terminal group by one or more oxygen atoms or sulfur atoms, and a C 2 -C 10 linear chain inserted by one or more oxygen atoms or sulfur atoms. An alkylene group, a C 2 -C 10 branched alkylene group inserted by one or more oxygen atoms or sulfur atoms, an unsubstituted C 6 -C 20 arylene group, or a substituted C 6 -C 20 arylene; Y 2 is O, S, NR 18 or OC(O); R 15 and R 16 are each independently one of the following groups: a hydrogen atom, a C 1 -C 18 alkyl group, a carboxyl group substituted C 1 -C 5 alkyl, C 1 -C 4 alkoxy substituted acyl C 1 -C 5 alkyl group, R 2 C (O) O substituted C 1 -C 4 alkyl, C 5- C 7 cycloalkyl, phenyl; or optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, Heteroaryl, CN, C 1 -C 4 alkanomethoxy, aryloxy substituted C 2 -C 18 alkyl; or C 5 -C 7 cycloalkylene, phenylene, O, S , C 2 -C 18 alkyl group inserted in NR 17 ; or any C 5 -C 7 cycloalkyl group substituted by one or more C 1 -C 4 alkyl groups, a phenyl group, a halogen atom, CN; or any By one or more C 1 -C 4 alkyl groups, C 1 -C 4 alkoxy groups, carboxyl groups, C 1 -C 12 alkyl fluorenyl groups, C 5 -C 6 cycloalkylcarbenyl groups, C 5 -C a 6 -cycloalkyl-substituted C 2 -C 4 alkylfluorenyl group, a benzhydryl group, an XR 17 group, a halogen atom, a phenyl group substituted by CN; R 17 is a C 1 -C 4 alkyl group; R 18 , R 19 Each of them is independently one of the following groups: or a C 1 -C 5 alkyl group substituted by a hydrogen atom, a C 1 -C 18 alkyl group, a C 1 -C 4 alkoxyfluorenyl group, and R 2 C(O a C 1 -C 4 alkyl group, a C 5 -C 7 cycloalkyl group, a phenyl group substituted by O; or optionally substituted by one or more halogen atoms, a C 1 -C 4 alkyl group, a C 3 -C 7 naphthenic ring a C 1 -C 18 alkyl group substituted with a heterocycloalkyl group, a phenyl group, a heteroaryl group, a CN, a C 1 -C 4 alkyl alkoxy group, an aryloxy group; or optionally one or more C 3 -C 7 cycloalkylene, phenylene, O, S, NR 17 inserted C 2 -C 18 alkyl; or any C 5 -C 7 cycloalkyl substituted by one or more C 1 -C 4 alkyl, phenyl, halogen atom, CN; or optionally Or C 2 -C substituted by a plurality of C 1 -C 4 alkyl groups, carboxyl groups, C 1 -C 12 alkyl fluorenyl groups, C 5 -C 6 cycloalkylcarbenyl groups, C 5 -C 6 cycloalkyl groups a 4- alkyl fluorenyl group, an aryl fluorenyl group, an XR 17 group, a phenyl group, a halogen atom, a phenyl group substituted by CN; and R 20 , R 21 , R 22 , and R 23 are each independently one of the following groups; a hydrogen atom, a C 1 -C 18 alkyl group, a C 3 -C 7 cycloalkyl group; or a C 1 -C 18 alkyl group substituted by a halogen, CN, a C 1 -C 4 alkoxy group; a plurality of oxygen atoms, a C 5 -C 7 cycloalkylene group, a C 2 -C 18 alkyl group in which a phenylene group is inserted; or a C 1 -C 3 substituted by a phenyl group or a C 3 -C 7 cycloalkyl group ; Alkyl; or phenyl, naphthyl, benzhydryl; or optionally halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenoxy a phenylthio group, an NR 24 R 25 , a C 1 -C 12 alkyl fluorenyl group, a phenyl group substituted with a benzamidine group, a naphthyl group, a benzamidine group; each of R 24 and R 25 is a C 1 -C 4 group; Alkyl; or NR 24 R 25 together is morpholine, piperididine, piperazine, N-methyl piperazine, pyrrole.

本發明還提供一種不對稱二酮化合物的中間體，為一種二酮肟化合物，如下列結構通式Ⅵ、Ⅶ化合物所示： The present invention also provides an intermediate of an asymmetric diketone compound, which is a diketone oxime compound, as shown by the following compounds of the formula VI, VII:

其中，基團Ar1 、Ar2 、X1 、Y1 、R1 的定義同系列1中通式I化合物相應基團定義；另外，X3 為O、S或NR22 ；Z1 為下列群組的其中之一：C1 -C10 直鏈亞烷基、C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 支鏈亞烷基、無取代基的C6 -C20 亞芳基、或有取代基的C6 -C20 亞芳基；Y2 為O、S、NR18 或O-C(O)； R15 、R16 各自獨立地為下列群組的其中之一：氫原子、C1 -C18 烷基、羧基所取代的C1 -C5 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基；或任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C2 -C18 烷基；或被C5 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；或任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；或任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基取代的C2 -C4 烷基醯基、苯甲醯基、XR17 、鹵素原子、CN所取代的苯基；R17 為C1 -C4 烷基；R18 、R19 各自獨立地為下列群組的其中之一：氫原子、C1 -C18 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基；或任意被一個或多個鹵素原子、C1 -C4 烷基、C3 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C1 -C18 烷基；或任意被一個或多個C3 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基； 或任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；或任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基所取代的C2 -C4 烷基醯基、芳基醯基、XR17 、苯基、鹵素原子、CN所取代的苯基；R20 、R21 、R22 、R23 各自獨立地為下列群組的其中之一：氫原子、C1 -C18 烷基、C3 -C7 環烷基；或被鹵素、CN、C1 -C4 烷氧基所取代的C1 -C18 烷基；或被一個或多個氧原子、C5 -C7 亞環烷基、亞苯基所***的C2 -C18 烷基；或被苯基、C3 -C7 環烷基所取代的C1 -C3 烷基；或苯基、萘基、苯甲醯基；或任意被鹵素、C1 -C4 烷基、C1 -C4 烷氧基、C1 -C4 烷基硫基、苯氧基、苯硫基、NR24 R25 、C1 -C12 烷基醯基、苯甲醯基所取代的苯基、萘基、苯甲醯基；R24 、R25 各自為C1 -C4 烷基；或NR24 R25 一起為嗎福林(morpholine)，哌啶(piperidine)，哌啶(piperazine)，N-甲基哌啶(N-methyl piperazine)，吡咯(pyrrole)。 Wherein the definition of the groups Ar 1 , Ar 2 , X 1 , Y 1 , R 1 is the same as the corresponding group of the compound of the formula I in the series 1; in addition, X 3 is O, S or NR 22 ; Z 1 is the following group One of the group: a C 1 -C 10 linear alkylene group, a C 1 -C 10 branched alkylene group, a C 1 -C 10 linear chain attached to the terminal group by one or more oxygen or sulfur atoms An alkylene group, a C 1 -C 10 branched alkylene group bonded to a terminal group by one or more oxygen atoms or sulfur atoms, and a C 2 -C 10 linear chain inserted by one or more oxygen atoms or sulfur atoms. An alkylene group, a C 2 -C 10 branched alkylene group inserted by one or more oxygen atoms or sulfur atoms, an unsubstituted C 6 -C 20 arylene group, or a substituted C 6 -C 20 arylene; Y 2 is O, S, NR 18 or OC(O); R 15 and R 16 are each independently one of the following groups: a hydrogen atom, a C 1 -C 18 alkyl group, a carboxyl group. substituted C 1 -C 5 alkyl, C 1 -C 4 alkoxy substituted acyl C 1 -C 5 alkyl group, R 2 C (O) O substituted C 1 -C 4 alkyl, C 5- C 7 cycloalkyl, phenyl; or optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, Heteroaryl, CN, C 1 -C 4 alkanomethoxy, aryloxy substituted C 2 -C 18 alkyl; or C 5 -C 7 cycloalkylene, phenylene, O, S , C 2 -C 18 alkyl group inserted in NR 17 ; or any C 5 -C 7 cycloalkyl group substituted by one or more C 1 -C 4 alkyl groups, a phenyl group, a halogen atom, CN; or any By one or more C 1 -C 4 alkyl groups, C 1 -C 4 alkoxy groups, carboxyl groups, C 1 -C 12 alkyl fluorenyl groups, C 5 -C 6 cycloalkylcarbenyl groups, C 5 -C a 6 -cycloalkyl-substituted C 2 -C 4 alkylfluorenyl group, a benzhydryl group, an XR 17 group, a halogen atom, a phenyl group substituted by CN; R 17 is a C 1 -C 4 alkyl group; R 18 , R 19 are each independently one of the following groups: a hydrogen atom, C 1 -C 18 alkyl, C 1 -C 4 alkoxy substituted acyl C 1 -C 5 alkyl group, R 2 C (O) C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, phenyl substituted by O; or optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl a heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanomethoxy, aryloxy substituted C 1 -C 18 alkyl; or optionally substituted by one or more C 3 - C 7 cycloalkylene, phenylene, O, S, NR 17 Insertion of C 2 -C 18 alkyl; or optionally substituted with one or more C 1 -C 4 alkyl group, a phenyl group, a halogen atom, CN substituted C 5 -C 7 cycloalkyl; or an optionally substituted with one or more C 2 -C 4 alkyl, carboxy, C 1 -C 12 alkyl fluorenyl, C 5 -C 6 cycloalkylcarbenyl, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkane a fluorenyl group, an aryl fluorenyl group, an XR 17 group, a phenyl group, a halogen atom, a phenyl group substituted by CN; and R 20 , R 21 , R 22 , and R 23 are each independently one of the following groups: a hydrogen atom , C 1 -C 18 alkyl, C 3 -C 7 cycloalkyl; or C 1 -C 18 alkyl substituted by halogen, CN, C 1 -C 4 alkoxy; or by one or more oxygen An atom, a C 5 -C 7 cycloalkylene group, a C 2 -C 18 alkyl group in which a phenylene group is inserted; or a C 1 -C 3 alkyl group substituted by a phenyl group, a C 3 -C 7 cycloalkyl group; Or phenyl, naphthyl, benzhydryl; or optionally halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenoxy, phenyl sulfide a phenyl, a naphthyl, a benzhydryl group substituted with a NR 24 R 25 , a C 1 -C 12 alkyl fluorenyl group, a benzylidene group; each of R 24 and R 25 is a C 1 -C 4 alkyl group; or a NR 24 R 25 It is phenylephrine (morpholine), piperidine (piperidine), piperidine (piperazine), N- methylpiperidine (N-methyl piperazine), pyrrole (pyrrole).

當結構通式V、Ⅵ、Ⅶ化合物中的肟基有順反異構體時，得到的各中間體及最終產物通式I化合物是其異構體的混合物，經分離可以得到純化的各個異構體。When the thiol group in the compound of the general formula V, VI, VII has a cis-trans isomer, the obtained intermediate and the final product of the compound of the formula I are a mixture of isomers thereof, and the purified individual can be obtained by separation. Structure.

本發明還涉及一種光固化組合物，含有光引發劑(a)和至 少一種可進行自由基聚合的碳碳雙鍵化合物(b)，光引發劑(a)包含至少一種不對稱二肟酯化合物，包含前述結構通式I化合物。The present invention also relates to a photocurable composition comprising a photoinitiator (a) and to There is one less carbon-carbon double bond compound (b) which can be subjected to radical polymerization, and the photoinitiator (a) comprises at least one asymmetric dinonyl ester compound comprising the above-mentioned compound of the formula I.

光引發劑(a)除了含有至少一種前述的不對稱二肟酯化合物結構通式I化合物外，還進一步包含其他市售光引發劑作為共引發劑組分(c)。The photoinitiator (a) further comprises, as a co-initiator component (c), in addition to the at least one of the aforementioned asymmetric diterpene ester compound structures of the formula I.

前述光固化組合物，進一步含有其他添加劑(d)，例如可顯影樹脂、顏料、消泡劑等必要功能組分。The photocurable composition further contains other additives (d) such as a developable resin, a pigment, an antifoaming agent and the like.

以重量計，光引發劑(a)占全部固化組合物的0.05-25%，優選的為2-15%；其餘組分占除上述組分外的剩餘百分比。The photoinitiator (a) comprises from 0.05 to 25%, preferably from 2 to 15% by weight of the total of the cured composition; the balance of the remaining components in addition to the above components.

可進行自由基聚合的碳碳雙鍵化合物(b)即為光固化單體，其分子中包括一個碳碳雙鍵或兩個及兩個以上碳碳雙鍵，包含一個碳碳雙鍵的化合物(b)優選的為丙烯酸酯化合物、甲基丙烯酸酯化合物，例如一元醇的丙烯酸酯或甲基丙烯酸酯：丙烯酸甲酯、丙烯酸丁酯、丙烯酸2-乙基己酯、丙烯酸環己酯、丙烯酸異冰片酯、丙烯酸羥乙酯、甲基丙烯酸甲酯以及丙烯腈、N-二烷基丙烯醯胺、N-乙烯基吡咯烷酮、乙烯基苯、乙烯基乙酸酯、乙烯基醚。The carbon-carbon double bond compound (b) which can be subjected to radical polymerization is a photocurable monomer which includes a carbon-carbon double bond or two or more carbon-carbon double bonds in the molecule, and a compound containing one carbon-carbon double bond. (b) Preferred are acrylate compounds, methacrylate compounds, such as acrylates or methacrylates of monohydric alcohols: methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, acrylic acid Isobornyl ester, hydroxyethyl acrylate, methyl methacrylate and acrylonitrile, N-dialkyl acrylamide, N-vinyl pyrrolidone, vinyl benzene, vinyl acetate, vinyl ether.

包含兩個及兩個以上碳碳雙鍵的化合物(b)，例如烷基二元醇、多元醇的丙烯酸酯或甲基丙烯酸酯或者聚酯多元醇、聚醚多元醇、環氧樹脂多元醇、聚氨酯多元醇的丙烯酸酯、乙烯基醚以及不飽和二元羧酸多元醇的不飽和聚酯，例如聚乙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、多乙氧基化三羥甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯、聚酯低聚物丙烯酸酯、聚氨酯低 聚物丙烯酸酯、芳香族環氧樹脂丙烯酸酯、馬來酸乙二醇聚酯。a compound (b) comprising two or more carbon-carbon double bonds, such as an alkyl diol, an acrylate or methacrylate of a polyol or a polyester polyol, a polyether polyol, an epoxy resin polyol An acrylate of a polyurethane polyol, a vinyl ether, and an unsaturated polyester of an unsaturated dicarboxylic acid polyol, such as polyethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate Ester, polyethoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, polyester oligomer acrylate, low polyurethane Polymer acrylate, aromatic epoxy resin acrylate, maleic acid ethylene glycol polyester.

這些碳碳雙鍵化合物(b)不僅可以單獨使用，還可以兩種以上混合使用或混合物之間可以進行預共聚形成低聚物供配製組合物使用；當聚合單體中含有鹼溶性基團例如羧酸基時，得到具有鹼溶性的聚合物樹脂，可用於配製光致抗蝕劑或用於配製水分散乳液。These carbon-carbon double bond compounds (b) may be used alone or in combination of two or more, or may be pre-copolymerized to form an oligomer for use in formulating the composition; when the polymerizable monomer contains an alkali-soluble group, for example In the case of a carboxylic acid group, a polymer resin having an alkali solubility can be obtained, which can be used for formulating a photoresist or for formulating a water-dispersed emulsion.

除上述結構通式I化合物的不對稱二肟酯化合物作為光引發劑外，根據光固化組合物用途的需要，還可以複配其他類型市售光引發劑或助引發劑作為共引發劑組分(c)，通常是α-羥基酮類如2-羥基-2-甲基-1-苯丙酮、1-羥基環己基苯甲酮；α-氨基酮類如2-甲基-2-嗎福林基-(4-甲硫基苯)-1-丙酮、2-二甲基氨基-2-苯甲基-(4-嗎福林代苯基)-1-丁酮；2,2-二乙氧基-1,2-二苯乙酮；苯甲醯基甲酸甲酯、二乙二醇雙苯甲醯基甲酸、酯聚丁二醇雙苯甲醯基甲酸酯；(2,4,6-三甲基苯甲醯基)二苯基氧化膦、二(2,4,6-三甲基苯甲醯基)苯基氧化膦；二苯甲酮及其取代衍生物如二苯甲酮、4-甲基二苯甲酮、4-氯二苯甲酮、4-苯基二苯甲酮、2’-氯-4-苯基二苯甲酮、4-甲硫基二苯甲酮、4-(2-羥乙基硫代)二苯甲酮、4-羥基二苯甲酮月桂酸酯二苯甲酮-4-氧乙酸聚乙二醇酯；硫雜蒽酮及其取代衍生物如2-異丙基硫雜蒽酮、2,4-二乙基硫雜蒽酮、1-氯-4-丙氧基硫雜蒽酮、硫雜蒽酮-2-甲酸聚乙二醇酯、硫雜蒽酮-2-氧乙酸聚乙二醇酯；鹵代甲基三嗪如2-(4-甲氧基苯基)-4,6-二(三氯甲基)-[1,3,5]-三嗪；六芳基二咪唑類例如六鄰氯苯基二咪唑；二茂鐵類化合物；二茂鈦類化合物；香豆素；樟腦醌；吖啶類如9-苯基吖啶；胺類如4,4’-二(二乙基氨基)二苯甲酮、4-二甲氨基苯甲酸乙酯、三乙醇胺、甲基二乙醇胺或活性胺類化合物，如二乙胺與乙氧基化三羥甲基丙 烷三丙烯酸酯加成物；亞磷酸酯類如亞磷酸三苯酯、亞磷酸三月桂酯；鏈轉移劑例如己二硫醇、辛硫醇。In addition to the above-mentioned asymmetric diterpene ester compound of the compound of the formula I as a photoinitiator, other types of commercially available photoinitiators or co-initiators may be compounded as co-initiator components depending on the needs of the photocurable composition. (c), usually α-hydroxyketones such as 2-hydroxy-2-methyl-1-propiophenone, 1-hydroxycyclohexylbenzophenone; α-aminoketones such as 2-methyl-2-ifu Lin-(4-methylthiophenyl)-1-propanone, 2-dimethylamino-2-benzyl-(4-fosinophenyl)-1-butanone; 2,2-di Ethoxy-1,2-diacetophenone; methyl benzomethionate, diethylene glycol bisbenzoyl carboxylic acid, ester polybutylene glycol bis benzoate; (2, 4 ,6-trimethylbenzylidene)diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide; benzophenone and substituted derivatives thereof such as diphenyl Ketone, 4-methylbenzophenone, 4-chlorobenzophenone, 4-phenylbenzophenone, 2'-chloro-4-phenylbenzophenone, 4-methylthiodiphenyl Ketone, 4-(2-hydroxyethylthio)benzophenone, 4-hydroxybenzophenone laurate benzophenone-4-oxyacetic acid polyethylene glycol ester; thioxanthone and Substituted derivative 2-isopropylthioxanthone, 2,4-diethylthiazinone, 1-chloro-4-propoxythiazinone, thioxanthone-2-carboxylic acid polyethylene glycol ester, Thiophenone-2-oxoacetate polyethylene glycol ester; halomethyltriazine such as 2-(4-methoxyphenyl)-4,6-di(trichloromethyl)-[1,3 , 5]-triazine; hexaaryldiimidazoles such as hexa-chlorophenyldiimidazole; ferrocene compounds; ferrocene compounds; coumarin; camphorquinone; acridine such as 9-phenylindole Alkane such as 4,4'-bis(diethylamino)benzophenone, ethyl 4-dimethylaminobenzoate, triethanolamine, methyldiethanolamine or a reactive amine compound such as diethylamine Ethoxylated trimethylol Alkane triacrylate adducts; phosphites such as triphenyl phosphite, trilauryl phosphite; chain transfer agents such as hexanedithiol, octyl mercaptan.

添加劑(d)包含顏料及染料，顏料是印刷油墨和製備濾光器的必要成分，按使用需要可以分別是紅色、綠色、藍色、黑色、白色、黃色、品紅、青色及其他特定專用顏色，相應的顏料如炭黑、酞青藍、二氧化鈦等市售品種；顏料濃度一般占前述光固化組合物所有固體組分重量的10-30%。The additive (d) contains pigments and dyes, and the pigment is an essential component of the printing ink and the preparation filter, and can be red, green, blue, black, white, yellow, magenta, cyan and other specific special colors as needed. Corresponding pigments such as carbon black, indigo blue, titanium dioxide and the like are commercially available; the pigment concentration generally accounts for 10-30% by weight of all solid components of the aforementioned photocurable composition.

添加劑(d)還可以為酚類和受阻胺類阻聚劑，例如對甲氧基苯酚、亞硝基苯胲鋁絡合物阻聚劑；光吸收劑如2-(2’-羥基苯基)-苯並三氮唑類水楊酸酯類、三嗪類；流平劑例如乙烯基三乙氧基矽烷；潤濕劑、分散劑，它們的用量以達到光固化組合物性質指標為限，並無特別要求。The additive (d) may also be a phenolic and hindered amine polymerization inhibitor, such as a p-methoxyphenol, a nitrosophthalide aluminum complex polymerization inhibitor; a light absorber such as 2-(2'-hydroxyphenyl). - benzotriazole salicylates, triazines; leveling agents such as vinyl triethoxy decane; wetting agents, dispersing agents, the amount of which is limited to the properties of the photocurable composition There are no special requirements.

添加劑(d)還包括可顯影樹脂，其中鹼溶性可顯影樹脂，例如含有羧酸側鏈的聚丙烯酸酯共聚物，共聚單體可選自丙烯酸或甲基丙烯酸、丙烯酸烷基酯、甲基丙烯酸烷基酯、苯乙烯、低聚苯乙烯；溶劑可顯影樹脂例子有纖維素酯和纖維素醚、聚乙酸乙烯酯、聚乙烯醇縮丁醛、聚苯乙烯、聚碳酸酯、聚氯乙烯、聚酯、聚醯亞胺這些常規品種的樹脂；當可顯影樹脂為鹼溶性樹脂時，光固化組合物可用於光致抗蝕劑和用於顯示器件中彩色濾光片的生產。The additive (d) further includes a developable resin in which an alkali-soluble developable resin such as a polyacrylate copolymer containing a carboxylic acid side chain, the comonomer may be selected from acrylic acid or methacrylic acid, alkyl acrylate, methacrylic acid. Alkyl ester, styrene, low polystyrene; examples of solvent developable resins are cellulose ester and cellulose ether, polyvinyl acetate, polyvinyl butyral, polystyrene, polycarbonate, polyvinyl chloride, Conventional varieties of resins such as polyester and polyimine; when the developable resin is an alkali-soluble resin, the photocurable composition can be used for photoresists and for the production of color filters in display devices.

前述光固化組合物組合物進一步含有熱乾燥樹脂和熱固性樹脂組分(e)，例如纖維素溶液、聚異氰酸酯、聚醯亞胺，他們適合於光固化、熱固化分段處理的流程要求。The aforementioned photocurable composition composition further contains a thermally dry resin and a thermosetting resin component (e) such as a cellulose solution, a polyisocyanate, a polyimine, which are suitable for the flow requirements of the photocuring and heat curing segmentation treatment.

前述光固化組合物中還允許加入至少一種具有環氧基團的 化合物作為熱固性組分(f)和一種環氧基固化促進劑(g)；具有環氧基團的化合物作為熱固性組分(f)可以使用公知的熱固性環氧化合物，例如脂肪族環氧樹脂或芳香族環氧樹脂，優選雙酚S型環氧樹脂如日本化學公司生產的BPS-200，雙酚A型環氧樹脂，線型酚醛環氧樹脂等及他們的部分酯化物，在組合物中相對於100份重量比例的組分(b)，組分(f)的用量為30-70份。It is also allowed to add at least one epoxy group in the aforementioned photocurable composition. a compound as a thermosetting component (f) and an epoxy curing accelerator (g); a compound having an epoxy group as the thermosetting component (f) may be a known thermosetting epoxy compound such as an aliphatic epoxy resin or An aromatic epoxy resin, preferably a bisphenol S type epoxy resin such as BPS-200, a bisphenol A type epoxy resin, a novolac epoxy resin, etc., and a partial esterified product thereof, which are relatively in the composition. The component (f) is used in an amount of 30 to 70 parts by weight based on 100 parts by weight of the component (b).

當使用熱固性組分(f)時，任選地使用環氧基固化促進劑(g)作為協同組分能起到良好的固化促進作用，例子有胺類促進劑、咪唑類促進劑及其他通常使用的環氧樹脂硬化劑，用量不超過熱固性組分(f)重量的5%。When the thermosetting component (f) is used, an epoxy curing accelerator (g) is optionally used as a synergistic component to provide a good curing promotion effect, and examples are an amine accelerator, an imidazole accelerator, and the like. The epoxy resin hardener used is not more than 5% by weight of the thermosetting component (f).

除上述組分(a)、(b)、(c)、(d)、(e)、(f)、(g)外，前述光固化組合物中還可以使用本領域技術所常用的其他添加劑(h)，它們包括：用於改善光固化組合物的粘合性和成膜硬度等的添加劑之一是無機填料，例如硫酸鋇、粉末二氧化矽、滑石粉、碳酸鈣、雲母粉等，用量占組合物總重量的30%以內；前述光固化組合物還可以根據應用領域的需要被溶劑稀釋後使用，合適的溶劑是：酮類，例如甲基乙基酮，環己酮；烴類，例如甲苯、二甲苯、辛烷、石油醚、石腦油；醇類，例如正丁醇、丙二醇等；醇醚及其酯類，例如丙二醇單甲醚、二乙二醇單甲醚、丙二醇單甲醚乙酸酯、3-甲氧基丙酸甲酯等；醯胺類例如N,N-二甲基甲醯胺。In addition to the above components (a), (b), (c), (d), (e), (f), (g), other additives commonly used in the art may be used in the aforementioned photocurable composition. (h), they include: one of additives for improving the adhesion and film forming hardness of the photocurable composition, such as barium sulfate, powdered cerium oxide, talc, calcium carbonate, mica powder, etc. The amount is within 30% of the total weight of the composition; the photocurable composition can also be used after being diluted with a solvent according to the needs of the application field, and suitable solvents are: ketones such as methyl ethyl ketone, cyclohexanone; hydrocarbons For example, toluene, xylene, octane, petroleum ether, naphtha; alcohols such as n-butanol, propylene glycol, etc.; alcohol ethers and esters thereof, such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, methyl 3-methoxypropionate, etc.; guanamines such as N,N-dimethylformamide.

前述光固化組合物或其被溶劑稀釋的混合物按油墨的生產方法配製完成後，避光保存。The photocurable composition or the solvent-diluted mixture thereof is prepared in the ink production method and stored in the dark.

前述光固化組合物的用途是用於製造帶有顏色的或透明的下列製品之一：塗料、粘合劑或油墨、光致抗蝕劑及光阻劑，再將該製品用於印刷、3D列印、顯示器件中彩色濾光片的生產、圖像複製技術、印刷電路板介質層、電子器件封裝、光學開關、三維模具、石英纖維保護層、醫療製品。The use of the aforementioned photocurable composition is for the manufacture of one of the following articles with color or transparency: paint, adhesive or ink, photoresist and photoresist, and then the article is used for printing, 3D Production of color filters in printing and display devices, image reproduction technology, printed circuit board dielectric layers, electronic device packaging, optical switches, three-dimensional molds, quartz fiber protective layers, medical products.

本發明提供一種前述光固化組合物中碳碳雙鍵化合物進行固化的方法，即前述光固化組合物被塗布於基材上形成塗佈層，用190nm-600nm光線照射使塗佈層固化。光線來自太陽，汞燈，高壓汞燈或LED燈，包括用190-600nm範圍內的光波或者是經過光柵控制輸出光波長的光波輻射該塗佈層，也可以用360nm-410nm之間任一一定波長範圍的LED光源例如365nmLED光源照射固化該光固化組合物塗布層；所述LED的定義為發光半導體二極體。The present invention provides a method for curing a carbon-carbon double bond compound in the photocurable composition, that is, the photocurable composition is applied onto a substrate to form a coating layer, and the coating layer is cured by irradiation with light at 190 nm to 600 nm. The light comes from the sun, mercury lamp, high-pressure mercury lamp or LED lamp, including the light wave in the range of 190-600nm or the light wave which is controlled by the grating to control the wavelength of the output light. It can also be used between 360nm-410nm. A light source of a predetermined wavelength range, such as a 365 nm LED light source, illuminates the coating layer of the photocurable composition; the LED is defined as a light emitting semiconductor diode.

前述光固化組合物製作凸起圖案的方法是，先將光固化組合物用溶劑稀釋；後將稀釋後的光固化組合物塗布於基材上，經烘乾、曝光、顯影方法除去未曝光部分得到凸起圖案。The photocurable composition is formed by forming a convex pattern by first diluting the photocurable composition with a solvent; then, applying the diluted photocurable composition to a substrate, and removing the unexposed portion by drying, exposure, and development. A raised pattern is obtained.

本發明中含有至少一種具有結構通式I化合物的不對稱二肟酯化合物、光固化單體、鹼溶性樹脂、顏料及添加劑的光固化組合物，可以用作光刻膠，具有高的光敏感性，易於被鹼性水溶液顯影，不溶脹變形，成像效果清晰，適合於製成刻蝕光刻膠，阻焊光刻膠；用於圖像顯示和記錄材料；用LED燈固化的噴墨油墨；用於LCD、OLED、PDP的生產過程中，也能用於各種印刷版的製造及電子線路版或積體電路的生產過程中，還能用於形成各種電子元件的隔離塗層。A photocurable composition containing at least one asymmetric diterpene ester compound having a structural formula I, a photocurable monomer, an alkali soluble resin, a pigment and an additive, which can be used as a photoresist and having high light sensitivity Sexual, easy to be developed by alkaline aqueous solution, non-swelling deformation, clear imaging effect, suitable for etching photoresist, solder resist photoresist; for image display and recording materials; inkjet ink cured with LED lamp Used in the production process of LCD, OLED, PDP, can also be used in the manufacture of various printing plates and in the production process of electronic circuit boards or integrated circuits, and can also be used to form barrier coatings for various electronic components.

前述光固化組合物具有優良的抗氧氣阻聚作用和耐熱加工性能，滿足彩色濾光片生產工藝要求，特別適合於液晶顯示器、有機半導體電致發光顯示器的生產。The photocurable composition has excellent anti-oxidation inhibition and heat-resistant processing properties, meets the requirements of the color filter production process, and is particularly suitable for the production of liquid crystal displays and organic semiconductor electroluminescent displays.

使用本發明的光固化組合物作為光阻劑，依序經過塗布、曝光、顯影、熱處理過程而，形成黑色及紅綠藍三色圖案，得到完整的彩色濾光片，這些濾色器的基材可以是玻璃或有機聚合物膜及陶瓷片。The photocurable composition of the present invention is used as a photoresist, sequentially subjected to coating, exposure, development, and heat treatment to form a black, red, green, and blue three-color pattern to obtain a complete color filter, and the basis of these color filters. The material may be a glass or organic polymer film and a ceramic sheet.

本發明的內容還包括用前述光固化組合物製造的彩色濾光片。The present invention also encompasses color filters made with the aforementioned photocurable compositions.

將前述光固化組合物塗布於平板或曲面基材上，經烘乾得到膜層；經掩膜曝光、顯影方法除去未曝光部分得到凸起圖像，包含黑色、紅色、綠色、藍色圖元的彩色濾光片，經由含有本發明中具有結構通式I化合物的不對稱二肟酯化合物、光固化單體、鹼溶性樹脂及相應顏料、助劑構成的光固化組合物的塗布、曝光、顯影、熱處理過程得到，其中也包含清洗等必要的處理過程。The photocurable composition is coated on a flat or curved substrate, and dried to obtain a film layer; the unexposed portion is removed by mask exposure and development to obtain a convex image including black, red, green, and blue primitives. The color filter is coated, exposed, and coated with a photocurable composition comprising an asymmetric diterpene ester compound having a structural formula I of the present invention, a photocurable monomer, an alkali-soluble resin, and a corresponding pigment or auxiliary. The development and heat treatment processes are obtained, and the necessary treatment processes such as cleaning are also included.

使用本領域通常使用的塗布技術如旋塗、輥塗、噴塗、轉印等方法將本發明的光固化組合物均勻塗覆於待塗基材上，塗布量依所需確定，通常的厚度為0.1微米至1毫米；光固化組合物含有溶劑組分時，用加熱法例如80℃乾燥法使溶劑揮發，而不揮發組分形成膠層留在基材上。The photocurable composition of the present invention is uniformly applied to a substrate to be coated by a coating technique commonly used in the art such as spin coating, roll coating, spray coating, transfer, etc., and the coating amount is determined as required, and the usual thickness is 0.1 μm to 1 mm; when the photocurable composition contains a solvent component, the solvent is volatilized by a heating method such as 80 ° C drying, and the non-volatile component forms a gel layer remaining on the substrate.

下一步是曝光，如果不是使用UV鐳射直接曝光，就將具有圖像的掩膜置於膠層上，紫外或可見光光源發射一定範圍波長的光線以設定能量穿過掩膜透光部分進行曝光，於是，膠層受光部分產生固化，被遮蔽部分不產生固化。The next step is exposure. If it is not directly exposed by UV laser, the mask with the image is placed on the glue layer, and the ultraviolet or visible light source emits a range of wavelengths of light to set the energy through the transparent portion of the mask for exposure. Thus, the adhesive layer is cured by the light-receiving portion, and the shielded portion is not cured.

接下來是顯影，除去未曝光部分得到凸起圖案；顯影工藝以本領域熟練技術人員公知的參數操作，例如30℃噴淋，漂洗；通常使用鹼性水溶液顯影，例如鹼金屬的氫氧化物、碳酸鹽的水溶液，氨水，也可在必要時向水溶液中添加定量潤濕劑如表面活性劑、有機溶劑如環己酮、丙酮、乙二醇***等；將曝光膜浸入顯影液浴或將顯影液噴霧到曝光膜上的顯影方式都是可以的，具體的顯影溫度和時間視顯影效果而定；用於顯影的鹼溶液是將鹼性物質溶解于水或含有水溶性有機溶劑的水溶液中，其中鹼性物質的例子有氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、三乙醇胺、嗎福林、磷酸三鈉，重量濃度範圍0.1-10%；上述水溶液還可以加入重量濃度0.05-5%的表面活性劑。Subsequent to development, removing the unexposed portions to obtain a raised pattern; the developing process is operated by parameters well known to those skilled in the art, such as 30 ° C spraying, rinsing; typically using an alkaline aqueous solution, such as an alkali metal hydroxide, An aqueous solution of carbonate, ammonia water, or a quantitative wetting agent such as a surfactant, an organic solvent such as cyclohexanone, acetone, ethylene glycol ether or the like may be added to the aqueous solution as necessary; the exposed film is immersed in a developing bath or developed The development method of the liquid spray onto the exposure film is ok, and the specific development temperature and time depend on the development effect; the alkali solution used for development is to dissolve the alkaline substance in water or an aqueous solution containing a water-soluble organic solvent. Examples of the alkaline substance are sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, triethanolamine, orofolium, and trisodium phosphate, and the weight concentration ranges from 0.1 to 10%; It is also possible to add a surfactant having a concentration of 0.05 to 5% by weight.

最後的熱處理過程能夠優化圖像牢度，一般是在200-260℃熱爐中烘烤15-45分鐘。The final heat treatment process optimizes image fastness and is typically baked in a hot oven at 200-260 ° C for 15-45 minutes.

基於此按照公知的彩色濾光片的生產工藝，使用本發明組合物可以製造出彩色濾光片器件，並顯示出優良的加工性能，陣列清晰、光透過率高，用於生產高品質顯示器。Based on this, in accordance with the production process of the known color filter, the color filter device can be manufactured using the composition of the present invention, and exhibits excellent processability, clear array, high light transmittance, and is used for producing a high quality display.

下述實施例能夠更詳細地說明本發明，涉及用量時都以重量計，特別指出的除外。The following examples are illustrative of the invention in more detail, all in terms of amounts, unless otherwise indicated.

實施例1 合成5-苯硫基茚滿-1-酮 Example 1 Synthesis of 5-phenylthioindan-1-one

稱量33.3g(0.2mol)5-氯-1-茚酮在50ml三口瓶中，加入30mlN,N-二甲基甲醯胺(DMF)，30.0g(0.27mol)苯硫酚，36g無水碳酸鉀， 氮氣保護，40-45℃攪拌6h；減壓回收DMF，將剩餘物加入到100ml水中，用25ml 1,2-二氯乙烷萃取兩次，合併1,2-二氯乙烷溶液，用10ml水洗滌兩次，在布氏漏斗中鋪濾紙，用它抽濾有機相，濾液濃縮至乾，剩餘物用甲醇重結晶，乾燥後得淺黃色結晶43.4g，收率90.3%，HPLC分析純度98.2%，熔程46.0-48.0℃。Weigh 33.3g (0.2mol) of 5-chloro-1-indanone in a 50ml three-necked flask, add 30ml of N,N-dimethylformamide (DMF), 30.0g (0.27mol) of thiophenol, 36g of anhydrous carbonic acid Potassium, Nitrogen protection, stirring at 40-45 ° C for 6 h; DMF was recovered under reduced pressure, the residue was added to 100 ml of water, extracted twice with 25 ml of 1,2-dichloroethane, and the solution of 1,2-dichloroethane was combined with 10 ml. The mixture was washed twice with water, and the paper was filtered in a Buchner funnel. The organic phase was filtered with suction, and the filtrate was concentrated to dryness. The residue was crystallised from methanol and dried to yield 43.4 g of pale yellow crystals with a yield of 90.3%. %, melting range 46.0-48.0 °C.

實施例2 合成5-(4-辛醯基苯硫基)茚滿-1-酮 Example 2 Synthesis of 5-(4-octylphenylthio)indan-1-one

稱取實施例1的產物5-苯硫基茚滿-1-酮24.04g(0.1mol)溶於120ml1,2-二氯乙烷，降溫到5-10℃，加入28g(0.21mol)無水三氯化鋁，攪拌滴加17.9g(0.11mol)辛醯氯，加完後攪拌4h，用稀鹽酸處理反應液，分離有機溶液，再水洗一次，濃縮回收1,2-二氯乙烷，將剩餘物在100ml乙醇中重結晶，得到白色結晶33.1g，收率90.1%，熔程74.3-75.2℃，1 H-NMR資料表明所得產物為5-(4-辛醯基苯硫基)茚滿-1-酮；1 H-NMR(CDCl3 )，δ(ppm)值數據：0.8848(t,3H,CH3 )，1.2892-1.3412(m,8H,4CH2 )，1.7359(m,2H,CH2 )，2.7066(t,2H,c-CH2 )，2.9526(t,2H,CH2 )，3.0961(t,2H,c-CH2 )，7.2740/7.3008(d,1H,ArH)，7.3734(s,1H,ArH)，7.4525/7.4797(d,2H,2ArH)，7.6677/7.6945(d,1H,ArH)，7.9221/7.9493(d,2H,2ArH)。The product of Example 1 was weighed to give 5-phenylthioindan-1-one 24.04 g (0.1 mol) dissolved in 120 ml of 1,2-dichloroethane, cooled to 5-10 ° C, and added 28 g (0.21 mol) of anhydrous three. Aluminum chloride, 17.9g (0.11mol) of octyl chloride was added dropwise with stirring. After the addition, the mixture was stirred for 4 hours. The reaction solution was treated with dilute hydrochloric acid. The organic solution was separated, washed once, and concentrated to recover 1,2-dichloroethane. The residue was recrystallized from 100 ml of ethanol to give white crystals (33.1 g, yield: 90.1%, melting range: 74.3-75.2 ° C, 1 H-NMR data indicated that the product was 5-(4-octylphenylthio)indan-1 - ketone; 1 H-NMR (CDCl 3 ), δ (ppm) value data: 0.8848 (t, 3H, CH 3 ), 1.2892-1.3412 (m, 8H, 4CH 2 ), 1.7359 (m, 2H, CH 2 ) , 2.7066 (t, 2H, c-CH 2 ), 2.9526 (t, 2H, CH 2 ), 3.0961 (t, 2H, c-CH 2 ), 7.2740/7.3008 (d, 1H, ArH), 7.3734 (s, 1H, ArH), 7.4525/7.4797 (d, 2H, 2ArH), 7.6677/7.6945 (d, 1H, ArH), 7.9221/7.9493 (d, 2H, 2ArH).

實施例3 合成5-(4-辛醯基苯硫基)茚滿-1,2-二酮-2-肟 Example 3 Synthesis of 5-(4-octylphenylthio)indan-1,2-dione-2-indole

取實施例2所得產物5-(4-辛醯基苯硫基)茚滿-1-酮18.4g (0.05mol)，用150ml乙醇溶解在250ml三口瓶中，再加36%濃鹽酸2g，水浴15-20℃保溫攪拌，15min內滴加6.2g(0.06mol)亞硝酸正丁酯，25℃攪拌5h後將反應液降溫到5-10℃，過濾析出的黃色固體，乾燥後18.7g，分析純度98.90%，熔程162.7-164.0℃，1 H-NMR資料表明所得產物為5-(4-辛醯基苯硫基)茚滿-1,2-二酮-2-肟，收率94.2%；1 H-NMR(CDCl3 )，δ(ppm)值數據：0.8866(t,3H,CH3 )，1.2965-1.3512(m,8H,4CH2 )，1.7493(m,2H,CH2 )，2.9737(t,2H,CH2 )，3.7977(s,2H,c-CH2 )，7.2674/7.2943(d,1H,ArH)，7.3320(s,1H,ArH)，7.5281/7.5558(d,2H,2ArH)，7.7707/7.7977(d,1H,2ArH)，7.9648/7.9925(d,2H,2ArH)，12.4460(s,1H,NOH)。The product obtained in Example 2, 5-(4-octylphenylthio)indan-1-one, 18.4 g (0.05 mol) was dissolved in a 250 ml three-necked flask with 150 ml of ethanol, and then added with 36% concentrated hydrochloric acid 2 g, water bath 15- The mixture was stirred at 20 ° C, and 6.2 g (0.06 mol) of n-butyl nitrite was added dropwise in 15 min. After stirring at 25 ° C for 5 h, the reaction solution was cooled to 5-10 ° C, and the precipitated yellow solid was filtered. After drying, 18.7 g, the purity was 98.90. %, melting range 162.7-164.0 ° C, 1 H-NMR data showed that the product was 5-(4-octylphenylthio)indan-1,2-dione-2-indole, yield 94.2%; 1 H- NMR (CDCl 3 ), δ (ppm) value data: 0.8866 (t, 3H, CH 3 ), 1.2965-1.3512 (m, 8H, 4CH 2 ), 1.7493 (m, 2H, CH 2 ), 2.9737 (t, 2H) , CH 2 ), 3.7977 (s, 2H, c-CH 2 ), 7.2674/7.2943 (d, 1H, ArH), 7.3320 (s, 1H, ArH), 7.5281/7.5558 (d, 2H, 2ArH), 7.7707/ 7.7977 (d, 1H, 2ArH), 7.9648/7.9925 (d, 2H, 2ArH), 12.4460 (s, 1H, NOH).

實施例4 合成二肟化物 Example 4 Synthesis of Ditelluride

取實施例2所得產物5-(4-辛醯基苯硫基)茚滿-1,2-二酮-2-肟7.95g(0.02mol)，用二甲基亞碸40ml溶解，加入36%濃鹽酸0.5g，水浴20-25℃保溫攪拌，15min內滴加3.1g(0.03mol)亞硝酸正丁酯，攪拌10h後將反應液降溫到5-10℃，過濾析出的黃色固體，乾燥後7.72g，分析純度96.80%，收率90.5%；熔程171.0-173.0℃，1 H-NMR資料表明所得產物為雙肟化物，1 H-NMR(DMSO-d6 )，δ(ppm)值數據：0.850(t,3H,CH3 )，1.272-1.492(m,8H,4CH2 )，2.616(t,2H,CH2 )，3.738(s,2H,c-CH2 )，7.299/7.319(d,1H,ArH)，7.435(s,1H,ArH)，7.557/7.578(d,2H,2ArH)，7.719/7.739(d,1H,2ArH)，7.847/7.867(d,2H,2ArH)，12.446(s,1H,NOH)，12.651(s,1H,NOH)。The product obtained in Example 2 was obtained as 5-(4-octylphenylthio)indan-1,2-dione-2-indole 7.95 g (0.02 mol), dissolved in 40 ml of dimethylhydrazine, and 36% concentrated hydrochloric acid was added. 0.5g, water bath 20-25 ° C insulation stirring, adding 3.1g (0.03mol) n-butyl nitrite in 15min, stirring for 10h, the reaction liquid was cooled to 5-10 ° C, the precipitated yellow solid was filtered, 7.72g after drying The purity of the analysis was 96.80%, the yield was 90.5%; the melting range was 171.0-173.0 °C, and the 1 H-NMR data showed that the obtained product was a double telluride, 1 H-NMR (DMSO-d 6 ), δ (ppm) value data: 0.850 (t, 3H, CH 3 ), 1.272-1.492 (m, 8H, 4CH 2 ), 2.616 (t, 2H, CH 2 ), 3.738 (s, 2H, c-CH 2 ), 7.299/7.319 (d, 1H) , ArH), 7.435 (s, 1H, ArH), 7.557/7.578 (d, 2H, 2ArH), 7.719/7.739 (d, 1H, 2ArH), 7.847/7.867 (d, 2H, 2ArH), 12.446(s, 1H, NOH), 12.651 (s, 1H, NOH).

實施例5 合成二肟酯ⅡA1 Example 5 Synthesis of Diterpene Ester IIA1

取實施例4產物4.27g(0.01mol)溶於25ml1,2-二氯乙烷，滴加3.1g(0.03mol)醋酐，20-25℃水浴中反應6h；反應液用25ml水洗滌兩次，分出水相，有機相用1.5g無水硫酸鈉乾燥2h，過濾去除乾燥劑，減壓蒸乾濾液；剩餘物中加入15ml乙酸乙酯，加熱至全溶，加入0.05g活性炭回流0.5h，熱過濾分離活性炭，向濾液中加入15ml正己烷，冷卻降溫，析出結晶，抽濾，真空乾燥濾餅得到黃色結晶產物4.47g，含量98.0%，收率87.8%；熔程和1 H-NMR(CDCl3 )，δ(ppm)值數據見表1。4.27 g (0.01 mol) of the product of Example 4 was dissolved in 25 ml of 1,2-dichloroethane, 3.1 g (0.03 mol) of acetic anhydride was added dropwise, and the reaction was carried out for 6 h in a water bath at 20-25 ° C; the reaction solution was washed twice with 25 ml of water. The aqueous phase was separated, and the organic phase was dried over 1.5 g of anhydrous sodium sulfate for 2 h. The desiccant was removed by filtration, and the filtrate was evaporated to dryness under reduced pressure. 15 ml of ethyl acetate was added to the residue, and the mixture was heated to dissolve. The activated carbon was separated by filtration, 15 ml of n-hexane was added to the filtrate, cooled to cool, crystals were precipitated, filtered, and the filter cake was vacuum dried to obtain a yellow crystalline product of 4.47 g, content: 98.0%, yield: 87.8%; melting range and 1 H-NMR (CDCl) 3 ), δ (ppm) value data are shown in Table 1.

實施例6 合成5-(4-戊醯基苯硫基)茚滿-1-酮 Example 6 Synthesis of 5-(4-pentenylphenylthio)indan-1-one

按實施例2的方法，用戊醯氯代替辛醯氯，得到5-(4-戊醯基苯硫基)茚滿-1-酮，收率93.0%，熔程74.1-75.8℃，1 H-NMR資料表明所得產物為5-[4-(3-環戊基丙醯基)苯硫基]茚滿-1-酮；1 H-NMR(CDCl3 )，δ(ppm)值數據：0.9590(t,3H,CH3 )，1.3533-1.4768(sextet,2H,CH2 )，1.7274(quintet,2H,CH2 )，2.7047(t,2H,c-CH2 Ar)，2.9585(t,2H,CH2 )，3.0961(t,2H,c-CH2 CO)，7.2745/7.3030(d,1H,ArH)，7.3760(s,1H,ArH)，7.4513/7.4791(d,2H,2ArH)，7.6683/7.6952(d,1H,ArH)，7.9213/7.9490(d,2H,2ArH)。In the same manner as in Example 2, pentyl chloride was used instead of octyl chloride to obtain 5-(4-pentenylphenylthio)indan-1-one, the yield was 93.0%, and the melting range was 74.1-75.8 ° C, 1 H. -NMR data showed that the obtained product was 5-[4-(3-cyclopentylpropenyl)phenylthio]indan-1-one; 1 H-NMR (CDCl 3 ), δ (ppm) value data: 0.9590 (t, 3H, CH 3 ), 1.3533-1.4768 (sextet, 2H, CH 2 ), 1.7274 (quintet, 2H, CH 2 ), 2.7047 (t, 2H, c-CH 2 Ar), 2.9585 (t, 2H, CH 2), 3.0961 (t, 2H, c-CH 2 CO), 7.2745 / 7.3030 (d, 1H, ArH), 7.3760 (s, 1H, ArH), 7.4513 / 7.4791 (d, 2H, 2ArH), 7.6683 / 7.6952 (d, 1H, ArH), 7.9213/7.9490 (d, 2H, 2ArH).

實施例7 合成5-(4-戊醯基苯硫基)茚滿-1,2-二酮-2-肟 Example 7 Synthesis of 5-(4-pentylphenylthio)indan-1,2-dione-2-indole

按照實施例3的肟化反應方法，以實施例6的產物為原料，用二甲基亞碸代替乙醇作為溶劑進行肟化反應，HPLC分析產生單肟化產物，不分離出單肟化產物。According to the deuteration reaction method of Example 3, the product of Example 6 was used as a raw material, and hydrazine reaction was carried out by using dimethyl hydrazine instead of ethanol as a solvent, and HPLC analysis revealed that the mono-deuterated product was not isolated.

實施例8 合成二肟化物 Example 8 Synthesis of Ditelluride

在實施例7的反應液中繼續滴加同樣重量的亞硝酸正丁酯進行第二肟化反應，10h後按實施例4的方法處理得黃色固體，純度96.50%，其中順式異構體含量3.30%，反式異構體含量93.20%，收率85.0%；1 H-NMR資料表明所得產物為雙肟化物，1 H-NMR(DMSO-d6 )，δ(ppm)值數據：0.9073(t,3H,CH3 )，1.4514-1.5741(sextet,2H,CH2 )，2.5879(t,2H,CH2 )，3.7380(s,2H,c-CH2 )，7.2916/7.3192(d,1H,ArH)，7.5172(s,1H,ArH)，7.5562/7.5836(d,2H,2ArH)，7.7166/7.7437(d,1H,ArH)，7.8505/7.8779(d,2H,2ArH)，12.4769(s,1H,NOH)，12.6651(s,1H,NOH)。In the reaction liquid of Example 7, the same weight of n-butyl nitrite was continuously added dropwise to carry out the second deuteration reaction, and after 10 h, the yellow solid was obtained by the method of Example 4, and the purity was 96.50%, wherein the cis isomer content. 3.30%, the content of trans isomer is 93.20%, the yield is 85.0%; 1 H-NMR data shows that the obtained product is a double telluride, 1 H-NMR (DMSO-d 6 ), δ (ppm) value data: 0.9073 ( t, 3H, CH 3 ), 1.4514-1.5741 (sextet, 2H, CH 2 ), 2.5879 (t, 2H, CH 2 ), 3.7380 (s, 2H, c-CH 2 ), 7.2916/7.3192 (d, 1H, ArH), 7.5172 (s, 1H, ArH), 7.5562/7.5836 (d, 2H, 2ArH), 7.7166/7.7437 (d, 1H, ArH), 7.8505/7.8779 (d, 2H, 2ArH), 12.7769 (s, 1H) , NOH), 12.6661 (s, 1H, NOH).

實施例9 合成二肟酯ⅡA6 Example 9 Synthesis of Diterpene Ester IIA6

按照實施例5的反應方法，以實施例8的產物為原料，進行酯 化反應，經純化處理得黃色固體，純度98.65%，其中順式異構體含量1.25%，反式異構體含量97.40%，收率60.3%；1 H-NMR資料表明所得產物為ⅡA6；1 H-NMR(CDCl3 )，δ(ppm)值數據見表1According to the reaction method of Example 5, the product of Example 8 was used as a raw material, and the esterification reaction was carried out to obtain a yellow solid with a purity of 98.65%, wherein the cis isomer content was 1.25%, and the trans isomer content was 97.40. %, yield 60.3%; 1 H-NMR data indicate that the resulting product is ⅱA6; 1 H-NMR (CDCl 3), δ (ppm) value of the data in Table 1

實施例10 合成5-[4-(3-環戊丙醯基)苯硫基]茚滿-1-酮 Example 10 Synthesis of 5-[4-(3-cyclopentenyl)phenylthio]indan-1-one

按實施例2的方法，用3-環戊基丙醯氯代替辛醯氯，得到5-[4-(3-環戊丙醯基)苯硫基]茚滿-1-酮，收率92.0%，熔程88.5-90.0℃，1 H-NMR資料表明所得產物為5-[4-(3-環戊基丙醯基)苯硫基]茚滿-1-酮；1 H-NMR(CDCl3 )，δ(ppm)值數據：1.1072(m,2H,CH2 )，1.5328-1.8691(m,9H,4CH2 +1CH)，2.7067(t,2H,c-CH2 )，2.9689(t,2H,CH2 )，3.0974(t,2H,c-CH2 )，7.278/7.3048(d,1H,ArH)，7.3766(s,1H,ArH)，7.4531/7.4803(d,2H,2ArH)，7.6695/7.7963(d,1H,2ArH)，7.9245/7.9517(d,2H,2ArH)。In the same manner as in Example 2, 3-cyclopentylpropionyl chloride was used instead of octyl chloride to obtain 5-[4-(3-cyclopentenyl)phenylthio]indan-1-one in a yield of 92.0. %, melting range 88.5-90.0 ° C, 1 H-NMR data indicated that the product obtained was 5-[4-(3-cyclopentylpropenyl)phenylthio]indan-1-one; 1 H-NMR (CDCl) 3 ), δ (ppm) value data: 1.1072 (m, 2H, CH 2 ), 1.5328-1.8691 (m, 9H, 4CH 2 +1CH), 2.7067 (t, 2H, c-CH 2 ), 2.9689 (t, 2H,CH 2 ), 3.0974 (t, 2H, c-CH 2 ), 7.278/7.3048 (d, 1H, ArH), 7.3766 (s, 1H, ArH), 7.4531/7.4803 (d, 2H, 2ArH), 7.6695 /7.7963 (d, 1H, 2ArH), 7.9245/7.9517 (d, 2H, 2ArH).

實施例11 合成5-[4-(3-環戊基丙醯基)苯硫基]茚滿-1,2-二酮-2-肟 Example 11 Synthesis of 5-[4-(3-cyclopentylpropenyl)phenylthio]indan-1,2-dione-2-indole

按照實施例3的肟化反應方法，以實施例10的產物為原料，用亞硝酸異戊酯代替亞硝酸正丁酯進行肟化反應，析出黃色固體產物，烘乾溶劑，純度96%，1 H-NMR資料表明所得產物為5-[4-(3-環戊基丙醯基)苯硫基]茚滿-1,2-二酮-2-肟，收率95.5%；1 H-NMR(DMSO-d6 )，δ(ppm)值 數據：1.1081(m,2H,CH2 )，1.4795-1.7602(m,9H,4CH2 )，3.0258(t,2H,CH2 )，3.7342(s,2H,c-CH2 )，7.3186/7.3451(d,1H,ArH)，7.5243(s,1H,ArH)，7.5667/7.5923(d,2H,2ArH)，7.7103/7.7370(d,1H,2ArH)，7.9987/8.0238(d,2H,2ArH)，12.6685(s,1H,NOH)。Oximation according to the method of Example 3, to the product of Example 10 as starting material in place of isoamyl nitrite with n-butyl nitrite oximation reaction, the precipitated yellow solid, drying the solvent, a purity of 96%, 1 H-NMR data indicated that the obtained product was 5-[4-(3-cyclopentylpropenyl)phenylthio]indan-1,2-dione-2-indole, yield 95.5%; 1 H-NMR (DMSO-d 6 ), δ (ppm) value data: 1.1081 (m, 2H, CH 2 ), 1.4795-1.7602 (m, 9H, 4CH 2 ), 3.0258 (t, 2H, CH 2 ), 3.7342 (s, 2H, c-CH 2 ), 7.3186/7.3451 (d, 1H, ArH), 7.5243 (s, 1H, ArH), 7.5667/7.5923 (d, 2H, 2ArH), 7.7103/7.7370 (d, 1H, 2ArH), 7.9987/8.0238 (d, 2H, 2ArH), 12.6665 (s, 1H, NOH).

實施例12 合成二肟化物 Example 12 Synthesis of Ditelluride

按照實施例4的反應方法，以實施例11的產物為原料，用亞硝酸異戊酯代替亞硝酸正丁酯進行第二肟化反應，經純化處理得黃色固體，純度95.50%，其中順式異構體含量5.10%，反式異構體含量90.40%，收率88.3%；1 H-NMR資料表明所得產物為雙肟化物，1 H-NMR(DMSO-d6 )，δ(ppm)值數據：1.1766-1.6286(m,8H,4CH2 )，2.1325(heptet,1H,CH)，2.6489/2.6739(d,2H,CH2 )，3.7410(s,2H,c-CH2 )，7.2981/7.3249(d,1H,ArH)，7.5258/7.5529(d,2H,2ArH)，7.5879(s,1H,ArH)，7.7188/7.7459(d,1H,2ArH)，7.8404/7.8680(d,2H,2ArH)，12.4514(s,1H,NOH)，12.6649(s,1H,NOH)。According to the reaction method of Example 4, the product of Example 11 was used as a raw material, and the second deuteration reaction was carried out by using isoamyl nitrite instead of n-butyl nitrite to obtain a yellow solid with a purity of 95.50%, wherein cis is The isomer content was 5.10%, the trans isomer content was 90.40%, and the yield was 88.3%. The 1 H-NMR data indicated that the obtained product was a double telluride, 1 H-NMR (DMSO-d 6 ), δ (ppm) value. Data: 1.1766-1.6286 (m, 8H, 4CH 2 ), 2.1325 (heptet, 1H, CH), 2.6489/2.6739 (d, 2H, CH 2 ), 3.7410 (s, 2H, c-CH 2 ), 7.2981/7.3249 (d, 1H, ArH), 7.5258/7.5529 (d, 2H, 2ArH), 7.5879 (s, 1H, ArH), 7.7188/7.7459 (d, 1H, 2ArH), 7.8404/7.8680 (d, 2H, 2ArH), 12.4514 (s, 1H, NOH), 12.6649 (s, 1H, NOH).

實施例13 合成二肟酯ⅡA3 Example 13 Synthesis of Diterpene Ester IIA3

按照實施例5的反應方法，以實施例12的產物為原料，進行酯化反應，經純化處理得黃色固體，純度98.65%，其中順式異構體含量 1.50%，反式異構體含量97.15%，收率60.3%；1 H-NMR資料表明所得產物為I A3；1 H-NMR(CDCl3 )，δ(ppm)值數據見表1。According to the reaction method of Example 5, the product of Example 12 was used as a raw material, and the esterification reaction was carried out to obtain a yellow solid with a purity of 98.65%, wherein the cis isomer content was 1.50%, and the trans isomer content was 97.15. %, yield 60.3%; 1 H-NMR data indicate that the resulting product is I A3; 1 H-NMR ( CDCl 3), δ (ppm) value of the data in Table 1.

實施例14 鹼溶性樹脂製備 Example 14 Preparation of alkali soluble resin

將甲基丙烯酸苄酯180g、甲基丙烯酸60g、甲基丙烯酸羥乙酯60g、偶氮二異丁腈15g、十二硫醇6g與甲苯1000ml混勻並放入恒壓滴液漏斗中；將1000ml甲苯放入三口燒瓶，安裝攪拌、恆壓滴液漏斗和溫度計， 開啟攪拌，用氮氣置換燒瓶中氣體；加熱燒瓶使溶劑溫度達到80-85℃，保溫，開始滴加單體混合溶液，約1h滴完；繼續反應6h；自然冷卻降溫，停止攪拌，等樹脂沉降後，吸取上部澄清溶液，過濾下部含溶劑的樹脂，並用500ml甲苯淋洗樹脂濾餅；減壓烘乾濾餅，得到白色粉末狀固體樹脂250g；將其用PMA(丙二醇甲醚醋酸酯)1000g溶解為20%溶液備用。180 g of benzyl methacrylate, 60 g of methacrylic acid, 60 g of hydroxyethyl methacrylate, 15 g of azobisisobutyronitrile, 6 g of dodecyl mercaptan and 1000 ml of toluene were mixed and placed in a constant pressure dropping funnel; 1000 ml of toluene was placed in a three-necked flask, and a stirring, constant pressure dropping funnel and thermometer were installed. Turn on the stirring, replace the gas in the flask with nitrogen; heat the flask to bring the solvent temperature to 80-85 ° C, keep warm, start to add the monomer mixed solution, drop about 1 h; continue the reaction for 6 h; cool down naturally, stop stirring, wait for resin to settle. After that, the upper clear solution was taken up, the lower solvent-containing resin was filtered, and the resin cake was rinsed with 500 ml of toluene; the filter cake was dried under reduced pressure to obtain 250 g of a white powdery solid resin; PMA (propylene glycol methyl ether acetate) 1000 g was used. Dissolve in 20% solution for use.

實施例15 光刻膠的製備及顯影 Example 15 Preparation and Development of Photoresist

按表2中配方15A、15B、15C(光引發劑為OXE01)、15D(光引發劑為OXE02)的重量配比將所有組分按油墨的製備方法製成光固化組合物，呈流動性液態。According to the weight ratio of formula 15A, 15B, 15C (photoinitiator is OXE01) and 15D (photoinitiator is OXE02) in Table 2, all the components are made into photocurable composition according to the preparation method of ink, which is liquid liquid. .

應用線棒法將上述液態組合物塗布於玻璃表面，經80℃烘烤3分鐘，將溶劑PMA揮發掉，測量剩餘物膠膜厚度為2微米。The above liquid composition was applied to the surface of the glass by a wire bar method, baked at 80 ° C for 3 minutes, and the solvent PMA was volatilized, and the thickness of the remaining film was measured to be 2 μm.

在膜上放置21階灰梯度尺，用365nm光柵篩檢程式過濾2000W高壓汞燈光線，膜與光柵距離10cm，使曝光量達到800mJ/cm2 。A 21-step gray gradient ruler was placed on the film, and a 2000 W high-pressure mercury light line was filtered by a 365 nm grating screening procedure, and the distance between the film and the grating was 10 cm, so that the exposure amount reached 800 mJ/cm 2 .

在30℃的1%碳酸鈉溶液浴中浸泡1min，記錄能夠顯示的最大留膜階數，數字越大，所測量的組合物光感度越強，光刻膠的光固化率和成膜性能越高，結果列於表3。Soak for 1 min in a 1% sodium carbonate solution bath at 30 ° C, and record the maximum film retention order that can be displayed. The higher the number, the stronger the photo-sensitivity of the measured composition, and the more the photocuring rate and film-forming property of the photoresist High, the results are listed in Table 3.

表3中的顯影結果顯示，使用實施例9和實施例13的光引發劑配製的光固化組合物，其光感度顯著優於使用OXE01和OXE02配製的光固化組合物，提高了光刻膠的光固化率和成膜性能。The development results in Table 3 show that the photocurable compositions formulated using the photoinitiators of Example 9 and Example 13 exhibited significantly better photosensitivity than the photocurable compositions formulated with OXE01 and OXE02, which improved the photoresist. Light curing rate and film forming properties.

實施例16 光固化組合物凝膠轉化率測試實驗 Example 16 Photocuring composition gel conversion rate test experiment

應用線棒法將上述實施例15表2中配方15A、15B、15C、15D的組合物塗布於玻璃表面，經80℃烘烤3min，將溶劑PMA揮發掉，測量剩餘物膠膜厚度為2微米。The composition of the formulations 15A, 15B, 15C, 15D in Table 2 of the above Example 15 was applied to the surface of the glass by a wire bar method, baked at 80 ° C for 3 minutes, and the solvent PMA was volatilized, and the thickness of the remaining film was measured to be 2 μm. .

用365nm光柵篩檢程式過濾2000W高壓汞燈光線，膜與光柵距離10cm，使曝光量分別達到200，400，600mJ/cm2 。固化後用不銹鋼網包裹樣板，稱量重量W1 ，丙酮浸泡72小時，烘乾測量殘餘膜重量W2 ，W1 /W2 為凝膠轉化率gel%，結果見表4。The 2000W high-pressure mercury light line was filtered by a 365 nm grating screening program, and the distance between the film and the grating was 10 cm, so that the exposure amount reached 200,400,600 mJ/cm 2 , respectively. After curing, the sample was wrapped with a stainless steel mesh, and the weight W 1 was weighed and soaked in acetone for 72 hours. The residual film weight W 2 was measured by drying, and W 1 /W 2 was gel conversion rate gel%. The results are shown in Table 4.

由表4可以得出結論：在光刻膠配方中，實施例9和實施例13的光引發劑使雙鍵聚合度更高，具有顯著更高的活性。It can be concluded from Table 4 that the photoinitiators of Examples 9 and 13 have a higher degree of double bond polymerization and a significantly higher activity in the photoresist formulation.

實施例17 LED光源固化光敏性組合物及固化效率測試實驗 Example 17 LED light source curing photosensitive composition and curing efficiency test experiment

將實施例15中光固化組合物15A、15B、15C、15D，用線棒法塗布於玻璃表面，經80℃烘烤3min，將溶劑PMA揮發掉，測量剩餘物膠膜厚度為2微米，然後按照下面方法進行固化。The photocurable compositions 15A, 15B, 15C, and 15D in Example 15 were applied to the surface of the glass by a wire bar method, baked at 80 ° C for 3 minutes, and the solvent PMA was volatilized, and the thickness of the remaining film was measured to be 2 μm. Curing was carried out as follows.

固化裝置：LEDUV固化裝置，型號：UV-101D(北京岩田博遠科技股份有限公司)。Curing device: LEDUV curing device, model: UV-101D (Beijing Iwata Boyuan Technology Co., Ltd.).

光源：UV-LED點光源，直徑：10mm；波長：365nm，最大照度：40mw/cm2 .Light source: UV-LED point source, diameter: 10 mm; wavelength: 365 nm, maximum illumination: 40 mw/cm 2 .

固化條件：工作距離：21mm；照射時間：1s。Curing conditions: working distance: 21 mm; irradiation time: 1 s.

固化效率表徵方法為：用點光源照射1s後，將整個玻璃片置於丙酮溶液中浸泡5s，取出後，測量固化膜圖形直徑，數值越大說明其感亮度高，固化效率越高，表5為測量結果，從表5中的測量結果可以看出，以LED光源固化阻焊油墨或光刻膠用光敏性組合物時，本發明所提供的光敏組合物相對於現有的以OXE01、OXE02為光引發劑的組合物具有更高的光敏感度。The curing efficiency is characterized by: after irradiating with a point light source for 1 s, the whole glass piece is immersed in an acetone solution for 5 s, and after taking out, the cured film pattern diameter is measured. The larger the value, the higher the brightness and the higher the curing efficiency, Table 5 For the measurement results, it can be seen from the measurement results in Table 5 that when the photosensitive composition for curing the solder resist ink or the photoresist is cured by the LED light source, the photosensitive composition provided by the present invention is compared with the existing ones using OXE01 and OXE02. The composition of the photoinitiator has a higher light sensitivity.

實施例18 印刷油墨配製和高壓汞燈固化 Example 18 Printing Ink Formulation and High Pressure Mercury Lamp Curing

配方組成比例：環氧樹脂丙烯酸酯預聚物(長興化學 621-100)50份，聚酯丙烯酸酯預聚物(長興化學6311-10)10份，TPGDA(長興化學EM223)30份，炭黑(Degussa公司P25)4份，光引發劑6份；混合研磨到細度2um以下，得到油墨樣品18A-18D；用420目絲網印刷到鋁板上，通過高壓汞燈下固化，按實施例16方法測凝膠轉化率gel%，表6為測量結果，從表6中的測量結果可以看出，經高壓汞燈照射，本發明化合物產生的凝膠轉化率顯著高於對照化合物。Formula composition ratio: epoxy resin acrylate prepolymer (Changxing Chemical 621-100) 50 parts, polyester acrylate prepolymer (Changxing Chemical 6311-10) 10 parts, TPGDA (Changxing Chemical EM223) 30 parts, carbon black (Degussa P25) 4 parts, photoinitiator 6 parts; mixing Grinding to a fineness of 2 um or less, ink samples 18A-18D were obtained; screen printing onto a aluminum plate with a 420 mesh, curing under a high pressure mercury lamp, and gel conversion rate gel% was measured according to the method of Example 16, and Table 6 is a measurement result. It can be seen from the measurement results in Table 6 that the gel conversion rate of the compound of the present invention was significantly higher than that of the control compound by irradiation with a high pressure mercury lamp.

實施例19 印刷油墨配製和LED面光源固化 Example 19 Printing Ink Formulation and LED Surface Light Curing

配方組成比例：環氧樹脂丙烯酸酯預聚物50份，聚酯丙烯酸酯預聚物10份，TPGDA 30份，黃3G(BASF公司)4份，光引發劑6份；混合研磨到細度2um以下得到油墨樣品19A-19D，塗布到玻璃板上；用365nm LED面光源燈固化，曝光量86mJ/cm2 ；按實施例16方法測凝膠轉化率gel%，測量結果見表7，從表7中的測量結果可以看出，經365nmLED光源照射，本發明化合物產生的凝膠轉化率顯著高於對照化合物。Formulation ratio: 50 parts of epoxy acrylate prepolymer, 10 parts of polyester acrylate prepolymer, 30 parts of TPGDA, 4 parts of yellow 3G (BASF), 6 parts of photoinitiator; mixed grinding to fineness 2um The ink samples 19A-19D were obtained and applied to a glass plate; cured with a 365 nm LED surface light source, and the exposure amount was 86 mJ/cm 2 ; the gel conversion rate gel% was measured according to the method of Example 16, and the measurement results are shown in Table 7, from the table. As can be seen from the measurement results in 7, the gel conversion rate of the compound of the present invention was significantly higher than that of the control compound by irradiation with a 365 nm LED light source.

實施例20 濾光膜用光阻油墨配製和曝光顯影 Example 20 Filter Film Prepared with Photoresist Ink and Exposure Developed

配方組成：鹼溶性樹脂溶液500份(實施例14)，二季戊四醇六丙烯酸酯(Cytec公司DPHA)100份，光引發劑100份，助引發劑BCIM(2,2’-二鄰氯苯基-4,,4’,5,5’-四苯基聯咪唑)20份，炭黑(Degussa公司P25)分散液500份(含炭黑20%)，按油墨製備方法研磨均勻，按其所用光引發劑不同，共有20A-20E五種油墨。Formulation composition: 500 parts of alkali-soluble resin solution (Example 14), 100 parts of dipentaerythritol hexaacrylate (Cytec DPHA), 100 parts of photoinitiator, co-initiator BCIM (2,2'-di-o-chlorophenyl- 4,4',5,5'-tetraphenylbiimidazole) 20 parts, carbon black (Degussa P25) dispersion 500 parts (containing carbon black 20%), according to the ink preparation method, grinding evenly, according to the light used Different initiators, there are five inks of 20A-20E.

分別塗布，減壓烘乾，厚1um，覆以圖案掩膜，用365nmLED面光源曝光，曝光量100mJ/cm2 ，用含1%NaOH和2%丙酮的水溶液顯影30S，用體視電子顯微鏡檢測圖案形態和牢度，形態和牢度觀察評價：1.曝光部分完整無脫落；2.曝光部分無脫落有翹邊；3.曝光部分邊緣不齊；4.曝光部分不完整；5.曝光部分已脫落。Coated separately, dried under reduced pressure, 1 μm thick, covered with a pattern mask, exposed with a 365 nm LED surface light source, exposed at 100 mJ/cm 2 , developed with 30% aqueous solution of 1% NaOH and 2% acetone, and examined by stereoscopic electron microscopy. Pattern morphology and fastness, morphology and fastness observation and evaluation: 1. The exposed part is intact without falling off; 2. The exposed part has no peeling and curling; 3. The exposed part is not edged; 4. The exposed part is incomplete; 5. The exposed part Has fallen off.

實驗結果評價見表8，從表8的結果可以看出，含有本發明化合物的油墨曝光顯影後圖案邊緣清晰整齊，牢固無脫落，本發明化合物性能表現顯著優於對照化合物。The evaluation of the experimental results is shown in Table 8. From the results of Table 8, it can be seen that the ink containing the compound of the present invention has a clear and tidy pattern edge after exposure and development, and is firm and non-shedding, and the performance of the compound of the present invention is remarkably superior to that of the control compound.

實施例21 濾光膜用光阻油墨配製和曝光顯影 Example 21 Filter Film Prepared with Photoresist Ink and Exposure Developed

配方組成：鹼溶性樹脂溶液500份(實施例14)，二季戊四醇六丙烯酸酯(Cytec公司)100份，光引發劑100份，紅顏料L3920(BASF公司)100份，按油墨製備方法研磨均勻，得到21A-21E五種油墨。Formulation composition: 500 parts of alkali-soluble resin solution (Example 14), 100 parts of dipentaerythritol hexaacrylate (Cytec), 100 parts of photoinitiator, 100 parts of red pigment L3920 (BASF), and uniformly polished according to the ink preparation method. Five inks of 21A-21E were obtained.

塗布，減壓烘乾，厚2um，覆以圖案掩膜，用365nmLED面光源曝光，曝光量86mJ/cm2 ，用含1%NaOH和2%丙酮的水溶液顯影30S，用體視電子顯微鏡檢測圖案牢度和形態，評價方法同實施例20；實驗結果評價見表9，從表9的結果可以看出，含有本發明化合物的油墨曝光顯影後圖案邊緣清晰整齊，牢固無脫落，本發明化合物性能表現顯著優於對照化合物。Coating, drying under reduced pressure, thickness 2 μm, covered with a pattern mask, exposed with a 365 nm LED surface light source, exposure amount 86 mJ/cm 2 , developed with an aqueous solution containing 1% NaOH and 2% acetone for 30S, and detected by a stereoscopic microscope The fastness and morphology were evaluated in the same manner as in Example 20; the evaluation of the experimental results is shown in Table 9. From the results of Table 9, it can be seen that the ink containing the compound of the present invention has a clear and tidy edge after exposure and development, and is firm and non-shedding, and the properties of the compound of the present invention. The performance was significantly better than the control compound.

實施例22 濾光膜用光阻油墨配製和曝光顯影 Example 22 Filter Film Prepared with Photoresist Ink and Exposure Developed

配方組成：鹼溶性樹脂溶液500份(實施例14)，二季戊四醇六丙烯酸酯(Cytec公司)100份，光引發劑10份，紅顏料L3920(BASF公司)100份；按油墨製備方法研磨均勻，得到22A-22E五種油墨。Formulation composition: 500 parts of alkali-soluble resin solution (Example 14), 100 parts of dipentaerythritol hexaacrylate (Cytec), 10 parts of photoinitiator, 100 parts of red pigment L3920 (BASF company); Five inks of 22A-22E were obtained.

塗布，減壓烘乾，厚2um，覆以圖案掩膜，用365nmLED面光源曝光，曝光量86mJ/cm2 ，用含1%NaOH和2%丙酮的水溶液顯影30S，用體視電子顯微鏡檢測圖案牢度和形態，評價方法同實施例20，實驗結果評價見表10，從表10的結果可以看出，含有本發明化合物的油墨曝光顯影後圖案邊緣清晰整齊，牢固無脫落，本發明化合物性能表現顯著優於對照化合物。Coating, drying under reduced pressure, 2 μm thick, covered with a pattern mask, exposed with a 365 nm LED surface light source, exposure amount 86 mJ/cm 2 , developed with an aqueous solution containing 1% NaOH and 2% acetone for 30S, and detected by stereoscopic microscope The fastness and morphology were evaluated in the same manner as in Example 20. The evaluation of the experimental results is shown in Table 10. From the results of Table 10, it can be seen that the ink containing the compound of the present invention has a clear and tidy edge after exposure and development, and is firm and non-shedding, and the properties of the compound of the present invention. The performance was significantly better than the control compound.

表10 紅色光阻油墨曝光評價 Table 10 Red photoresist ink exposure evaluation

Claims (26)

一種不對稱二肟酯化合物，為下列結構通式I： 其中，該Ar1 選自被該X1 所取代的C6 -C20 鄰亞芳基或C3 -C20 鄰亞雜芳基，該C6 -C20 鄰亞芳基或該C3 -C20 鄰亞雜芳基以相鄰的兩個原子與該Y1 和羰基相連構成並環結構，其餘原子上的取代基各自由下列所構成的群組選出：氫原子、鹵素原子、C1 -C12 烷基、C5 -C7 環烷基、C5 -C7 環烷基所取代的C1 -C4 烷基、C1 -C12 烷氧基、C1 -C4 烷基苄氧基、C1 -C3 亞烷基二氧基、R2 C(O)O、C1 -C12 烷基硫基、C1 -C4 烷基苯硫基、CN、羧基、C1 -C12 烷氧基羰基、芳基羰基、雜芳基羰基、X3 R18 、C1 -C4 烷基苯氧基、C1-C8烷基醯基苯氧基、C5 -C6 環烷基醯基苯氧基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯氧基、芳基醯基苯氧基、雜芳基醯基苯氧基、R2 C(O)O取代的C1 -C4 烷基硫基、C1 -C4 烷基苯硫基、C1 -C8 烷基醯基苯硫基、C5 -C6 環烷基醯基苯硫基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯硫基、芳基醯基苯硫基、雜芳基醯基苯硫基；被一個或多個C1 -C12 烷氧基、C1 -C4 烷基苄氧基、R2 C(O)O取代 的C1 -C4 烷氧基；苯基及任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、芳基醯基、雜芳基醯基、X3 R17 、苯基、鹵素原子、CN取代的苯基；及環氧丙基，其中環氧基任意地與C1 -C4 烷基醛、酮縮合；該X3 選自O、S及NR22 ；該Ar2 選自：通過該X1 與該Ar1 相連接的C6 -C20 亞芳基、通過該X1 與該Ar1 相連接的C3 -C20 亞雜芳基；該n為0或1；該X1 由下列所構成的群組選出：O、S、NR18 及Y2 -Z1 -Y2 ；該Y1 由下列所構成的群組選出：(CH2 )m CR15 R16 、NR19 、O(CR15 R16 )m 、S(CR15 R16 )m 、(CR15 R16 )m C=O及S=O，該m為0或1；該Z1 由下列所構成的群組選出：C1 -C10 直鏈亞烷基、C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 支鏈亞烷基、無取代基的C6 -C20 亞芳基、及有取代基的C6 -C20 亞芳基；該Y2 由下列所構成的群組選出：O、S、NR18 及O-C(O)； 該R1 由下列所構成的群組選出：氫原子、C1 -C18 烷基、二苯基膦醯基，二(C1 -C4 烷氧基)膦醯基；任意被一個或多個C3 -C7 環烷基、苯基、OR20 、SR21 、NR22 R23 所取代的C2 -C18 烷基，其中苯基被任意一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代；被C3 -C7 亞環烷基、亞苯基、O、S、NR22 所***的C2 -C18 烷基；C3 -C8 環烷基、CN、NO2 、苯基；被任意一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代的苯基；C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或多個鹵素原子、C1 -C4 烷基、C5 環烷基、C6 環烷基、苯基、CN、OH、X3 R20 所取代；C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或多個的亞苯基、X3 ***；苯基未被取代的苯甲醯基、苯氧基羰基；以及苯基被任意一個或多個鹵素原子、C1 -C4 烷基、C5 環烷基、C6 環烷基、苯基、CN、OH、X2 R20 所取代的苯甲醯基、苯氧基羰基；該R2 、該R3 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C1 -C18 烷氧基、C2 -C18 烯基、苯基、萘基、C5 -C7 環烷基；任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷 基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C2 -C18 烯基；被C5 -C7 環亞烷基、亞苯基、O、S、NR17 所***的C2 -C18 烯基；任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代且被C5 -C7 環亞烷基、亞苯基、O、S、NR17 所***的C2 -C18 烯基；任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C2 -C18 烷基；任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；苯基未被取代的苯甲醯基、苯氧基羰基；苯基被任意一個或多個鹵素原子R17- 、C5 環烷基、C6 環烷基、CN、OH、XR17 取代的苯甲醯基、苯氧基羰基；苯基或萘基；任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、苯基、鹵素原子、CN所取代的苯基；任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、苯基、鹵素原子、CN所取代的萘基；該R15 、R16 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、羧基所取代的C1 -C5 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環 烷基、苯基；任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C2 -C18 烷基；被C5 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基取代的C2 -C4 烷基醯基、苯甲醯基、XR17 、鹵素原子、CN所取代的苯基；該R17 為C1 -C4 烷基；該R18 、該R19 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基；任意被一個或多個鹵素原子、C1 -C4 烷基、C3 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C1 -C18 烷基；任意被一個或多個C3 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；以及任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、C5 -C6 環 烷基甲醯基、C5 -C6 環烷基所取代的C2 -C4 烷基醯基、芳基醯基、XR17 、苯基、鹵素原子、CN所取代的苯基；該R20 、該R21 、該R22 、該R23 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C3 -C7 環烷基；被鹵素、CN、C1 -C4 烷氧基所取代的C1 -C18 烷基；被一個或多個氧原子、C5 -C7 亞環烷基、亞苯基所***的C2 -C18 烷基；被苯基、C3 -C7 環烷基所取代的C1 -C3 烷基；苯基、萘基、苯甲醯基；以及任意被鹵素、C1 -C4 烷基、C1 -C4 烷氧基、C1 -C4 烷基硫基、苯氧基、苯硫基、NR24 R25 、C1 -C12 烷基醯基、苯甲醯基所取代的苯基、萘基、苯甲醯基；該R24 、該R25 各自為C1 -C4 烷基；或NR24 R25 一起為嗎福林，哌啶，哌，N-甲基哌，吡咯。An asymmetric diterpene ester compound having the following structural formula I: Wherein the Ar 1 is selected from a C 6 -C 20 o-arylene or a C 3 -C 20 o-heteroaryl group substituted by the X 1 , the C 6 -C 20 o-arylene group or the C 3 - The C 20 ortho-heteroaryl group is bonded to the Y 1 and a carbonyl group by two adjacent atoms to form a ring structure, and the substituents on the remaining atoms are each selected from the group consisting of a hydrogen atom, a halogen atom, and C 1 . -C 12 alkyl, C 5 -C 7 cycloalkyl, C 1 -C 4 alkyl substituted by C 5 -C 7 cycloalkyl, C 1 -C 12 alkoxy, C 1 -C 4 alkyl Benzyloxy, C 1 -C 3 alkylenedioxy, R 2 C(O)O, C 1 -C 12 alkylthio, C 1 -C 4 alkylphenylthio, CN, carboxyl, C 1 -C 12 alkoxycarbonyl, arylcarbonyl, heteroarylcarbonyl, X 3 R 18 , C 1 -C 4 alkylphenoxy, C1-C8 alkylnonylphenoxy, C 5 -C 6 Cycloalkyl nonylphenoxy, C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkylnonylphenoxy, arylnonylphenoxy, heteroarylnonylphenoxy, R 2 C(O)O substituted C 1 -C 4 alkylthio, C 1 -C 4 alkylphenylthio, C 1 -C 8 alkylmercaptophenylthio, C 5 -C 6 cycloalkyl Mercaptophenylthio, C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkyl fluorenyl a phenylthio group, an arylsulfonylphenylthio group, a heteroarylmercaptophenylthio group; one or more C 1 -C 12 alkoxy groups, a C 1 -C 4 alkylbenzyloxy group, R 2 C ( O) O-substituted C 1 -C 4 alkoxy; phenyl and optionally substituted by one or more C 1 -C 4 alkyl groups, carboxyl groups, C 1 -C 12 alkyl fluorenyl groups, aryl fluorenyl groups, heteroaryl groups acyl group, X 3 R 17, a phenyl group, a halogen atom, CN substituted phenyl; and glycidyl group, an epoxy group which is optionally C 1 -C 4 alkyl group with an aldehyde, ketone condensate; X 3 is selected from the from O, S and NR 22; the Ar 2 is selected from: X 1 C 1 through which is connected to the Ar is 6 -C 20 arylene group, by which the Ar 1 X 1 connected to C 3 -C 20 a heteroarylene; the n is 0 or 1; the X 1 is selected from the group consisting of O, S, NR 18 and Y 2 -Z 1 -Y 2 ; the Y 1 is composed of the following group Selected: (CH 2 ) m CR 15 R 16 , NR 19 , O(CR 15 R 16 ) m , S(CR 15 R 16 ) m , (CR 15 R 16 ) m C=O and S=O, the m Is 0 or 1; the Z 1 is selected from the group consisting of C 1 -C 10 linear alkylene, C 1 -C 10 branched alkylene, linked by one or more oxygen or sulfur atoms the end groups C 1 -C 10 linear alkylene, One or more oxygen atom or sulfur atom attached to the end groups C 1 -C 10 branched alkylene, substituted by one or more oxygen atoms or sulfur atom inserted straight chain C 2 -C 10 alkylene group, is one or more oxygen atom or sulfur atom inserted branched C 2 -C 10 alkylene group unsubstituted C 6 -C 20 arylene group, and an optionally substituted C 6 -C 20 arylene; The Y 2 is selected from the group consisting of O, S, NR 18 and OC(O); the R 1 is selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a diphenyl group. Phosphonium, bis(C 1 -C 4 alkoxy)phosphonium; optionally substituted by one or more C 3 -C 7 cycloalkyl, phenyl, OR 20 , SR 21 , NR 22 R 23 C 2 -C 18 alkyl, wherein phenyl is any one or more of halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN , C 1 -C 4 alkyl alkoxy, aryloxy substituted; C 2 -C 18 alkyl inserted by C 3 -C 7 cycloalkylene, phenylene, O, S, NR 22 ; 3 -C 8 cycloalkyl, CN, NO 2, phenyl; optionally one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl Phenyl, heteroaryl, CN, C 1 -C 4 alkanoyl group, acyl group, aryloxy-substituted phenyl; C 1 -C 12 alkyl acyl, C 1 -C 12 alkoxycarbonyl, wherein the alkoxy group optionally substituted with one or more halogen atoms, C 1 -C 4 alkyl, C 5 cycloalkyl, C 6 cycloalkyl, phenyl, CN, OH, X 3 R substituted 20; C 1 -C 12 alkyl A fluorenyl group, a C 1 -C 12 alkoxycarbonyl group, wherein the alkyl group is optionally interrupted by one or more phenylene groups, X 3 ; a phenyl unsubstituted benzamidine group, a phenoxycarbonyl group; a benzylidene group or a benzene substituted with any one or more halogen atoms, C 1 -C 4 alkyl, C 5 cycloalkyl, C 6 cycloalkyl, phenyl, CN, OH, X 2 R 20 oxycarbonyl group; the R 2, R 3 are each independently of the selected from the group consisting of the following: a hydrogen atom, C 1 -C 18 alkyl, C 1 -C 18 alkoxy, C 2 -C 18 alkenyl , phenyl, naphthyl, C 5 -C 7 cycloalkyl; optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyl group, aryloxy group, acyl substituted C 2 -C 18 alkenyl group; a C 5 -C 7 cycloalkylene, phenylene O, S, NR 17 inserted C 2 -C 18 alkenyl; optionally substituted with one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl , heteroaryl, CN, C 1 -C 4 alkanoyl group, aryloxy group, acyl and substituted by C 5 -C 7 cycloalkylene, phenylene, O, S, NR 17 C 2 inserted -C 18 alkenyl; optionally substituted with one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C a C 2 -C 18 alkyl group substituted with a 4 -alkyloxy group or an aryloxy group; any C 5 -C 7 substituted by one or more C 1 -C 4 alkyl groups, a phenyl group, a halogen atom, and CN a cycloalkyl group; a phenyl unsubstituted benzhydryl group, a phenoxycarbonyl group; a phenyl group of any one or more halogen atoms R 17- , C 5 cycloalkyl, C 6 cycloalkyl, CN, OH, XR 17 substituted benzinyl, phenoxycarbonyl; phenyl or naphthyl; optionally substituted by one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy, phenyl, halogen atom, CN Substituted phenyl; any naphthyl group substituted by one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy, phenyl, halogen atom, CN; 15 and R 16 are each independently selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a C 1 -C 5 alkyl group substituted by a carboxyl group, and a C 1 -C 4 alkoxyfluorenyl group. Substituted C 1 -C 5 alkyl, C 2 -C 4 alkyl substituted by R 2 C(O)O, C 5 -C 7 cycloalkyl, phenyl; optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanomethoxy, aryloxy substituted C 2 - C 18 alkyl; C 2 -C 18 alkyl group inserted by C 5 -C 7 cycloalkylene, phenylene, O, S, NR 17 ; optionally by one or more C 1 -C 4 alkyl groups a phenyl group, a halogen atom, a C 5 -C 7 cycloalkyl group substituted by CN; optionally substituted by one or more C 1 -C 4 alkyl groups, C 1 -C 4 alkoxy group, carboxyl group, C 1 -C 12 Alkyl fluorenyl, C 5 -C 6 cycloalkylcarbenyl, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkyl fluorenyl, benzhydryl, XR 17 , halogen atom, CN a substituted phenyl group; the R 17 is a C 1 -C 4 alkyl group; the R 18 and the R 19 are each independently selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a C 1 - Substituted by C 4 alkoxy fluorenyl C 1 -C 5 alkyl, C 2 -C 4 alkyl substituted by R 2 C(O)O, C 5 -C 7 cycloalkyl, phenyl; optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyl group, aryloxy group, acyl substituted with a C 1 -C 18 alkyl; any C 2 -C 18 alkyl group inserted by one or more C 3 -C 7 cycloalkylene, phenylene, O, S, NR 17 ; optionally by one or more C 1 - a C 4 alkyl group, a phenyl group, a halogen atom, a C 5 -C 7 cycloalkyl group substituted by CN; and optionally one or more C 1 -C 4 alkyl groups, a carboxyl group, a C 1 -C 12 alkyl fluorenyl group , C 5 -C 6 cycloalkylcarbinyl, C 2 -C 4 alkylfluorenyl substituted by C 5 -C 6 cycloalkyl, arylsulfonyl, XR 17 , phenyl, halogen atom, CN a substituted phenyl group; the R 20 , the R 21 , the R 22 and the R 23 are each independently selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a C 3 -C 7 naphthenic group a C 1 -C 18 alkyl group substituted by halogen, CN, C 1 -C 4 alkoxy; inserted by one or more oxygen atoms, a C 5 -C 7 cycloalkylene group, a phenylene group C 2 -C 18 alkyl; Phenyl, C 3 -C 7 cycloalkyl substituted C 1 -C 3 alkyl group; a phenyl group, a naphthyl group, a benzoyl group; and optionally substituted by halogen, C 1 -C. 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenoxy, phenylthio, NR 24 R 25 , C 1 -C 12 alkyl fluorenyl, phenyl substituted with phenyl fluorenyl, naphthyl , benzylidene; the R 24 , the R 25 are each a C 1 -C 4 alkyl group; or the NR 24 R 25 together is a phenylephrine, piperidine, piperidine , N-methyl pipe , pyrrole. 根據請求項1所述的不對稱二肟酯化合物，其中該結構通式I化合物進一步為下列結構通式Ⅱ化合物： 其中，該R4 、該R5 、該R6 、該R7 、該R8 、該R9 、該R10 各自獨立地由下列所構成的群組選出為：氫原子、鹵素原子、C1 -C12 烷基、C5 -C7 環烷基、C5 -C7 環烷基取代的C1 -C4 烷基、C1 -C12 烷氧基、苯基、C1 -C4 烷基苄氧基；任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、芳基醯基、雜芳基醯基、X3 R17 、苯基、鹵素原子、CN取代的苯基；被一個或多個C1 -C12 烷氧基、C1 -C4 烷基苄氧基、R2 C(O)O取代的C1 -C4 烷氧基、R2 C(O)O、CN、羧基、C1 -C12 烷氧基羰基、芳基羰基、雜芳基羰基、X3 R18 ；C1 -C4 烷基苯氧基、C1 -C4 烷基苯硫基、C1 -C8 烷基醯基苯氧基、芳基醯基苯氧基、雜芳基醯基苯氧基、C5 -C6 環烷基醯基苯氧基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯氧基、C1 -C3 亞烷基二氧基、C1 -C12 烷基硫基、R2 C(O)O取代的C1 -C4 烷基硫基、R2 C(O)O取代的C1 -C4 烷基苯硫基、C1 -C8 烷基醯基苯硫基、芳基醯基苯硫基、雜芳基醯基苯硫基、C5 -C6 環烷基醯基苯硫基取代的C1 -C4 烷基醯基苯硫基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯硫基；及環氧丙基，其中環氧基任意地與C1 -C4 烷基醛、酮縮合；X1 由下列所構成的群組選出：O，S及NR18 ；Y1 由下列所構成的群組選出：O、S及CR15 R16 。The asymmetric diterpene ester compound according to claim 1, wherein the compound of the formula I is further a compound of the following formula II: Wherein R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each independently selected from the group consisting of: a hydrogen atom, a halogen atom, C 1 -C 12 alkyl, C 5 -C 7 cycloalkyl, C 5 -C 7 cycloalkyl substituted C 1 -C 4 alkyl, C 1 -C 12 alkoxy, phenyl, C 1 -C 4 Alkylbenzyloxy; optionally substituted by one or more C 1 -C 4 alkyl, carboxy, C 1 -C 12 alkyl fluorenyl, aryl fluorenyl, heteroaryl fluorenyl, X 3 R 17 , phenyl , a halogen atom, CN substituted phenyl; substituted by one or more C 1 -C 12 alkoxy, C 1 -C 4 alkylbenzyl group, R 2 C (O) O-substituted C 1 -C 4 alkoxy Oxyl, R 2 C(O)O, CN, carboxyl, C 1 -C 12 alkoxycarbonyl, arylcarbonyl, heteroarylcarbonyl, X 3 R 18 ; C 1 -C 4 alkylphenoxy, C 1 -C 4 alkylphenylthio, C 1 -C 8 alkylmercaptophenoxy, arylnonylphenoxy, heteroarylnonylphenoxy, C 5 -C 6 cycloalkylhydrazine Phenoxy group, C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkyl nonylphenoxy group, C 1 -C 3 alkylenedioxy group, C 1 -C 12 alkylthio group, R 2 C(O)O substituted C 1 -C 4 alkylthio, R 2 C(O)O substituted C 1 -C 4 alkylphenylthio, C 1 -C 8 alkylmercaptophenylthio, arylmercaptophenylthio, heteroarylnonylphenylthio, C 5 -C 6 cycloalkylindolyl a phenylthio substituted C 1 -C 4 alkylmercaptophenylthio group, a C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkylmercaptophenylthio group; and an epoxy propyl group, wherein the epoxy group The base is arbitrarily condensed with a C 1 -C 4 alkyl aldehyde, a ketone; X 1 is selected from the group consisting of O, S and NR 18 ; Y 1 is selected from the group consisting of O, S and CR 15 R 16 . 根據請求項2所述的不對稱二肟酯化合物，其中該結構通式Ⅱ化合物中，該R4 、該R5 、該R6 、該R7 、該R8 、該R9 、該R10 均為氫原子； 該X1 選自O及S；該Y1 選自下列所構成的群組：CH2 、CHCH3 及C(CH3 )2 ；n=1；該R1 選自下列所構成的群組：C1 -C12 烷基；及任意被一個或多個C3 -C7 環烷基、苯基、OR20 、SR21 、NR22 R23 取代的C1 -C12 烷基；該R2 、該R3 各自獨立地為甲基，乙基，苯基，2-甲基苯基，3-甲基苯基，2,4,6-三甲基苯基及2,6-二甲氧基苯基。The asymmetric diterpene ester compound according to claim 2, wherein in the compound of the formula II, the R 4 , the R 5 , the R 6 , the R 7 , the R 8 , the R 9 , the R 10 Is a hydrogen atom; the X 1 is selected from O and S; and the Y 1 is selected from the group consisting of CH 2 , CHCH 3 and C(CH 3 ) 2 ; n=1; the R 1 is selected from the following a group consisting of: C 1 -C 12 alkyl; and any C 1 -C 12 alkane substituted by one or more C 3 -C 7 cycloalkyl, phenyl, OR 20 , SR 21 , NR 22 R 23 The R 2 and the R 3 are each independently methyl, ethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 2,4,6-trimethylphenyl and 2, 6-Dimethoxyphenyl. 根據請求項1所述的不對稱二肟酯化合物，進一步結構為下列其中之一： According to the asymmetric diterpene ester compound described in claim 1, the structure is further one of the following: 根據請求項1所述的不對稱二肟酯化合物，其中該Ar2 通過該X1 與該Ar1 相連接時，與該X1 鄰位的該Ar2 碳原子選擇式的以直鍵、碳原子、羰基、O、S及NR18 其中一種方式與該Ar1 相連接構成環狀結構。The asymmetric diterpene ester compound according to claim 1, wherein when the Ar 2 is bonded to the Ar 1 through the X 1 , the Ar 2 carbon atom ortho to the X 1 is a direct bond or a carbon One of the atoms, a carbonyl group, O, S, and NR 18 is bonded to the Ar 1 to form a cyclic structure. 根據請求項1或5所述的不對稱二肟酯化合物，其中該R15 、該R16 與其共同所連的碳原子一起構成環狀且成環的原子數為4-7。The requested item 1 or 5, wherein the asymmetric two oxime ester compound, wherein the R 15, R 16 which are attached to their common carbon atom and together form a cyclic ring atoms is 4-7. 根據請求項1或5所述的不對稱二肟酯化合物，其中該R15 、該R16 分別與相鄰的取代基一起構成環狀且成環的原子數為4-7。The asymmetric diterpene ester compound according to claim 1 or 5, wherein the R 15 and the R 16 each form a cyclic ring together with an adjacent substituent and the number of atoms in the ring is 4-7. 根據請求項1或5所述的不對稱二肟酯化合物，其中該R18 通過直鍵、碳原子、羰基與該Ar1 或該Ar2 其中之一中的芳環相連構成新的環。The asymmetric diterpene ester compound according to claim 1 or 5, wherein the R 18 is bonded to an aromatic ring in one of the Ar 1 or the Ar 2 through a straight bond, a carbon atom or a carbonyl group to form a new ring. 根據請求項5所述的不對稱二肟酯化合物，其中該R18 通過直鍵、碳原子、羰基與該Ar1 或該Ar2 其中之一中的芳環相連構成新的環。The asymmetric diterpene ester compound according to claim 5, wherein the R 18 is bonded to the aromatic ring in one of the Ar 1 or the Ar 2 through a direct bond, a carbon atom or a carbonyl group to form a new ring. 根據請求項6所述的不對稱二肟酯化合物，其中該R18 通過直鍵、碳原子、羰基與該Ar1 或該Ar2 其中之一中的芳環相連構成新的環。The asymmetric diterpene ester compound according to claim 6, wherein the R 18 is bonded to an aromatic ring in one of the Ar 1 or the Ar 2 through a straight bond, a carbon atom or a carbonyl group to form a new ring. 根據請求項7所述的不對稱二肟酯化合物，其中該R18 通過直鍵、碳原子、羰基與該Ar1 或該Ar2 其中之一中的芳環相連構成新的環。The asymmetric diterpene ester compound according to claim 7, wherein the R 18 is bonded to an aromatic ring in one of the Ar 1 or the Ar 2 through a straight bond, a carbon atom or a carbonyl group to form a new ring. 一種製造請求項1或4所述不對稱二肟酯化合物的方法，包含以下步驟：(1)步驟1：將下列結構通式Ⅳ化合物中環戊酮羰基的鄰位亞甲基上進行選擇性肟化，肟化的方法是將該結構通式Ⅳ化合物與亞硝酸烷基酯在酸性溶液中發生肟化反應，得到酮肟化合物為結構通式V化合物； (2)步驟2：將該結構通式V化合物繼續進行第二次肟化，第二次肟化方法為下列兩者其中之一：方法A：將該結構通式V化合物與亞硝酸烷基酯在酸性溶液中發生肟化反應，得到對應的第二次肟化中間體結構通式Ⅵ化合物；方法B：將該結構通式V化合物在羥胺溶液中發生側鏈R1 CH2 CO中羰基的肟化反應，得到對應的第二次肟化中間體結構通式Ⅶ化合物； (3)步驟3：該第二次肟化中間體Ⅵ或Ⅶ化合物其中之一與下列醯化試劑： 或其等價醯化試劑發生酯化反應得到對應該結構通式I化合物。A process for producing the asymmetric diterpene ester compound of claim 1 or 4, which comprises the steps of: (1) Step 1: Selectively fluorene the ortho-methylene group of the cyclopentanone carbonyl group in the following compound of the formula IV; The method of deuteration is to carry out the oximation reaction of the compound of the formula IV and the alkyl nitrite in an acidic solution to obtain a ketone oxime compound as a compound of the formula V; (2) Step 2: The compound of the formula V is further subjected to a second deuteration, and the second deuteration method is one of the following: Method A: the compound of the formula V and the alkyl nitrite The ester undergoes a deuteration reaction in an acidic solution to obtain a corresponding second deuterated intermediate structure of the compound of the formula VI; Method B: the compound of the formula V is subjected to a carbonyl group in the side chain R 1 CH 2 CO in a hydroxylamine solution. a deuteration reaction to obtain a corresponding second deuterated intermediate structure of the compound of formula VII; (3) Step 3: The second deuteration intermediate VI or VII compound is one of the following deuteration reagents: Or an esterification reaction of its equivalent deuteration reagent gives a compound of the formula I. 一種不對稱二酮化合物，如結構通式Ⅳ所示： 其中， 該Ar1 選自被該X1 所取代的C6 -C20 鄰亞芳基或C3 -C20 鄰亞雜芳基，該C6 -C20 鄰亞芳基或該C3 -C20 鄰亞雜芳基以相鄰的兩個原子與該Y1 和羰基相連構成並環結構，其餘原子上的取代基各自由下列所構成的群組選出：氫原子、鹵素原子、C1 -C12 烷基、C5 -C7 環烷基、C5 -C7 環烷基所取代的C1 -C4 烷基、C1- C12 烷氧基、C1 -C4 烷基苄氧基、C1 -C3 亞烷基二氧基、R2 C(O)O、C1 -C12 烷基硫基、C1 -C4 烷基苯硫基、CN、羧基、C1 -C12 烷氧基羰基、芳基羰基、雜芳基羰基、X3 R18 、C1 -C4 烷基苯氧基、C1-C8烷基醯基苯氧基、C5 -C6 環烷基醯基苯氧基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯氧基、芳基醯基苯氧基、雜芳基醯基苯氧基、R2 C(O)O取代的C1 -C4 烷基硫基、C1 -C4 烷基苯硫基、C1 -C8 烷基醯基苯硫基、C5 -C6 環烷基醯基苯硫基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯硫基、芳基醯基苯硫基、雜芳基醯基苯硫基；被一個或多個C1 -C12 烷氧基、C1 -C4 烷基苄氧基、R2 C(O)O取代的C1 -C4 烷氧基；苯基及任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、芳基醯基、雜芳基醯基、X3 R17 、苯基、鹵素原子、CN取代的苯基；環氧丙基，其中環氧基任意地與C1 -C4 烷基醛、酮縮合；該X3 選自O、S及NR22 ；該Ar2 選自：通過該X1 與該Ar1 相連接的C6 -C20 亞芳基、通過該X1 與該Ar1 相連接的C3 -C20 亞雜芳基；該X1 由下列所構成的群組選出：O、S、NR18 及Y2 -Z1 -Y2 ；該Y1由下列所構成的群組選出：(CH2 )m CR15 R16 、NR19 、O(CR15 R16 )m 、S(CR15 R16 )m 、(CR15 R16 )m C=O及S=O，該m為0或1；該Z1 由下列所構成的群組選出：C1 -C10 直鏈亞烷基、C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 支鏈亞烷基、無取代基的C6 -C20 亞芳基、及有取代基的C6 -C20 亞芳基；該Y2 由下列所構成的群組選出：O、S、NR18 及O-C(O)；該R1 由下列所構成的群組選出：氫原子、C1 -C18 烷基、二苯基膦醯基，二(C1 -C4 烷氧基)膦醯基；任意被一個或多個C3 -C7 環烷基、苯基、OR20 、SR21 、NR22 R23 所取代的C2 -C18 烷基，其中苯基被任意一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代；被C3 -C7 亞環烷基、亞苯基、O、S、NR22 所***的C2 -C18 烷基；C3 -C8 環烷基、CN、NO2 、苯基；被任意一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷 基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代的苯基；C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或多個鹵素原子、C1 -C4 烷基、C5 環烷基、C6 環烷基、苯基、CN、OH、X3 R20 所取代；C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或多個的亞苯基、X3 ***；苯基未被取代的苯甲醯基、苯氧基羰基；苯基被任意一個或多個鹵素原子、C1 -C4 烷基、C5 環烷基、C6 環烷基、苯基、CN、OH、X2 R20 所取代的苯甲醯基、苯氧基羰基；該R15 、該R16 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、羧基所取代的C1 -C5 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基；任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C2 -C18 烷基；被C5 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基取代的C2 -C4 烷基醯基、苯甲醯基、XR17 、鹵素原子、CN所取代的苯基； 該R17 為C1 -C4 烷基；該R18 、該R19 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基；任意被一個或多個鹵素原子、C1 -C4 烷基、C3 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C1 -C18 烷基；任意被一個或多個C3 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；以及任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基所取代的C2 -C4 烷基醯基、芳基醯基、XR17 、苯基、鹵素原子、CN所取代的苯基；該R20 、該R21 、該R22 、該R23 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C3 -C7 環烷基；被鹵素、CN、C1 -C4 烷氧基所取代的C1 -C18 烷基；被一個或多個氧原子、C5 -C7 亞環烷基、亞苯基所***的C2 -C18 烷基；被苯基、C3 -C7 環烷基所取代的C1 -C3 烷基；苯基、萘基、苯甲醯基；以及任意被鹵素、C1 -C4 烷基、C1 -C4 烷氧基、C1 -C4 烷基硫基、苯氧 基、苯硫基、NR24 R25 、C1 -C12 烷基醯基、苯甲醯基所取代的苯基、萘基、苯甲醯基；該R24 、該R25 各自為C1 -C4 烷基；或NR24 R25 一起為嗎福林，哌啶，哌，N-甲基哌，吡咯。An asymmetric diketone compound, as shown in Structural Formula IV: Wherein the Ar 1 is selected from a C 6 -C 20 o-arylene or a C 3 -C 20 o-heteroaryl group substituted by the X 1 , the C 6 -C 20 o-arylene group or the C 3 - The C 20 ortho-heteroaryl group is bonded to the Y 1 and a carbonyl group by two adjacent atoms to form a ring structure, and the substituents on the remaining atoms are each selected from the group consisting of a hydrogen atom, a halogen atom, and C 1 . -C 12 alkyl, C 5 -C 7 cycloalkyl, C 1 -C 4 alkyl substituted by C 5 -C 7 cycloalkyl, C 1 -C 12 alkoxy, C 1 -C 4 alkyl Benzyloxy, C 1 -C 3 alkylenedioxy, R 2 C(O)O, C 1 -C 12 alkylthio, C 1 -C 4 alkylphenylthio, CN, carboxyl, C 1 -C 12 alkoxycarbonyl, arylcarbonyl, heteroarylcarbonyl, X 3 R 18 , C 1 -C 4 alkylphenoxy, C1-C8 alkylnonylphenoxy, C 5 -C 6 Cycloalkyl nonylphenoxy, C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkylnonylphenoxy, arylnonylphenoxy, heteroarylnonylphenoxy, R 2 C(O)O substituted C 1 -C 4 alkylthio, C 1 -C 4 alkylphenylthio, C 1 -C 8 alkylmercaptophenylthio, C 5 -C 6 cycloalkyl acyl phenyl group, C 5 -C 6 cycloalkyl substituted acyl C 1 -C 4 alkyl Phenylthio, phenylthio aryl acyl, heteroaryl acyl phenyl group; substituted with one or more C 1 -C 12 alkoxy, C 1 -C 4 alkylbenzyl group, R 2 C ( O) O-substituted C 1 -C 4 alkoxy; phenyl and optionally substituted by one or more C 1 -C 4 alkyl groups, carboxyl groups, C 1 -C 12 alkyl fluorenyl groups, aryl fluorenyl groups, heteroaryl groups acyl group, X 3 R 17, a phenyl group, a halogen atom, CN substituted phenyl; glycidyl group, an epoxy group which is optionally C 1 -C 4 alkyl group with an aldehyde, ketone condensate; X 3 is selected from the O, S and NR 22; the Ar 2 is selected from: X 1 C 1 through which is connected to the Ar is 6 -C 20 arylene group, C 1 connected to the Ar through the X 1 3 -C 20 alkylene a heteroaryl group; the X 1 is selected from the group consisting of O, S, NR 18 and Y 2 -Z 1 -Y 2 ; the Y1 is selected from the group consisting of: (CH 2 ) m CR 15 R 16, NR 19, O ( CR 15 R 16) m, S (CR 15 R 16) m, (CR 15 R 16) m C = O and S = O, the m is 0 or 1; the Z 1 by a the group consisting of the following is selected: C 1 -C 10 linear alkylene, C 1 -C 10 branched alkylene group, an oxygen atom or a sulfur atom attached to one or more end groups C 1 -C 10 Linear alkylene group, one or more C atom or sulfur atom attached to a terminal end 1 -C 10 branched alkylene, substituted by one or more oxygen atoms or sulfur atom inserted straight chain C 2 -C 10 alkylene group, substituted with one or more oxygen or sulfur atom inserted branched C 2 -C 10 alkylene group unsubstituted C 6 -C 20 arylene group, and an optionally substituted C 6 -C 20 arylene; Y 2 of the following The group formed is selected from: O, S, NR 18 and OC(O); the R 1 is selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a diphenylphosphonium group, and two (C 1 -C 4 alkoxy)phosphonium; any C 2 -C 18 substituted by one or more C 3 -C 7 cycloalkyl, phenyl, OR 20 , SR 21 , NR 22 R 23 An alkyl group wherein the phenyl group is any one or more of halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 -alkoxy, aryloxy substituted; C 2 -C 18 alkyl inserted by C 3 -C 7 cycloalkylene, phenylene, O, S, NR 22 ; C 3 -C 8 ring alkyl, CN, NO 2, phenyl; optionally one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl , CN, C 1 -C 4 alkanoyl group, acyl group, aryloxy-substituted phenyl; C 1 -C 12 alkyl acyl, C 1 -C 12 alkoxycarbonyl, wherein the alkyl group optionally substituted with one or more Halogen atom, C 1 -C 4 alkyl group, C 5 cycloalkyl group, C 6 cycloalkyl group, phenyl group, CN, OH, X 3 R 20 substituted; C 1 -C 12 alkyl fluorenyl group, C 1 -C 12 alkoxycarbonyl group, wherein the alkyl group is optionally interrupted by one or more phenylene groups, X 3 ; phenyl unsubstituted benzamidine group, phenoxycarbonyl group; phenyl group is optionally one or more a halogen atom, C 1 -C 4 alkyl, C 5 cycloalkyl, C 6 cycloalkyl, phenyl, CN, OH, X 2 R 20 substituted benzoyl group, phenoxycarbonyl group; the R 15 Each of R 16 is independently selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a C 1 -C 5 alkyl group substituted by a carboxyl group, and a C 1 -C 4 alkoxyfluorenyl group. Substituted C 1 -C 5 alkyl, C 2 -C 4 alkyl substituted by R 2 C(O)O, C 5 -C 7 cycloalkyl, phenyl; optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 substituted cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, the CN, C 1 -C 4 alkanoyl group, acyl group, aryloxy C 2 -C 18 alkyl; C 2 -C 18 alkyl group inserted by C 5 -C 7 cycloalkylene, phenylene, O, S, NR 17 ; optionally by one or more C 1 -C 4 An alkyl group, a phenyl group, a halogen atom, a C 5 -C 7 cycloalkyl group substituted by CN; optionally substituted by one or more C 1 -C 4 alkyl groups, C 1 -C 4 alkoxy group, carboxyl group, C 1 - C 12 alkyl fluorenyl, C 5 -C 6 cycloalkylcarbenyl, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkyl fluorenyl, benzhydryl, XR 17 , halogen atom, a phenyl group substituted by CN; the R 17 is a C 1 -C 4 alkyl group; the R 18 and the R 19 are each independently selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, C 1 -C 4 alkoxy substituted acyl C 1 -C 5 alkyl group, R 2 C (O) O substituted C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, phenyl; Any one or more halogen atoms, C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkoxy, a C 1 -C 18 alkyl group substituted with an aryloxy group; any C 2 -C 18 alkane inserted by one or more C 3 -C 7 cycloalkylene groups, phenylene groups, O, S, NR 17 group; optionally substituted with one or more C 1 -C 4 alkyl A phenyl group, a halogen atom, CN substituted C 5 -C 7 cycloalkyl; and optionally substituted with one or more C 1 -C 4 alkyl, carboxy, C 1 -C 12 alkyl acyl, C 5 -C a 6 -cycloalkylcarbinyl group, a C 2 -C 4 alkylfluorenyl group substituted with a C 5 -C 6 cycloalkyl group, an arylsulfonyl group, an XR 17 group, a phenyl group, a halogen atom, a phenyl group substituted by CN; The R 20 , the R 21 , the R 22 and the R 23 are each independently selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a C 3 -C 7 cycloalkyl group; a C 1 -C 18 alkyl group substituted by a C 1 -C 4 alkoxy group; a C 2 -C 18 inserted by one or more oxygen atoms, a C 5 -C 7 cycloalkylene group, or a phenylene group; An alkyl group; a C 1 -C 3 alkyl group substituted by a phenyl group, a C 3 -C 7 cycloalkyl group; a phenyl group, a naphthyl group, a benzhydryl group; and optionally a halogen, a C 1 -C 4 alkyl group, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenoxy, phenylthio, NR 24 R 25, C 1 -C 12 acyl group, benzoyl group substituted with benzene a base group, a naphthyl group, a benzamidine group; the R 24 and the R 25 are each a C 1 -C 4 alkyl group; or the NR 24 R 25 together is a phenylephrine, piperidine, piperidine , N-methyl pipe , pyrrole. 一種酮肟化合物，如結構通式V化合物： 其中，該Ar1 選自被該X1 所取代的C6 -C20 鄰亞芳基或C3 -C20 鄰亞雜芳基，該C6 -C20 鄰亞芳基或該C3 -C20 鄰亞雜芳基以相鄰的兩個原子與該Y1 和羰基相連構成並環結構，其餘原子上的取代基各自由下列所構成的群組選出：氫原子、鹵素原子、C1 -C12 烷基、C5 -C7 環烷基、C5 -C7 環烷基所取代的C1 -C4 烷基、C1- C12 烷氧基、C1 -C4 烷基苄氧基、C1 -C3 亞烷基二氧基、R2 C(O)O、C1 -C12 烷基硫基、C1 -C4 烷基苯硫基、CN、羧基、C1 -C12 烷氧基羰基、芳基羰基、雜芳基羰基、X3 R18 、C1 -C4 烷基苯氧基、C1-C8烷基醯基苯氧基、C5 -C6 環烷基醯基苯氧基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯氧基、芳基醯基苯氧基、雜芳基醯基苯氧基、R2 C(O)O取代的C1 -C4 烷基硫基、C1 -C4 烷基苯硫基、C1 -C8 烷基醯基苯硫基、C5 -C6 環烷基醯基苯硫基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯硫基、芳基醯基苯硫基、雜芳基醯基苯硫基；被一個或多個C1 -C12 烷氧基、C1 -C4 烷基苄氧基、R2 C(O)O取代的C1 -C4 烷氧基；苯基及任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、芳基醯基、雜芳基醯基、X3 R17 、苯基、鹵素原子、CN取代的苯基；環氧丙基，其中環氧基任意地與C1 -C4 烷基醛、酮縮合；該X3 選自下列所構成的群組O、S及NR22 ；該Ar2 選自下列所構成的群組：通過該X1 與該Ar1 相連接的C6 -C20 亞芳基、通過該X1 與該Ar1 相連接的C3 -C20 亞雜芳基；該X1 由下列所構成的群組選出：O、S、NR18 及Y2 -Z1 -Y2 ；該Y1由下列所構成的群組選出：(CH2 )m CR15 R16 、NR19 、O(CR15 R16 )m 、S(CR15 R16 )m 、(CR15 R16 )m C=O及S=O，該m為0或1；該Z1 由下列所構成的群組選出：C1 -C10 直鏈亞烷基、C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 支鏈亞烷基、無取代基的C6 -C20 亞芳基、及有取代基的C6 -C20 亞芳基； 該Y2 由下列所構成的群組選出：O、S、NR18 及O-C(O)；該R1 由下列所構成的群組選出：氫原子、C1 -C18 烷基、二苯基膦醯基，二(C1 -C4 烷氧基)膦醯基；任意被一個或多個C3 -C7 環烷基、苯基、OR20 、SR21 、NR22 R23 所取代的C2 -C18 烷基，其中苯基被任意一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代；被C3 -C7 亞環烷基、亞苯基、O、S、NR22 所***的C2 -C18 烷基；C3 -C8 環烷基、CN、NO2 、苯基；被任意一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代的苯基；C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或多個鹵素原子、C1 -C4 烷基、C5 環烷基、C6 環烷基、苯基、CN、OH、X3 R20 所取代；C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或多個的亞苯基、X3 ***；苯基未被取代的苯甲醯基、苯氧基羰基；苯基被任意一個或多個鹵素原子、C1 -C4 烷基、C5 環烷基、C6 環烷基、苯基、CN、OH、X2 R20 所取代的苯甲醯基、苯氧基羰基；該R15 、該R16 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、羧基所取代的C1 -C5 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環 烷基、苯基；任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C2 -C18 烷基；被C5 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基取代的C2 -C4 烷基醯基、苯甲醯基、XR17 、鹵素原子、CN所取代的苯基；該R17 為C1 -C4 烷基；該R18 、該R19 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基；任意被一個或多個鹵素原子、C1 -C4 烷基、C3 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C1 -C18 烷基；任意被一個或多個C3 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；以及任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、C5 -C6 環 烷基甲醯基、C5 -C6 環烷基所取代的C2 -C4 烷基醯基、芳基醯基、XR17 、苯基、鹵素原子、CN所取代的苯基；該R20 、該R21 、該R22 、該R23 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C3 -C7 環烷基；被鹵素、CN、C1 -C4 烷氧基所取代的C1 -C18 烷基；被一個或多個氧原子、C5 -C7 亞環烷基、亞苯基所***的C2 -C18 烷基；被苯基、C3 -C7 環烷基所取代的C1 -C3 烷基；苯基、萘基、苯甲醯基；以及任意被鹵素、C1 -C4 烷基、C1 -C4 烷氧基、C1 -C4 烷基硫基、苯氧基、苯硫基、NR24 R25 、C1 -C12 烷基醯基、苯甲醯基所取代的苯基、萘基、苯甲醯基；該R24 、該R25 各自為C1 -C4 烷基；或NR24 R25 一起為嗎福林，哌啶，哌，N-甲基哌，吡咯。A ketoxime compound, such as a compound of formula V: Wherein the Ar 1 is selected from a C 6 -C 20 o-arylene or a C 3 -C 20 o-heteroaryl group substituted by the X 1 , the C 6 -C 20 o-arylene group or the C 3 - The C 20 ortho-heteroaryl group is bonded to the Y 1 and a carbonyl group by two adjacent atoms to form a ring structure, and the substituents on the remaining atoms are each selected from the group consisting of a hydrogen atom, a halogen atom, and C 1 . -C 12 alkyl, C 5 -C 7 cycloalkyl, C 1 -C 4 alkyl substituted by C 5 -C 7 cycloalkyl, C 1 -C 12 alkoxy, C 1 -C 4 alkyl Benzyloxy, C 1 -C 3 alkylenedioxy, R 2 C(O)O, C 1 -C 12 alkylthio, C 1 -C 4 alkylphenylthio, CN, carboxyl, C 1 -C 12 alkoxycarbonyl, arylcarbonyl, heteroarylcarbonyl, X 3 R 18 , C 1 -C 4 alkylphenoxy, C1-C8 alkylnonylphenoxy, C 5 -C 6 Cycloalkyl nonylphenoxy, C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkylnonylphenoxy, arylnonylphenoxy, heteroarylnonylphenoxy, R 2 C(O)O substituted C 1 -C 4 alkylthio, C 1 -C 4 alkylphenylthio, C 1 -C 8 alkylmercaptophenylthio, C 5 -C 6 cycloalkyl Mercaptophenylthio, C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkyl fluorenyl a phenylthio group, an arylsulfonylphenylthio group, a heteroarylmercaptophenylthio group; one or more C 1 -C 12 alkoxy groups, a C 1 -C 4 alkylbenzyloxy group, R 2 C ( O) O-substituted C 1 -C 4 alkoxy; phenyl and optionally substituted by one or more C 1 -C 4 alkyl groups, carboxyl groups, C 1 -C 12 alkyl fluorenyl groups, aryl fluorenyl groups, heteroaryl groups acyl group, X 3 R 17, a phenyl group, a halogen atom, CN substituted phenyl; glycidyl group, an epoxy group which is optionally C 1 -C 4 alkyl group with an aldehyde, ketone condensate; X 3 is selected from the the following group consisting of O, S and NR 22; Ar 2 is selected from the group consisting of: X 1 C 1 through which is connected to the Ar is 6 -C 20 arylene group, X 1 and through which The Ar 1 -linked C 3 -C 20 heteroarylene; the X 1 is selected from the group consisting of O, S, NR 18 and Y 2 -Z 1 -Y 2 ; Group selection: (CH 2 ) m CR 15 R 16 , NR 19 , O(CR 15 R 16 ) m , S(CR 15 R 16 ) m , (CR 15 R 16 ) m C=O and S=O m is 0 or 1; the Z 1 is selected from the group consisting of C 1 -C 10 linear alkylene, C 1 -C 10 branched alkylene, by one or more oxygen atoms or Sulfur atom attached to the terminal group a C 1 -C 10 linear alkylene group, a C 1 -C 10 branched alkylene group bonded to a terminal group by one or more oxygen or sulfur atoms, inserted by one or more oxygen or sulfur atoms a C 2 -C 10 linear alkylene group, a C 2 -C 10 branched alkylene group inserted by one or more oxygen atoms or sulfur atoms, an unsubstituted C 6 -C 20 arylene group, and a C 6 -C 20 arylene group of a substituent; the Y 2 is selected from the group consisting of O, S, NR 18 and OC(O); the R 1 is selected from the group consisting of: a hydrogen atom , C 1 -C 18 alkyl, diphenylphosphinyl, bis(C 1 -C 4 alkoxy)phosphonium; optionally substituted by one or more C 3 -C 7 cycloalkyl, phenyl, OR 20, SR 21, NR 22 R 23 substituted C 2 -C 18 alkyl, wherein the phenyl group optionally one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heteroalkyl Cycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanomethoxy, aryloxy substituted; C 3 -C 7 cycloalkylene, phenylene, O, S, NR 22 Inserted C 2 -C 18 alkyl; C 3 -C 8 cycloalkyl, CN, NO 2 , phenyl; by any one or more of halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanomethoxy, aryloxy substituted phenyl; C 1 -C 12 alkyl fluorenyl, C 1 -C 12 alkoxycarbonyl, wherein the alkyl group is optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 cycloalkyl, C 6 cycloalkyl, phenyl, CN, OH, X 3 R 20 substituted; C 1 -C 12 alkyl fluorenyl, C 1 -C 12 alkoxycarbonyl, wherein alkyl is optionally inserted by one or more phenylene groups, X 3 ; phenyl unsubstituted Benzomethyl, phenoxycarbonyl; phenyl is optionally one or more halogen atoms, C 1 -C 4 alkyl, C 5 cycloalkyl, C 6 cycloalkyl, phenyl, CN, OH, X 2 a benzyl group and a phenoxycarbonyl group substituted by R 20 ; the R 15 and the R 16 are each independently selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, and a C group substituted by a carboxyl group; 1 -C 5 alkyl, C 1 -C 4 alkoxy substituted acyl C 1 -C 5 alkyl group, R 2 C (O) O substituted C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, phenyl; optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 2 -C 18 alkyl group substituted by C 1 -C 4 alkyl alkoxy group, aryloxy group; C inserted by C 5 -C 7 cycloalkylene group, phenylene group, O, S, NR 17 2 -C 18 alkyl; C 5 -C 7 cycloalkyl optionally substituted by one or more C 1 -C 4 alkyl, phenyl, halogen atom, CN; optionally by one or more C 1 -C 4- alkyl, C 1 -C 4 alkoxy, carboxy, C 1 -C 12 alkyl fluorenyl, C 5 -C 6 cycloalkylcarbenyl, C 5 -C 6 cycloalkyl substituted C 2 - a C 4 alkyl fluorenyl group, a benzhydryl group, an XR 17 group, a halogen atom, a phenyl group substituted by CN; the R 17 is a C 1 -C 4 alkyl group; and the R 18 and the R 19 are each independently derived from the following is selected the group consisting of: hydrogen, C 1 -C 18 alkyl, C 1 -C 4 alkoxy substituted acyl C 1 -C 5 alkyl group, R 2 C (O) O substituted with a C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, phenyl; optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl, heterocycloalkyl, benzene a C 1 -C 18 alkyl group substituted with a heteroaryl group, a CN, a C 1 -C 4 alkyl alkoxy group or an aryloxy group; optionally substituted by one or more C 3 -C 7 cycloalkylene groups phenyl, O, S, NR 17 inserted C 2 -C 18 Group; optionally substituted by one or more C 1 -C 4 alkyl group, a phenyl group, a halogen atom, CN C 5 -C 7 cycloalkyl; and optionally substituted with one or more C 1 -C 4 alkyl, Carboxyl group, C 1 -C 12 alkylfluorenyl group, C 5 -C 6 cycloalkylcarbenyl group, C 2 -C 4 alkylfluorenyl group substituted by C 5 -C 6 cycloalkyl group, aryl fluorenyl group, XR 17 , a phenyl group, a halogen atom, a phenyl group substituted by CN; the R 20 , the R 21 , the R 22 , and the R 23 are each independently selected from the group consisting of hydrogen atoms, C 1 -C 18 alkyl, C 3 -C 7 cycloalkyl; C 1 -C 18 alkyl substituted by halogen, CN, C 1 -C 4 alkoxy; by one or more oxygen atoms, C 5 -C 7 a C 2 -C 18 alkyl group in which a cycloalkylene group or a phenylene group is inserted; a C 1 -C 3 alkyl group substituted with a phenyl group, a C 3 -C 7 cycloalkyl group; a phenyl group, a naphthyl group, a phenyl group Anthracenyl; and optionally halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenoxy, phenylthio, NR 24 R 25 , C 1 a -C 12 alkyl fluorenyl group, a phenyl group substituted with a benzyl fluorenyl group, a naphthyl group, a benzhydryl group; the R 24 and the R 25 are each a C 1 -C 4 alkyl group; or NR 24 R 25 together What? Lin, piperidine, , N-methyl pipe , pyrrole. 一種不對稱二酮肟化合物，選自下列結構式Ⅵ及Ⅶ化合物所構成群組之其中之一： 其中，該Ar1 選自被該X1 所取代的C6 -C20 鄰亞芳基或C3 -C20 鄰亞雜芳基， 該C6 -C20 鄰亞芳基或該C3 -C20 鄰亞雜芳基以相鄰的兩個原子與該Y1 和羰基相連構成並環結構，其餘原子上的取代基各自由下列所構成的群組選出：氫原子、鹵素原子、C1 -C12 烷基、C5 -C7 環烷基、C5 -C7 環烷基所取代的C1 -C4 烷基、C1- C12 烷氧基、C1 -C4 烷基苄氧基、C1 -C3 亞烷基二氧基、R2 C(O)O、C1 -C12 烷基硫基、C1 -C4 烷基苯硫基、CN、羧基、C1 -C12 烷氧基羰基、芳基羰基、雜芳基羰基、X3 R18 、C1 -C4 烷基苯氧基、C1-C8烷基醯基苯氧基、C5 -C6 環烷基醯基苯氧基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯氧基、芳基醯基苯氧基、雜芳基醯基苯氧基、R2 C(O)O取代的C1 -C4 烷基硫基、C1 -C4 烷基苯硫基、C1 -C8 烷基醯基苯硫基、C5 -C6 環烷基醯基苯硫基、C5 -C6 環烷基取代的C1 -C4 烷基醯基苯硫基、芳基醯基苯硫基、雜芳基醯基苯硫基；被一個或多個C1 -C12 烷氧基、C1 -C4 烷基苄氧基、R2 C(O)O取代的C1 -C4 烷氧基；苯基及任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、芳基醯基、雜芳基醯基、X3 R17 、苯基、鹵素原子、CN取代的苯基；環氧丙基，其中環氧基任意地與C1 -C4 烷基醛、酮縮合；該X3 選自O、S及NR22 ；該Ar2 選自：通過該X1 與該Ar1 相連接的C6 -C20 亞芳基、通過該X1 與該Ar1 相連接的C3 -C20 亞雜芳基； 該X1 由下列所構成的群組選出：O、S、NR18 及Y2 -Z1 -Y2 ；該Y1由下列所構成的群組選出：(CH2 )m CR15 R16 、NR19 、O(CR15 R16 )m 、S(CR15 R16 )m 、(CR15 R16 )m C=O及S=O，該m為0或1；該Z1 由下列所構成的群組選出：C1 -C10 直鏈亞烷基、C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C1 -C10 支鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 直鏈亞烷基、被一個或多個氧原子或硫原子所***的C2 -C10 支鏈亞烷基、無取代基的C6 -C20 亞芳基、及有取代基的C6 -C20 亞芳基；該Y2 由下列所構成的群組選出：O、S、NR18 及O-C(O)；該R1 由下列所構成的群組選出：氫原子、C1 -C18 烷基、二苯基膦醯基，二(C1 -C4 烷氧基)膦醯基；任意被一個或多個C3 -C7 環烷基、苯基、OR20 、SR21 、NR22 R23 所取代的C2 -C18 烷基，其中苯基被任意一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代；被C3 -C7 亞環烷基、亞苯基、O、S、NR22 所***的C2 -C18 烷基；C3 -C8 環烷基、CN、NO2 、苯基；被任意一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基取代的苯基； C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或多個鹵素原子、C1 -C4 烷基、C5 環烷基、C6 環烷基、苯基、CN、OH、X3 R20 所取代；C1 -C12 烷基醯基、C1 -C12 烷氧基羰基，其中烷基任意被一個或多個的亞苯基、X3 ***；苯基未被取代的苯甲醯基、苯氧基羰基；苯基被任意一個或多個鹵素原子、C1 -C4 烷基、C5 環烷基、C6 環烷基、苯基、CN、OH、X2 R20 所取代的苯甲醯基、苯氧基羰基；該R15 、該R16 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、羧基所取代的C1 -C5 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基；任意被一個或多個鹵素原子、C1 -C4 烷基、C5 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C2 -C18 烷基；被C5 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；任意被一個或多個C1 -C4 烷基、C1 -C4 烷氧基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基取代的C2 -C4 烷基醯基、苯甲醯基、XR17 、鹵素原子、CN所取代的苯基；該R17 為C1 -C4 烷基； 該R18 、該R19 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C1 -C4 烷氧基醯基所取代的C1 -C5 烷基、R2 C(O)O所取代的C1 -C4 烷基、C5 -C7 環烷基、苯基；任意被一個或多個鹵素原子、C1 -C4 烷基、C3 -C7 環烷基、雜環烷基、苯基、雜芳基、CN、C1 -C4 烷醯氧基、芳醯氧基所取代的C1 -C18 烷基；任意被一個或多個C3 -C7 亞環烷基、亞苯基、O、S、NR17 所***的C2 -C18 烷基；任意被一個或多個C1 -C4 烷基、苯基、鹵素原子、CN所取代的C5 -C7 環烷基；以及任意被一個或多個C1 -C4 烷基、羧基、C1 -C12 烷基醯基、C5 -C6 環烷基甲醯基、C5 -C6 環烷基所取代的C2 -C4 烷基醯基、芳基醯基、XR17 、苯基、鹵素原子、CN所取代的苯基；該R20 、該R21 、該R22 、該R23 各自獨立地由下列所構成的群組選出：氫原子、C1 -C18 烷基、C3 -C7 環烷基；被鹵素、CN、C1 -C4 烷氧基所取代的C1 -C18 烷基；被一個或多個氧原子、C5 -C7 亞環烷基、亞苯基所***的C2 -C18 烷基；被苯基、C3 -C7 環烷基所取代的C1 -C3 烷基；苯基、萘基、苯甲醯基；以及任意被鹵素、C1 -C4 烷基、C1 -C4 烷氧基、C1 -C4 烷基硫基、苯氧基、苯硫基、NR24 R25 、C1 -C12 烷基醯基、苯甲醯基所取代的苯基、 萘基、苯甲醯基；該R24 、該R25 各自為C1 -C4 烷基；或NR24 R25 一起為嗎福林，哌啶，哌，N-甲基哌，吡咯。An asymmetric diketone oxime compound selected from the group consisting of the following compounds of the formulae VI and VII: Wherein the Ar 1 is selected from a C 6 -C 20 o-arylene or a C 3 -C 20 o-heteroaryl group substituted by the X 1 , the C 6 -C 20 o-arylene group or the C 3 - The C 20 ortho-heteroaryl group is bonded to the Y 1 and a carbonyl group by two adjacent atoms to form a ring structure, and the substituents on the remaining atoms are each selected from the group consisting of a hydrogen atom, a halogen atom, and C 1 . -C 12 alkyl, C 5 -C 7 cycloalkyl, C 1 -C 4 alkyl substituted by C 5 -C 7 cycloalkyl, C 1 -C 12 alkoxy, C 1 -C 4 alkyl Benzyloxy, C 1 -C 3 alkylenedioxy, R 2 C(O)O, C 1 -C 12 alkylthio, C 1 -C 4 alkylphenylthio, CN, carboxyl, C 1 -C 12 alkoxycarbonyl, arylcarbonyl, heteroarylcarbonyl, X 3 R 18 , C 1 -C 4 alkylphenoxy, C1-C8 alkylnonylphenoxy, C 5 -C 6 Cycloalkyl nonylphenoxy, C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkylnonylphenoxy, arylnonylphenoxy, heteroarylnonylphenoxy, R 2 C(O)O substituted C 1 -C 4 alkylthio, C 1 -C 4 alkylphenylthio, C 1 -C 8 alkylmercaptophenylthio, C 5 -C 6 cycloalkyl acyl phenyl group, C 5 -C 6 cycloalkyl substituted acyl C 1 -C 4 alkyl Phenylthio, phenylthio aryl acyl, heteroaryl acyl phenyl group; substituted with one or more C 1 -C 12 alkoxy, C 1 -C 4 alkylbenzyl group, R 2 C ( O) O-substituted C 1 -C 4 alkoxy; phenyl and optionally substituted by one or more C 1 -C 4 alkyl groups, carboxyl groups, C 1 -C 12 alkyl fluorenyl groups, aryl fluorenyl groups, heteroaryl groups acyl group, X 3 R 17, a phenyl group, a halogen atom, CN substituted phenyl; glycidyl group, an epoxy group which is optionally C 1 -C 4 alkyl group with an aldehyde, ketone condensate; X 3 is selected from the O, S and NR 22; the Ar 2 is selected from: X 1 C 1 through which is connected to the Ar is 6 -C 20 arylene group, C 1 connected to the Ar through the X 1 3 -C 20 alkylene Heteroaryl; the X 1 is selected from the group consisting of O, S, NR 18 and Y 2 -Z 1 -Y 2 ; the Y1 is selected from the group consisting of: (CH 2 ) m CR 15 R 16, NR 19, O ( CR 15 R 16) m, S (CR 15 R 16) m, (CR 15 R 16) m C = O and S = O, the m is 0 or 1; the Z 1 by a the group consisting of the following is selected: C 1 -C 10 linear alkylene, C 1 -C 10 branched alkylene group, an oxygen atom or a sulfur atom attached to one or more end groups C 1 -C 10 Linear alkylene group, one or more C atom or sulfur atom attached to a terminal end 1 -C 10 branched alkylene, substituted by one or more oxygen atoms or sulfur atom inserted straight chain C 2 -C 10 alkylene group, substituted with one or more oxygen or sulfur atom inserted branched C 2 -C 10 alkylene group unsubstituted C 6 -C 20 arylene group, and an optionally substituted C 6 -C 20 arylene; Y 2 of the following The group formed is selected from: O, S, NR 18 and OC(O); the R 1 is selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a diphenylphosphonium group, and two (C 1 -C 4 alkoxy)phosphonium; any C 2 -C 18 substituted by one or more C 3 -C 7 cycloalkyl, phenyl, OR 20 , SR 21 , NR 22 R 23 An alkyl group wherein the phenyl group is any one or more of halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 -alkoxy, aryloxy substituted; C 2 -C 18 alkyl inserted by C 3 -C 7 cycloalkylene, phenylene, O, S, NR 22 ; C 3 -C 8 ring alkyl, CN, NO 2, phenyl; optionally one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl , CN, C 1 -C 4 alkanoyl group, acyl group, aryloxy-substituted phenyl; C 1 -C 12 alkyl acyl, C 1 -C 12 alkoxycarbonyl, wherein the alkyl group optionally substituted with one or more Halogen atom, C 1 -C 4 alkyl group, C 5 cycloalkyl group, C 6 cycloalkyl group, phenyl group, CN, OH, X 3 R 20 substituted; C 1 -C 12 alkyl fluorenyl group, C 1 -C 12 alkoxycarbonyl group, wherein the alkyl group is optionally interrupted by one or more phenylene groups, X 3 ; phenyl unsubstituted benzamidine group, phenoxycarbonyl group; phenyl group is optionally one or more a halogen atom, C 1 -C 4 alkyl, C 5 cycloalkyl, C 6 cycloalkyl, phenyl, CN, OH, X 2 R 20 substituted benzoyl group, phenoxycarbonyl group; the R 15 Each of R 16 is independently selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a C 1 -C 5 alkyl group substituted by a carboxyl group, and a C 1 -C 4 alkoxyfluorenyl group. Substituted C 1 -C 5 alkyl, C 2 -C 4 alkyl substituted by R 2 C(O)O, C 5 -C 7 cycloalkyl, phenyl; optionally substituted by one or more halogen atoms, C substituted 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyl group, aryloxy group, acyl C 2 -C 18 alkyl radical; a C 5 -C 7 cycloalkylene, phenylene, O, S, NR 17 inserted C 2 -C 18 alkyl; optionally substituted with one or more C 1 -C a C 5 -C 7 cycloalkyl group substituted with 4 alkyl, phenyl, halogen atom, CN; optionally substituted by one or more C 1 -C 4 alkyl groups, C 1 -C 4 alkoxy group, carboxyl group, C 1 -C 12 alkyl fluorenyl, C 5 -C 6 cycloalkylcarbenyl, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkyl fluorenyl, benzhydryl, XR 17 , halogen atom a phenyl group substituted by CN; the R 17 is a C 1 -C 4 alkyl group; and the R 18 and the R 19 are each independently selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, C 1 -C 4 alkoxy substituted acyl C 1 -C 5 alkyl group, R 2 C (O) O substituted C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, phenyl Any one or more halogen atoms, C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkoxy a C 1 -C 18 alkyl group substituted with an aryloxy group; any C 2 -C 18 inserted by one or more C 3 -C 7 cycloalkylene groups, phenylene groups, O, S, NR 17 alkyl; optionally substituted with one or more C 1 -C 4 alkoxy , A phenyl group, a halogen atom, CN substituted C 5 -C 7 cycloalkyl; and optionally substituted with one or more C 1 -C 4 alkyl, carboxy, C 1 -C 12 acyl group, C 5 - a C 6 cycloalkylcarbinyl group, a C 2 -C 4 alkylfluorenyl group substituted with a C 5 -C 6 cycloalkyl group, an arylsulfonyl group, an XR 17 group, a phenyl group, a halogen atom, a phenyl group substituted by CN The R 20 , the R 21 , the R 22 , and the R 23 are each independently selected from the group consisting of a hydrogen atom, a C 1 -C 18 alkyl group, a C 3 -C 7 cycloalkyl group; C 1 -C 18 alkyl group substituted by CN, C 1 -C 4 alkoxy group; C 2 -C inserted by one or more oxygen atoms, C 5 -C 7 cycloalkylene group, phenylene group 18 alkyl; C 1 -C 3 alkyl substituted by phenyl, C 3 -C 7 cycloalkyl; phenyl, naphthyl, benzhydryl; and optionally halogen, C 1 -C 4 alkyl , C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenoxy, phenylthio, NR 24 R 25 , C 1 -C 12 alkyl fluorenyl, benzylidene substituted Phenyl, naphthyl, benzhydryl; the R 24 , the R 25 are each a C 1 -C 4 alkyl group; or the NR 24 R 25 together is a phenylephrine, piperidine, piperidine , N-methyl pipe , pyrrole. 一種光固化組合物，含有光引發劑和至少一種可進行自由基聚合的碳碳雙鍵化合物，該光引發劑包含至少一種請求項1中所述之不對稱二肟酯化合物。 A photocurable composition comprising a photoinitiator and at least one carbon-carbon double bond compound which is capable of undergoing radical polymerization, the photoinitiator comprising at least one asymmetric diterpene ester compound described in claim 1. 根據請求項16所述的光固化組合物，進一步含有添加劑。 The photocurable composition according to claim 16, further comprising an additive. 根據請求項17所述的光固化組合物，以重量計，該光引發劑占全部組合物的0.05-25%，該碳碳雙鍵化合物及該添加劑占除上述組分外的剩餘百分比。 The photocurable composition according to claim 17, wherein the photoinitiator accounts for 0.05 to 25% by weight of the total composition, and the carbon-carbon double bond compound and the additive account for the remaining percentage other than the above components. 根據請求項16或17所述的光固化組合物，其中該碳碳雙鍵化合物為丙烯酸酯化合物或甲基丙烯酸酯化合物。 The photocurable composition according to claim 16 or 17, wherein the carbon-carbon double bond compound is an acrylate compound or a methacrylate compound. 根據請求項17的光固化組合物，其中該添加劑選自於顯影樹脂、顏料及染料。 The photocurable composition according to claim 17, wherein the additive is selected from the group consisting of a developing resin, a pigment, and a dye. 一種光固化組合物的應用方法，包括(1)先將請求項16或17所述的光固化組合物用於製造帶有顏色的或透明的下列製品之一：塗料、油墨、粘合劑、光致抗蝕劑及光阻劑；以及(2)將該製品用於印刷、3D列印、顯示器件中彩色濾光片的生產、電子器件封裝、印刷電路板介質層。 A method of applying a photocurable composition, comprising: (1) using the photocurable composition of claim 16 or 17 first for producing one of the following colored or transparent articles: paint, ink, adhesive, Photoresist and photoresist; and (2) the article is used in printing, 3D printing, color filter production in display devices, electronic device packaging, printed circuit board dielectric layers. 一種光固化組合物的固化方法，將請求項16或17任一項所述的光固化組合物形成塗布層於基材上，用波長為190-600nm的光線照射使該塗 布層固化。 A method for curing a photocurable composition, the photocurable composition according to any one of claims 16 or 17 is formed on a substrate, and irradiated with light having a wavelength of 190 to 600 nm to make the coating. The layer is cured. 根據請求項22所述光固化組合物的固化方法，該光線來自太陽、汞燈、高壓汞燈或LED燈。 According to the curing method of the photocurable composition of claim 22, the light is from a sun, a mercury lamp, a high pressure mercury lamp or an LED lamp. 一種以光固化組合物製作凸起圖案的方法，先將請求項16或17任一項所述的光固化組合物用溶劑稀釋；再將稀釋後的該光固化組合物塗布於基材上，經烘乾、曝光、以及用顯影方法除去未曝光部分而得到凸起圖案。 A method for producing a raised pattern by using a photocurable composition, the photocurable composition according to any one of claims 16 or 17 is diluted with a solvent; and the diluted photocurable composition is applied to a substrate. The unexposed portion is removed by drying, exposure, and development to obtain a raised pattern. 一種彩色濾光片，包含黑色、紅色、綠色、藍色圖元，由包含至少一種請求項1或4所述的不對稱二肟酯化合物、光固化單體、鹼溶性樹脂、顏料及添加劑構成的組合物，依序經過塗布、曝光、顯影、熱處理過程而得到。 A color filter comprising black, red, green, and blue primitives, comprising an asymmetric diterpene ester compound, photocurable monomer, alkali soluble resin, pigment, and additive comprising at least one of claims 1 or 4. The composition is obtained by sequential coating, exposure, development, and heat treatment. 一種彩色濾光片的製造方法，該彩色濾光片包含黑色、紅色、綠色、藍色圖元，該製造方法是將含有至少一種請求項1或4所述之不對稱二肟酯化合物、光固化單體、鹼溶性樹脂、顏料及添加劑構成的組合物，依序進行塗布、曝光、顯影、熱處理，最後得到該彩色濾光片。 A method of manufacturing a color filter comprising black, red, green, and blue primitives, the method of manufacturing comprising at least one asymmetric diterpene ester compound according to claim 1 or 4, light The composition comprising a curing monomer, an alkali-soluble resin, a pigment, and an additive is sequentially coated, exposed, developed, and heat-treated, and finally the color filter is obtained.
TW103130220A 2014-06-09 2014-09-02 Asymmetric dioxime ester and corresponding intermediate, manufacturing method and applications. TWI495631B (en)

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