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TW201723096A - Photosensitive resin composition and uses thereof - Google Patents

Photosensitive resin composition and uses thereof Download PDF

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Publication number
TW201723096A
TW201723096A TW104144797A TW104144797A TW201723096A TW 201723096 A TW201723096 A TW 201723096A TW 104144797 A TW104144797 A TW 104144797A TW 104144797 A TW104144797 A TW 104144797A TW 201723096 A TW201723096 A TW 201723096A
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Taiwan
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group
carbon atoms
alkyl group
phenyl
carbon number
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TW104144797A
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Chinese (zh)
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許承昌
謝栢源
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奇美實業股份有限公司
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Priority to TW104144797A priority Critical patent/TW201723096A/en
Priority to CN201611234706.XA priority patent/CN106959581A/en
Publication of TW201723096A publication Critical patent/TW201723096A/en

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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509Filters, e.g. light shielding masks
    • G02F1/133514Colour filters
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007Filters, e.g. additive colour filters; Components for display devices
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a photosensitive resin composition and a color filter and a liquid crystal display element manufactured by the photosensitive resin composition. The photosensitive resin composition includes a pigment (A), a dye (B), an alkali-soluble resin (C), a compound having an unsaturated ethylenically group (D), a photoinitiator (E) and a thermal acid generating agent (F). The color filter formed by the photosensitive resin composition has good change rate for film thickness of thermal solvent.

Description

感光性樹脂組成物及其應用 Photosensitive resin composition and application thereof

本發明係有關一種感光性樹脂組成物,及使用該感光性樹脂組成物以製造彩色濾光片及液晶顯示元件。特別是提供一種感光性樹脂組成物,該感光性樹脂組成物所製得之彩色濾光片具有良好熱溶劑膜厚變化率。 The present invention relates to a photosensitive resin composition and a photosensitive resin composition using the same to produce a color filter and a liquid crystal display element. In particular, a photosensitive resin composition is provided, and the color filter obtained by the photosensitive resin composition has a good thermal solvent film thickness change rate.

目前,彩色濾光片已被廣泛地應用在彩色液晶顯示器、彩色傳真機、彩色攝影機等辦公器材之領域。隨著市場需求日漸擴大,彩色濾光片之製作技術亦趨向多樣化,目前已開發染色法、印刷法、電鍍法以及分散法等製造方法,其中以分散法為主流製程。 At present, color filters have been widely used in the fields of color liquid crystal displays, color facsimile machines, color cameras and the like. As the market demand is expanding, the production technology of color filters is also diversified. At present, dyeing methods, printing methods, electroplating methods, and dispersion methods have been developed, among which the dispersion method is the mainstream process.

分散法之製程係先將著色顏料分散於感光性樹脂中,再將該感光性樹脂塗佈於玻璃基板上,經過曝光、顯像等步驟,即可製得特定圖案。經重複三次操作,即可製得紅色(R),綠色(G)及藍色(B)之畫素著色層之圖案,之後視需要可於畫素著色層之圖案上施加保護膜。 In the dispersion method, the coloring pigment is first dispersed in a photosensitive resin, and the photosensitive resin is applied onto a glass substrate, and a specific pattern can be obtained by exposure, development, and the like. After repeating the operation three times, a pattern of a red (R), green (G), and blue (B) pixel colored layer can be obtained, and then a protective film can be applied to the pattern of the pixel colored layer as needed.

用於分散法製程中之感光性樹脂如日本特開平6-95211號公報及特開平8-183819號公報所揭示者,例如以(甲基)丙烯酸為單體成分所聚合而成之共聚物,其係作為感光性樹脂之鹼可溶性樹脂。 For example, as disclosed in Japanese Laid-Open Patent Publication No. Hei. It is used as an alkali-soluble resin of a photosensitive resin.

然而,於彩色濾光片之製造過程中,需經歷多次熱處理步驟,如紅色(R),綠色(G)及藍色(B)等畫素著色層圖案形成後之後烤 (post-bake)步驟及透明導電膜(ITO膜)之形成步驟等,該等步驟一般皆需於200℃以上之高溫下操作,但上述習知之感光性樹脂若於180℃下加熱1小時左右,則易於其畫素著色層中產生顏料凝集粒子(一般顏料凝集粒子之粒徑介於1μm至10μm),且該畫素著色層之耐熱性亦不佳。 However, in the manufacturing process of the color filter, it is necessary to undergo multiple heat treatment steps, such as red (R), green (G) and blue (B), etc. (post-bake) step and formation step of transparent conductive film (ITO film), etc., these steps generally need to be operated at a high temperature of 200 ° C or higher, but the above-mentioned photosensitive resin is heated at 180 ° C for about 1 hour. It is easy to produce pigment agglomerated particles in the pixel colored layer (generally, the pigment agglomerated particles have a particle diameter of 1 μm to 10 μm), and the heat resistance of the pixel colored layer is also poor.

為改善上述之問題,日本特開2001-075273中揭示了一種感光性樹脂組成物,其包含羧酸基之不飽和單體與含有環氧丙基之單體所聚合而得之聚合物,並利用上述聚合物作為感光性樹脂之鹼可溶性樹脂。然而,利用前述習知技術之感光性樹脂組成物所製得之彩色濾光片,仍具有熱溶劑膜厚變化率不佳的問題。 In order to improve the above-mentioned problem, a photosensitive resin composition comprising a polymer obtained by polymerizing an unsaturated monomer of a carboxylic acid group and a monomer containing a glycidyl group is disclosed in Japanese Laid-Open Patent Publication No. 2001-075273, and The above polymer is used as an alkali-soluble resin of a photosensitive resin. However, the color filter obtained by using the photosensitive resin composition of the prior art described above still has a problem that the rate of change of the film thickness of the hot solvent is not good.

因此,如何克服熱溶劑膜厚變化率不佳之問題以達到目前業界的要求,為本發明所屬技術領域中努力研究之目標。 Therefore, how to overcome the problem of poor rate of change of the thickness of the hot solvent film to meet the requirements of the current industry is an object of diligent research in the technical field to which the present invention pertains.

本發明利用提供含有特殊熱酸發生劑之感光性樹脂組成物,而得到熱溶劑膜厚變化率佳之彩色濾光片用感光性樹脂組成物。 In the present invention, a photosensitive resin composition containing a special thermal acid generator is provided, and a photosensitive resin composition for a color filter having a high change rate of a film thickness of a hot solvent is obtained.

因此,本發明提供一種感光性樹脂組成物,其包含:顏料(A);染料(B);鹼可溶性樹脂(C);具有乙烯性不飽和基之化合物(D);光起始劑(E);具有式(I)所示結構之熱酸發生劑(F);及溶劑(G);R1f(SO3R2f)a 式(I) Accordingly, the present invention provides a photosensitive resin composition comprising: a pigment (A); a dye (B); an alkali-soluble resin (C); a compound (D) having an ethylenically unsaturated group; and a photoinitiator (E) a thermal acid generator (F) having the structure represented by the formula (I); and a solvent (G); R 1f (SO 3 R 2f ) a (I)

於式(I)中,R1f及R2f各自獨立地表示任意的取代基;及a表示1以上之整數。 In the formula (I), R 1f and R 2f each independently represent an arbitrary substituent; and a represents an integer of 1 or more.

本發明亦提供一種彩色濾光片之製造方法,其係使用前述之感光性樹脂組成物形成一畫素層。 The present invention also provides a method of producing a color filter which forms a pixel layer using the above-mentioned photosensitive resin composition.

本發明又提供一種彩色濾光片,其係由前述之方法所製得。 The present invention further provides a color filter which is produced by the aforementioned method.

本發明再提供一種液晶顯示元件,係包含前述之彩色濾光。 The present invention further provides a liquid crystal display element comprising the aforementioned color filter.

本發明提供一種感光性樹脂組成物,其包含:顏料(A);染料(B);鹼可溶性樹脂(C);具有乙烯性不飽和基之化合物(D);光起始劑(E);具有式(I)所示結構之熱酸發生劑(F);及溶劑(G);R1f(SO3R2f)a 式(I) The present invention provides a photosensitive resin composition comprising: a pigment (A); a dye (B); an alkali-soluble resin (C); a compound (D) having an ethylenically unsaturated group; and a photoinitiator (E); Thermal acid generator (F) having the structure represented by formula (I); and solvent (G); R 1f (SO 3 R 2f ) a formula (I)

於式(I)中,R1f及R2f各自獨立地表示任意的取代基;及a表示1以上之整數。 In the formula (I), R 1f and R 2f each independently represent an arbitrary substituent; and a represents an integer of 1 or more.

根據本發明之顏料(A)可為無機顏料、有機顏料或上述之組合。 The pigment (A) according to the present invention may be an inorganic pigment, an organic pigment or a combination thereof.

該無機顏料可為金屬氧化物、金屬錯鹽等金屬化合物,其可選自於鐵、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、亞鉛、銻等金屬的氧化物、前述金屬的複合氧化物以及金屬錯鹽。 The inorganic pigment may be a metal compound such as a metal oxide or a metal salt, which may be selected from the group consisting of oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, lead, and antimony, and the foregoing. A composite oxide of a metal and a metal salt.

該有機顏料可選自於C.1.顏料黃1、3、11、12、13、 14、15、16、17、20、24、31、53、55、60、61、65、71、73、74、81、83、93、95、97、98、99、100、101、104、106、108、109、110、113、114、116、117、119、120、126、127、128、129、138、139、150、151、152、153、154、155、156、166、167、168、175;C.I.顏料橙1、5、13、14、16、17、24、34、36、38、40、43、46、49、51、61、63、64、71、73;C.I.顏料紅1、2、3、4、5、6、7、8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、31、32、37、38、40、41、42、48:1、48:2、48:3、48:4、49:1、49:2、50:1、52:1、53:1、57、57:1、57:2、58:2、58:4、60:1、63:1、63:2、64:1、81:1、83、88、90:1、97、101、102、104、105、106、108、112、113、114、122、123、144、146、149、150、151、155、166、168、170、171、172、174、175、176、177、178、179、180、185、187、188、190、193、194、202、206、207、208、209、215、216、220、224、226、242、243、245、254、255、264、265;C.I.顏料紫1、14、19、23、29、32、33、36、37、38、39、40、50;C.I.顏料藍1、2、15、15:1、15:2、15:3、15:4、15:5、15:6、16、21、22、60、61、64、66;C.I.顏料綠7、36、37、42、58;C.I.顏料棕23、25、28;以及C.I.顏料黑1、7。上述之有機顏料可單獨一種或混合複數種使用。 The organic pigment may be selected from C.1. Pigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175; CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 2 24, 226, 242, 243, 245, 254, 255, 264, 265; CI Pigment Violet 1, 14, 19, 23, 29, 32, 33, 36, 37, 38, 39, 40, 50; CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 21, 22, 60, 61, 64, 66; CI Pigment Green 7, 36 , 37, 42, 58; CI pigment brown 23, 25, 28; and CI pigment black 1, 7. The above organic pigments may be used singly or in combination of plural kinds.

該顏料(A)之平均粒子徑較佳為10nm至200nm;更佳為20nm至150nm;最佳為30nm至130nm。 The average particle diameter of the pigment (A) is preferably from 10 nm to 200 nm; more preferably from 20 nm to 150 nm; most preferably from 30 nm to 130 nm.

基於該鹼可溶性樹脂(C)之使用量為100重量份,該顏料(A)之使用量為30重量份至300重量份;較佳為40重量份至250重量份;更佳為50重量份至200重量份。 The pigment (A) is used in an amount of 30 parts by weight to 300 parts by weight based on 100 parts by weight of the alkali-soluble resin (C); preferably 40 parts by weight to 250 parts by weight; more preferably 50 parts by weight. Up to 200 parts by weight.

必要時,該顏料(A)也能選擇性地使用分散劑,例如:陽離子系、陰離子系、非離子系、兩性、聚矽氧烷系、氟系等之界面 活性劑。 If necessary, the pigment (A) can also selectively use a dispersant such as a cationic, anionic, nonionic, amphoteric, polyoxyalkylene, or fluorine-based interface. Active agent.

前述之界面活性劑可包含但不限於聚環氧乙烷十二烷基醚、聚環氧乙烷硬脂醯醚、聚環氧乙烷油醚等之聚環氧乙烷烷基醚類;聚環氧乙烷辛基苯醚、聚環氧乙烷壬基苯醚等之聚環氧乙烷烷基苯醚類界面活性劑;聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯等之聚乙二醇二酯類界面活性劑;山梨糖醇酐脂肪酸酯類界面活性劑;脂肪酸改質的聚酯類界面活性劑;三級胺改質的聚胺基甲酸酯類界面活性劑;信越化學工業製造,型號為KP之商品、Toray Dow Corning Silicon製造,型號為SF-8427之商品、共榮社油脂化學工業製造,型號為Polyflow之商品、得克姆公司(Tochem Products Co.,Ltd.)製造,型號為F-Top之商品、大日本印墨化學工業製造,型號為Megafac之產品、住友3M製造,型號為Fluorad之產品、旭硝子製造,型號為Asahi Guard及Surflon之商品。界面活性劑可單獨一種或混合複數種使用。 The aforementioned surfactant may include, but is not limited to, polyethylene oxide alkyl ethers such as polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether; Polyethylene oxide alkyl phenyl ether surfactants such as polyethylene oxide octyl phenyl ether and polyethylene oxide nonyl phenyl ether; polyethylene glycol dilaurate and polyethylene glycol Polyethylene glycol diester surfactant such as fatty acid ester; sorbitan fatty acid ester surfactant; fatty acid modified polyester surfactant; tertiary amine modified polyurethane Surfactant; manufactured by Shin-Etsu Chemical Co., Ltd., model KP, manufactured by Toray Dow Corning Silicon, model SF-8427, manufactured by Kyoritsu Oil & Fat Chemical Industry, model Polyflow, Tochem Products Co.,Ltd.), model F-Top, manufactured by Dainippon Ink Chemical Industry, model Megafac, Sumitomo 3M, model Fluorad, Asahi Glass, model Asahi Guard and Surflon commodity. The surfactants may be used singly or in combination of plural kinds.

根據本發明之染料(B)可搭配顏料(A)使用,本發明所屬技術領域中具通常知識者可選擇特定光譜之染料(B),於本發明之具體例中,該染料(B)為偶氮染料、偶氮金屬錯合物染料、蒽醌染料、靛藍染料、硫靛染料、酞菁染料、二苯甲烷染料、三苯甲烷染料、呫噸染料、噻嗪染料、陽離子染料、菁染料、硝基染料、喹啉染料、萘醌染料、惡嗪染料等。 The dye (B) according to the present invention can be used in combination with the pigment (A), and those having ordinary skill in the art to which the present invention pertains can select a dye (B) of a specific spectrum. In the specific example of the present invention, the dye (B) is Azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, sulfonium dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes , nitro dyes, quinoline dyes, naphthoquinone dyes, oxazine dyes, and the like.

於本發明之較佳具體例中,該染料(B)為C.I.溶劑紅2、C.I.溶劑紅24、C.I.溶劑紅27、C.I.溶劑紅49、C.I.溶劑紅52、C.I.溶劑紅57、C.I.溶劑紅89、C.I.溶劑紅111、C.I.溶劑紅114、C.I.溶劑紅119、C.I.溶劑紅124、C.I.溶劑紅135、C.I.溶劑紅136、C.I.溶劑紅137、C.I.溶劑紅138、C.I.溶劑紅139、C.I.溶劑紅143、C.I.溶劑紅144、C.I.溶劑紅145、C.I.溶劑紅146、C.I.溶劑紅147、C.I.溶劑紅148、C.I.溶劑紅149、C.I.溶劑紅150、C.I.溶劑紅151、C.I.溶劑紅 152、C.I.溶劑紅155、C.I.溶劑紅156、C.I.溶劑紅162、C.I.溶劑紅168、C.I.溶劑紅169、C.I.溶劑紅170、C.I.溶劑紅171、C.I.溶劑紅172、C.I.溶劑紅177、C.I.溶劑紅178、C.I.溶劑紅179、C.I.溶劑紅181、C.I.溶劑紅190、C.I.溶劑紅191、C.I.溶劑紅194、C.I.溶劑紅199、C.I.溶劑紅200、C.I.溶劑紅201、C.I.溶劑紅299、C.I.直接紅2、C.I.直接紅81、C.I.酸性紅1、C.I.酸性紅14、C.I.酸性紅27、C.I.酸性紅52、C.I.酸性紅87、C.I.酸性紅88、C.I.酸性紅289、C.I.鹼性紅1、C.I.媒介紅3、C.I.冰染紅21、C.I.還原紅1、C.I.還原紅2、C.I.還原紅15、C.I.還原紅23、C.I.還原紅41、C.I.還原紅47、C.I.分散紅1、C.I.分散紅11、C.I.分散紅15、C.I.分散紅22、C.I.分散紅60、C.I.分散紅92、C.I.分散紅146、C.I.分散紅191、C.I.分散紅283、C.I.分散紅288、C.I.活性紅12。上述之染料可依所需之性質單獨或混合使用。 In a preferred embodiment of the present invention, the dye (B) is CI Solvent Red 2, CI Solvent Red 24, CI Solvent Red 27, CI Solvent Red 49, CI Solvent Red 52, CI Solvent Red 57, CI Solvent Red 89. , CI Solvent Red 111, CI Solvent Red 114, CI Solvent Red 119, CI Solvent Red 124, CI Solvent Red 135, CI Solvent Red 136, CI Solvent Red 137, CI Solvent Red 138, CI Solvent Red 139, CI Solvent Red 143 , CI Solvent Red 144, CI Solvent Red 145, CI Solvent Red 146, CI Solvent Red 147, CI Solvent Red 148, CI Solvent Red 149, CI Solvent Red 150, CI Solvent Red 151, CI Solvent Red 152, CI solvent red 155, CI solvent red 156, CI solvent red 162, CI solvent red 168, CI solvent red 169, CI solvent red 170, CI solvent red 171, CI solvent red 172, CI solvent red 177, CI solvent red 178, CI solvent red 179, CI solvent red 181, CI solvent red 190, CI solvent red 191, CI solvent red 194, CI solvent red 199, CI solvent red 200, CI solvent red 201, CI solvent red 299, CI direct red 2, CI direct red 81, CI acid red 1, CI acid red 14, CI acid red 27, CI acid red 52, CI acid red 87, CI acid red 88, CI acid red 289, CI alkaline red 1, CI medium Red 3, CI ice stained red 21, CI reduced red 1, CI reduced red 2, CI reduced red 15, CI reduced red 23, CI reduced red 41, CI reduced red 47, CI dispersed red 1, CI dispersed red 11, CI Disperse red 15, CI dispersed red 22, CI dispersed red 60, CI dispersed red 92, CI dispersed red 146, CI dispersed red 191, CI dispersed red 283, CI dispersed red 288, CI active red 12. The above dyes may be used singly or in combination depending on the desired properties.

基於該鹼可溶性樹脂(C)之使用量為100重量份,該染料(B)之使用量為5重量份至50重量份;較佳為10重量份至45重量份;更佳為15重量份至40重量份。 The dye (B) is used in an amount of 5 parts by weight to 50 parts by weight, based on the amount of the alkali-soluble resin (C), preferably 10 parts by weight to 45 parts by weight; more preferably 15 parts by weight. Up to 40 parts by weight.

根據本發明之鹼可溶性樹脂(C)包含一第一鹼可溶性樹脂(C-1),該第一鹼可溶性樹脂(C-1)係由一混合物進行聚合反應所製得,且該混合物包含一具有至少二個環氧基之環氧化合物(c-1-1)及一具有至少一個羧酸基及至少一個乙烯性不飽和基之化合物(c-1-2)。除此之外,上述混合物更可選擇性地包含羧酸酐化合物(c-1-3)及/或含環氧基的化合物(c-1-4)。 The alkali-soluble resin (C) according to the present invention comprises a first alkali-soluble resin (C-1) obtained by a polymerization reaction of a mixture, and the mixture contains one An epoxy compound (c-1-1) having at least two epoxy groups and a compound (c-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group. In addition to the above, the above mixture may more optionally contain a carboxylic anhydride compound (c-1-3) and/or an epoxy group-containing compound (c-1-4).

該具有至少二個環氧基的環氧化合物(c-1-1)可具有如下式(II-1)或下式(II-2)所示之結構。在此處,「環氧化合物(c-1-1)可具有如下式(II-1)或下式(II-2)所示之結構」的敘述亦涵蓋了具有如下式(II-1)所示之結構的化合物及具有如下式(II-2)所示之結構的化合物同時存在而作為環氧化合物(c-1-1)的情形。具體而言,前述具有至少二個 環氧基的環氧化合物(c-1-1)例如是具有如下式(II-1)所示之結構: The epoxy compound (c-1-1) having at least two epoxy groups may have a structure represented by the following formula (II-1) or the following formula (II-2). Here, the description that the epoxy compound (c-1-1) may have a structure represented by the following formula (II-1) or the following formula (II-2) also encompasses the following formula (II-1) The compound having the structure shown and the compound having the structure represented by the following formula (II-2) exist simultaneously as the epoxy compound (c-1-1). Specifically, the epoxy compound (c-1-1) having at least two epoxy groups as described above has, for example, a structure represented by the following formula (II-1):

於式(II-1)中,R1c、R2c、R3c以及R4c分別為相同或不同,且表示氫原子、鹵素原子、碳數為1至5之烷基、碳數為1至5之烷氧基、碳數為6至12之芳香基或碳數為6至12之芳烷基。 In the formula (II-1), R 1c , R 2c , R 3c and R 4c are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and a carbon number of 1 to 5. An alkoxy group, an aromatic group having 6 to 12 carbon atoms or an aralkyl group having 6 to 12 carbon atoms.

前述式(II-1)之具有至少二個環氧基的環氧化合物(c-1-1)可包括由雙酚芴型化合物(bisphenol fluorene)與鹵化環氧丙烷(epihalohydrin)反應而得之含環氧基之雙酚芴型化合物,但並不限於此。 The epoxy compound (c-1-1) having at least two epoxy groups of the above formula (II-1) may include a reaction of a bisphenol fluorene with an epihalohydrin. An epoxy group-containing bisphenol quinone type compound, but is not limited thereto.

作為上述雙酚芴型化合物的具體例,可列舉但不限於:9,9-雙(4-羥基苯基)芴〔9,9-bis(4-hydroxy phenyl)fluorene〕、9,9-雙(4-羥基-3-甲基苯基)芴〔9,9-bis(4-hydroxy-3-methylphenyl)fluorene〕、9,9-雙(4-羥基-3-氯苯基)芴〔9,9-bis(4-hydroxy-3-chlorophenyl)fluorene〕、9,9-雙(4-羥基-3-溴苯基)芴〔9,9-bis(4-hydroxy-3-bromophenyl)fluorene〕、9,9-雙(4-羥基-3-氟苯基)芴〔9,9-bis(4-hydroxy-3-fluorophenyl)fluorene〕、9,9-雙(4-羥基-3-甲氧基苯基)芴〔9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene〕、9,9-雙(4-羥基-3,5-二甲基苯基)芴〔9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene〕、9,9-雙(4-羥基-3,5-二氯苯基)芴〔9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene〕、9,9-雙(4-羥基-3,5-二溴苯基)芴〔9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene〕等化合物。 Specific examples of the bisphenol quinone type compound include, but are not limited to, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-double (4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene [9] ,9-bis(4-hydroxy-3-chlorophenyl)fluorene],9,9-bis(4-hydroxy-3-bromophenyl)fluorene 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxy 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene [9,9-bis (4-hydroxy-3,5-dimethylphenyl)fluorene],9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene [9,9-bis(4-hydroxy-3,5-dichlorophenyl) a compound such as fluorene], 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene.

上述鹵化環氧丙烷(epihalohydrin)可包括但不限於3-氯- 1,2-環氧丙烷(epichlorohydrin)或3-溴-1,2-環氧丙烷(epibromohydrin)等。 The above-mentioned epihalohydrin may include, but is not limited to, 3-chloro- 1,2-propylene oxide (epichlorohydrin) or 3-bromo-1,2-epoxypropane (epibromohydrin).

上述由雙酚芴型化合物與鹵化環氧丙烷反應所得之含環氧基之雙酚芴型化合物包含但不限於:(1)新日鐵化學(Nippon Steel Chemical Co.,Ltd)所製造之商品:例如ESF-300等;(2)大阪瓦斯(Osaka Gas Co.,Ltd)所製造之商品:例如PG-100、EG-210等;(3)短信科技(S.M.S Technology Co.,Ltd)所製造之商品:例如SMS-F9PhPG、SMS-F9CrG、SMS-F914PG等。 The epoxy group-containing bisphenol quinone type compound obtained by reacting the bisphenol quinoid compound with the halogenated propylene oxide includes, but is not limited to: (1) a product manufactured by Nippon Steel Chemical Co., Ltd. : for example, ESF-300, etc.; (2) goods manufactured by Osaka Gas Co., Ltd.: for example, PG-100, EG-210, etc.; (3) manufactured by SMS Technology Co., Ltd. Goods such as SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, and the like.

其次,該具有至少二個環氧基的環氧化合物(c-1-1)亦可具有如下式(II-2)所示之結構: Next, the epoxy compound (c-1-1) having at least two epoxy groups may have a structure represented by the following formula (II-2):

於式(II-2)中,R5c至R18c分別為相同或不同,且可各自獨立表示氫原子、鹵素原子、碳數為1至8之烷基或碳數為6至15之芳香基;及g表示0至10的整數。 In the formula (II-2), R 5c to R 18c are the same or different, and each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms. ; and g represents an integer from 0 to 10.

前述式(II-2)之具有至少二個環氧基的環氧化合物(c-1-1)例如是藉由在鹼金屬氫氧化物存在下,使具有下式(II-2-1)結構之化合物與鹵化環氧丙烷進行反應而得。 The epoxy compound (c-1-1) having at least two epoxy groups of the above formula (II-2) is, for example, obtained by the following formula (II-2-1) in the presence of an alkali metal hydroxide The compound of the structure is obtained by reacting with a halogenated propylene oxide.

在式(II-2-1)中,R5c至R18c以及g之定義係分別與式(II-2)中之R5c至R18c以及g之定義相同,在此不另贅述。 In formula (II-2-1), R 5c R 18c is defined to g, respectively, and the lines 5c and R 18c is defined to g of the same formula R (II-2) in the, and is not repeated herein.

再者,前述式(II-2)之具有至少二個環氧基的環氧化合物(c-1-1)例如是在酸觸媒存在下,使用具有下式(II-2-2)結構之化合物與酚(phenol)類進行縮合反應後,形成具有式(II-2-1)結構之化合物。接著,藉由加入過量的鹵化環氧丙烷進行脫鹵化氫反應(dehydrohalogenation),而獲得如式(II-2)所示之具有至少二個環氧基的環氧化合物(c-1-1)。 Further, the epoxy compound (c-1-1) having at least two epoxy groups of the above formula (II-2) is, for example, in the presence of an acid catalyst, and has a structure of the following formula (II-2-2). The compound is subjected to a condensation reaction with a phenol to form a compound having the structure of the formula (II-2-1). Next, dehydrohalogenation is carried out by adding an excess of halogenated propylene oxide to obtain an epoxy compound (c-1-1) having at least two epoxy groups as shown in the formula (II-2). .

在上式(II-2-2)中,R19c與R20c分別為相同或不同之氫原子、鹵素原子、碳數為1至8之烷基或碳數為6至15之芳香基;T1及T2分別為相同或不同之鹵素原子、碳數為1至6之烷基或碳數為1至6之烷氧基。較佳地,前述之鹵素原子可例如氯或溴,前述之烷基可例如甲基、乙基或第三丁基,前述之烷氧基可例如甲氧基或乙氧基。 In the above formula (II-2-2), R 19c and R 20c are the same or different hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms; 1 and T 2 are each the same or different halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. Preferably, the aforementioned halogen atom may be, for example, chlorine or bromine, and the aforementioned alkyl group may be, for example, a methyl group, an ethyl group or a third butyl group, and the aforementioned alkoxy group may be, for example, a methoxy group or an ethoxy group.

作為上述酚類的具體例,可列舉但不限於如:酚(phenol)、甲酚(cresol)、乙酚(ethylphenol)、n-丙酚(n-propylphenol)、異丁酚(isobutylphenol)、t-丁酚(t-butylphenol)、辛酚(octylphenol)、壬基苯酚(nonylphenol)、茬酚(xylenol)、甲基丁基苯酚(methylbutylphenol)、二第三丁基酚(di-t-butylphenol)、乙烯苯酚(vinylphenol)、丙烯苯酚(propenylphenol)、乙炔苯酚(ethinylphenol)、環戊苯酚(cyclopentylphenol)、環己基酚(cyclohexylphenol)或環己基甲酚(cyclohexylcresol)等。上述酚類一般可單獨或混合多種使用。 Specific examples of the above phenols include, but are not limited to, phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t. -t-butylphenol, octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol , vinylphenol, propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol or cyclohexylcresol. The above phenols can be generally used singly or in combination of two or more.

基於上述具有式(II-2-2)結構之化合物的使用量為1莫耳,酚類的使用量為0.5莫耳至20莫耳,其中以2莫耳至15莫耳較佳。 The compound having the structure of the above formula (II-2-2) is used in an amount of 1 mole, and the phenol is used in an amount of 0.5 mole to 20 moles, preferably 2 moles to 15 moles.

作為上述酸觸媒的具體例,可列舉但不限於如:鹽酸、 硫酸、對甲苯磺酸(p-toluenesulfonic acid)、草酸(oxalic acid)、三氟化硼(boron trifluoride)、無水氯化鋁(anhydrous aluminium chloride)、氯化鋅(zinc chloride)等,其中以對甲苯磺酸、硫酸或鹽酸較佳。上述酸觸媒可單獨或混合多種使用。 Specific examples of the acid catalyst include, but are not limited to, hydrochloric acid, Sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminium chloride, zinc chloride, etc. Toluenesulfonic acid, sulfuric acid or hydrochloric acid is preferred. The above acid catalysts may be used singly or in combination of two or more.

另外,上述酸觸媒之使用量雖無特別之限制,但基於上述具有式(II-2-2)結構之化合物的使用量為100重量百分比(wt%),酸觸媒的使用量較佳為0.1wt%至30wt%。 Further, the amount of the acid catalyst used is not particularly limited, but the amount of the acid catalyst used is preferably 100% by weight (wt%) based on the compound having the structure of the formula (II-2-2). It is from 0.1 wt% to 30 wt%.

上述縮合反應可在無溶劑或是在有機溶劑存在下進行。其次,上述有機溶劑的具體例可列舉但不限於如:甲苯(toluene)、二甲苯(xylene)或甲基異丁基酮(methyl isobutyl ketone)等。上述有機溶劑可單獨或混合多種使用。 The above condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Specific examples of the organic solvent include, but are not limited to, toluene, xylene, or methyl isobutyl ketone. The above organic solvents may be used singly or in combination of two or more.

基於具有式(II-2-2)結構之化合物及酚類的使用量總和為100wt%,上述有機溶劑的使用量為50wt%至300wt%,其中以100wt%至250wt%較佳。另外,上述縮合反應的操作溫度為40℃至180℃,且縮合反應的操作時間為1小時至8小時。 The total amount of the compound and the phenol used based on the structure of the formula (II-2-2) is 100% by weight, and the above organic solvent is used in an amount of 50% by weight to 300% by weight, preferably 100% by weight to 250% by weight. Further, the above condensation reaction has an operation temperature of 40 ° C to 180 ° C, and the operation time of the condensation reaction is 1 hour to 8 hours.

在完成上述縮合反應後,可進行中和處理或水洗處理。上述中和處理是將反應後的溶液之pH值調整為pH 3至pH 7,其中以pH 5至pH 7較佳。上述水洗處理可使用中和劑來進行,此中和劑為鹼性物質,且其具體例可列舉:氫氧化鈉(sodium hydroxide)、氫氧化鉀(potassium hydroxide)等鹼金屬氫氧化物;氫氧化鈣(calcium hydroxide)、氫氧化鎂(magnesium hydroxide)等鹼土類金屬氫氧化物;二伸乙三胺(diethylene triamine)、三伸乙四胺(triethylene tetramine)、苯胺(aniline)、苯二胺(phenylene diamine)等有機胺;以及氨(ammonia)、磷酸二氫鈉(sodium dihydrogen phosphate)等。上述水洗處理可採用習知方法進行,例如,在反應後的溶液中,加入含中和劑的水溶液,反覆進行萃取即可。經中和處理或水洗處理後,經減 壓加熱處理,將未反應的酚類及溶劑予以餾除,並進行濃縮,即可獲得具有式(II-2-1)結構之化合物。 After completion of the above condensation reaction, a neutralization treatment or a water washing treatment may be carried out. The above neutralization treatment is to adjust the pH of the solution after the reaction to pH 3 to pH 7, preferably pH 5 to pH 7. The water washing treatment may be carried out using a neutralizing agent, and the neutralizing agent is an alkaline substance, and specific examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and hydrogen; Alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; diethylene triamine, triethylene tetramine, aniline, phenylenediamine Organic amines such as (phenylene diamine); and ammonia, sodium dihydrogen phosphate, and the like. The above washing treatment can be carried out by a conventional method. For example, an aqueous solution containing a neutralizing agent is added to the solution after the reaction, and extraction can be carried out repeatedly. After neutralization treatment or water washing treatment, after reduction The compound which has a structure of the formula (II-2-1) can be obtained by subjecting the unreacted phenols and the solvent to distillation and concentrating by pressure heat treatment.

作為上述鹵化環氧丙烷的具體例,可例舉但不限於如:3-氯-1,2-環氧丙烷(3-chloro-1,2-epoxypropane)、3-溴-1,2-環氧丙烷(3-bromo-1,2-epoxypropane)或上述任意組合。在進行上述脫鹵化氫反應之前,可預先添加或於反應過程中添加氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物。上述脫鹵化氫反應的操作溫度為20℃至120℃,其操作時間範圍為1小時至10小時。 Specific examples of the halogenated propylene oxide include, but are not limited to, 3-chloro-1,2-epoxypropane and 3-bromo-1,2-ring. Oxypropane (3-bromo-1, 2-epoxypropane) or any combination of the above. An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or added to the reaction before the dehydrohalogenation reaction. The above dehydrohalogenation reaction has an operating temperature of from 20 ° C to 120 ° C and an operation time ranging from 1 hour to 10 hours.

於本發明之具體例中,上述脫鹵化氫反應中所添加之鹼金屬氫氧化物亦可使用其水溶液。在此具體例中,將上述鹼金屬氫氧化物水溶液連續添加至脫鹵化氫反應系統內的同時,可於減壓或常壓下,連續蒸餾出水及鹵化環氧丙烷,藉此分離並除去水,同時可將鹵化環氧丙烷連續地回流至反應系統內。 In a specific example of the present invention, an aqueous solution of the alkali metal hydroxide added to the dehydrohalogenation reaction may be used. In this specific example, while the aqueous alkali metal hydroxide solution is continuously added to the dehydrohalogenation reaction system, water and halogenated propylene oxide can be continuously distilled off under reduced pressure or normal pressure, thereby separating and removing water. At the same time, the halogenated propylene oxide can be continuously refluxed into the reaction system.

上述脫鹵化氫反應進行前,亦可添加氯化四甲銨(tetramethyl ammonium chloride)、溴化四甲銨(tetramethyl ammonium bromide)、三甲基苄基氯化銨(trimethyl benzyl ammonium chloride)等的四級銨鹽作為觸媒,並在50℃至150℃下,反應1小時至5小時,再加入鹼金屬氫氧化物或其水溶液,於20℃至120℃的溫度下,使其反應1小時至10小時,以進行脫鹵化氫反應。 Before the dehydrohalogenation reaction is carried out, tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethyl benzyl ammonium chloride or the like may be added. The ammonium salt is used as a catalyst, and reacted at 50 ° C to 150 ° C for 1 hour to 5 hours, and then an alkali metal hydroxide or an aqueous solution thereof is added thereto, and the reaction is carried out at a temperature of 20 ° C to 120 ° C for 1 hour. 10 hours for the dehydrohalogenation reaction.

基於上述具有式(II-2-1)結構之化合物中的羥基總當量為1當量,上述鹵化環氧丙烷的使用量可為1當量至20當量,其中以2當量至10當量較佳。基於上述具有式(C-II-1)結構之化合物中的羥基總當量為1當量,上述脫鹵化氫反應中添加的鹼金屬氫氧化物的使用量可為0.8當量至15當量,其中以0.9當量至11當量較佳。 The halogenated propylene oxide may be used in an amount of from 1 equivalent to 20 equivalents, preferably from 2 equivalents to 10 equivalents, based on 1 equivalent of the total hydroxyl group in the compound of the above formula (II-2-1). The alkali metal hydroxide added in the above dehydrohalogenation reaction may be used in an amount of from 0.8 equivalents to 15 equivalents, based on 0.9 equivalents based on the total hydroxyl group equivalent of the above compound having the structure of the formula (C-II-1). Equivalent to 11 equivalents is preferred.

此外,為了使上述脫鹵化氫反應順利進行,除了可添加甲醇、乙醇等醇類之外,亦可添加二甲碸(dimethyl sulfone)、二甲亞 碸(dimethyl sulfoxide)等非質子性(aprotic)的極性溶媒等來進行反應。在使用醇類的情況下,基於上述鹵化環氧丙烷的總量為100wt%,醇類的使用量可為2wt%至20wt%,較佳為4wt%至15wt%。在使用非質子性的極性溶媒的例子中,基於鹵化環氧丙烷的總量為100wt%,非質子性的極性溶媒的使用量可為5wt%至100wt%,其中,以10wt%至90wt%較佳。 Further, in order to smoothly carry out the above-described dehydrohalogenation reaction, in addition to an alcohol such as methanol or ethanol, dimethyl sulfone or dimethyl ya may be added. The reaction is carried out by using an aprotic polar solvent such as dimethyl sulfoxide. In the case of using an alcohol, the alcohol may be used in an amount of 2% by weight to 20% by weight, preferably 4% by weight to 15% by weight based on the total amount of the above-mentioned halogenated propylene oxide being 100% by weight. In the case of using an aprotic polar solvent, the total amount of the aprotic polar solvent may be from 5 wt% to 100 wt%, wherein 10 wt% to 90 wt%, based on the total amount of the halogenated propylene oxide, is 100 wt%. good.

在完成脫鹵化氫反應後,可選擇性地進行水洗處理。之後,利用加熱減壓的方式除去鹵化環氧丙烷、醇類及非質子性的極性溶媒等。上述加熱減壓例如是於溫度為110℃至250℃,且壓力為1.3kPa(10mmHg)以下的環境下進行。 After completion of the dehydrohalogenation reaction, a water washing treatment can be selectively performed. Thereafter, the halogenated propylene oxide, the alcohol, and the aprotic polar solvent are removed by heating and decompression. The heating and depressing is performed, for example, in an environment having a temperature of 110 ° C to 250 ° C and a pressure of 1.3 kPa (10 mmHg) or less.

為了避免形成之環氧樹脂含有加水分解性鹵素,可將脫鹵化氫反應後的溶液加入甲苯、甲基異丁基酮(methyl isobutyl ketone)等溶劑,並加入氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物水溶液,再次進行脫鹵化氫反應。在脫鹵化氫反應中,基於上述具有式(II-2-1)結構之化合物中的羥基總當量為1當量,鹼金屬氫氧化物的使用量為0.01莫耳至0.3莫耳,其中,以0.05莫耳至0.2莫耳較佳。另外,上述脫鹵化氫反應的操作溫度範圍為50℃至120℃,且其操作時間範圍為0.5小時至2小時。 In order to prevent the formed epoxy resin from containing a hydrolyzable halogen, the solution after the dehydrohalogenation reaction may be added to a solvent such as toluene or methyl isobutyl ketone, and a base such as sodium hydroxide or potassium hydroxide may be added. The metal hydroxide aqueous solution is again subjected to a dehydrohalogenation reaction. In the dehydrohalogenation reaction, the total equivalent weight of the hydroxyl group in the compound having the structure of the above formula (II-2-1) is 1 equivalent, and the alkali metal hydroxide is used in an amount of 0.01 mol to 0.3 mol, wherein 0.05 moles to 0.2 moles are preferred. Further, the above dehydrohalogenation reaction has an operating temperature in the range of 50 ° C to 120 ° C and an operation time ranging from 0.5 hour to 2 hours.

在完成脫鹵化氫反應後,藉由過濾及水洗等步驟去除鹽類。此外,亦可利用加熱減壓的方式,將甲苯、甲基異丁基酮等溶劑予以餾除,而可獲得如式(II-2)所示之具有至少二個環氧基的環氧化合物(c-1-1)。上述式(II-2)之具有至少二個環氧基的環氧化合物(c-1-1)可包含但不限於如商品名為NC-3000、NC-3000H、NC-3000S及NC-3000P等日本化藥(Nippon Kayaku Co.Ltd.)所製造之商品。 After completion of the dehydrohalogenation reaction, the salts are removed by filtration, washing, and the like. Further, a solvent such as toluene or methyl isobutyl ketone may be distilled off by heating and decompression to obtain an epoxy compound having at least two epoxy groups as shown in the formula (II-2). (c-1-1). The epoxy compound (c-1-1) having at least two epoxy groups of the above formula (II-2) may include, but is not limited to, trade names NC-3000, NC-3000H, NC-3000S, and NC-3000P. A product manufactured by Nippon Kayaku Co. Ltd..

前述具有至少一個羧酸基及至少一個乙烯性不飽和基的化合物(c-1-2)例如是選自於由以下(1)至(3)所組成之群組:(1)丙烯 酸、甲基丙烯酸、2-甲基丙烯醯氧乙基丁二酸(2-methacryloyloxyethylbutanedioic acid)、2-甲基丙烯醯氧丁基丁二酸、2-甲基丙烯醯氧乙基己二酸、2-甲基丙烯醯氧丁基己二酸、2-甲基丙烯醯氧乙基六氫鄰苯二甲酸、2-甲基丙烯醯氧乙基馬來酸、2-甲基丙烯醯氧丙基馬來酸、2-甲基丙烯醯氧丁基馬來酸、2-甲基丙烯醯氧丙基丁二酸、2-甲基丙烯醯氧丙基己二酸、2-甲基丙烯醯氧丙基四氫鄰苯二甲酸、2-甲基丙烯醯氧丙基鄰苯二甲酸、2-甲基丙烯醯氧丁基鄰苯二甲酸、或2-甲基丙烯醯氧丁基氫鄰苯二甲酸;(2)由含羥基之(甲基)丙烯酸酯與二元羧酸化合物反應而得之化合物,其中二元羧酸化合物包含但不限於己二酸、丁二酸、馬來酸、鄰苯二甲酸;(3)由含羥基之(甲基)丙烯酸酯與羧酸酐化合物反應而得之半酯化合物,其中含羥基之(甲基)丙烯酸酯包含但不限於2-羥基乙基丙烯酸酯〔(2-hydroxyethyl)acrylate〕、2-羥基乙基甲基丙烯酸酯〔(2-hydroxyethyl)methacrylate〕、2-羥基丙基丙烯酸酯〔(2-hydroxypropyl)acrylate〕、2-羥基丙基甲基丙烯酸酯〔(2-hydroxypropyl)methacrylate〕、4-羥基丁基丙烯酸酯〔(4-hydroxybutyl)acrylate〕、4-羥基丁基甲基丙烯酸酯[(4-hydroxybutyl)methacrylate〕、或季戊四醇三甲基丙烯酸酯等。另外,此處所述之羧酸酐化合物可與下述第一鹼可溶性樹脂(C-1)之混合物所含的羧酸酐化合物(c-1-3)相同,故於此不再贅述。 The aforementioned compound (c-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is, for example, selected from the group consisting of the following (1) to (3): (1) propylene Acid, methacrylic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methylpropenyloxybutyl succinic acid, 2-methylpropenyl oxyethyl adipate , 2-methylpropenyloxybutyl adipate, 2-methylpropenyloxyethylhexahydrophthalic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxyl Propyl maleic acid, 2-methylpropenyloxybutyl maleic acid, 2-methylpropenyloxypropyl succinic acid, 2-methylpropenyloxypropyl adipate, 2-methylpropene醯Phenylpropyltetrahydrophthalic acid, 2-methylpropenyl propyl phthalate, 2-methylpropenyl butyl phthalate, or 2-methyl propylene oxybutyl hydride Phthalic acid; (2) a compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a dicarboxylic acid compound, wherein the dicarboxylic acid compound includes, but is not limited to, adipic acid, succinic acid, and malay Acid, phthalic acid; (3) a half ester compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a carboxylic anhydride compound, wherein the hydroxyl group-containing (meth) acrylate includes but is not limited to 2-hydroxy group B Propylene 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, or pentaerythritol trimethyl Acrylate and the like. Further, the carboxylic anhydride compound described herein may be the same as the carboxylic anhydride compound (c-1-3) contained in the mixture of the first alkali-soluble resin (C-1) described below, and thus will not be described herein.

上述第一鹼可溶性樹脂(C-1)之混合物更可選擇性地包含羧酸酐化合物(c-1-3)及/或含環氧基的化合物(c-1-4)。上述羧酸酐化合物(c-1-3)可選自由以下(1)至(2)所組成之群組:(1)丁二酸酐(butanedioic anhydride)、順丁烯二酸酐(maleic anhydride)、衣康酸酐(Itaconic anhydride)、鄰苯二甲酸酐(phthalic anhydride)、四氫鄰苯二甲酸酐(tetrahydrophthalic anhydride)、六氫鄰苯二甲酸酐(hexahydrophthalic anhydride)、甲基四氫鄰苯二甲酸酐、甲基六氫鄰 苯二甲酸酐、甲基橋亞甲基四氫鄰苯二甲酸酐(methyl endo-methylene tetrahydro phthalic anhydride)、氯茵酸酐(chlorendic anhydride)、戊二酸酐或偏三苯甲酸酐(1,3-dioxoisobenzofuran-5-carboxylic anhydride)等二元羧酸酐化合物;以及(2)二苯甲酮四甲酸二酐(benzophenone tetracarboxylic dianhydride,簡稱BTDA)、雙苯四甲酸二酐或雙苯醚四甲酸二酐等四元羧酸酐化合物。 The mixture of the above first alkali-soluble resin (C-1) may more optionally contain a carboxylic anhydride compound (c-1-3) and/or an epoxy group-containing compound (c-1-4). The above carboxylic anhydride compound (c-1-3) may be selected from the group consisting of (1) to (2): (1) butanedioic anhydride, maleic anhydride, and clothing. Itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride Methyl hexahydroortho Phthalic anhydride, methyl endo-methylene tetrahydro phthalic anhydride, chlorendic anhydride, glutaric anhydride or trimellitic anhydride (1,3- a dicarboxylic acid anhydride compound such as dioxoisobenzofuran-5-carboxylic anhydride; and (2) benzophenone tetracarboxylic dianhydride (BTDA), diphenyltetracarboxylic dianhydride or diphenyl ether tetracarboxylic dianhydride. A quaternary carboxylic anhydride compound.

上述含環氧基的化合物(c-1-4)例如是選自甲基丙烯酸環氧丙酯、3,4-環氧基環己基甲基丙烯酸酯、含不飽和基的縮水甘油醚化合物、含環氧基的不飽和化合物或上述之任意組合所組成的群組。前述含不飽和基的縮水甘油醚化合物包含但不限於商品名Denacol EX-111、EX-121 Denacol、Denacol EX-141、Denacol EX-145、Denacol EX-146、Denacol EX-171、Denacol EX-192等的化合物(以上為長瀨化成工業株式會社之商品)。 The epoxy group-containing compound (c-1-4) is, for example, selected from the group consisting of glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and an unsaturated group-containing glycidyl ether compound. An epoxy group-containing unsaturated compound or a group consisting of any combination of the above. The unsaturated group-containing glycidyl ether compound includes, but is not limited to, the trade names Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, and Denacol EX-192. Compound (the above is a product of Nagase Chemical Industry Co., Ltd.).

前述第一鹼可溶性樹脂(C-1)可由式(II-1)之具有至少二個環氧基的環氧化合物(c-1-1)與具有至少一個羧酸基及至少一個乙烯性不飽和基的化合物(c-1-2)進行聚合反應,形成含羥基的反應產物,接著,再添加羧酸酐化合物(c-1-3)進行反應所製得。基於上述含羥基的反應產物的羥基總當量為1當量,羧酸酐化合物(c-1-3)所含有的酸酐基的當量較佳為0.4當量至1當量,更佳為0.75當量至1當量。當使用多個羧酸酐化合物(c-1-3)時,可於反應中依序添加或同時添加。當使用二元羧酸酐化合物及四元羧酸酐化合物作為羧酸酐化合物(c-1-3)時,二元羧酸酐化合物及四元羧酸酐化合物的莫耳比例較佳為1/99至90/10,更佳為5/95至80/20。另外,上述反應的操作溫度範圍例如是在50℃至130℃的範圍。 The aforementioned first alkali-soluble resin (C-1) may be an epoxy compound (c-1-1) having at least two epoxy groups of the formula (II-1) and having at least one carboxylic acid group and at least one ethylenicity The saturated group compound (c-1-2) is subjected to a polymerization reaction to form a hydroxyl group-containing reaction product, followed by addition of a carboxylic anhydride compound (c-1-3) to carry out a reaction. The equivalent weight of the hydroxyl group-based reaction product is 1 equivalent, and the equivalent weight of the acid anhydride group contained in the carboxylic anhydride compound (c-1-3) is preferably 0.4 equivalent to 1 equivalent, more preferably 0.75 equivalent to 1 equivalent. When a plurality of carboxylic anhydride compounds (c-1-3) are used, they may be added sequentially or simultaneously in the reaction. When a dicarboxylic anhydride compound and a tetracarboxylic anhydride compound are used as the carboxylic anhydride compound (c-1-3), the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound is preferably from 1/99 to 90/ 10, more preferably 5/95 to 80/20. Further, the operating temperature range of the above reaction is, for example, in the range of 50 ° C to 130 ° C.

前述第一鹼可溶性樹脂(C-1)可由式(II-2)之具有至少二個環氧基的環氧化合物(c-1-1)與具有至少一個羧酸基及至少一個乙烯 性不飽和基的化合物(c-1-2)進行反應,形成含羥基的反應產物,接著,再藉由添加羧酸酐化合物(c-1-3)及/或含環氧基的化合物(c-1-4)進行聚合反應所製得。基於式(II-2)之具有至少二個環氧基的環氧化合物(c-1-1)上的環氧基總當量為1當量,上述具有至少一個羧酸基及至少一個乙烯性不飽和基的化合物(c-1-2)的酸價當量較佳為0.8當量至1.5當量,更佳為0.9當量至1.1當量。基於上述含羥基的反應產物的羥基總量為100莫耳百分比(莫耳%),羧酸酐化合物(c-1-3)的使用量較佳為10莫耳%至100莫耳%,更佳為20莫耳%至100莫耳%,特佳為30莫耳%至100莫耳%。 The aforementioned first alkali-soluble resin (C-1) may be an epoxy compound (c-1-1) having at least two epoxy groups of the formula (II-2) and having at least one carboxylic acid group and at least one ethylene The unsaturated group-containing compound (c-1-2) is reacted to form a hydroxyl group-containing reaction product, followed by addition of a carboxylic anhydride compound (c-1-3) and/or an epoxy group-containing compound (c). -1-4) obtained by carrying out a polymerization reaction. The epoxy group compound (c-1-1) having at least two epoxy groups based on the formula (II-2) has a total equivalent weight of 1 equivalent, and the above has at least one carboxylic acid group and at least one ethylenicity. The acid value equivalent of the saturated group compound (c-1-2) is preferably from 0.8 equivalents to 1.5 equivalents, more preferably from 0.9 equivalents to 1.1 equivalents. The total amount of hydroxyl groups based on the above hydroxyl group-containing reaction product is 100 mol% (mol%), and the carboxylic anhydride compound (c-1-3) is preferably used in an amount of 10 mol% to 100 mol%, more preferably It is from 20 mol% to 100 mol%, particularly preferably from 30 mol% to 100 mol%.

在製備上述第一鹼可溶性樹脂(C-1)時,為了加速反應,通常會於反應溶液中添加鹼性化合物作為反應觸媒。上述反應觸媒可單獨或混合使用,且上述反應觸媒包含但不限於:三苯基膦(triphenyl phosphine)、三苯基銻(triphenyl stibine)、三乙胺(triethylamine)、三乙醇胺(triethanolamine)、氯化四甲基銨(tetramethyl ammonium chloride)、氯化苄基三乙基銨(benzyltriethyl ammonium chloride)等。基於上述具有至少二個環氧基的環氧化合物(c-1-1)與具有至少一個羧酸基及至少一個乙烯性不飽和基的化合物(c-1-2)的使用量總和為100重量份,反應觸媒的使用量較佳為0.01重量份至10重量份,更佳為0.3重量份至5重量份。 In the preparation of the above first alkali-soluble resin (C-1), in order to accelerate the reaction, a basic compound is usually added as a reaction catalyst to the reaction solution. The above reaction catalysts may be used singly or in combination, and the above reaction catalysts include, but are not limited to, triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine. , tetramethyl ammonium chloride, benzyltriethyl ammonium chloride, and the like. The total amount of the epoxy compound (c-1-1) having at least two epoxy groups and the compound (c-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100. The amount of the reaction catalyst used is preferably from 0.01 part by weight to 10 parts by weight, more preferably from 0.3 part by weight to 5 parts by weight.

此外,為了控制聚合度,通常還會於反應溶液中添加聚合抑制劑(polymerization inhibitor)。上述聚合抑制劑可包含但不限於:甲氧基酚(methoxyphenol)、甲基氫醌(methylhydroquinone)、氫醌(hydroquinone)、2,6-二第三丁基對甲酚(2,6-di-t-butyl-p-cresol)或吩噻嗪(phenothiazine)等。一般而言,上述聚合抑制劑可單獨或混合多種使用。基於上述具有至少二個環氧基的環氧化合物(c-1-1)與具有至少一個羧酸基及至少一個乙烯性不飽和基的化合物(c-1-2)的使用量總和 為100重量份,聚合抑制劑的使用量較佳為0.01重量份至10重量份,更佳為0.1重量份至5重量份。 Further, in order to control the degree of polymerization, a polymerization inhibitor is usually added to the reaction solution. The above polymerization inhibitor may include, but is not limited to, methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-cresol (2,6-di) -t-butyl-p-cresol) or phenothiazine. In general, the above polymerization inhibitors may be used singly or in combination of two or more. The sum of the amounts of use of the above epoxy compound (c-1-1) having at least two epoxy groups and the compound (c-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group The polymerization inhibitor is preferably used in an amount of from 0.01 part by weight to 10 parts by weight, more preferably from 0.1 part by weight to 5 parts by weight, per 100 parts by weight.

在製備該第一鹼可溶性樹脂(C-1)時,必要時可使用聚合反應溶劑。作為上述聚合反應溶劑的具體例,可列舉如:乙醇、丙醇、異丙醇、丁醇、異丁醇、2-丁醇、己醇或乙二醇等醇類化合物;甲乙酮或環己酮等酮類化合物;甲苯或二甲苯等芳香族烴類化合物;賽珞素(cellosolve)或丁基賽珞素(butyl cellosolve)等賽珞素類化合物;卡必妥(carbitol)或丁基卡必妥(butyl carbitol)等卡必妥類化合物;丙二醇單甲醚(propylene glycol monomethyl ether)等丙二醇烷基醚類化合物;二丙二醇單甲醚〔di(propylene glycol)methyl ether〕等多丙二醇烷基醚〔poly(propylene glycol)alkyl ether〕類化合物;醋酸乙酯、醋酸丁酯、乙二醇乙醚醋酸酯(ethylene glycol monoethyl ether acetate)或丙二醇甲醚醋酸酯(propylene glycol methyl ether acetate)等醋酸酯類化合物;乳酸乙酯(ethyl lactate)或乳酸丁酯(butyl lactate)等乳酸烷酯(alkyl lactate)類化合物;或二烷基二醇醚類;或3-乙氧基丙酸乙酯。上述聚合反應溶劑一般可單獨或混合多種使用。另外,上述第一鹼可溶性樹脂(C-1)的酸價較佳為50mgKOH/g至200mgKOH/g,更佳為60mgKOH/g至150mgKOH/g。 In the preparation of the first alkali-soluble resin (C-1), a polymerization solvent can be used as necessary. Specific examples of the polymerization reaction solvent include alcohol compounds such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol; methyl ethyl ketone or cyclohexanone; Ketone compounds; aromatic hydrocarbon compounds such as toluene or xylene; celecin compounds such as cellosolve or butyl cellosolve; carbitol or butyl carbene Carbene-like compounds such as butyl carbitol; propylene glycol alkyl ether compounds such as propylene glycol monomethyl ether; polypropylene glycol alkyl ethers such as di(propylene glycol) methyl ether [poly(propylene glycol) alkyl ether] compound; acetate such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate or propylene glycol methyl ether acetate a compound; an alkyl lactate compound such as ethyl lactate or butyl lactate; or a dialkyl glycol ether; or ethyl 3-ethoxypropionate. The above polymerization solvent can be generally used singly or in combination of two or more. Further, the acid value of the above first alkali-soluble resin (C-1) is preferably from 50 mgKOH/g to 200 mgKOH/g, more preferably from 60 mgKOH/g to 150 mgKOH/g.

另外,上述第一鹼可溶性樹脂(C-1)藉由膠體滲透層析儀(Gel Permeation Chromatography,GPC)測定之聚苯乙烯換算的數目平均分子量一般為500至10,000,較佳為800至8,000,更佳為1,000至6,000。 Further, the first alkali-soluble resin (C-1) has a polystyrene-equivalent number average molecular weight of from 500 to 10,000, preferably from 800 to 8,000, as measured by Gel Permeation Chromatography (GPC). More preferably from 1,000 to 6,000.

於本發明之具體例中,基於該鹼可溶性樹脂(C)之使用量為100重量份,該第一鹼可溶性樹脂(C-1)之使用量範圍為0重量份至90重量份;較佳為10重量份至80重量份;更佳為20重量份至70重量份。當使用該第一鹼可溶性樹脂(C-1)時,該感光性樹脂組成物所形 成之彩色濾光片其熱溶劑膜厚變化率更佳。 In a specific example of the present invention, the first alkali-soluble resin (C-1) is used in an amount ranging from 0 parts by weight to 90 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C); preferably. It is 10 parts by weight to 80 parts by weight; more preferably 20 parts by weight to 70 parts by weight. When the first alkali-soluble resin (C-1) is used, the photosensitive resin composition is shaped The color filter has a better change rate of the thermal solvent film thickness.

根據本發明之鹼可溶性樹脂(C)可更包含第二鹼可溶性樹脂(C-2),其係由具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)以及其他可共聚合之乙烯性不飽和單體(c-2-2)共聚合後,與具有環氧基之乙烯性不飽和單體(c-2-3)反應而得。 The alkali-soluble resin (C) according to the present invention may further comprise a second alkali-soluble resin (C-2) which is an ethylenically unsaturated monomer having one or more carboxylic acids or carboxylic anhydrides (c-2-1) And another copolymerizable ethylenically unsaturated monomer (c-2-2), which is obtained by copolymerization with an ethylenically unsaturated monomer (c-2-3) having an epoxy group.

在一實施例中,該第二鹼可溶性樹脂(C-2)係先將具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)與其他可共聚合之乙烯性不飽和單體(c-2-2)進行雙鍵共聚合反應,以形成一聚合物,其中此聚合物之側鏈具有羧酸基。然後,此聚合物之側鏈中的羧酸基與具有環氧基之乙烯性不飽和單體(c-2-3)進行加成反應,而製得第二鹼可溶性樹脂(C-2)。 In one embodiment, the second alkali-soluble resin (C-2) is first copolymerizable with an ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acids or carboxylic anhydrides. The ethylenically unsaturated monomer (c-2-2) undergoes double bond copolymerization to form a polymer in which the side chain of the polymer has a carboxylic acid group. Then, the carboxylic acid group in the side chain of the polymer is subjected to an addition reaction with the ethylenically unsaturated monomer (c-2-3) having an epoxy group to prepare a second alkali-soluble resin (C-2). .

在另一實施例中,該第二鹼可溶性樹脂(C-2)係先將其他可共聚合之乙烯性不飽和單體(c-2-2)與具有環氧基之乙烯性不飽和單體(c-2-3)進行雙鍵共聚合反應,以形成一聚合物,其中此聚合物之側鏈具有環氧基。然後,此聚合物之側鏈中的環氧基與具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)進行加成反應,而製得該第二鹼可溶性樹脂(C-2)。 In another embodiment, the second alkali-soluble resin (C-2) is a copolymerizable ethylenically unsaturated monomer (c-2-2) and an ethylenically unsaturated monomer having an epoxy group. The body (c-2-3) undergoes a double bond copolymerization reaction to form a polymer in which the side chain of the polymer has an epoxy group. Then, an epoxy group in the side chain of the polymer is subjected to an addition reaction with an ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acids or carboxylic anhydrides to prepare the second base. Soluble resin (C-2).

在又一實施例中,該第二鹼可溶性樹脂(C-2)係先將其他可共聚合之乙烯性不飽和單體(c-2-2)與具有環氧基之乙烯性不飽和單體(c-2-3)進行雙鍵共聚合反應,以形成一聚合物,其中此聚合物之側鏈具有環氧基。然後,此聚合物之側鏈中的環氧基與具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)進行加成反應後,進一步與酸酐類化合物進行半酯化反應而製得該第二鹼可溶性樹脂(C-2)。 In still another embodiment, the second alkali-soluble resin (C-2) firstly copolymerizes another copolymerizable ethylenically unsaturated monomer (c-2-2) with an ethylenically unsaturated monomer having an epoxy group. The body (c-2-3) undergoes a double bond copolymerization reaction to form a polymer in which the side chain of the polymer has an epoxy group. Then, the epoxy group in the side chain of the polymer is subjected to an addition reaction with the ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acids or carboxylic anhydrides, and further subjected to an acid anhydride compound. The second alkali-soluble resin (C-2) is obtained by a half esterification reaction.

前述之具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1),其中,該具有一個或一個以上羧酸之乙烯性不飽和單 體可包含但不限於不飽和單羧酸化合物、不飽和多羧酸化合物、具有不飽和基及一個羧酸基之多環化合物,或具有不飽和基及多個羧酸基之多環化合物。 The aforementioned ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acids or carboxylic anhydrides, wherein the ethylenically unsaturated monomer having one or more carboxylic acids The body may include, but is not limited to, an unsaturated monocarboxylic acid compound, an unsaturated polycarboxylic acid compound, a polycyclic compound having an unsaturated group and a carboxylic acid group, or a polycyclic compound having an unsaturated group and a plurality of carboxylic acid groups.

前述不飽和單羧酸化合物可包含但不限於(甲基)丙烯酸、丁烯酸、α-氯丙烯酸、乙基丙烯酸、肉桂酸、2-(甲基)丙烯醯乙氧基丁二酸酯(2-(meth)acryloyloxy ethyl succinate monoester)、2-(甲基)丙烯醯乙氧基六氫化苯二甲酸酯、2-(甲基)丙烯醯乙氧基苯二甲酸酯或omega-羧酸基聚己內酯多元醇單丙烯酸酯等。該omega-羧酸基聚己內酯多元醇單丙烯酸酯可為東亞合成製造,型號為ARONIX M-5300之商品。 The aforementioned unsaturated monocarboxylic acid compound may include, but is not limited to, (meth)acrylic acid, crotonic acid, α -chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-(methyl)acrylic acid ethoxylated succinate ( 2-(meth)acryloyloxy ethyl succinate monoester), 2-(methyl)acryl oxime ethoxy hexahydrophthalate, 2-(meth) propylene ethoxy ethoxylate or omega-carboxylate Acid-based polycaprolactone polyol monoacrylate or the like. The omega-carboxylic acid polycaprolactone polyol monoacrylate can be manufactured by East Asia Synthetic, model ARONIX M-5300.

前述不飽和多羧酸化合物可包含但不限於馬來酸、富馬酸、甲基富馬酸、衣康酸或檸康酸等。 The aforementioned unsaturated polycarboxylic acid compound may include, but is not limited to, maleic acid, fumaric acid, methyl fumaric acid, itaconic acid or citraconic acid, and the like.

前述具有不飽和基及一個羧酸基之多環化合物可包含但不限於5-羧酸基雙環[2.2.1]庚-2-烯、5-羧酸基-5-甲基雙環[2.2.1]庚-2-烯、5-羧酸基-5-乙基雙環[2.2.1]庚-2-烯、5-羧酸基-6-甲基雙環[2.2.1]庚-2-烯或5-羧酸基-6-乙基雙環[2.2.1]庚-2-烯等。 The above polycyclic compound having an unsaturated group and a carboxylic acid group may include, but is not limited to, 5-carboxylic acid bicyclo [2.2.1] hept-2-ene, 5-carboxylic acid-5-methyl bicyclo [2.2. 1]hept-2-ene, 5-carboxylic acid-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxylic acid-6-methylbicyclo[2.2.1]hept-2- Alkene or 5-carboxylic acid-6-ethylbicyclo[2.2.1]hept-2-ene and the like.

前述具有不飽和基及多個羧酸基的多環化合物可例如5,6-二羧酸基二環[2.2.1]庚-2-烯等。 The above polycyclic compound having an unsaturated group and a plurality of carboxylic acid groups may be, for example, 5,6-dicarboxylic acidbicyclo[2.2.1]hept-2-ene or the like.

較佳地,前述具有一個或一個以上羧酸之乙烯性不飽和單體是選自於丙烯酸、甲基丙烯酸、2-甲基丙烯醯乙氧基丁二酸酯、2-甲基丙烯醯基乙氧基六氫化苯二甲酸酯,或上述化合物之任意組合。 Preferably, the aforementioned ethylenically unsaturated monomer having one or more carboxylic acids is selected from the group consisting of acrylic acid, methacrylic acid, 2-methylpropenyl ethoxy succinate, and 2-methyl acrylonitrile. Ethoxy hexahydrophthalate, or any combination of the above.

前述具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1),其中,前述具有一個或一個以上羧酸酐之乙烯性不飽和單體可包含但不限於不飽和羧酸酐化合物或具有不飽和基與羧酸酐的多環化合物。 The aforementioned ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acids or carboxylic anhydrides, wherein the aforementioned ethylenically unsaturated monomer having one or more carboxylic anhydrides may include, but is not limited to, unsaturated A carboxylic anhydride compound or a polycyclic compound having an unsaturated group and a carboxylic anhydride.

前述不飽和羧酸酐化合物可包含但不限於馬來酸酐、富馬酸酐、甲基富馬酸酐、衣康酸酐或檸康酸酐等。前述具有不飽和基及羧酸酐的多環化合物可包含但不限於5,6-二羧酸酐二環[2.2.1]庚-2-烯等。 The aforementioned unsaturated carboxylic anhydride compound may include, but is not limited to, maleic anhydride, fumaric anhydride, methyl fumaric anhydride, itaconic anhydride or citraconic anhydride, and the like. The above polycyclic compound having an unsaturated group and a carboxylic anhydride may include, but is not limited to, 5,6-dicarboxylic anhydride bicyclo[2.2.1]hept-2-ene and the like.

較佳地,前述具有一個或一個以上羧酸酐之乙烯性不飽和單體為馬來酸酐。 Preferably, the aforementioned ethylenically unsaturated monomer having one or more carboxylic anhydrides is maleic anhydride.

上述之具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)可單獨一種或混合複數種使用。 The above ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acids or carboxylic anhydrides may be used singly or in combination of plural kinds.

於本發明之具體例中,基於該第二鹼可溶性樹脂(C-2)之該具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)及該其他可共聚合之乙烯性不飽和單體(c-2-2)共聚合用單體之使用量為100重量份,該具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)之使用量為10重量份至90重量份;較佳為15重量份至85重量份;更佳為20重量份至80重量份。 In a specific example of the present invention, the ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acids or carboxylic anhydrides based on the second alkali-soluble resin (C-2) and the other The copolymerized ethylenically unsaturated monomer (c-2-2) copolymerization monomer is used in an amount of 100 parts by weight, the ethylenically unsaturated monomer having one or more carboxylic acids or carboxylic anhydrides (c- 2-1) is used in an amount of 10 parts by weight to 90 parts by weight; preferably 15 parts by weight to 85 parts by weight; more preferably 20 parts by weight to 80 parts by weight.

前述其他可共聚合之乙烯性不飽和單體(c-2-2)可包含但不限於(甲基)丙烯酸烷基酯、(甲基)丙烯酸脂環族酯、(甲基)丙烯酸芳基酯、不飽和二羧酸酯、(甲基)丙烯酸羥烷酯、具有(甲基)丙烯酸酯基的聚醚、苯乙烯化合物或上述化合物以外的不飽和化合物。 The aforementioned other copolymerizable ethylenically unsaturated monomer (c-2-2) may include, but is not limited to, alkyl (meth)acrylate, alicyclic (meth)acrylate, aryl (meth)acrylate An ester, an unsaturated dicarboxylic acid ester, a hydroxyalkyl (meth) acrylate, a polyether having a (meth) acrylate group, a styrene compound or an unsaturated compound other than the above compounds.

上述之(甲基)丙烯酸烷基酯可包含但不限於(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁基酯或(甲基)丙烯酸第三丁基酯等。 The above alkyl (meth)acrylate may include, but is not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( N-butyl acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate or t-butyl (meth)acrylate.

上述之(甲基)丙烯酸脂環族酯可包含但不限於(甲基)丙烯酸環己酯、(甲基)丙烯酸-2-甲基環己酯、(甲基)丙烯酸雙環戊酯{或稱三環[5.2.1.02,6]癸-8-基(甲基)丙烯酸酯}、(甲基)丙烯酸二環戊氧基乙酯、(甲基)丙烯酸異冰片酯或(甲基)丙烯酸四氫呋喃酯等。 The above (meth) acrylate cycloaliphatic ester may include, but is not limited to, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate {or Tricyclo [5.2.1.0 2,6 ]癸-8-yl (meth) acrylate}, dicyclopentyloxy (meth) acrylate, isobornyl (meth) acrylate or (meth) acrylate Tetrahydrofuran ester and the like.

上述(甲基)丙烯酸芳基酯可包含但不限於(甲基)丙烯酸苯基酯或甲基丙烯酸苯甲酯等。 The above aryl (meth)acrylate may include, but is not limited to, phenyl (meth)acrylate or benzyl methacrylate.

前述不飽和二羧酸酯可包含但不限於馬來酸二乙酯、富馬酸二乙酯或衣康酸二乙酯等。 The aforementioned unsaturated dicarboxylic acid ester may include, but is not limited to, diethyl maleate, diethyl fumarate or diethyl itaconate.

前述(甲基)丙烯酸羥烷酯可包含但不限於(甲基)丙烯酸-2-羥基乙酯或(甲基)丙烯酸-2-羥基丙酯等。 The aforementioned hydroxyalkyl (meth)acrylate may include, but is not limited to, 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate.

前述具有(甲基)丙烯酸酯基的聚醚可包含但不限於聚乙二醇單(甲基)丙烯酸酯或聚丙二醇單(甲基)丙烯酸酯等。 The aforementioned polyether having a (meth) acrylate group may include, but not limited to, polyethylene glycol mono(meth)acrylate or polypropylene glycol mono(meth)acrylate.

前述苯乙烯系化合物可包含但不限於苯乙烯、α-甲基苯乙烯、間-甲基苯乙烯,對-甲基苯乙烯或對-甲氧基苯乙烯等。 The styrene-based compound may include, but is not limited to, styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene or p-methoxystyrene.

上述化合物以外之不飽和化合物可包含但不限於丙烯腈、甲基丙烯腈、氯乙烯、偏二氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙烯乙酯、1,3-丁二烯、異戊二烯、2,3-二甲基1,3-丁二烯、N-丁二醯亞胺基-3-馬來醯亞胺苯甲酸酯、N-丁二醯亞胺基-4-馬來醯亞胺丁酸酯、N-丁二醯亞胺基-6-馬來醯亞胺己酸酯、N-丁二醯亞胺基-3-馬來醯亞胺丙酸酯、N-(9-吖啶基)馬來醯亞胺、N-辛基馬來醯亞胺(N-octylmaleimide)、N-環己基馬來醯亞胺(N-cyclohexylmaleimide)或N-苯基馬來醯亞胺(N-phenylmaleimide)等。 The unsaturated compound other than the above compounds may include, but not limited to, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl ethyl ester, 1,3-butadiene, Isoprene, 2,3-dimethyl1,3-butadiene, N-butylenediamine-3-maleimide benzoate, N-butanediimide- 4-maleimide butyrate, N-butanediamine-6-maleimide caproate, N-butylenediamine-3-maleimide propionate , N-(9-acridinyl)maleimide, N-octylmaleimide, N-cyclohexylmaleimide or N-phenyl N-phenylmaleimide and the like.

前述其他可共聚合之乙烯性不飽和單體(c-2-2)可單獨一種或混合複數種使用。 The other copolymerizable ethylenically unsaturated monomer (c-2-2) may be used singly or in combination of plural kinds.

較佳地,前述其他可共聚合之乙烯性不飽和單體(c-2-2)是選自於(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸第三丁基酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸雙環戊酯、甲基丙烯酸異冰片酯、(甲基)丙烯酸二環戊氧基乙酯、苯乙烯、對-甲氧基苯乙烯或上述化合物之任意組合。 Preferably, the other copolymerizable ethylenically unsaturated monomer (c-2-2) is selected from the group consisting of methyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylic acid 2- Hydroxyethyl ester, tert-butyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl methacrylate, dicyclopentyloxy (meth)acrylate Ethyl ester, styrene, p-methoxystyrene or any combination of the above.

於本發明之具體例中,基於該第二鹼可溶性樹脂(C-2) 之該具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)及該其他可共聚合之乙烯性不飽和單體(c-2-2)共聚合用單體之使用量總和為100重量份,該其他可共聚合之乙烯性不飽和單體(c-2-2)之使用量為10重量份至90重量份;較佳為15重量份至85重量份;更佳為20重量份至80重量份。 In a specific example of the present invention, based on the second alkali-soluble resin (C-2) The ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acids or carboxylic anhydrides and the other copolymerizable ethylenically unsaturated monomer (c-2-2) copolymerization single The total amount of the monomers used is 100 parts by weight, and the other copolymerizable ethylenically unsaturated monomer (c-2-2) is used in an amount of 10 parts by weight to 90 parts by weight; preferably 15 parts by weight to 85 parts by weight. More preferably, it is 20 parts by weight to 80 parts by weight.

該具有環氧基之乙烯性不飽和單體(c-2-3)可包含但不限於具有環氧基的(甲基)丙烯酸酯化合物、具有環氧基的α-烷基丙烯酸酯化合物或環氧丙醚化合物等。 The epoxy group-containing ethylenically unsaturated monomer (c-2-3) may include, but is not limited to, a (meth) acrylate compound having an epoxy group, an α -alkyl acrylate compound having an epoxy group or A glycidyl ether compound or the like.

前述具有環氧基的(甲基)丙烯酸酯化合物可包含但不限於(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸2-甲基環氧丙酯、(甲基)丙烯酸3,4-環氧丁酯、(甲基)丙烯酸6,7-環氧庚酯、(甲基)丙烯酸3,4-環氧環己酯或(甲基)丙烯酸3,4-環氧環己基甲酯等。 The above epoxy group-containing (meth) acrylate compound may include, but is not limited to, glycidyl (meth) acrylate, 2-methyl propyl propyl (meth) acrylate, (meth) acrylate 3, 4 -butyl butyl acrylate, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate or 3,4-epoxycyclohexyl (meth) acrylate Wait.

前述具有環氧基的α-烷基丙烯酸酯化合物可包含但不限於α-乙基丙烯酸環氧丙酯、α-正丙基丙烯酸環氧丙酯、α-正丁基丙烯酸環氧丙酯或α-乙基丙烯酸-6,7-環氧庚酯等。 The aforementioned epoxy group-containing α -alkyl acrylate compound may include, but is not limited to, α -ethyl methacrylate, propyl α -n-propyl acrylate, α -n-butyl butyl acrylate or --ethyl acrylate-6,7-epoxyheptyl ester and the like.

前述環氧丙醚化合物可包含但不限於鄰-乙烯基苯甲基環氧丙醚(o-vinylbenzylglycidylether)、間-乙烯基苯甲基環氧丙醚(m-vinylbenzylglycidylether)或對-乙烯基苯甲基環氧丙醚(p-vinylbenzylglycidylether)等。 The aforementioned glycidyl ether compound may include, but is not limited to, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether or p-vinylbenzene. P-vinylbenzylglycidylether or the like.

該具有環氧基之乙烯性不飽和單體(c-2-3)可單獨一種或混合複數種使用。 The epoxy group-containing ethylenically unsaturated monomer (c-2-3) may be used singly or in combination of plural kinds.

較佳地,前述具有環氧基之乙烯性不飽和單體(c-2-3)是選自於甲基丙烯酸環氧丙酯、甲基丙烯酸2-甲基環氧丙酯、甲基丙烯酸3,4-環氧環己基甲酯、甲基丙烯酸6,7-環氧庚酯、鄰-乙烯基苯甲基環氧丙醚、間-乙烯基苯甲基環氧丙醚、對-乙烯基苯甲基環氧丙醚或上述化合物之任意組合。 Preferably, the epoxy group-containing ethylenically unsaturated monomer (c-2-3) is selected from the group consisting of glycidyl methacrylate, 2-methylglycidyl methacrylate, and methacrylic acid. 3,4-epoxycyclohexylmethyl ester, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-ethylene Benzomethyl epoxidized ether or any combination of the above.

於本發明之具體例中,基於該第二鹼可溶性樹脂(C-2)之該具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)及該其他可共聚合之乙烯性不飽和單體(c-2-2)共聚合用單體之使用量總和為100重量份,該具有環氧基之乙烯性不飽和單體(c-2-3)之使用量範圍為1重量份至35重量份;較佳為3重量份至30重量份;更佳為5重量份至25重量份。 In a specific example of the present invention, the ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acids or carboxylic anhydrides based on the second alkali-soluble resin (C-2) and the other The total amount of the monomer for copolymerization of the copolymerized ethylenically unsaturated monomer (c-2-2) is 100 parts by weight, and the epoxy group-containing ethylenically unsaturated monomer (c-2-3) The amount used is in the range of 1 part by weight to 35 parts by weight; preferably 3 parts by weight to 30 parts by weight; more preferably 5 parts by weight to 25 parts by weight.

另外,上述第二鹼可溶性樹脂(C-2)藉由膠體滲透層析儀(Gel Permeation Chromatography,GPC)測定之聚苯乙烯換算的數目平均分子量一般為1000至35,000,較佳為3,000至30,000,更佳為5,000至25,000。 Further, the second alkali-soluble resin (C-2) has a polystyrene-equivalent number average molecular weight of from 1,000 to 35,000, preferably from 3,000 to 30,000, as measured by Gel Permeation Chromatography (GPC). More preferably 5,000 to 25,000.

於本發明之具體例中,基於該鹼可溶性樹脂(C)之使用量為100重量份,該第二鹼可溶性樹脂(C-2)之使用量為10重量份至100重量份;較佳為20重量份至90重量份;更佳為30重量份至80重量份。 In a specific example of the present invention, the amount of the alkali-soluble resin (C) used is 100 parts by weight, and the second alkali-soluble resin (C-2) is used in an amount of 10 parts by weight to 100 parts by weight; preferably 20 parts by weight to 90 parts by weight; more preferably 30 parts by weight to 80 parts by weight.

根據本發明之具有乙烯性不飽和基之化合物(D)可包含具有至少一個乙烯性不飽和基之不飽和化合物及具有至少二個乙烯性不飽和基之不飽和化合物。 The compound (D) having an ethylenically unsaturated group according to the present invention may contain an unsaturated compound having at least one ethylenically unsaturated group and an unsaturated compound having at least two ethylenically unsaturated groups.

上述具有至少一個乙烯性不飽和基之不飽和化合物的具體例可包含但不限於丙烯醯胺、丙烯醯嗎啉、甲基丙烯醯嗎啉、丙烯酸-7-胺基-3,7-二甲基辛酯、甲基丙烯酸-7-胺基-3,7-二甲基辛酯、異丁氧基甲基丙烯醯胺、異丁氧基甲基甲基丙烯醯胺、丙烯酸異冰片基氧乙酯、甲基丙烯酸異冰片基氧乙酯、丙烯酸異冰片酯、甲基丙烯酸異冰片酯、丙烯酸-2-乙基己酯、甲基丙烯酸-2-乙基己酯、乙基二甘醇丙烯酸酯、乙基二甘醇甲基丙烯酸酯、第三辛基丙烯醯胺、第三辛基甲基丙烯醯胺、二丙酮丙烯醯胺、二丙酮甲基丙烯醯胺、丙烯酸二甲胺基酯、甲基丙烯酸二甲胺基酯、丙烯酸十二烷基酯、甲基丙烯 酸十二烷基酯、丙烯酸二環戊烯氧乙酯、甲基丙烯酸二環戊烯氧乙酯、丙烯酸二環戊烯酯、甲基丙烯酸二環戊烯酯、氮,氮-二甲基丙烯醯胺、氮,氮-二甲基甲基丙烯醯胺、丙烯酸四氯苯酯、甲基丙烯酸四氯苯酯、丙烯酸-2-四氯苯氧基乙酯、甲基丙烯酸-2-四氯苯氧基乙酯、丙烯酸四氫糠酯、甲基丙烯酸四氫糠酯、丙烯酸四溴苯酯、甲基丙烯酸四溴苯酯、丙烯酸-2-四溴苯氧基乙酯、甲基丙烯酸-2-四溴苯氧基乙酯、丙烯酸-2-三氯苯氧基乙酯、甲基丙烯酸-2-三氯苯氧基乙酯、丙烯酸三溴苯酯、甲基丙烯酸三溴苯酯、丙烯酸-2-三溴苯氧基乙酯、甲基丙烯酸-2-三溴苯氧基乙酯、丙烯酸-2-羥乙酯、甲基丙烯酸-2-羥乙酯、丙烯酸-2-羥丙酯、甲基丙烯酸-2-羥丙酯、乙烯基己內醯胺、氮-乙烯基皮酪烷酮、丙烯酸苯氧基乙酯、甲基丙烯酸苯氧基乙酯、丙烯酸五氯苯酯、甲基丙烯酸五氯苯酯、丙烯酸五溴苯酯、甲基丙烯酸五溴苯酯、聚單丙烯酸乙二醇酯、聚單甲基丙烯酸乙二醇酯、聚單丙烯酸丙二醇酯、聚單甲基丙烯酸丙二醇酯、丙烯酸冰片酯,或甲基丙烯酸冰片酯等。其中,該具有至少一個乙烯性不飽和基之不飽和化合物可單獨一種使用或混合複數種使用。 Specific examples of the above unsaturated compound having at least one ethylenically unsaturated group may include, but are not limited to, acrylamide, propylene morpholine, methacryl hydrazine, acrylic-7-amino-3,7-dimethyl Kesin ester, -7-amino-3,7-dimethyloctyl methacrylate, isobutoxymethyl acrylamide, isobutoxymethyl methacrylamide, isobornyl acrylate Ethyl ester, isobornyl oxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, ethyl diglycol Acrylate, ethyl diglycol methacrylate, third octyl acrylamide, third octyl methacrylamide, diacetone acrylamide, diacetone methacrylamide, dimethylamino acrylate Ester, dimethylamino methacrylate, dodecyl acrylate, methacryl Dodecyl acid ester, dicyclopentene oxyethyl acrylate, dicyclopentene oxyethyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, nitrogen, nitrogen-dimethyl Acrylamide, nitrogen, nitrogen-dimethylmethacrylamide, tetrachlorophenyl acrylate, tetrachlorophenyl methacrylate, 2-tetrachlorophenoxyethyl acrylate, -2- methacrylate Chlorophenoxyethyl ester, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, tetrabromophenyl acrylate, tetrabromophenyl methacrylate, 2-tetrabromophenoxyethyl acrylate, methacrylic acid -2-tetrabromophenoxyethyl ester, 2-trichlorophenoxyethyl acrylate, 2-trichlorophenoxyethyl methacrylate, tribromophenyl acrylate, tribromophenyl methacrylate , 2-tribromophenoxyethyl acrylate, 2-tribromophenoxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy acrylate Propyl ester, 2-hydroxypropyl methacrylate, vinyl caprolactam, nitrogen-vinyl tyrosinone, phenoxyethyl acrylate, phenoxyethyl methacrylate, pentachlorophenyl acrylate A Pentachlorophenyl acrylate, pentabromophenyl acrylate, pentabromophenyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, poly propylene glycol monoacrylate, poly propylene glycol monomethacrylate Ester, borneol acrylate, or borneol methacrylate. Among them, the unsaturated compound having at least one ethylenically unsaturated group may be used singly or in combination of plural kinds.

上述具有至少二個乙烯性不飽和基之不飽和化合物的具體例可包含但不限於乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、二丙烯酸二環戊烯酯、二甲基丙烯酸二環戊烯酯、三甘醇二丙烯酸酯、四甘醇二丙烯酸酯、四甘醇二甲基丙烯酸酯、三(2-羥乙基)異氰酸酯二丙烯酸酯、三(2-羥乙基)異氰酸酯二甲基丙烯酸酯、三(2-羥乙基)異氰酸酯三丙烯酸酯、三(2-羥乙基)異氰酸酯三甲基丙烯酸酯、己內酯改質之三(2-羥乙基)異氰酸酯三丙烯酸酯、己內酯改質之三(2-羥乙基)異氰酸酯三甲基丙烯酸酯、三丙烯酸三羥甲基丙酯、三甲基丙烯酸三羥甲基丙酯、環氧乙烷(以下簡稱EO)改質之三丙烯酸三羥甲基丙酯、EO改質之三甲基丙烯酸三羥甲基丙酯、環氧丙烷(以下簡稱 PO)改質之三丙烯酸三羥甲基丙酯、PO改質之三甲基丙烯酸三羥甲基丙酯、三甘醇二丙烯酸酯、三甘醇二甲基丙烯酸酯、新戊二醇二丙烯酸酯、新戊二醇二甲基丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、1,6-己二醇二丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、聚酯二丙烯酸酯、聚酯二甲基丙烯酸酯、聚乙二醇二丙烯酸酯、聚乙二醇二甲基丙烯酸酯、二季戊四醇六丙烯酸酯(dipentaerythritol hexaacrylate;DPHA)、二季戊四醇六甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇五甲基丙烯酸酯、二季戊四醇四丙烯酸酯、二季戊四醇四甲基丙烯酸酯、己內酯改質之二季戊四醇六丙烯酸酯、己內酯改質之二季戊四醇六甲基丙烯酸酯、己內酯改質之二季戊四醇五丙烯酸酯、己內酯改質之二季戊四醇五甲基丙烯酸酯、四丙烯酸二三羥甲基丙酯、四甲基丙烯酸二三羥甲基丙酯、EO改質之雙酚A二丙烯酸酯、EO改質之雙酚A二甲基丙烯酸酯、PO改質之雙酚A二丙烯酸酯、PO改質之雙酚A二甲基丙烯酸酯、EO改質之氫化雙酚A二丙烯酸酯、EO改質之氫化雙酚A二甲基丙烯酸酯、PO改質之氫化雙酚A二丙烯酸酯、PO改質之氫化雙酚A二甲基丙烯酸酯、PO改質之甘油三丙酸酯、EO改質之雙酚F二丙烯酸酯、EO改質之雙酚F二甲基丙烯酸酯、酚醛聚縮水甘油醚丙烯酸酯、酚醛聚縮水甘油醚甲基丙烯酸酯、日本東亞合成株式會社製造且型號為TO-1382之商品,或者由日本化藥股份有限公司製造且其型號為KAYARAD DPCA-20、KAYARAD DPCA-30、KAYARAD DPCA-60或KAYARAD DPCA-120之商品等。其中,該具有至少二個乙烯性不飽和基之不飽和化合物可單獨一種使用或混合複數種使用。 Specific examples of the above unsaturated compound having at least two ethylenically unsaturated groups may include, but are not limited to, ethylene glycol diacrylate, ethylene glycol dimethacrylate, dicyclopentenyl diacrylate, and dimethacrylic acid. Dicyclopentenyl ester, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tris(2-hydroxyethyl)isocyanate diacrylate, tris(2-hydroxyethyl) Isocyanate dimethacrylate, tris(2-hydroxyethyl)isocyanate triacrylate, tris(2-hydroxyethyl)isocyanate trimethacrylate, caprolactone modified tris(2-hydroxyethyl)isocyanate Triacrylate (caprolactone modified) tris(2-hydroxyethyl)isocyanate trimethacrylate, trimethylolpropyl triacrylate, trimethylolpropyl trimethacrylate, ethylene oxide ( Hereinafter referred to as EO) modified trimethylol propyl triacrylate, EO modified trimethylol propyl trimethacrylate, propylene oxide (hereinafter referred to as PO) modified trimethylol propyl triacrylate, PO modified trimethylol propyl trimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, neopentyl glycol Acrylate, neopentyl glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, polyester diacrylate, polyester dimethacrylate, poly Ethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate , dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, caprolactone modified dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexamethacrylate, caprolactone modified dipenta Alcohol pentaacrylate, caprolactone modified dipentaerythritol pentamethyl acrylate, ditrimethylol propyl tetraacrylate, ditrimethylol propyl tetramethacrylate, EO modified bisphenol A diacrylic acid Ester, EO modified bisphenol A dimethacrylate, PO modified bisphenol A diacrylate, PO modified bisphenol A dimethacrylate, EO modified hydrogenated bisphenol A diacrylate EO modified hydrogenated bisphenol A dimethacrylate, PO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A dimethacrylate, PO modified triglyceride EO modified bisphenol F diacrylate, EO modified bisphenol F dimethacrylate, phenolic polyglycidyl ether acrylate, phenolic polyglycidyl ether methacrylate, manufactured by Japan East Asia Synthetic Co., Ltd. The product of model TO-1382, or the product of KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 or KAYARAD DPCA-120 manufactured by Nippon Kayaku Co., Ltd., etc. Among them, the unsaturated compound having at least two ethylenically unsaturated groups may be used singly or in combination of plural kinds.

較佳地,該具有乙烯性不飽和基之化合物(D)是選自於三丙烯酸三羥甲基丙酯、EO改質之三丙烯酸三羥甲基丙酯、PO改質 之三丙烯酸三羥甲基丙酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇四丙烯酸酯、己內酯改質之二季戊四醇六丙烯酸酯、四丙烯酸二三羥甲基丙酯、PO改質之甘油三丙酸酯,KAYARAD DPCA-20、KAYARAD DPCA-30、KAYARAD DPCA-60或KAYARAD DPCA-120或上述化合物之任意組合。 Preferably, the compound (D) having an ethylenically unsaturated group is selected from trimethylolpropyl acrylate, EO-modified trimethylolpropyl acrylate, and PO modification. Trimethylol propyl acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate, Ditrimethylolpropyl methacrylate, PO modified tripropionate, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 or KAYARAD DPCA-120 or any combination of the above.

上述具有乙烯性不飽和基之化合物(D)可單獨一種使用或混合複數種使用。 The above compound (D) having an ethylenically unsaturated group may be used singly or in combination of plural kinds.

基於該鹼可溶性樹脂(C)之使用量為100重量份,該具有乙烯性不飽和基之化合物(D)之使用量為20重量份至200重量份;較佳為30重量份至180重量份;更佳為50重量份至150重量份。 The compound (D) having an ethylenically unsaturated group is used in an amount of 20 parts by weight to 200 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C); preferably 30 parts by weight to 180 parts by weight. More preferably, it is 50 parts by weight to 150 parts by weight.

根據本發明之光起始劑(E)可包含具有如式(III)所示結構之一光起始劑(E-1): The photoinitiator (E) according to the present invention may comprise a photoinitiator (E-1) having a structure as shown in formula (III):

於式(III)中,E1、E2、E3、E4、E5、E6、E7及E8分別獨立代 表氫原子、碳數為1至20之烷基、、COE16、OE17、鹵素、NO2;或E1及E2、E2及E3、E3及E4、E5及E6、E6及E7或E7及E8分別獨 立代表經取代之碳數為2至10之烯基;或E1及E2、E2及E3、E3及E4、E5及E6、E6及E7或E7及E8分別獨立地共同代表-(CH2)p-W-(CH2)q-;或E1及E2、E2及E3、E3及E4、E5及E6、E6及E7或E7及E8分別獨 立地代表,其中至少一E1及E2、E2及E3、E3及 E4、E5及E6、E6及E7或E7及E8E9、E10、E11及E12分別獨立代表氫原子、碳數為1至20之烷基,碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自苯基、鹵素、CN、OH、SH、碳數為1至4之烷氧基、(CO)OH或(CO)O(R1),其中R1代表碳數為1至4之烷基;或E9、E10、E11及E12分別獨立地代表未經取代之苯基或經如下所示之至少一基團取代之苯基,且至少一基團係選自碳數為1至6之烷基、鹵素、CN、OE17、SE18或NE19E20;或E9、E10、E11及E12分別獨立地代表鹵素、CN、OE17、SE18、SOE18、SO2E18或NE19E20,其中取代基OE17、SE18或NE19E20係選擇性地經由基團E17、E18、E19及/或E20與式(III)之萘環的一個碳原子形成五員環或六員環;或 E9、E10、E11及E12分別獨立地代表、COE16或NO2;W代表O、S、NE26或單鍵,p代表0至3之整數,q代表1至3之整數,Z1代表CO或單鍵;E13代表碳數為1至20之烷基,碳數為1至20之烷基係未經取 代或經如下所示之至少一基團取代,其中上述之至少一基團係選自鹵素、E17、COOE17、OE17、SE18、CONE19E20、NE19E20、PO(OCkH2k+1)2;或E13代表碳數為2至20之烷基,碳數為2至20之烷基間雜有一或多個O、S、SO、SO2、NE26或CO;或E13代表碳數為2至12之烯基,碳數為2至12之烯基係未經間雜或間雜有一或多個O、CO或NE26,其中經間雜且碳數為2至20之烷基及未經間雜或經間雜之碳數為2至12之烯基係未經取代或經至少一鹵素取代;或E13代表碳數為4至8之環烯基、碳數為2至12之炔基、或未經間雜或間雜有一或多個O、S、CO或NE26之碳數為3至10之環烷基;或E13代表苯基或萘基,且其各未經取代或經如下所示之至少一基團取代,其中該至少一基團係選自OE17、SE18、NE19E20、COE16、CN、NO2、鹵素、碳數為1至20之烷基、碳數為1至4之鹵代烷基,間雜有一或多個O、S、CO或NE26且碳數為2至20的烷基;或苯基或萘基各經未間雜或間雜有一或多個O、S、CO或NE26間雜且碳數為3至10之環烷基所取代;k代表1至10之整數;E14代表氫原子、碳數為3至8之環烷基、碳數為2至5之烯基、碳數為1至20之烷氧基或未經取代或經如下所示之至少一基團取代之碳數為1至20之烷基,且至少一基團係選自鹵素、苯基、碳數為1至20之烷基苯基或CN;或E14代表苯基或萘基,其各未經取代或經如下所示之至少一基團取代,且至少一基團係選自碳數為1至6之烷基、碳數為1至 4之鹵代烷基、鹵素、CN、OE17、SE18及/或NE19E20;或E14代表碳數為3至20之雜芳基、碳數為1至8之烷氧基、苄氧基或苯氧基,苄氧基及苯氧基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自碳數為1至6之烷基、碳數為1至4之鹵代烷基及/或鹵素;E15代表碳數為6至20之芳香基或碳數為3至20之雜芳基,其各未經取代或經如下所示之至少一基團取代,且至少一基團係選自苯基、鹵素、碳數為1至4之鹵代烷基、CN、NO2、OE17、SE18、NE19E20、PO(OCkH2k+1)2、與SO鍵結且碳數為1至10之烷基、與SO2鍵結且碳數為1至10之烷基、間雜有一或多個O、S或NE26且碳數為2至20之烷基;或者,碳數為6至20之芳香基或碳數為3至20之雜芳基各經碳數為1至20之烷基取代,其中碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素、COOE17、CONE19E20、苯基、碳數為3至8之環烷基、碳數為3至20之雜芳基、碳數為6至20之芳氧基羰基、碳數為3至20之雜芳氧基羰基、OE17、SE18或NE19E20;或E15代表氫原子、碳數為2至12之烯基、未經間雜或間雜有一或多個O、CO或NE26且碳數為3至8之環烷基;或E15代表碳數為1至20之烷基,碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素、OE17、SE18、碳數為3至8之環烷基、碳數為3至20之雜芳基、碳數為6至20之芳氧基羰基、碳數為3至20之雜芳氧基羰基、NE19E20、COOE17、CONE19E20、PO(OCkH2k+1)2或苯基,其中該碳數為1至20之烷基係經苯基取代,且苯基係經鹵素、碳數為1至20之烷基、碳數 為1至4之鹵代烷基、OE17、SE18或NE19E20取代;或E15代表碳數為2至20之烷基,碳數為2至20之烷基係間雜有一或多個O、SO或SO2,經間雜且碳數為2至20之烷基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素、OE17、COOE17、CONE19E20、苯基或經OE17、SE18或NE19E20取代之苯基;或E15代表碳數為2至20之烷醯基或苯甲醯基,其係未經取代或經如下所示之至少一基團取代,且至少一基團係選自碳數為1至6之烷基、鹵素、苯基、OE17、SE18或NE19E20;或E15代表未經取代或經至少一OE17取代之萘甲醯基或係碳數為3至14之雜芳基羰基;或E15代表碳數為2至12之烷氧基羰基,碳數為2至12之烷氧基羰基係未經間雜或間雜有一或多個O,其中經間雜或未經間雜且碳數為2至12之烷氧基羰基係未經取代或經至少一羥基取代;或E15代表苯氧基羰基,苯氧基羰基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自碳數為1至6之烷基、鹵素、碳數為1至4之鹵代烷基、苯基、OE17、SE18或NE19E20;或E15代表CN、CONE19E20、NO2、碳數為1至4之鹵代烷基、S(O)r-R2、與S(O)r鍵結之苯基,其中與S(O)r鍵結之苯基係未經取代或經碳數為1至12之烷基或SO2-R2取代,且R2代表碳數為1至6之烷基;或E15代表與SO2O鍵結之苯基,其中與SO2O鍵結之苯基係未經取代或經碳數為1至12之烷基取代;或E15代表二苯基膦醯基或二(R3)-膦醯基,且R3代表碳數為1至4之烷氧基; r表示1至2之整數;E'14代表具有針對E14定義中其中之一者;E'15代表具有針對E15定義中其中之一者;Z2代表-O-、-S-、-SO-或-SO2-;Z3代表-O-、-CO-、-S-或單鍵;E16代表碳數為6至20之芳香基或碳數為3至20之雜芳基,其各未經取代或經如下所示之至少一基團取代,且至少一基團係選自苯基、鹵素、碳數為1至4之鹵代烷基、CN、NO2、OE17、SE18、NE19E20、間雜有一或多個O、S或NE26且碳數為1至20之烷基,或者碳數為1至20之烷基,其中碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,其中至少一基團係選自鹵素、COOE17、CONE19E20、苯基、碳數為3至8之環烷基、碳數為3至20之雜芳基、碳數為6至20之芳氧基羰基、碳數為3至20之雜芳氧基羰基、OE17、SE18或NE19E20;或E16代表氫原子或碳數為1至20之烷基,其中碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素、苯基、OH、SH、CN、碳數為3至6之烯氧基、OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R1)、O(CO)-苯基或(CO)OH或(CO)O(R1);或E16代表碳數為2至12之烷基,碳數為2至12之烷基係間雜有一或多個O、S或NE26;或E16代表(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4)、碳數為2至12之烯基或碳數為3至8之環烷基,其中該R4代表碳數為1至8之烷基;或E16代表經SE18取代之苯基,其中E18代表鍵結至COE16所附接之咔唑部份之苯基或萘基環的單鍵; n代表1至20之整數;E17代表氫原子、苯基-R5、碳數為1至20之烷基,其係未經取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素、OH、SH、CN、碳數為3至6之烯氧基、OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R1)、O(CO)-(R6)、與O(CO)鍵結之苯基、(CO)OH、(CO)O(R1)、碳數為3至20之環烷基、SO2-(R7)、O(R7)或間雜有一或多個O且碳數為3至20之環烷基,其中R5代表碳數為1至3之烷基、R6代表碳數為2至4之烯基,且R7代表碳數為1至4之鹵代烷基;或E17代表碳數為2至20之烷基,且碳數為2至20之烷基係間雜有一或多個O、S或NE26;或E17代表(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4)、碳數為1至8之烷醯基、碳數為2至12之烯基、碳數為3至6之烯醯基或碳數為3至20之環烷基,其中碳數為3至20之環烷基係未經間雜或間雜有一或多個O、S、CO或NE26;或E17代表碳數為1至8之烷基與碳數為3至10之環烷基鍵結所形成之基團,且上述基團係未經間雜或間雜有一或多個O;或E17代表苯甲醯基,苯甲醯基係未取代或經如下所示之至少一基團取代,且至少一基團係選自碳數為1至6之烷基、鹵素、OH或碳數為1至3之烷氧基;或E17代表苯基、萘基或碳數為3至20之雜芳基,其各未經取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素、OH、碳數為1至12之烷基、碳數為1至12之烷氧基、CN、NO2、苯基-R8、苯氧基、碳數為1至12之烷基硫基、苯基硫基、N(R9)2、二苯基-胺基或,其中R8代表碳數為1至 3之烷氧基,且R9代表碳數為1至12之烷基;或 E17與具有之苯基或萘基環之其中一個碳原子形成單鍵;E18代表氫原子、碳數為2至12之烯基、碳數為3至20之環烷基或苯基-R5,其中碳數為2至12之烯基、碳數為3至20之環烷基及苯基-R5係未經間雜或間雜有一或多個O、S、CO、NE26或COOE17;或E18代表碳數為1至20之烷基,碳數為1至20之烷基係未取代或經如下所示之至少一基團取代,且至少一基團係選自OH、SH、CN、碳數為3至6之烯氧基、OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R6)、O(CO)-(R1)、O(CO)-苯基或(CO)OE17;或E18代表碳數為2至20之烷基,碳數為2至20之烷基係間雜有一或多個O、S、CO、NE26或COOE17;或E18代表(CH2CH2O)nH、(CH2CH2O)n(CO)-(R4)、碳數為2至8之烷醯基或碳數為3至6之烯醯基;或E18代表苯甲醯基,苯甲醯基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自碳數為1至6之烷基、鹵素、OH、碳數為1至4之烷氧基或碳數為1至4之烷基硫基;或E18代表苯基、萘基或碳數為3至20之雜芳基,其各未取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素、碳數為1至12之烷基、碳數為1至4之鹵代烷基、碳數為1至12之烷氧基、CN、NO2、苯基-R8、苯氧基、碳數為1至12之烷基硫基、苯基硫基、N(R9)2、二苯基胺基、(CO)O(R4)、CO-R4、 (CO)N(R4)2E19及E20分別獨立地代表氫原子、碳數為1至20之烷基、碳數為2至4之羥基烷基、碳數為2至10之烷氧基烷基、碳數為2至5之烯基、碳數為3至20之環烷基、苯基-R5、碳數為1至8之烷醯基、碳數為1至8之烷醯基氧基、碳數為3至12之烯醯基、SO2-R7或苯甲醯基;或E19及E20代表苯基、萘基或碳數為3至20之雜芳基,其各未經取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素、碳數為1至4之鹵代烷基、碳數為1至20之烷氧基、碳數為1至12之烷基、苯甲醯基或碳數為1至12之烷氧基;或E19及E20係與所鍵結之氮原子一起形成未經間雜或間雜有O、S或NE17之五員或六員飽和或不飽和環,且五員或六員飽和或不飽和環係未經取代或經如下所示之至少一基團取代,其中至少一基團係選自碳數為1至20之烷基、碳數為1至20之烷氧基、=O、OE17、SE18、NE21E22、(CO)E23、NO2、鹵素、碳數為1 至4之鹵代烷基、CN、苯基、,或者未經間雜或間雜有一或多個O、S、CO或NE17且碳數為3至20之環烷基;或E19及E20係與所附接之氮原子一起形成雜芳香族環系統,該雜芳香族環系統係未經取代或經如下所示之至少一基團取代,且至少一基團係選自碳數為1至20之烷基、碳數為1至4之鹵代烷基、碳數為1至20之烷氧基、=O、OE17、SE18、NE21E22、 (CO)E23、鹵素、NO2、CN、苯基,或者未經間雜或間雜有一或多個O、S、CO或NE17且碳數為3至20的環烷基;E21及E22分別獨立地代表氫原子、碳數為1至20之烷基、碳 數為1至4之鹵代烷基、碳數為3至10之環烷基或苯基;E21及E22與其所鍵接之氮原子一起形成未經間雜或間雜有O、S或NE26之五員或六員飽和或不飽和環,其中五員或六員飽和或不飽和環係未稠合或與苯環稠合;E23代表氫原子、OH、碳數為1至20之烷基、碳數為1至4之鹵代烷基、間雜有至少一O、CO或NE26且碳數為2至20的烷基、未經間雜或間雜有O、S、CO或NE26且碳數為3至20之環烷基;或E23代表苯基、萘基、苯基-R1、OE17、SE18或NE21E22;E24代表(CO)OE17、CONE19E20、(CO)E17或具有針對E19及E20定義中其中之一者;E25代表COOE17、CONE19E20、(CO)E17;或E25具有針對E17定義中其中之一者;E26代表氫原子、碳數為1至20之烷基、碳數為1至4之鹵代烷基、間雜有一或多個O或CO且碳數為2至20之烷基;或E26代表苯基-R1、未經間雜或間雜有一或多個O或CO且碳數為3至8之環烷基;或E26代表(CO)E19;或E26代表苯基,苯基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自碳數為1至20之烷基、鹵素、碳數為1至4之鹵代烷基、OE17、SE18、 NE19E20,但條件為如式(III)所示之結構的光 起始劑(E-1)具有至少一個 In the formula (III), E 1 , E 2 , E 3 , E 4 , E 5 , E 6 , E 7 and E 8 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, , COE 16 , OE 17 , halogen, NO 2 or ; Or E 1 and E 2, E 2, and E 3, E 3 and E 4, E 5 and E 6, E 6 or E 7 and E 7 and E 8 each independently represent by Alternate carbon number is 2 to 10 alkenyl; or E 1 and E 2 , E 2 and E 3 , E 3 and E 4 , E 5 and E 6 , E 6 and E 7 or E 7 and E 8 are respectively independent Commonly represented by -(CH 2 ) p -W-(CH 2 ) q -; or E 1 and E 2 , E 2 and E 3 , E 3 and E 4 , E 5 and E 6 , E 6 and E 7 or E 7 and E 8 are independently represented Wherein at least one of E 1 and E 2 , E 2 and E 3 , E 3 and E 4 , E 5 and E 6 , E 6 and E 7 or E 7 and E 8 are E 9 , E 10 , E 11 and E 12 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms which is unsubstituted or has at least one group as shown below. Substituted, and at least one group is selected from the group consisting of phenyl, halogen, CN, OH, SH, alkoxy having a carbon number of 1 to 4, (CO)OH or (CO)O(R 1 ), wherein R 1 represents An alkyl group having 1 to 4 carbon atoms; or E 9 , E 10 , E 11 and E 12 each independently representing an unsubstituted phenyl group or a phenyl group substituted with at least one group as shown below, and at least one The group is selected from the group consisting of an alkyl group having a carbon number of 1 to 6, a halogen, CN, OE 17 , SE 18 or NE 19 E 20 ; or E 9 , E 10 , E 11 and E 12 independently representing a halogen, CN, OE 17 , SE 18 , SOE 18 , SO 2 E 18 or NE 19 E 20 wherein the substituents OE 17 , SE 18 or NE 19 E 20 are selectively via groups E 17 , E 18 , E 19 and/or E 20 and a carbon atom of the naphthalene ring of formula (III) form a five-membered or six-membered ring; or E 9 , E 10 , E 11 and E 12 are independently represented , COE 16 or NO 2 ; W represents O, S, NE 26 or a single bond, p represents an integer from 0 to 3, q represents an integer from 1 to 3, Z 1 represents CO or a single bond; and E 13 represents a carbon number of 1. The alkyl group to 20, the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, wherein at least one of the above groups is selected from the group consisting of halogen, E 17 , COOE 17 , OE 17 , SE 18 , CONE 19 E 20 , NE 19 E 20 , PO(OC k H 2k+1 ) 2 or Or E 13 represents an alkyl group having 2 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, or one or more O, S, SO, SO 2 , NE 26 or CO; or E 13 represents a carbon number of The alkenyl group of 2 to 12, the alkenyl group having 2 to 12 carbon atoms, having no or hetero or one or more O, CO or NE 26 , wherein the alkyl group having 2 to 20 carbon atoms and unintercalated Or an alkenyl group having a carbon number of 2 to 12 which is unsubstituted or substituted with at least one halogen; or E 13 represents a cycloalkenyl group having 4 to 8 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, or One or more O, S, CO or NE 26 carbon atoms having 3 to 10 carbon atoms; or E 13 representing a phenyl or naphthyl group, each of which is unsubstituted or as shown below Substituting at least one group, wherein the at least one group is selected from the group consisting of OE 17 , SE 18 , NE 19 E 20 , , COE 16 , CN, NO 2 , halogen, alkyl having 1 to 20 carbon atoms, haloalkyl having 1 to 4 carbon atoms, intermixed with one or more O, S, CO or NE 26 and having a carbon number of 2 to An alkyl group of 20; or a phenyl or naphthyl group each substituted with one or more cycloalkyl groups having one or more O, S, CO or NE 26 and having a carbon number of 3 to 10; k represents 1 to 10 An integer; E 14 represents a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or unsubstituted or at least as shown below a group substituted with an alkyl group having 1 to 20 carbon atoms, and at least one group selected from the group consisting of halogen, phenyl, alkylphenyl having 1 to 20 carbon atoms or CN; or E 14 representing phenyl or naphthalene a group, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a halogen, and CN. , OE 17 , SE 18 and/or NE 19 E 20 ; or E 14 represents a heteroaryl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a benzyloxy group or a phenoxy group, benzyloxy group And phenoxy are unsubstituted or substituted by at least one group as shown below, and at least A group selected from an alkyl group having a carbon number of 1 to 6 carbon atoms, a haloalkyl group of 1 to 4 and / or halogen; E 15 represents a carbon atoms or an aromatic group of 6 to 20 carbon atoms as the hetero 3-20 An aryl group, each unsubstituted or substituted with at least one group as shown below, and at least one group selected from the group consisting of phenyl, halogen, haloalkyl having 1 to 4 carbon atoms, CN, NO 2 , OE 17 , SE 18 , NE 19 E 20 , PO(OC k H 2k+1 ) 2 , an alkyl group bonded to SO and having a carbon number of 1 to 10, an alkyl group bonded to SO 2 and having a carbon number of 1 to 10 a heterocyclic group having one or more O, S or NE 26 and having a carbon number of 2 to 20; or a heteroaryl group having a carbon number of 6 to 20 or a heteroaryl group having a carbon number of 3 to 20 each having a carbon number of An alkyl group substituted with 1 to 20, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of halogen, COOE 17 , and CONE 19 E 20. A phenyl group, a cycloalkyl group having 3 to 8 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, an aryloxycarbonyl group having 6 to 20 carbon atoms, and a heteroaryloxy group having 3 to 20 carbon atoms. a carbonyl group, OE 17 , SE 18 or NE 19 E 20 ; or E 15 represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having one or more O, CO or NE 26 and having a carbon number of 3 to 8; or E 15 representing an alkyl group having 1 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms Substituted or substituted with at least one group as shown below, and at least one group selected from the group consisting of halogen, OE 17 , SE 18 , a cycloalkyl group having a carbon number of 3 to 8, and a carbon number of 3 to 20 Aryl group, aryloxycarbonyl group having 6 to 20 carbon atoms, heteroaryloxycarbonyl group having 3 to 20 carbon atoms, NE 19 E 20 , COOE 17 , CONE 19 E 20 , PO(OC k H 2k+1 ) 2 , , Or a phenyl group, wherein the alkyl group having 1 to 20 carbon atoms is substituted with a phenyl group, and the phenyl group is halogen, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or OE 17 , SE 18 or NE 19 E 20 substituted; or E 15 represents an alkyl group having 2 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, one or more O, SO or SO 2 , interstitial and carbon The alkyl group of 2 to 20 is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from halogen, OE 17 , COOE 17 , CONE 19 E 20 , phenyl or OE 17. A phenyl substituted with SE 18 or NE 19 E 20 ; or E 15 represents an alkanoyl or benzylidene group having a carbon number of 2 to 20, which is unsubstituted or substituted with at least one group as shown below And at least one group is selected from the group consisting of a C 1 to 6 alkyl group, a halogen, a phenyl group, an OE 17 , SE 18 or NE 19 E 20 ; or E 15 represents an unsubstituted or substituted by at least one OE 17 a naphthylmethyl group or a heteroarylcarbonyl group having a carbon number of 3 to 14; or E 15 represents an alkoxycarbonyl group having 2 to 12 carbon atoms, and an alkoxycarbonyl group having 2 to 12 carbon atoms is unintercalated or Miscellaneous with one or more O, Carbon atoms and an alkoxycarbonyl group having 2 to 12 lines of unsubstituted or substituted by at least one hydroxyl group; or E 15 Representative phenoxycarbonyl, phenoxycarbonyl unsubstituted or system of at least one group shown by the following Substituted, and at least one group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, OE 17 , SE 18 or NE 19 E 20 ; or E 15 represents CN, CONE 19 E 20 , NO 2 , haloalkyl having 1 to 4 carbon atoms, S(O) r -R 2 , phenyl group bonded to S(O) r , wherein it is bonded to S(O) r The phenyl group is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms or SO 2 -R 2 , and R 2 represents an alkyl group having 1 to 6 carbon atoms; or E 15 represents a bond with SO 2 O a phenyl group in which a phenyl group bonded to SO 2 O is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms; or E 15 represents a diphenylphosphinium group or a di(R 3 )-phosphonium group. And R 3 represents an alkoxy group having a carbon number of 1 to 4; r represents an integer of 1 to 2; E' 14 represents one of the definitions for E 14 ; and E' 15 represents a definition for E 15 one of those; Z 2 Representative -O -, - S -, - SO- or -SO 2 -; Z 3 Representative -O -, - CO -, - S- or a single bond E 16 represents a carbon atoms or an aromatic group of 6 to 20 carbon atoms of the 3 to 20 hetero aryl group, each of which is unsubstituted or substituted with at least one of the groups shown below, and at least one group selected from benzyl a halogen group having a carbon number of 1 to 4, CN, NO 2 , OE 17 , SE 18 , NE 19 E 20 , an alkane having one or more O, S or NE 26 and having a carbon number of 1 to 20 a group, or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, wherein at least one group is selected from the group consisting of halogen and COOE 17 , Cone 19 E 20 , phenyl, cycloalkyl having 3 to 8 carbon atoms, heteroaryl having 3 to 20 carbon atoms, aryloxycarbonyl having 6 to 20 carbon atoms, carbon number 3 to 20 a heteroaryloxycarbonyl group, OE 17 , SE 18 or NE 19 E 20 ; or E 16 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or Substituted by at least one group as shown below, and at least one group selected from the group consisting of halogen, phenyl, OH, SH, CN, alkenyloxy having 3 to 6 carbon atoms, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(R 1 ), O(CO)-(R 1 ), O(CO)-phenyl or (CO)OH or (CO)O ( R 1 ); or E 16 represents an alkyl group having 2 to 12 carbon atoms, an alkyl interstitial having 2 to 12 carbon atoms, or one or more O, S or NE 26 ; or E 16 represents (CH 2 CH 2 O) n+1 H, (CH 2 CH 2 O) n (CO)-(R 4 ), an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, wherein R 4 represents carbon An alkyl group of 1 to 8; or E 16 represents a phenyl group substituted with SE 18 , wherein E 18 represents a single bond bonded to the phenyl or naphthyl ring of the carbazole moiety to which COE 16 is attached; An integer representing from 1 to 20; E 17 represents a hydrogen atom, a phenyl-R 5 group, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group as shown below, and at least one group The group is selected from the group consisting of halogen, OH, SH, CN, an alkenyloxy group having a carbon number of 3 to 6, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(R 1 ), O(CO)-(R 1 ), O(CO)-(R 6 ), phenyl group bonded to O(CO), (CO)OH, (CO)O(R 1 ), cycloalkyl group having 3 to 20 carbon atoms, SO 2 -(R 7 ), O(R 7 ) or a cycloalkyl group having one or more O and having a carbon number of 3 to 20, wherein R 5 represents an alkyl group having 1 to 3 carbon atoms, and R 6 represents a carbon number of 2 to 4 alkenyl groups, and R 7 represents a haloalkyl group having 1 to 4 carbon atoms; or E 17 represents An alkyl group having 2 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms having one or more O, S or NE 26 ; or E 17 representing (CH 2 CH 2 O) n+1 H, ( CH 2 CH 2 O) n (CO)-(R 4 ), an alkanoyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an olefin group having 3 to 6 carbon atoms or a carbon number a cycloalkyl group of 3 to 20, wherein the cycloalkyl group having a carbon number of 3 to 20 is undoped or hetero-doped with one or more O, S, CO or NE 26 ; or E 17 represents a carbon number of 1 to 8. a group formed by bonding an alkyl group to a cycloalkyl group having a carbon number of 3 to 10, and the above group is undoped or hetero-has one or more O; or E 17 represents a benzamidine group, a benzamidine group Is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen, OH or an alkoxy group having 1 to 3 carbon atoms; or E 17 represents a phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of halogen, OH, and carbon number. is an alkyl group of 1 to 12 carbon atoms, alkoxy of 1 to 12, CN, NO 2, phenyl -R 8, a phenoxy group, an alkyl group having a carbon number of 1 to 12 Group, a phenyl group, N (R 9) 2, diphenyl - group or Wherein R 8 represents an alkoxy group having a carbon number of 1 to 3, and R 9 represents an alkyl group having a carbon number of 1 to 12; or E 17 and has or One of the carbon atoms of the phenyl or naphthyl ring forms a single bond; E 18 represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or a phenyl-R 5 group, wherein An alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a phenyl-R 5 group having no or hetero or one or more O, S, CO, NE 26 or COOE 17 ; or E 18 represents an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from OH, SH, CN, Alkenyloxy group having 3 to 6 carbon atoms, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(R 1 ), O(CO)-(R 6 ), O(CO)-(R 1 ), O(CO)-phenyl or (CO)OE 17 ; or E 18 represents an alkyl group having 2 to 20 carbon atoms, and an alkyl group having 2 to 20 carbon atoms, one or more O, S, CO, NE 26 or COOE 17 ; or E 18 represents (CH 2 CH 2 O) n H, (CH 2 CH 2 O) n (CO)-(R 4 ), an alkanoyl group having a carbon number of 2 to 8 or a carbon number of Or an alkylene group of 3 to 6; or E 18 represents a benzamidine group, which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a carbon number of 1 to 6 alkyl, halogen, OH, carbon An alkoxy group having 1 to 4 carbon atoms or an alkyl group of 1 to 4; or E 18 represents phenyl, naphthyl or heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or follows At least one group is substituted, and at least one group is selected from the group consisting of halogen, an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and CN. , NO 2 , phenyl-R 8 , phenoxy, alkylthio having 1 to 12 carbon atoms, phenylthio group, N(R 9 ) 2 , diphenylamino group, (CO)O(R) 4 ), CO-R 4 , (CO)N(R 4 ) 2 or E 19 and E 20 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, and a carbon number of 2 Alkenyl group to 5, cycloalkyl group having 3 to 20 carbon atoms, phenyl-R 5 , alkanoyl group having 1 to 8 carbon atoms, alkyl alkoxy group having 1 to 8 carbon atoms, carbon number 3 to 12 olefinic groups, SO 2 -R 7 or benzamidine groups; or E 19 and E 20 represent a phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or Substituting at least one group as shown below, and the at least one group is selected from the group consisting of halogen, a halogenated alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkyl group having 1 to 12 carbon atoms a benzyl group or a benzepidine group or an alkoxy group having a carbon number of 1 to 12; or an E 19 and E 20 group together with a bonded nitrogen atom to form a five member or a heterogeneous or intervening O, S or NE 17 a six-membered saturated or unsaturated ring, and a five or six member saturated or unsaturated ring system is unsubstituted or substituted with at least one group as shown below, wherein at least one group is selected from a carbon number of 1 to 20 alkyl group, an alkoxy group having a carbon number of 1 to 20, = O, OE 17, SE 18, NE 21 E 22, (CO) E 23 NO 2, a halogen, a haloalkyl group having a carbon number of 1 to 4, CN, phenyl, Or a cycloalkyl group having one or more O, S, CO or NE 17 and having a carbon number of 3 to 20 without interstitial or heterogeneous; or E 19 and E 20 together with the attached nitrogen atom to form a heteroaromatic a ring system, wherein the heteroaromatic ring system is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and a carbon number of 1 to 4 Haloalkyl, alkoxy with 1 to 20 carbon atoms, =0, OE 17 , SE 18 , NE 21 E 22 , (CO)E 23 , , halogen, NO 2 , CN, phenyl, or a cycloalkyl group having one or more O, S, CO or NE 17 and having a carbon number of 3 to 20 without interstitial or heterogeneous; E 21 and E 22 independently representing a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group; and E 21 and E 22 together with the nitrogen atom to which they are bonded Forming a five- or six-membered saturated or unsaturated ring with no interstitial or interstitial O, S or NE 26 , wherein five or six members of the saturated or unsaturated ring system are not fused or fused to the benzene ring; E 23 represents a hydrogen atom, OH, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having at least one O, CO or NE 26 and having a carbon number of 2 to 20, without impurity or a cycloalkyl group having O, S, CO or NE 26 and having a carbon number of 3 to 20; or E 23 representing a phenyl group, a naphthyl group, a phenyl-R 1 , an OE 17 , SE 18 or NE 21 E 22 ; 24 represents (CO) OE 17 , CONE 19 E 20 , (CO) E 17 or has one of the definitions for E 19 and E 20 ; E 25 represents COOE 17 , CONE 19 E 20 , (CO) E 17 ; or E 25 with E 17 in which is defined for one person; E 26 represents a hydrogen atom, a C Alkyl of 1 to 20 carbon atoms, a haloalkyl group of 1 to 4, intermingled with one or more O or CO and alkyl having 2 to 20; or E 26 represents phenyl -R 1, intermingled or without a cycloalkyl group having one or more O or CO and having a carbon number of 3 to 8; or E 26 representing (CO)E 19 ; or E 26 representing a phenyl group, the phenyl group being unsubstituted or at least as shown below Substituting a group, and the at least one group is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a halogen, a halogenated alkyl group having 1 to 4 carbon atoms, OE 17 , SE 18 , NE 19 E 20 or , but the photoinitiator (E-1) having the structure of the formula (III) has at least one or

該具有式(III)所示結構之光起始劑(E-1)的特徵在於其咔唑部分上包含至少一成環(anne1ated)不飽和環。換言之,至少一對E1及E2、E2及E3、E3及E4、E5及E6、E6及E7或E7及E8 The photoinitiator (E-1) having the structure represented by the formula (III) is characterized in that it contains at least one annened unsaturated ring on the carbazole moiety. In other words, at least one pair of E 1 and E 2 , E 2 and E 3 , E 3 and E 4 , E 5 and E 6 , E 6 and E 7 or E 7 and E 8 are

前述所稱之碳數為1至20之烷基係直鏈或支鏈且係例如碳數為1至18、碳數為1至4、碳數為1至12、碳數為1至8、碳數為1至8或碳數為1至4之烷基,或碳數為4至12或碳數為4至8之烷基。具體例子如甲基、乙基、丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、戊基、己基、庚基、2,4,4-三甲基戊基、2-乙基己基、辛基、壬基、癸基、十二基、十四基、十五基、十六基、十八基及二十基。碳數為1至6之烷基具有與上述碳數為1至20之烷基相同的定義,且具有最高相應的碳原子數。 The above-mentioned alkyl group having a carbon number of 1 to 20 is linear or branched and has, for example, a carbon number of 1 to 18, a carbon number of 1 to 4, a carbon number of 1 to 12, and a carbon number of 1 to 8. An alkyl group having 1 to 8 carbon atoms or 1 to 4 carbon atoms, or an alkyl group having 4 to 12 carbon atoms or 4 to 8 carbon atoms. Specific examples are methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl Pentyl, 2-ethylhexyl, octyl, decyl, decyl, dodecyl, tetradecyl, fifteen, hexadecyl, octadecyl and decyl. The alkyl group having 1 to 6 carbon atoms has the same definition as the above-mentioned alkyl group having 1 to 20 carbon atoms, and has the highest corresponding number of carbon atoms.

該含有至少一碳-碳多鍵之未經取代或經取代之碳數為1至20之烷基即為後述之烯基。 The unsubstituted or substituted alkyl group having 1 to 20 carbon atoms containing at least one carbon-carbon multiple bond is an alkenyl group described later.

該碳數為1至4之鹵代烷基係如後述所定義經鹵素取代且如前述所定義之碳數為1至4之烷基。烷基基團可例如為單-或多鹵化,直至所有氫原子替換為鹵素,且可例如為CjHwXy,其中w+y=2j+1且X為鹵素,較佳為氟原子。具體例子如氯甲基、三氯甲基、三氟甲基或2-溴丙基,尤其為三氟甲基或三氯甲基。 The haloalkyl group having 1 to 4 carbon atoms is an alkyl group having a carbon number of 1 to 4 which is substituted by a halogen as defined below and which is as defined above. The alkyl group can be, for example, mono- or polyhalogenated until all hydrogen atoms are replaced by a halogen, and can be, for example, C j H w X y , wherein w+y=2j+1 and X is a halogen, preferably a fluorine atom. . Specific examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl.

該碳數為2至4之羥基烷基意指經一或兩個氧原子取代之碳數為2至4之烷基。烷基可為直鏈或支鏈。具體例子如2-羥基乙基、1-羥基乙基、1-羥基丙基、2-羥基丙基、3-羥基丙基、1-羥基丁基、4-羥基丁基、2-羥基丁基、3-羥基丁基、2,3-二羥基丙基或2,4-二羥基丁基。 The hydroxyalkyl group having 2 to 4 carbon atoms means an alkyl group having 2 to 4 carbon atoms which is substituted by one or two oxygen atoms. The alkyl group can be straight or branched. Specific examples are 2-hydroxyethyl, 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 4-hydroxybutyl, 2-hydroxybutyl , 3-hydroxybutyl, 2,3-dihydroxypropyl or 2,4-dihydroxybutyl.

該碳數為2至10之烷氧基烷基係經一O間雜之碳數為2至10之烷基。碳數為2至10之烷基具有與前述碳數為1至20之烷基的相同定義,且具有最高相應碳原子數。具體例子如甲氧基甲基、甲氧基乙基、甲氧基丙基、乙氧基甲基、乙氧基乙基、乙氧基丙基、丙氧基 甲基、丙氧基乙基、丙氧基丙基。 The alkoxyalkyl group having 2 to 10 carbon atoms is an alkyl group having 2 to 10 carbon atoms. The alkyl group having a carbon number of 2 to 10 has the same definition as the aforementioned alkyl group having 1 to 20 carbon atoms, and has the highest corresponding number of carbon atoms. Specific examples are methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxy Methyl, propoxyethyl, propoxypropyl.

該間雜有一或多個O、S、NE26或CO之碳數為2至20之烷基係例如經O、S、NE26或CO間雜1至9次、1至5次、1至3次、1次或2次。若存在一個以上的間雜基團,則其為相同種類或不同。兩個氧原子由至少一個亞甲基,較佳為至少兩個亞甲基(即伸乙基)隔開。該等烷基係直鏈或支鏈。舉例而言,將存在以下結構單元:-CH2-CH2-O-CH2CH3、-[CH2CH2O]y-CH3(其中y=1至9)、-(CH2-CH2O)7-CH2CH3、-CH2-CH(CH3)-O-CH2-CH2CH3、-CH2-CH(CH3)-O-CH2-CH3、-CH2-CH2-S-CH2CH3、-CH2-CH(CH3)-NE26-CH2-CH3、-CH2-CH2-COO-CH2CH3或-CH2-CH(CH3)-OCO-CH2-CH2CH3The alkyl group having one or more of O, S, NE 26 or CO having a carbon number of 2 to 20 is, for example, 1 to 9 times, 1 to 5 times, 1 to 3 times by O, S, NE 26 or CO. , 1 or 2 times. If more than one meso group is present, it is the same species or different. The two oxygen atoms are separated by at least one methylene group, preferably at least two methylene groups (i.e., exoethyl groups). These alkyl groups are linear or branched. For example, the following structural units will be present: -CH 2 -CH 2 -O-CH 2 CH 3 , -[CH 2 CH 2 O] y -CH 3 (where y = 1 to 9), -(CH 2 - CH 2 O) 7 -CH 2 CH 3 , -CH 2 -CH(CH 3 )-O-CH 2 -CH 2 CH 3 , -CH 2 -CH(CH 3 )-O-CH 2 -CH 3 ,- CH 2 -CH 2 -S-CH 2 CH 3 , -CH 2 -CH(CH 3 )-NE 26 -CH 2 -CH 3 , -CH 2 -CH 2 -COO-CH 2 CH 3 or -CH 2 - CH(CH 3 )-OCO-CH 2 -CH 2 CH 3 .

於本發明中,碳數為3至10之環烷基、碳數為3至10之環烷基及碳數為3至8之環烷基可理解為至少包含一個環之烷基。具體例子如環丙基、環丁基、環戊基、環己基、環辛基、戊基環戊基及環己基。於本發明中,碳數為3至10之環烷基亦涵蓋二環的例子,也就 是橋聯環,具體例子可例如,及 其他相應的環。其他具體例可例如為 (例如)或等結構,以及橋聯或稠合 環系統,舉例而言,此處之定義亦包含等結構,其中R10代表伸烷基,R11代表烷基。 In the present invention, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a cycloalkyl group having 3 to 8 carbon atoms are understood to be an alkyl group having at least one ring. Specific examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, pentylcyclopentyl and cyclohexyl. In the present invention, a cycloalkyl group having a carbon number of 3 to 10 also encompasses an example of a bicyclic ring, that is, a bridged ring, and specific examples can be, for example, , , , and other corresponding rings. Other specific examples can be, for example, , (E.g )or Equal structure, as well as bridging or fused ring systems, for example, the definition here also includes or And other structures wherein R 10 represents an alkylene group and R 11 represents an alkyl group.

該經O、S、NE26或CO間雜之碳數為3至20的環烷基具有與前述相同之定義,其中烷基至少一個-CH2-基團係替換為O、S、 NE26或CO。具體例子如(例如 等結構。 The cycloalkyl group having 3 to 20 carbon atoms between O, S, NE 26 or CO has the same definition as defined above, wherein at least one -CH 2 - group of the alkyl group is replaced by O, S, NE 26 or CO. Specific examples are as , , (E.g , or And other structures.

該碳數為1至8之烷基與碳數為3至10之環烷基鍵結所形成之基團係指經至少一個具有最多8個碳原子之烷基取代的如前述所 定義之碳數為3至10之環烷基。具體例子為等。 The group formed by the alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 3 to 10 carbon atoms means a carbon as defined above substituted with at least one alkyl group having at most 8 carbon atoms. The number is from 3 to 10 cycloalkyl groups. The specific example is or Wait.

該間雜有一或多個O之碳數為1至8的烷基與碳數為3至10之環烷基鍵結所形成之基團係指經至少一個具有最多8個碳原子之烷基取代的如前述所定義之間雜有一或多個O之碳數為3至10之環烷 基。具體例子如等。 The group formed by the one or more alkyl groups having 1 to 8 carbon atoms bonded to a cycloalkyl group having 3 to 10 carbon atoms is substituted by at least one alkyl group having up to 8 carbon atoms. One or more of the cycloalkyl groups having a carbon number of from 3 to 10 are defined as defined above. Specific examples are as or Wait.

該碳數為1至12的烷氧基係經一個氧原子取代之碳數為1至12的烷基。碳數為1至12的烷基具有如前述碳數為1至20的烷基的相同定義,且具有最高相應的碳原子數。碳數為1至4的烷氧基係直鏈或支鏈,例如甲氧基、乙氧基、丙氧基、異丙氧基、正丁氧基、第二丁氧基、異丁氧基或第三丁氧基。碳數為1至8的烷氧基和碳數為1至4之烷氧基係與前述定義相同,且具有最高相應的碳原子數。 The alkoxy group having 1 to 12 carbon atoms is an alkyl group having 1 to 12 carbon atoms which is substituted with one oxygen atom. The alkyl group having a carbon number of 1 to 12 has the same definition of the alkyl group having a carbon number of 1 to 20 as described above, and has the highest corresponding number of carbon atoms. The alkoxy group having a carbon number of 1 to 4 is a straight chain or a branched chain, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a n-butoxy group, a second butoxy group, an isobutoxy group. Or a third butoxy group. The alkoxy group having 1 to 8 carbon atoms and the alkoxy group having 1 to 4 carbon atoms are the same as defined above, and have the highest corresponding number of carbon atoms.

該碳數為1至12之烷基硫基係經一個硫原子取代之碳數為1至12之烷基。該碳數為1至12的烷基具有如前述碳數為1至20的烷基的相同定義,且具有最高相應的碳原子數。碳數為1至4的烷基硫基係直鏈或支鏈,例如甲基硫基、乙基硫基、丙基硫基、異丙基硫基、正丁基硫基、第二丁基硫基、異丁基硫基、第三丁基硫基。 The alkylthio group having 1 to 12 carbon atoms is an alkyl group having 1 to 12 carbon atoms which is substituted by a sulfur atom. The alkyl group having 1 to 12 carbon atoms has the same definition as the above-mentioned alkyl group having 1 to 20 carbon atoms, and has the highest corresponding number of carbon atoms. An alkylthio group having a carbon number of 1 to 4 is a straight chain or a branched chain, such as a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, an n-butylthio group, a second butyl group. Sulfur, isobutylthio, tert-butylthio.

該苯基-R5可例如為芐基、苯基乙基、α-甲基苄基或 α,α-二甲基-苄基,尤其為苄基。 The phenyl-R 5 may, for example, be benzyl, phenylethyl, α -methylbenzyl or α , α -dimethyl-benzyl, especially benzyl.

該苯基-R8可例如為苄氧基、苯基乙氧基、α-甲基苄氧基或α,α-二甲基苄氧基,尤其為苄氧基。 The phenyl-R 8 may, for example, be a benzyloxy group, a phenylethoxy group, an α -methylbenzyloxy group or an α , α -dimethylbenzyloxy group, especially a benzyloxy group.

該碳數為2至12之烯基係單-或多不飽和且係例如為碳數為2至10之烯基、碳數為2至8之烯基、碳數為2至5之烯基。具體例子如乙烯基、烯丙基、甲基烯丙基、1,1-二甲基烯丙基、1-丁烯基、3-丁烯基、2-丁烯基、1,3-戊二烯基、5-己烯基、7-辛烯基或十二烯基,尤其為烯丙基。碳數為2至5之烯基具有如前述碳數為2至12的烯基的相同定義,且具有最高相應的碳原子數。 The alkenyl group having 2 to 12 carbon atoms is mono- or polyunsaturated and is, for example, an alkenyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms. . Specific examples are vinyl, allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentyl Dienyl, 5-hexenyl, 7-octenyl or dodecenyl, especially allyl. The alkenyl group having 2 to 5 carbon atoms has the same definition of the alkenyl group having a carbon number of 2 to 12 as described above, and has the highest corresponding number of carbon atoms.

間雜有一或多個O、S、NE26或CO之碳數為2至12之烯基係例如經O、S、NE26或CO間雜1至9次、1至5次、1至3次、1次或2次。若存在一個以上的間雜基團,則其為相同種類或不同。兩個氧原子由至少一個亞甲基,較佳為至少兩個亞甲基(即伸乙基)隔開。烯基係直鏈或支鏈且如前述所定義。舉例而言,可形成以下結構單元:-CH=CH-O-CH2CH3、-CH=CH-O-CH=CH2等。 An alkenyl group having one or more O, S, NE 26 or CO having a carbon number of 2 to 12, for example, 1 to 9 times, 1 to 5 times, 1 to 3 times by O, S, NE 26 or CO, 1 or 2 times. If more than one meso group is present, it is the same species or different. The two oxygen atoms are separated by at least one methylene group, preferably at least two methylene groups (i.e., exoethyl groups). The alkenyl group is straight or branched and is as defined above. For example, the following structural units can be formed: -CH=CH-O-CH 2 CH 3 , -CH=CH-O-CH=CH 2 and the like.

該碳數為4至8的環烯基具有至少一雙鍵,且可例如為碳數為4至6之環烯基或碳數為6至8之環烯基。具體例子如環丁烯基、環戊烯基、環己烯基或環辛烯基,尤其為環戊烯基及環己烯基,較佳為環己烯基。 The cycloalkenyl group having 4 to 8 carbon atoms has at least one double bond, and may be, for example, a cycloalkenyl group having 4 to 6 carbon atoms or a cycloalkenyl group having 6 to 8 carbon atoms. Specific examples are cyclobutenyl, cyclopentenyl, cyclohexenyl or cyclooctenyl, especially cyclopentenyl and cyclohexenyl, preferably cyclohexenyl.

該碳數為3至6之烯氧基係單或多不飽和,且具有如前述烯基之定義的其中一者,且附接氧基具有最高相應的碳原子數。具體例子如烯丙氧基、甲基烯丙氧基、丁烯氧基、戊烯氧基、1,3-戊二烯氧基、5-己烯氧基。 The alkenyloxy group having a carbon number of 3 to 6 is mono- or polyunsaturated, and has one of the definitions of the alkenyl group as described above, and the attached oxy group has the highest corresponding number of carbon atoms. Specific examples are allyloxy, methallyloxy, butenyloxy, pentenyloxy, 1,3-pentadienyloxy, 5-hexenyloxy.

該碳數為2至12之炔基為單或多不飽和直鏈或支鏈,且可例如為碳數為2至8之炔基、碳數為2至6之炔基或碳數為2至4之炔基。具體例子如乙炔基、丙炔基、丁炔基、1-丁炔基、3-丁炔基、2- 丁炔基、戊炔基己炔基、2-己炔基、5-己炔基、辛炔基等。 The alkynyl group having 2 to 12 carbon atoms is a mono- or polyunsaturated linear or branched chain, and may, for example, be an alkynyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 6 carbon atoms or a carbon number of 2 Alkynyl group to 4. Specific examples are ethynyl, propynyl, butynyl, 1-butynyl, 3-butynyl, 2- Butynyl, pentynylhexynyl, 2-hexynyl, 5-hexynyl, octynyl and the like.

該碳數為2至20之烷醯基係直鏈或支鏈,且可例如為碳數為2至18、碳數為2至14、碳數為2至12、碳數為2至8、碳數為2至6或碳數為2至4之烷醯基或碳數為4至12或碳數為4至8之烷醯基。具體例子如乙醯基、丙醯基、丁醯基、異丁醯基、戊醯基、己醯基、庚醯基、辛醯基、壬醯基、癸醯基、十二醯基、十四醯基、十五醯基、十六醯基、十八醯基、二十醯基,較佳為乙醯基。碳數為1至8之烷醯基具有如前述之碳數為2至20之烷醯基相同的定義,且具有最高相應碳原子數。 The alkane group having a carbon number of 2 to 20 is linear or branched, and may have, for example, a carbon number of 2 to 18, a carbon number of 2 to 14, a carbon number of 2 to 12, and a carbon number of 2 to 8. An alkanoyl group having a carbon number of 2 to 6 or a carbon number of 2 to 4 or an alkanoyl group having a carbon number of 4 to 12 or a carbon number of 4 to 8. Specific examples are, for example, ethyl, propyl, butyl, isobutyl, pentylene, hexyl, decyl, octyl, fluorenyl, fluorenyl, fluorenyl, tetradecyl, fifteen Sulfhydryl, hexadecanyl, octadecyl, and decyl, preferably acetyl. The alkylhydrazine group having a carbon number of 1 to 8 has the same definition as the alkynylene group having a carbon number of 2 to 20 as described above, and has the highest corresponding number of carbon atoms.

該碳數為2至12之烷氧基羰基係直鏈或支鏈,且係例如甲氧基羰基、乙氧基羰基、丙氧基羰基、正丁氧基羰基、異丁氧基羰基、1,1-二甲基丙氧基羰基、戊氧基羰基、己氧基羰基、庚氧基羰基、辛氧基羰基、壬氧基羰基、癸氧基羰基或十二氧基羰基,尤其為甲氧基羰基、乙氧基羰基、丙氧基羰基、正丁氧基羰基或異丁氧基羰基,較佳為甲氧基羰基。 The alkoxycarbonyl group having 2 to 12 carbon atoms is linear or branched, and is, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a n-butoxycarbonyl group, an isobutoxycarbonyl group, and 1 , 1-dimethylpropoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl, especially A The oxycarbonyl group, the ethoxycarbonyl group, the propoxycarbonyl group, the n-butoxycarbonyl group or the isobutoxycarbonyl group is preferably a methoxycarbonyl group.

該間雜有一或多個O之碳數為2至12之烷氧基羰基可為直鏈或支鏈。兩個氧原子由至少兩個亞甲基(即伸乙基)隔開。該經間雜之烷氧基羰基未經取代或經一或多個羥基取代。碳數為6至20之芳氧基羰基可例如為苯基氧基羰基(=苯基-O-(CO)O-)、萘氧基羰基、蒽氧基羰基等。碳數為5至20之雜芳基羰基可為與-O-CO-鍵結之碳數為5至20之雜芳基。 The alkoxycarbonyl group having one or more carbon atoms of 2 to 12 may be linear or branched. The two oxygen atoms are separated by at least two methylene groups (ie, ethyl groups). The meta-alkyloxycarbonyl group is unsubstituted or substituted with one or more hydroxyl groups. The aryloxycarbonyl group having a carbon number of 6 to 20 may, for example, be a phenyloxycarbonyl group (=phenyl-O-(CO)O-), a naphthyloxycarbonyl group, a decyloxycarbonyl group or the like. The heteroarylcarbonyl group having a carbon number of 5 to 20 may be a heteroaryl group having a carbon number of 5 to 20 bonded to -O-CO-.

該碳數為3至10之環烷基羰基可為與CO鍵結之碳數為3至10之環烷基,其中環烷基具有與前述相同之定義,且具有最高相應的碳原子數。間雜有一或多個O、S、NE26或CO之碳數為3至10之環烷基羰基係指經間雜的與CO鍵結之環烷基,其中經間雜的環烷基具有與前述相同之定義。 The cycloalkylcarbonyl group having a carbon number of 3 to 10 may be a cycloalkyl group having a carbon number of 3 to 10 bonded to the CO, wherein the cycloalkyl group has the same definition as described above and has the highest corresponding number of carbon atoms. A cycloalkylcarbonyl group having one or more carbon atoms of 3 to 10 in the group consisting of O, S, NE 26 or CO means a heterocyclic CO-bonded cycloalkyl group, wherein the heterocyclic cycloalkyl group has the same The definition.

該碳數為3至10之環烷氧基羰基可為與-O-(CO)-鍵結之碳數為3至10之環烷基,其中環烷基具有與前述相同之定義,且具有最高相應的碳原子數。間雜有一或多個O、S、NE26或CO之碳數為3至10之環烷氧基羰基係指經間雜的與-O-(CO)-鍵結之環烷基,其中經間雜的環烷基具有與前述相同之定義。 The cycloalkoxycarbonyl group having 3 to 10 carbon atoms may be a cycloalkyl group having a carbon number of 3 to 10 bonded to -O-(CO)-, wherein the cycloalkyl group has the same definition as described above and has The highest corresponding number of carbon atoms. A cycloalkoxycarbonyl group having one or more O, S, NE 26 or CO having a carbon number of 3 to 10 is a hetero- and -O-(CO)-bonded cycloalkyl group, wherein The cycloalkyl group has the same definition as described above.

該碳數為1至20之烷基苯基係指經至少一個烷基取代之苯基,其中碳原子之總合最多為20。 The alkylphenyl group having 1 to 20 carbon atoms means a phenyl group substituted with at least one alkyl group, wherein the total of the carbon atoms is at most 20.

該碳數為6至20之芳基可例如為苯基、萘基、蒽基、菲基、芘基、1,2-苯並菲基、并四苯基、聯伸三苯基等,尤其為苯基或萘基,較佳為苯基。萘基係1-萘基或2-萘基。 The aryl group having 6 to 20 carbon atoms may, for example, be a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an anthracenyl group, a 1,2-benzophenanthrenyl group, a tetraphenylene group, a co-triphenyl group, etc., especially Phenyl or naphthyl, preferably phenyl. Naphthyl 1-naphthyl or 2-naphthyl.

在本發明之光起始劑(E-1)之內容中,該碳數為3至20之雜芳基包含單環或多環系統,例如稠合環系統。具體例為噻吩基、苯并[b]噻吩基、萘并[2,3-b]噻吩基、噻蒽基、呋喃基、二苯并呋喃基、唏基、呫噸基、噻噸基、啡噁噻基、吡咯基、咪唑基、吡唑基、吡嗪基、嘧啶基、噠嗪基、中氮茚基、異吲哚基、吲哚基、吲唑基、嘌呤基、喹嗪基、異喹啉基、喹啉基、酞嗪基、萘啶基、喹噁啉基、喹唑啉基、啉基、喋啶基、咔唑基、β-哢啉基、菲啶基、吖啶基、萘嵌間二氮苯基、菲咯啉基、吩嗪基、異噻唑基、吩噻嗪基、異噁唑基、呋呫基、吩噁基、7-菲基、蒽醌-2-基(=9,10-二側氧基-9,10-二氫蒽-2-基)、3-苯并[b]噻吩基、5-苯并[b]噻吩基、2-苯并[b]噻吩基、4-二苯并呋喃基、4,7-二苯并呋喃基、4-甲基-7-二苯并呋喃基、2-呫噸基、8-甲基-2-呫噸基、3-呫噸基、2-啡噁噻基、2,7-啡噁噻基、2-吡咯基、3-吡咯基、5-甲基-3-吡咯基、2-咪唑基、4-咪唑基、5-咪唑基、2-甲基-4-咪唑基、2-乙基-4-咪唑基、2-乙基-5-咪唑基、1H-四唑-5-基、3-吡唑基、1-甲基-3-吡唑基、1-丙基-4-吡唑基、2-吡嗪基、5,6-二甲基-2-吡嗪基、2-中氮茚基、2-甲基-3-異吲哚基、2-甲 基-1-異吲哚基、1-甲基-2-吲哚基、1-甲基-3-吲哚基、1,5-二甲基-2-吲哚基、1-甲基-3-吲唑基、2,7-二甲基-8-嘌呤基、2-甲氧基-7-甲基-8-嘌呤基、2-喹嗪基、3-異喹啉基、6-異喹啉基、7-異喹啉基、3-甲氧基-6-異喹啉基、2-喹啉基、6-喹啉基、7-喹啉基、2-甲氧基-3-喹啉基、2-甲氧基-6-喹啉基、6-酞嗪基、7-酞嗪基、1-甲氧基-6-酞嗪基、1,4-二甲氧基-6-酞嗪基、1,8-萘啶-2-基、2-喹噁啉基、6-喹噁啉基、2,3-二甲基-6-喹噁啉基、2,3-二甲氧基-6-喹噁啉基、2-喹唑啉基、7-喹唑啉基、2-二甲基胺基-6-喹唑啉基、3-啉基、6-啉基、7-啉基、3-甲氧基-7-啉基、2-喋啶基、6-喋啶基、7-喋啶基、6,7-二甲氧基-2-喋啶基、2-咔唑基、3-咔唑基、9-甲基-2-咔唑基、9-甲基-3-咔唑基、β-哢啉-3-基、1-甲基-β-哢啉-3-基、1-甲基-β-哢啉-6-基、3-菲啶基、2-吖啶基、3-吖啶基、2-萘嵌間二氮苯基、1-甲基-5-萘嵌間二氮苯基、5-菲咯啉基、6-菲咯啉基、1-吩嗪基、2-吩嗪基、3-異噻唑基、4-異噻唑基、5-異噻唑基、2-吩噻嗪基、3-吩噻嗪基、10-甲基-3-吩噻嗪基、3-異噁唑基、4-異噁唑基、5-異噁唑基、4-甲基-3-呋呫基、2-吩噁基、10-甲基-2-吩噁基等。 In the context of the photoinitiator (E-1) of the present invention, the heteroaryl group having a carbon number of from 3 to 20 comprises a monocyclic or polycyclic system such as a fused ring system. Specific examples are thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thioxyl, furyl, dibenzofuranyl, Sulfhydryl, xanthenyl, thioxanthyl, phenothiphenyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, carbazinyl, isodecyl, fluorenyl , carbazolyl, fluorenyl, quinazolyl, isoquinolyl, quinolyl, pyridazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, Polinyl, acridinyl, oxazolyl, β-carbolinyl, phenanthryl, acridine, naphthyldiazophenyl, phenanthroline, phenazinyl, isothiazolyl, phenothiazine , isoxazolyl, furazolyl, phenomethoxy, 7-phenanthryl, inden-2-yl (=9,10-di-oxy-9,10-dihydroindol-2-yl), 3 -benzo[b]thienyl, 5-benzo[b]thienyl, 2-benzo[b]thienyl, 4-dibenzofuranyl, 4,7-dibenzofuranyl, 4-methyl Base-7-dibenzofuranyl, 2-xanthene, 8-methyl-2-indenyl, 3-indolyl, 2-morphothinyl, 2,7-morphothinyl, 2 -pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-4 -Imidazolyl, 2-ethyl-5-imidazolyl, 1H-tetrazol-5-yl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl-4-pyrazolyl , 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindole , 1-methyl-2-indenyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indenyl, 1-methyl-3-oxazolyl, 2 ,7-dimethyl-8-fluorenyl, 2-methoxy-7-methyl-8-fluorene , 2-quinazinyl, 3-isoquinolinyl, 6-isoquinolinyl, 7-isoquinolyl, 3-methoxy-6-isoquinolinyl, 2-quinolinyl, 6- Quinolinyl, 7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolinyl, 6-pyridazinyl, 7-pyridazinyl, 1-methoxy -6-oxazinyl, 1,4-dimethoxy-6-pyridazinyl, 1,8-naphthyridin-2-yl, 2-quinoxalinyl, 6-quinoxalinyl, 2, 3-Dimethyl-6-quinoxalinyl, 2,3-dimethoxy-6-quinoxalinyl, 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino -6-quinazolinyl, 3- Lolinyl, 6- Olinyl group, 7- Lolinyl, 3-methoxy-7- Lolinyl, 2-acridinyl, 6-acridinyl, 7-acridinyl, 6,7-dimethoxy-2-acridinyl, 2-oxazolyl, 3-oxazolyl, 9- Methyl-2-oxazolyl, 9-methyl-3-oxazolyl, β-carboline-3-yl, 1-methyl-β-carboline-3-yl, 1-methyl-β- Porphyrin-6-yl, 3-phenanthryl, 2-acridinyl, 3-acridinyl, 2-naphthyldiazophenyl, 1-methyl-5-naphthyldiazophenyl, 5-phenanthroline, 6-phenanthroline, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazine , 3-phenothiazine, 10-methyl-3-phenothiazinyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 4-methyl-3-furazan Base, 2-oxo group, 10-methyl-2-phenoxy group, and the like.

較佳地,該碳數為3至20之雜芳基可為噻吩基、苯并[b]噻吩基、噻蒽基、噻噸基、1-甲基-2-吲哚基或1-甲基-3-吲哚基。更佳地,碳數為3至20之雜芳基可為噻吩基。 Preferably, the heteroaryl group having a carbon number of 3 to 20 may be a thienyl group, a benzo[b]thienyl group, a thioxanyl group, a thioxanthyl group, a 1-methyl-2-indenyl group or a 1-methyl group. Base-3-mercapto. More preferably, the heteroaryl group having a carbon number of 3 to 20 may be a thienyl group.

該碳數為4至20之雜芳基羰基係經由CO基團連接至分子其餘部分之如前述所定義之碳數為3至20之雜芳基。 The heteroarylcarbonyl group having 4 to 20 carbon atoms is a heteroaryl group having a carbon number of 3 to 20 as defined above, which is bonded to the remainder of the molecule via a CO group.

該經取代之芳基(苯基、萘基、碳數為6至20之芳基或碳數為5至20之雜芳基)係分別經1至7次、1至6次或1至4次,較佳地係經1次、2次或3次取代。所定義之芳基不能具有比芳基環上的自由位置為多之取代基。 The substituted aryl group (phenyl, naphthyl, aryl having 6 to 20 carbon atoms or heteroaryl having 5 to 20 carbon atoms) is 1 to 7 times, 1 to 6 times or 1 to 4, respectively. Preferably, it is substituted by 1, 2 or 3 times. The aryl group defined cannot have more substituents than the free position on the aryl ring.

該苯基環上之取代基較佳在苯基環上之位置4中或呈 3,4-、3,4,5-、2,6-、2,4-或2,4,6-組態。 The substituent on the phenyl ring is preferably in position 4 on the phenyl ring or 3,4-, 3,4,5-, 2,6-, 2,4- or 2,4,6-configuration.

該經至少一次間雜之基團係經間雜例如1至19次、1至15次、1至12次、1至9次、1至7次、1至5次、1至4次、1至3次或1次或2次(間雜原子數取決於擬間雜之碳原子數的多寡)。經至少一次取代之基團具有例如1至7個、1至5個、1至4個、1至3個或1個或2個相同或不同取代基。 The at least one heterozygous group is intermixed, for example, 1 to 19 times, 1 to 15 times, 1 to 12 times, 1 to 9 times, 1 to 7 times, 1 to 5 times, 1 to 4 times, 1 to 3 Second or one or two times (the number of heteroatoms depends on the number of carbon atoms in the interphase). The group substituted at least once has, for example, 1 to 7, 1 to 5, 1 to 4, 1 to 3 or 1 or 2 identical or different substituents.

經如上述所定義之該至少一取代基取代之基團係指具有至少一個相同或不同的取代基。鹵素係氟、氯、溴及碘,較佳為氟、氯及溴,更佳為氟及氯。 A group substituted with the at least one substituent as defined above means having at least one substituent which is the same or different. Halogen is fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine, more preferably fluorine and chlorine.

舉例來說,若E1及E2、E2及E3、E3及E4或E5及R6、E6及 E7、E7及E8分別獨立地為,則形成例如下式(IIIa)至式(IIIi)所示之結構,其中以式(IIIa)之結構為較佳。 For example, if E 1 and E 2 , E 2 and E 3 , E 3 and E 4 or E 5 and R 6 , E 6 and E 7 , E 7 and E 8 are each independently Then, for example, a structure represented by the following formula (IIIa) to formula (IIIi) is formed, and a structure of the formula (IIIa) is preferred.

,其中以式(IIIa)之結構為較佳。 Among them, the structure of the formula (IIIa) is preferred.

該式(III)的化合物之特徵在於至少一個苯基環與咔唑部分稠合,以形成「萘基」環。亦即上述式(IIIa)至式(IIIi)之結構中之一者係根據式(III)所繪示。 The compound of formula (III) is characterized in that at least one phenyl ring is partially fused to the carbazole to form a "naphthyl" ring. That is, one of the structures of the above formula (IIIa) to formula (IIIi) is depicted according to formula (III).

若E1及E2、E2及E3、E3及E4或E5及R6、E6及E7、E7及E8 分別獨立地為-(CH2)p-W-(CH2)q-,則形成例如等結構。 If E 1 and E 2 , E 2 and E 3 , E 3 and E 4 or E 5 and R 6 , E 6 and E 7 , E 7 and E 8 are each independently -(CH 2 ) p -W-( CH 2 ) q -, for example, or And other structures.

若苯基或萘基環上之取代基OE17、SE18、SOE18、SO2E18或NE19E20經由基團E17、E18、E19及/或E20與萘基環之一個碳原子形成五員或六員環,則獲得包含3個或更多個環(包括萘基環)之 結構。具體例子可例如為 If the substituent OE 17 , SE 18 , SOE 18 , SO 2 E 18 or NE 19 E 20 on the phenyl or naphthyl ring is via the groups E 17 , E 18 , E 19 and/or E 20 and the naphthyl ring When a carbon atom forms a five- or six-membered ring, a structure comprising three or more rings (including a naphthyl ring) is obtained. Specific examples can be, for example,

若E17與具有之基團的苯基或萘基環之一個碳原子形成單鍵,則形成例如 等結構。 If E 17 has or One of the carbon atoms of the phenyl or naphthyl ring of the group forms a single bond, for example, or And other structures.

若E16係經SE18取代之苯基,其中E18表示鍵結至具有COE16之咔唑部分的苯基或萘基環的單鍵,所形成之結構可例如為 。亦即,若E16係經SE18取代之苯基,其中基團E18表示鍵結至具有COE16之咔唑部分之苯基或萘基環的單鍵,而形成同時具有噻噸基部分與咔唑部分之一個苯基或萘基環。 If E 16 is a phenyl group substituted by SE 18 , wherein E 18 represents a single bond bonded to a phenyl or naphthyl ring having a carbazole moiety of COE 16 , the structure formed may be, for example, , . That is, if E 16 is a phenyl group substituted by SE 18 , wherein the group E 18 represents a single bond bonded to a phenyl or naphthyl ring having a carbazole moiety of COE 16 , and is formed to have a thioxyl moiety at the same time. a phenyl or naphthyl ring with a carbazole moiety.

若E19及E20係與所鍵結之氮原子一起形成未經間雜或間雜有O、S或NE17之五員或六員飽和或不飽和環,則所形成之飽和或不飽和環可例如為氮丙啶、吡咯、噻唑、吡咯啶、噁唑、吡啶、1,3-二嗪、1,2-二嗪、六氫吡啶或嗎啉。較佳地,若E19及E20係與所鍵結之氮原子一起形成未經間雜或間雜有O、S或NE17之五員或六員飽和或不飽和環,則形成未經間雜或間雜有O或NE17、尤其O之五員或六 員飽和環。 If E 19 and E 20 are formed together with the bonded nitrogen atom to form a five- or six-membered saturated or unsaturated ring without O or S, or N, S or NE 17 , the saturated or unsaturated ring may be formed. For example, aziridine, pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, hexahydropyridine or morpholine. Preferably, if E 19 and E 20 are formed together with the bonded nitrogen atom to form a five- or six-membered saturated or unsaturated ring without O or S, or N, S or NE 17 There are five or six member saturated rings of O or NE 17 , especially O.

若E21及E22係與所鍵結之氮原子一起形成未經間雜或間雜有O、S或NE26之五員或六員飽和或不飽和環,且苯環選擇性地與該飽和或不飽和環稠合,則所形成之飽和或不飽和環可例如為氮丙啶、吡咯、噻唑、吡咯啶、噁唑、吡啶、1,3-二嗪、1,2-二嗪、六氫 吡啶或嗎啉或相應成環(例如)。 If E 21 and E 22 together with the bonded nitrogen atom form a five- or six-membered saturated or unsaturated ring which is unintermixed or intermixed with O, S or NE 26 , and the benzene ring is selectively saturated with or When the unsaturated ring is fused, the saturated or unsaturated ring formed may be, for example, aziridine, pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, hexahydro Pyridine or morpholine or corresponding ring formation (eg ).

若E19及E20係與所鍵結之氮原子一起形成雜芳香族環系統,則雜芳香族環系統係指包含一個以上的環(例如2個或3個環)以及來自相同種類或不同種類之一個或一個以上雜原子。適合的雜原子可例如為N、S、O或P、尤其N、S或O。具體例子如咔唑、吲哚、異吲哚、吲唑、嘌呤、異喹啉、喹啉、哢啉、吩噻嗪等。 If E 19 and E 20 form a heteroaromatic ring system together with the bonded nitrogen atom, the heteroaromatic ring system means more than one ring (for example 2 or 3 rings) and from the same species or different One or more heteroatoms of the species. Suitable heteroatoms can be, for example, N, S, O or P, especially N, S or O. Specific examples are carbazole, anthracene, isoindole, carbazole, anthracene, isoquinoline, quinoline, porphyrin, phenothiazine and the like.

所述之「及/或」或「或/及」在本發明上下文中係表示不僅可存在所定義之取代基中的一者,而且可存在總共若干所定義之取代基,即不同替代物(取代基)之混合物。 The phrase "and/or" or "or/and" in the context of the present invention means that not only one of the defined substituents may be present, but also a plurality of defined substituents, ie, different substitutes. a mixture of substituents).

所述之「至少」係定義一者或一者以上,例如一者或兩者或三者、較佳一者或兩者。 By "at least" it is meant to define one or more, such as one or both or three, preferably one or both.

在整個本說明書及下文之申請專利範圍中,除非上下文另有要求,否則詞語「包含(comprise)」或變體(例如,「comprises」或「comprising」)應理解為暗指包括所述整數或步驟或整數群組或步驟群組,但並不排除任一其他整數或步驟或整數群組或步驟群組。所述之「(甲基)丙烯酸酯」在本發明上下文中意欲指丙烯酸酯以及相應甲基丙烯酸酯。 Throughout this specification and the claims below, the words "comprise" or variant (eg, "comprises" or "comprising") are understood to include the integer or A step or integer group or group of steps, but does not exclude any other integer or step or integer group or group of steps. The term "(meth)acrylate" as used in the context of the present invention is intended to mean the acrylate and the corresponding methacrylate.

本發明上下文中用於本發明化合物之文字中所示較佳者意欲指所有申請專利範圍類別,亦即亦指針對組合物、用途、方 法、彩色濾光片等之申請專利範圍。 The preferred embodiments shown in the text for the compounds of the present invention in the context of the present invention are intended to refer to all categories of claims, i.e., also to compositions, uses, and Patent application scope of laws, color filters, etc.

該式(III)所示之肟酯係藉由習知的方法製備,例如藉由在以下條件下使相應的肟與醯鹵,特別是氯化物或酸酐反應:在惰性溶劑(例如:第三丁基甲基醚、四氫呋喃(THF)或二甲基甲醯胺)中,在鹼(例如三乙胺或吡啶)存在時,或在鹼性溶劑(例如吡啶)中。在本發明之一實施例中,如式(IIIa)之化合物係以下列式(i)所示之方 法製備,其中E7係肟酯基團()且Z1係單鍵。而如式(IIIb)至式(IIIh)所示之化合物係以相同方法製備,但選用適合的肟來進行。 The oxime esters of the formula (III) are prepared by a conventional method, for example, by reacting the corresponding hydrazine with a hydrazine halide, particularly a chloride or an acid anhydride, under the following conditions: in an inert solvent (for example: third In butyl methyl ether, tetrahydrofuran (THF) or dimethylformamide, in the presence of a base such as triethylamine or pyridine, or in a basic solvent such as pyridine. In one embodiment of the invention, the compound of formula (IIIa) is prepared by the process of formula (i) wherein the E 7 is a decyl ester group ( And Z 1 is a single bond. While the compounds of the formula (IIIb) to the formula (IIIh) are prepared in the same manner, a suitable hydrazine is used.

於式(i)中,E1、E2、E5、E6、E8、E13、E14及E15係如前述所定義,X意指鹵素原子,尤其為氯原子。 In the formula (i), E 1 , E 2 , E 5 , E 6 , E 8 , E 13 , E 14 and E 15 are as defined above, and X means a halogen atom, especially a chlorine atom.

較佳地,E14為甲基。 Preferably, E 14 is a methyl group.

上述如式(i)所示之反應為於本技術領域具有通常知識者熟知,且通常在-15℃至+50℃之溫度下實施,較佳地係於0℃至25℃之溫度下實施。 The above reaction represented by the formula (i) is well known to those skilled in the art and is usually carried out at a temperature of from -15 ° C to +50 ° C, preferably at a temperature of from 0 ° C to 25 ° C. .

當Z1係CO時,相對應的肟係藉由用亞硝酸烷基酯(例如亞硝酸甲酯、亞硝酸乙酯、亞硝酸丙酯、亞硝酸丁酯或亞硝酸異戊酯)將亞甲基亞硝化來合成。然後,酯化係在與前述相同之條件下實施,詳細之製備方式係如式(ii)所示。 When Z 1 is CO, the corresponding lanthanide is obtained by using an alkyl nitrite (such as methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite or isoamyl nitrite). Methyl nitrosation to synthesize. Then, the esterification is carried out under the same conditions as described above, and the detailed preparation is as shown in the formula (ii).

因此,可藉由在鹼或鹼之混合物存在下使相應肟化合 物與如之醯鹵或如之酸酐反應,以製得如上述所定義式(III)的化合物,其中X為鹵素原子,且特別是氯原子,而E14之定義悉如前述。 Therefore, the corresponding hydrazine compound can be obtained by, for example, in the presence of a mixture of a base or a base. Halogen or as The anhydride is reacted to produce a compound of formula (III) as defined above wherein X is a halogen atom, and particularly a chlorine atom, and E 14 is as defined above.

所需作為起始材料之肟可藉由標準化學教材(例如J.March,Advanced Organic Chemistry,第4版,Wiley Interscience,1992)或專著(例如S.R.Sandler & W.Karo,Organic functional group preparations,第3卷,Academic Press)中所述多種方法來獲得。 The desired starting material can be obtained by standard chemistry textbooks (eg J. March, Advanced Organic Chemistry, 4th edition, Wiley Interscience, 1992) or monographs (eg SRSandler & W. Karo, Organic functional group preparations, A variety of methods are described in Volume 3, Academic Press).

最便利的一種方法係(例如)在極性溶劑(例如二甲基乙醯胺(DMA)、DMA水溶液、乙醇或乙醇水溶液)中使醛或酮與羥胺或其鹽反應。在此情形下,添加諸如乙酸鈉或吡啶等鹼來控制反應混合物之pH。眾所周知,反應速度具有pH依賴性,且可在開始時或在反應期間連續地添加鹼。亦可使用諸如吡啶等鹼性溶劑作為鹼及/或溶劑或共溶劑。反應溫度通常為室溫至混合物之回流溫度,一般為約20℃至120℃。 One of the most convenient methods is, for example, reacting an aldehyde or a ketone with hydroxylamine or a salt thereof in a polar solvent such as dimethylacetamide (DMA), aqueous DMA, ethanol or an aqueous ethanol solution. In this case, a base such as sodium acetate or pyridine is added to control the pH of the reaction mixture. It is well known that the reaction rate is pH dependent and the base can be added continuously at the beginning or during the reaction. An alkaline solvent such as pyridine can also be used as the base and/or solvent or co-solvent. The reaction temperature is usually from room temperature to the reflux temperature of the mixture, and is usually from about 20 ° C to 120 ° C.

相應酮中間體係(例如)藉由文獻(例如標準化學教材,例如J.March,Advanced Organic Chemistry,第4版,Wiley Interscience,1992)中所述方法來製備。另外,連續弗裏德-克拉夫茨 反應(Friedel-Crafts reaction)可有效用於合成中間體。此等反應為彼等熟習此項技術者所熟知。 The corresponding ketone intermediate system, for example, is prepared by methods described in the literature (e.g., standard chemistry textbooks, e.g., J. March, Advanced Organic Chemistry, 4th Ed., Wiley Interscience, 1992). In addition, continuous Fried-Krafts The Friedel-Crafts reaction is effective for the synthesis of intermediates. Such reactions are well known to those skilled in the art.

肟之另一便利合成係用亞硝酸或亞硝酸烷基酯將「活性」亞甲基亞硝化。鹼性條件(如(例如)Organic Syntheses coll.第VI卷(J.Wiley & Sons,New York,1988),第199頁及第840頁中所述)與酸性條件(如(例如)Organic Synthesis coll.第V卷,第32頁及第373頁,coll.第III卷,第191頁及第513頁,coll.第II卷,第202頁、第204頁及第363頁中所述)二者適於製備在本發明中用作起始材料之肟。一般自亞硝酸鈉產生亞硝酸。亞硝酸烷基酯可為(例如)亞硝酸甲酯、亞硝酸乙酯、亞硝酸丙酯、亞硝酸丁酯或亞硝酸異戊酯。 Another convenient synthesis of hydrazine is the nitrosation of "active" methylene groups with nitrous acid or alkyl nitrite. Basic conditions (as described, for example, in Organic Syntheses coll., Volume VI (J. Wiley & Sons, New York, 1988), pages 199 and 840) and acidic conditions (eg, for example, Organic Synthesis coll Volume V, pages 32 and 373, coll. Volume III, pages 191 and 513, coll. Volume II, pages 202, 204 and 363) It is suitable for the preparation of hydrazine used as a starting material in the present invention. Nitrous acid is generally produced from sodium nitrite. The alkyl nitrite can be, for example, methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite or isoamyl nitrite.

在另一實施例中,光起始劑(E-1)為游離式肟化合物,且具有如下式(IIIA)所示之結構: In another embodiment, the photoinitiator (E-1) is a free hydrazine compound and has the structure shown by the following formula (IIIA):

於式(IIIA)中,E1、E2、E3、E4、E5、E6、E7及E8分別獨立 代表氫原子、碳數為1至20之烷基、、COE16、OE17、 鹵素原子、NO2;或E1及E2、E2及E3、E3及E4、E5及E6、E6及E7或E7及E8分別獨 立代表經取代之碳數為2至10之烯基,或E1及E2、 E2及E3、E3及E4、E5及E6、E6及E7或E7及E8分別獨立地共同代表-(CH2)p-W-(CH2)q-;或E1及E2、E2及E3、E3及E4、E5及E6、E6及E7或E7及E8分別獨 立地共同代表,其中至少一E1及E2、E2及E3、 E3及E4、E5及E6、E6及E7或E7及E8E9、E10、E11及E12分別獨立代表氫原子、碳數為1至20之烷基,碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自苯基、鹵素原子、CN、OH、SH、碳數為1至4之烷氧基、(CO)OH或(CO)O(R1),其中R1代表碳數為1至4之烷基;或E9、E10、E11及E12分別獨立地代表未經取代之苯基或經如下所示之至少一基團取代之苯基,該至少一基團係選自碳數為1至6之烷基、鹵素原子、CN、OE17、SE18或NE19E20;或E9、E10、E11及E12分別獨立地代表鹵素原子、CN、OE17、SE18、SOE18、SO2E18或NE19E20,其中取代基OE17、SE18或NE19E20係選擇性地經由基團E17、E18、E19及/或E20與式(IIIA)中之萘環的一個碳原子形成五員環或六員環;或 E9、E10、E11及E12分別獨立地代表、COE16或NO2;W代表O、S、NE26或單鍵,p代表0至3之整數,q代表1至3之整數,Z1代表CO或單鍵;E13代表碳數為1至20之烷基,碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,其中上述之至少一基團係選自鹵素原子、E17、COOE17、OE17、SE18、CONE19E20、 NE19E20、PO(OCkH2k+1)2;或E13代表碳數為2至20之烷基,碳數為2至20之烷基係間雜有一或多個O、S、SO、SO2、NE26或CO;或E13代表碳數為2至12之烯基,碳數為2至12之烯基係未經間雜或間雜有一或多個O、CO或NE26,其中經間雜且碳數為2至20之烷基及未經間雜或經間雜之碳數為2至12之烯基係未經取代或經至少一鹵素原子取代;或E13代表碳數為4至8之環烯基、碳數為2至12之炔基、或未經間雜或間雜有一或多個O、S、CO或NE26之碳數為3至10之環烷基;或E13代表苯基或萘基,且其各未經取代或經如下所示之至少一基團取代,其中該至少一基團係選自OE17、SE18、NE19E20、COE16、CN、NO2、鹵素原子、碳數為1至20之烷基、碳數為1至4之鹵代烷基,間雜有一或多個O、S、CO或NE26且碳數為2至20的烷基;或其各經未間雜或間雜有一或多個O、S、CO或NE26且碳數為3至10之環烷基所取代;k代表1至10之整數;E15代表碳數為6至20之芳香基或碳數為3至20之雜芳基,其各未經取代或經如下所示之至少一基團取代,且至少一基團係選自苯基、鹵素原子、碳數為1至4之鹵代烷基、CN、NO2、OE17、SE18、NE19E20、PO(OCkH2k+1)2、與SO鍵結且碳數為1至10之烷基、與SO2鍵結且碳數為1至10之烷基、間雜有一或多個O、S或NE26且碳數為2至20之烷基;或其各經碳數為1至20之烷基取代,其中碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素原子、COOE17、 CONE19E20、苯基、碳數為3至8之環烷基、碳數為3至20之雜芳基、碳數為6至20之芳氧基羰基、碳數為3至20之雜芳氧基羰基、OE17、SE18或NE19E20;或E15代表氫原子、碳數為2至12之烯基、未經間雜或間雜有一或多個O、CO或NE26且碳數為3至8之環烷基;或E15代表碳數為1至20之烷基,碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素原子、OE17、SE18、碳數為3至8之環烷基、碳數為3至20之雜芳基、碳數為6至20之芳氧基羰基、碳數為3至20之雜芳氧基羰基、NE19E20、COOE17、CONE19E20、PO(OCkH2k+1)2或苯基,其中碳數為1至20之烷基係經苯基取代,且苯基係經鹵素原子、碳數為1至20之烷基、碳數為1至4之鹵代烷基、OE17、SE18或NE19E20取代;或E15代表碳數為2至20之烷基,碳數為2至20之烷基係間雜有一或多個O、SO或SO2,經間雜且碳數為2至20之烷基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素原子、OE17、COOE17、CONE19E20、苯基或經OE17、SE18或NE19E20取代之苯基;或E15代表碳數為2至20之烷醯基或苯甲醯基,其係未經取代或經如下所示之至少一基團取代,且至少一基團係選自碳數為1至6之烷基、鹵素原子、苯基、OE17、SE18或NE19E20;或E15代表未經取代或經至少一OE17取代之萘甲醯基或係碳數為3至14之雜芳基羰基;或E15代表碳數為2至12之烷氧基羰基,碳數為2至12之烷氧基羰基係未經間雜或間雜有一或多個O,其中經間雜或未經間雜且 碳數為2至12之烷氧基羰基係未經取代或經至少一羥基取代;或E15代表苯氧基羰基,苯氧基羰基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自碳數為1至6之烷基、鹵素原子、碳數為1至4之鹵代烷基、苯基、OE17、SE18或NE19E20;或E15代表CN、CONE19E20、NO2、碳數為1至4之鹵代烷基、S(O)r-R2、與S(O)r鍵結之苯基,其中與S(O)r鍵結之苯基係未經取代或經碳數為1至12之烷基或SO2-R2取代,且R2代表碳數為1至6之烷基;或E15代表與SO2O鍵結之苯基、二苯基膦醯基或二(R3)-膦醯基,其中與SO2O鍵結之苯基係未經取代或經碳數為1至12之烷基取代,且R3代表碳數為1至4之烷氧基;r表示1至2之整數;E'15代表具有針對E15定義中其中之一者;Z2代表O、S、SO或SO2;Z3代表O、CO、S或單鍵;E16代表碳數為6至20之芳基或碳數為3至20之雜芳基,其各未經取代或經如下所示之至少一基團取代,且至少一基團係選自苯基、鹵素原子、碳數為1至4之鹵代烷基、CN、NO2、OE17、SE18、NE19E20、間雜有一或多個O、S或NE26且碳數為1至20之烷基,或者碳數為1至20之烷基,其中碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,其中至少一基團係選自鹵素原子、COOE17、CONE19E20、苯基、碳數為3至8之環烷基、碳數為3至20之雜芳基、碳數為6至20之芳氧基羰基、碳數為3至20之雜芳氧基羰基、OE17、SE18或NE19E20;或E16代表氫原子或碳數為1至20之烷基,其中碳數為1至20之 烷基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素原子、苯基、OH、SH、CN、碳數為3至6之烯氧基、OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R1)、O(CO)苯基或(CO)OH或(CO)O(R1);或E16代表碳數為2至12之烷基,碳數為2至12之烷基係間雜有一或多個O、S或NE26;或E16代表(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4)、碳數為2至12之烯基或碳數為3至8之環烷基,其中該R4代表碳數為1至8之烷基;或E16代表經SE18取代之苯基,其中E18代表鍵結至COE16所附接之咔唑部份之苯基或萘基環的單鍵;n代表1至20之整數;E17代表氫原子、苯基-R5、碳數為1至20之烷基,其係未經取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素原子、OH、SH、CN、碳數為3至6之烯氧基、OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R1)、O(CO)-(R6)、與O(CO)鍵結之苯基、(CO)OH、(CO)O(R1)、碳數為3至20之環烷基、SO2-(R7)、O(R7)或間雜有一或多個O且碳數為3至20之環烷基,其中R5代表碳數為1至3之烷基、R6代表碳數為2至4之烯基,且R7代表碳數為1至4之鹵代烷基;或E17代表碳數為2至20之烷基,且碳數為2至20之烷基係間雜有一或多個O、S或NE26;或E17代表(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4)、碳數為1至8之烷醯基、碳數為2至12之烯基、碳數為3至6之烯醯基或碳數為3至20之環烷基,其係未經間雜或間雜有一或多個O、S、CO或NE26;或 E17代表碳數為1至8之烷基與碳數為3至10之環烷基鍵結所形成之基團,且上述基團係未經間雜或經間雜有一或多個O;或E17代表苯甲醯基,苯甲醯基係未取代或經如下所示之至少一基團取代,且該至少一基團係選自碳數為1至6之烷基、鹵素原子、OH或碳數為1至3之烷氧基;或E17代表苯基、萘基或碳數為3至20之雜芳基,其各未經取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素原子、OH、碳數為1至12之烷基、碳數為1至12之烷氧基、CN、NO2、苯基-R8、苯氧基、碳數為1至12之烷基硫基、苯基硫基、 N(R9)2、二苯基-胺基或,其中R8代表碳數為1至3之烷氧基,且R9代表碳數為1至12之烷基;或 E17與具有之苯基或萘基環之其中一個碳原子形成單鍵;E18代表氫原子、碳數為2至12之烯基、碳數為3至20之環烷基或苯基-R5,其中碳數為2至12之烯基、碳數為3至20之環烷基及苯基-R5係未經間雜或間雜有一或多個O、S、CO、NE26或COOE17;或E18代表碳數為1至20之烷基,碳數為1至20之烷基係未取代或經如下所式之至少一基團取代,且至少一基團係選自OH、SH、CN、碳數為3至6之烯氧基、OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R6)、O(CO)-(R1)、O(CO)-苯基或(CO)OE17;或E18代表碳數為2至20之烷基,碳數為2至20之烷基係間雜有一或多個O、S、CO、NE26或COOE17;或 E18代表(CH2CH2O)nH、(CH2CH2O)n(CO)-(R4)、碳數為2至8之烷醯基或碳數為3至6之烯醯基;或E18代表苯甲醯基,苯甲醯基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自碳數為1至6之烷基、鹵素原子、OH、碳數為1至4之烷氧基或碳數為1至4之烷基硫基;或E18代表苯基、萘基或碳數為3至20之雜芳基,其各未取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素原子、碳數為1至12之烷基、碳數為1至4之鹵代烷基、碳數為1至12之烷氧基、CN、NO2、苯基-R8、苯氧基、碳數為1至12之烷基硫基、苯基硫基、N(R9)2、二苯基胺基、(CO)O(R4)、CO-R4、 (CO)N(R4)2E19及E20分別獨立地代表氫原子、碳數為1至20之烷基、碳數為2至4之羥基烷基、碳數為2至10之烷氧基烷基、碳數為2至5之烯基、碳數為3至20之環烷基、苯基-R5、碳數為1至8之烷醯基、碳數為1至8之烷醯基氧基、碳數為3至12之烯醯基、SO2-R7或苯甲醯基;或E19及E20代表苯基、萘基或碳數為3至20之雜芳基,其各未經取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素原子、碳數為1至4之鹵代烷基、碳數為1至20之烷氧基、碳數為1至12之烷基、苯甲醯基或碳數為1至12之烷氧基;或E19及E20係與所鍵結之氮原子一起形成未經間雜或間雜有O、S或NE17之五員或六員飽和或不飽和環,且五員或六員飽和或不飽和環係未經取代或經如下所示之至少一基團取代,其中至少一基團係選自碳數為1至20之烷基、碳數為1至20之烷氧基、=O、OE17、SE18、NE21E22、(CO)E23、NO2、鹵素原子、碳 數為1至4之鹵代烷基、CN、苯基、,或者未經間雜或經至少一O、S、CO或NE17間雜且碳數為3至20之環烷基;或E19及E20係與所附接之氮原子一起形成雜芳香族環系統,該雜芳香族環系統係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自碳數為1至20之烷基、碳數為1至4之鹵代烷基、碳數為1至20之烷氧基、=O、OE17、SE18、NE21E22、 (CO)E23、鹵素原子、NO2、CN、苯基,或者未經間雜或間雜有一或多個O、S、CO或NE17且碳數為3至20的環烷基;E21及E22分別獨立地代表氫原子、碳數為1至20之烷基、碳數為1至4之鹵代烷基、碳數為3至10之環烷基或苯基;E21及E22與其所鍵接之氮原子一起形成未經間雜或間雜有O、S或NE26之五員或六員飽和或不飽和環,其中該五員或六員飽和或不飽和環係未稠合或與苯環稠合;E23代表氫原子、OH、碳數為1至20之烷基、碳數為1至4之鹵代烷基、間雜有至少一O、CO或NE26且碳數為2至20的烷基、未經間雜或間雜有O、S、CO或NE26且碳數為3至20之環烷基;或E23代表苯基、萘基、苯基-R1、OE17、SE18或NE21E22;E24代表(CO)OE17、CONE19E20、(CO)E17或具有針對E19及E20定義中其中之一者;E25代表COOE17、CONE19E20、(CO)E17;或具有針對E17定義中其中之一者;E26代表氫原子、碳數為1至20之烷基、碳數為1至4之鹵代烷基、間雜有至少一O或CO且碳數為2至20之烷基;或E26代表苯 基-R1、未經間雜或間雜有一或多個O或CO且碳數為3至8之環烷基;或E26代表(CO)E19;或E26代表苯基,E26係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自碳數為1至20之烷基、鹵素原子、碳數為1至4之鹵代烷基、OE17、SE18、 NE19E20,但條件為如式(IIIA)所示之結構的光起始劑(E-1)具有至少一個 In the formula (IIIA), E 1 , E 2 , E 3 , E 4 , E 5 , E 6 , E 7 and E 8 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, , COE 16 , OE 17 , halogen atom, NO 2 or ; Or E 1 and E 2, E 2, and E 3, E 3 and E 4, E 5 and E 6, E 6 or E 7 and E 7 and E 8 each independently represent by Alternate carbon number of 2 to 10, or E 1 and E 2 , E 2 and E 3 , E 3 and E 4 , E 5 and E 6 , E 6 and E 7 or E 7 and E 8 are independent Commonly represented by -(CH 2 ) p -W-(CH 2 ) q -; or E 1 and E 2 , E 2 and E 3 , E 3 and E 4 , E 5 and E 6 , E 6 and E 7 or E 7 and E 8 are independently represented Wherein at least one of E 1 and E 2 , E 2 and E 3 , E 3 and E 4 , E 5 and E 6 , E 6 and E 7 or E 7 and E 8 are E 9 , E 10 , E 11 and E 12 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms which is unsubstituted or has at least one group as shown below. Substituted, and at least one group is selected from the group consisting of a phenyl group, a halogen atom, CN, OH, SH, an alkoxy group having a carbon number of 1 to 4, (CO)OH or (CO)O(R 1 ), wherein R 1 Or an alkyl group having a carbon number of 1 to 4; or E 9 , E 10 , E 11 and E 12 each independently represent an unsubstituted phenyl group or a phenyl group substituted with at least one group as shown below, which is at least a group is selected from an alkyl group having a carbon number of 1 to 6, a halogen atom, CN, OE 17 , SE 18 or NE 19 E 20 ; or E 9 , E 10 , E 11 and E 12 each independently represent a halogen atom , CN, OE 17 , SE 18 , SOE 18 , SO 2 E 18 or NE 19 E 20 , wherein the substituent OE 17 , SE 18 or NE 19 E 20 is selectively via the groups E 17 , E 18 , E 19 And/or E 20 forms a five-membered or six-membered ring with one carbon atom of the naphthalene ring in formula (IIIA); or E 9 , E 10 , E 11 and E 12 independently represent , COE 16 or NO 2 ; W represents O, S, NE 26 or a single bond, p represents an integer from 0 to 3, q represents an integer from 1 to 3, Z 1 represents CO or a single bond; and E 13 represents a carbon number of 1. The alkyl group to 20, the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, wherein at least one of the above groups is selected from a halogen atom, E 17 , COOE 17 , OE 17 , SE 18 , CONE 19 E 20 , NE 19 E 20 , PO(OC k H 2k+1 ) 2 or Or E 13 represents an alkyl group having 2 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, or one or more O, S, SO, SO 2 , NE 26 or CO; or E 13 represents a carbon number An alkenyl group of 2 to 12, an alkenyl group having 2 to 12 carbon atoms, having no or hetero or one or more O, CO or NE 26 , wherein the alkyl group having a carbon number of 2 to 20 is inter The hetero or interstacked alkenyl group having a carbon number of 2 to 12 is unsubstituted or substituted with at least one halogen atom; or E 13 represents a cycloalkenyl group having 4 to 8 carbon atoms and an alkynyl group having 2 to 12 carbon atoms. Or a heterocyclic or heterozygous one or more of O, S, CO or NE 26 having a carbon number of 3 to 10; or E 13 representing a phenyl or naphthyl group, each of which is unsubstituted or Substituting at least one group shown, wherein the at least one group is selected from the group consisting of OE 17 , SE 18 , NE 19 E 20 , , COE 16 , CN, NO 2 , a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, intermixed with one or more O, S, CO or NE 26 and having a carbon number of 2 to 20 alkyl group; or each warp is not interrupted or is interrupted by one or more O, S, CO, or NE 26 carbon atoms and substituted with a cycloalkyl group of 3 to 10; K represents an integer of from 1 to 10; E 15 An aromatic group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a phenyl group, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, CN, NO 2 , OE 17 , SE 18 , NE 19 E 20 , PO(OC k H 2k+1 ) 2 , bonded to SO and having a carbon number of 1 to An alkyl group of 10, an alkyl group bonded to SO 2 and having a carbon number of 1 to 10, an intervening one or more O, S or NE 26 and an alkyl group having 2 to 20 carbon atoms; or each carbon number thereof An alkyl group substituted with 1 to 20, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, COOE 17 , CONE 19 E 20 , phenyl, cycloalkyl having 3 to 8 carbon atoms, heteroaryl having 3 to 20 carbon atoms An aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 3 to 20 carbon atoms, OE 17 , SE 18 or NE 19 E 20 ; or E 15 representing a hydrogen atom and having a carbon number of 2 to 12 An alkenyl group, a heterocyclo group having one or more O, CO or NE 26 and having a carbon number of 3 to 8; or E 15 representing an alkyl group having 1 to 20 carbon atoms and having a carbon number of 1 to The alkyl group of 20 is unsubstituted or substituted by at least one group as shown below, and at least one group is selected from a halogen atom, OE 17 , SE 18 , a cycloalkyl group having a carbon number of 3 to 8, and a carbon number. a heteroaryl group of 3 to 20, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 3 to 20 carbon atoms, NE 19 E 20 , COOE 17 , CONE 19 E 20 , PO (OC k H 2k+1 ) 2 , , Or a phenyl group, wherein the alkyl group having 1 to 20 carbon atoms is substituted with a phenyl group, and the phenyl group is a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or OE 17 , SE 18 or NE 19 E 20 substituted; or E 15 represents an alkyl group having 2 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms, one or more O, SO or SO 2 , interstitial and carbon The alkyl group of 2 to 20 is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, OE 17 , COOE 17 , CONE 19 E 20 , phenyl or via a phenyl group substituted with OE 17 , SE 18 or NE 19 E 20 ; or E 15 represents an alkanoyl group or a benzamidine group having a carbon number of 2 to 20, which is unsubstituted or has at least one group as shown below Substituted, and at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, a phenyl group, OE 17 , SE 18 or NE 19 E 20 ; or E 15 represents unsubstituted or via at least one OE 17 a substituted naphthylmethyl group or a heteroarylcarbonyl group having a carbon number of 3 to 14; or E 15 represents an alkoxycarbonyl group having 2 to 12 carbon atoms, and an alkoxycarbonyl group having 2 to 12 carbon atoms is not Miscellaneous or intermixed with one or more O And intermingled with or without a carbon number of alkoxycarbonyl group of 2 to 12 based unsubstituted or substituted with at least one hydroxyl group; or E 15 Representative phenoxycarbonyl, phenoxycarbonyl unsubstituted or system as shown by the following Substituting at least one group, and at least one group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, OE 17 , SE 18 or NE 19 E 20 Or E 15 represents CN, CONE 19 E 20 , NO 2 , a haloalkyl group having a carbon number of 1 to 4, S(O) r -R 2 , a phenyl group bonded to S(O)r, wherein O) The phenyl group of the r bond is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms or SO 2 -R 2 , and R 2 represents an alkyl group having 1 to 6 carbon atoms; or E 15 represents SO 2 O bonded phenyl, diphenylphosphonium or di(R 3 )-phosphonium, wherein the phenyl group bonded to SO 2 O is unsubstituted or substituted with a carbon number of 1 to 12 Substituted, and R 3 represents an alkoxy group having a carbon number of 1 to 4; r represents an integer from 1 to 2; E' 15 represents one of the definitions for E 15 ; Z 2 represents O, S, SO or SO 2 ; Z 3 represents O, CO, S or a single bond; E 16 represents an aryl group having 6 to 20 carbon atoms or a heteroaryl having 3 to 20 carbon atoms a group, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of a phenyl group, a halogen atom, a halogenated alkyl group having a carbon number of 1 to 4, CN, NO 2 , OE 17 , SE 18 , NE 19 E 20 , an alkyl group having one or more O, S or NE 26 and having a carbon number of 1 to 20, or an alkyl group having 1 to 20 carbon atoms, wherein the carbon number is 1 to 20 The alkyl group is unsubstituted or substituted with at least one group as shown below, wherein at least one group is selected from the group consisting of a halogen atom, COOE 17 , CONE 19 E 20 , a phenyl group, and a cycloalkyl group having a carbon number of 3 to 8. a heteroaryl group having 3 to 20 carbon atoms, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 3 to 20 carbon atoms, OE 17 , SE 18 or NE 19 E 20 ; or E 16 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from halogen. Atom, phenyl, OH, SH, CN, alkenyloxy group having 3 to 6 carbon atoms, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(R 1 ), O(CO)-(R 1 ) , O(CO)phenyl or (CO)OH or (CO)O(R 1 ); or E 16 represents an alkyl group having 2 to 12 carbons, One or more O, S or NE26 having an alkyl group having 2 to 12 carbon atoms; or E 16 representing (CH 2 CH 2 O) n+1 H, (CH 2 CH 2 O) n (CO)-( R 4 ), an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, wherein R 4 represents an alkyl group having 1 to 8 carbon atoms; or E 16 represents a benzene substituted by SE 18 a group, wherein E 18 represents a single bond bonded to the phenyl or naphthyl ring of the carbazole moiety to which the COE 16 is attached; n represents an integer from 1 to 20; E 17 represents a hydrogen atom, phenyl-R 5 , An alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, OH, SH, CN, and has a carbon number of 3 to 6 Alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(R 1 ), O(CO)-(R 1 ), O(CO)-(R 6 ), and O(CO) bond a phenyl group, (CO)OH, (CO)O(R 1 ), a cycloalkyl group having a carbon number of 3 to 20, SO 2 -(R 7 ), O(R 7 ) or a heterogeneous one or more O And a cycloalkyl group having 3 to 20 carbon atoms, wherein R 5 represents an alkyl group having 1 to 3 carbon atoms, R 6 represents an alkenyl group having 2 to 4 carbon atoms, and R 7 represents a carbon number of 1 to 4 Haloalkyl; or E 17 represents an alkyl group having 2 to 20 carbon atoms and a carbon number of 2 to 20 The alkyl interstitial is one or more of O, S or NE 26 ; or E 17 represents (CH 2 CH 2 O) n+1 H, (CH 2 CH 2 O) n (CO)-(R 4 ), carbon The alkylene group having 1 to 8 alkyl groups, an alkenyl group having 2 to 12 carbon atoms, an olefinic group having 3 to 6 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, which has no inter Or a plurality of O, S, CO or NE 26 ; or E 17 represents a group formed by bonding an alkyl group having 1 to 8 carbon atoms to a cycloalkyl group having 3 to 10 carbon atoms, and the above group is not Ory or interstitial with one or more O; or E 17 represents a benzhydryl group, the benzamyl group is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from carbon number An alkyl group of 1 to 6, a halogen atom, an OH or an alkoxy group having 1 to 3 carbon atoms; or E 17 represents a phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted Or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, OH, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, CN, NO 2 , phenyl-R 8 , phenoxy, alkylthio having 1 to 12 carbons, phenylthio, N(R 9 ) 2 , diphenyl-amine or Wherein R 8 represents an alkoxy group having a carbon number of 1 to 3, and R 9 represents an alkyl group having a carbon number of 1 to 12; or E 17 and has or One of the carbon atoms of the phenyl or naphthyl ring forms a single bond; E 18 represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or a phenyl-R 5 group, wherein An alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a phenyl-R 5 group having no or hetero or one or more O, S, CO, NE 26 or COOE 17; or E 18 An alkyl group having a carbon number of 1 to 20, an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group of the formula: wherein at least one group is selected from the group consisting of OH, SH, CN, carbon Number 3 to 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(R 1 ), O(CO)-(R 6 ), O(CO)-(R 1 ), O (CO)-phenyl or (CO)OE 17 ; or E 18 represents an alkyl group having 2 to 20 carbon atoms, and an alkyl group having 2 to 20 carbon atoms. One or more O, S, CO, NE 26 Or COOE 17 ; or E 18 represents (CH 2 CH 2 O) n H, (CH 2 CH 2 O) n (CO)-(R 4 ), an alkanoyl group having a carbon number of 2 to 8 or a carbon number of 3 An olefin group to 6; or E 18 represents a benzamidine group, which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a carbon number of 1 to 6 Alkyl group, halogen atom, OH, An alkoxy group having 1 to 4 carbon atoms or an alkylthio group having 1 to 4 carbon atoms; or E 18 representing a phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or Substituting at least one group as shown below, and at least one group is selected from the group consisting of a halogen atom, an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. Base, CN, NO 2 , phenyl-R 8 , phenoxy, alkylthio group having 1 to 12 carbon atoms, phenylthio group, N(R 9 ) 2 , diphenylamino group, (CO) O(R 4 ), CO-R 4 , (CO)N(R 4 ) 2 or E 19 and E 20 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, and a carbon number of 2 Alkenyl group to 5, cycloalkyl group having 3 to 20 carbon atoms, phenyl-R 5 , alkanoyl group having 1 to 8 carbon atoms, alkyl alkoxy group having 1 to 8 carbon atoms, carbon number 3 to 12 olefinic groups, SO 2 -R 7 or benzamidine groups; or E 19 and E 20 represent a phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or Substituting at least one group as shown below, and the at least one group is selected from the group consisting of a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number of 1 to 12 An alkyl group, a benzamidine group or an alkoxy group having a carbon number of 1 to 12; or an E 19 and E 20 group together with a bonded nitrogen atom to form a five-membered member having no inter or heterogeneous O, S or NE 17 Or a six-membered saturated or unsaturated ring, and the five or six member saturated or unsaturated ring system is unsubstituted or substituted with at least one group as shown below, wherein at least one group is selected from a carbon number of 1 to 20 Alkyl group, alkoxy group having 1 to 20 carbon atoms, =0, OE 17 , SE 18 , NE 21 E 22 , (CO)E 23 , NO 2 , a halogen atom, a halogenated alkyl group having a carbon number of 1 to 4, CN, a phenyl group, Or interrupted or not by at least one O, S, CO, or NE 17 carbon atoms and is interrupted by a cycloalkyl group having 3 to 20; or E 19 and E 20 together with the nitrogen atom based attached the heteroaromatic ring System, the heteroaromatic ring system is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and a carbon number of 1 to 4. Haloalkyl, alkoxy with 1 to 20 carbon atoms, =0, OE 17 , SE 18 , NE 21 E 22 , (CO)E 23 , a halogen atom, NO 2 , CN, phenyl, or a cycloalkyl group having one or more O, S, CO or NE 17 and having a carbon number of 3 to 20 without interstitial or heterogeneous; E 21 and E 22 are independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group; and a nitrogen atom to which E 21 and E 22 are bonded thereto Forming a five- or six-membered saturated or unsaturated ring having no or interstitial or O, S or NE 26 , wherein the five or six member saturated or unsaturated ring system is not fused or fused to the benzene ring; 23 represents a hydrogen atom, OH, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having at least one O, CO or NE 26 and having a carbon number of 2 to 20, which is not a cycloalkyl group having an O, S, CO or NE 26 and having a carbon number of 3 to 20; or E 23 representing a phenyl group, a naphthyl group, a phenyl-R 1 , OE 17 , SE 18 or NE 21 E 22 E 24 stands for (CO) OE 17 , CONE 19 E 20 , (CO) E 17 or has one of the definitions for E 19 and E 20 ; E 25 stands for COOE 17 , CONE 19 E 20 , (CO) E 17; or for those having one of the definitions E 17; E 26 represents a hydrogen atom, Alkyl having from 1 to 20, the haloalkyl group having a carbon number of 1 to 4, intermingled with at least one O or CO and alkyl having 2 to 20; or E 26 represents phenyl -R 1, not intermingled Or a heterocyclic group having one or more O or CO and having a carbon number of 3 to 8; or E 26 representing (CO)E 19 ; or E 26 representing a phenyl group, E 26 being unsubstituted or as shown below Substituting at least one group, and the at least one group is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, OE 17 , SE 18 , NE 19 E 20 or , but the photoinitiator (E-1) having the structure of the formula (IIIA) has at least one or

針對式(IIIA)所示之化合物所定義的基團,較佳者係對應於如下述針對式(III)之化合物所定義者,只是所定義的肟酯基團 (例如)皆替換為相應游離肟基團 The group defined for the compound represented by the formula (IIIA) preferably corresponds to the one defined for the compound of the formula (III) below, except for the defined oxime ester group (for example). Are replaced by corresponding free sulfonium groups

每一肟酯基團可以兩種構型(Z)或(E)存在。可藉由習用方法來分離異構體,但亦可使用異構體混合物作為(例如)光起始物質。因此,本發明之光起始劑(E-1),如式(III)所示之化合物,包含構型異構體之混合物。 Each oxime ester group can exist in two configurations (Z) or (E). The isomers can be separated by conventional methods, but a mixture of isomers can also be used as, for example, a photoinitiator. Accordingly, the photoinitiator (E-1) of the present invention, such as the compound of the formula (III), comprises a mixture of configurational isomers.

在一較佳之實施例中,光起始劑(C)包含如式(III)所示之結構的光起始劑(E-1),其中E1、E2、E3、E4、E5、E6、E7及E8分別 獨立代表氫原子、碳數為1至20之烷基、、COE16或NO2;或E1及E2、E2及E3、E3及E4、E5及E6、E6及E7或E7及E8分別獨 立地共同代表,其中至少一E1及E2、E2及E3、 E3及E4、E5及E6、E6及E7或E7及E8Z1代表CO或單鍵;E13代表碳數為1至20之烷基,碳數為1至20之烷基係未經取 代或經如下所示之至少一基團取代,且至少一基團係選自鹵素原子、OE17、SE18、COOE17、CONE19E20或PO(OCkH2k+1)2;或E13代表碳數為2至20之烷基,其係間雜有一或多個O、S、NE26或CO;或E13代表苯基或萘基,此二者係未經取代或經至少一 或COE16取代;E14代表碳數為1至20之烷基、苯基或碳數為1至8之烷氧基;E15代表苯基、萘基、碳數為3至20之雜芳基,其各未經取代或經如下所示之至少一基團取代,且該至少一基團係選自苯基、鹵素原子、碳數為1至4之鹵代烷基、OE17、SE18、間雜有至少一O或S且碳數為2至20之烷基,或其各經一或多個碳數為1至20之烷基取代,所述碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素原子、COOE17、CONE19E20、苯基、碳數為3至8之環烷基、碳數為3至20之雜芳基、碳數為6至20之芳氧基羰基、碳數為4至20之雜芳氧基羰基、OE17、SE18、NE19E20或PO(OCkH2k+1)2;或E15代表碳數為1至20之烷基,其係未經取代或經如下所示之至少一基團取代,且至少一基團係選自OE17、SE18、碳數為3至8之環烷基、碳數為3至20之雜芳基、NE19E20、COOE17、CONE19E20或PO(OCkH2k+1)2;E'14代表具有針對E14定義中其中之一者;E'15代表具有針對E15定義中其中之一者;E16代表苯基,其係未經取代或經如下所示之至少一基團取代,且至少一基團係選自OE17、SE18、NE19E20、間雜至少一O、 S或NE26且碳數為2至20之烷基;或E16代表苯基,其係經至少一碳數為1至20之烷基取代,其中碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素原子、COOE17、CONE19E20、苯基、碳數為3至8之環烷基、碳數為3至20之雜芳基、碳數為6至20之芳氧基羰基、碳數為4至20之雜芳氧基羰基、OE17、SE18或NE19E20;或E16代表碳數為1至20之烷基,E16係未經取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素原子、苯基、OH、SH、CN、碳數為3至6之烯氧基、OCH2CH2(CO)O(R1)、O(CO)-(R1)或(CO)O(R1);E17代表碳數為1至20之烷基,其係未經取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素原子、OCH2CH2(CO)O(R1)、O(R1)、(CO)O(R1)、碳數為3至20之環烷基,其中碳數為3至20之環烷基係未間雜或間雜至少一O;或E17代表碳數為2至20之烷基,碳數為2至20之烷基係間雜至少一O;E18代表經(CO)OE17取代之甲基;E19及E20分別獨立代表氫原子、苯基、碳數為1至20之烷基、碳數為1至8之烷醯基或碳數為1至8之烷醯基氧基;或E19及E20係與所鍵結之氮原子一起形成雜芳香族環系統,雜 芳香族環系統係未經取代或經取代,但條件為如式(III)所示結構之該光起始劑(E-1)具有至少一個 In a preferred embodiment, the photoinitiator (C) comprises a photoinitiator (E-1) of the structure shown in formula (III), wherein E 1 , E 2 , E 3 , E 4 , E 5 , E 6 , E 7 and E 8 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, , COE 16 or NO 2 ; or E 1 and E 2 , E 2 and E 3 , E 3 and E 4 , E 5 and E 6 , E 6 and E 7 or E 7 and E 8 are respectively independently represented Wherein at least one of E 1 and E 2 , E 2 and E 3 , E 3 and E 4 , E 5 and E 6 , E 6 and E 7 or E 7 and E 8 are Z 1 represents CO or a single bond; E 13 represents an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group The group is selected from a halogen atom, OE 17 , SE 18 , COOE 17 , CONE 19 E 20 or PO(OC k H 2k+1 ) 2 ; or E13 represents an alkyl group having a carbon number of 2 to 20, and the interstitial a plurality of O, S, NE 26 or CO; or E 13 represents a phenyl or naphthyl group, both of which are unsubstituted or at least one Or COE 16 substituted; E 14 represents an alkyl group having 1 to 20 carbon atoms, a phenyl group or an alkoxy group having 1 to 8 carbon atoms; and E 15 represents a phenyl group, a naphthyl group, and a heteroaryl group having a carbon number of 3 to 20. a group, each of which is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of a phenyl group, a halogen atom, a halogenated alkyl group having a carbon number of 1 to 4, OE 17 , SE 18 , An alkyl group having at least one O or S and having a carbon number of 2 to 20, or each of which is substituted with one or more alkyl groups having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is not Substituted or substituted with at least one group as shown below, and at least one group selected from the group consisting of a halogen atom, COOE 17 , CONE 19 E 20 , a phenyl group, a cycloalkyl group having a carbon number of 3 to 8, and a carbon number of a heteroaryl group of 3 to 20, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 4 to 20 carbon atoms, OE 17 , SE 18 , NE 19 E 20 or PO (OCkH 2k+1) 2 ; or E 15 represents an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from OE 17 , SE 18 , carbon number a cycloalkyl group of 3 to 8 carbon atoms, a heteroaryl group of from 3 to 20, NE 19 E 20 COOE 17, CONE 19 E 20 or PO (OC k H 2k + 1 ) 2; E '14 represents a definition of E 14 for one of the persons; E' 15 represents a 15 for one of those defined in E; E 16 represents a phenyl group which is unsubstituted or substituted with at least one group as shown below, and at least one group selected from OE 17 , SE 18 , NE 19 E 20 , at least one O, S or NE 26 And an alkyl group having a carbon number of 2 to 20; or E 16 represents a phenyl group which is substituted with at least one alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or Substituting at least one group as shown below, and at least one group is selected from the group consisting of a halogen atom, COOE 17 , CONE 19 E 20 , a phenyl group, a cycloalkyl group having a carbon number of 3 to 8, and a carbon number of 3 to 20. a heteroaryl group, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 4 to 20 carbon atoms, OE 17 , SE 18 or NE 19 E 20 ; or E 16 representing a carbon number of 1 to 20 The alkyl group, the E 16 group is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of a halogen atom, a phenyl group, an OH group, a SH group, and a carbon number of 3 to 6 carbon atoms. Oxygen, OCH 2 CH 2 (CO)O(R 1 ), O(CO)-(R 1 ) Or (CO)O(R 1 ); E 17 represents an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom. , OCH 2 CH 2 (CO)O(R 1 ), O(R 1 ), (CO)O(R 1 ), a cycloalkyl group having a carbon number of 3 to 20, wherein the number of carbon atoms is 3 to 20 The base is unintercalated or heterozygous at least one O; or E 17 represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is at least one O; E 18 represents a substitution by (CO)OE 17 Methyl; E 19 and E 20 each independently represent a hydrogen atom, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms or an alkanoyloxy group having 1 to 8 carbon atoms. Or the E 19 and E 20 systems together with the bonded nitrogen atom form a heteroaromatic ring system, the heteroaromatic ring system is unsubstituted or Substituting, but the photoinitiator (E-1) having the structure of the formula (III) has at least one

必須重視如上述所定義之式(III)的化合物,其中E1、 E2、E3、E4、E5、E6、E7及E8分別獨立代表氫原子、COE16或NO2; E3及E4一起為E9、E10、E11及E12為氫原子;Z1為單鍵;E13係碳數為1至20之烷基;E14係碳數為1至20之烷基;E15係碳數為1至20之烷基或經以下之至少一基團取代之苯基,其中至少一基團可為OE17或碳數為1至20之烷基;E16係苯基,苯基係經以下之至少一基團取代,其中至少一基團可為OE17或碳數為1至20之烷基;E17係未經取代或經至少一鹵素原子取代之碳數為1或20烷基或係間雜有至少一氧原子之碳數為1至20的烷基,但條件為如 式(III)所示之結構式之化合物中存在至少一個 Attention must be paid to compounds of formula (III) as defined above, wherein E 1 , E 2 , E 3 , E 4 , E 5 , E 6 , E 7 and E 8 each independently represent a hydrogen atom, COE 16 or NO 2 ; E 3 and E 4 together E 9, E 10, E 11 and E 12 is a hydrogen atom; Z 1 is a single bond; E 13 based alkyl group having a carbon number of 1 to 20; E 14 based alkyl group having a carbon number of 1 to 20; E 15 lines a phenyl group having 1 to 20 carbon atoms or substituted with at least one of the following groups, wherein at least one of the groups may be OE 17 or an alkyl group having 1 to 20 carbon atoms; E 16 phenyl group, phenyl group Substituting at least one of the following groups, wherein at least one of the groups may be OE 17 or an alkyl group having 1 to 20 carbon atoms; the E 17 group is unsubstituted or substituted with at least one halogen atom and has a carbon number of 1 or 20 An alkyl group or a system having at least one oxygen atom having 1 to 20 carbon atoms, provided that at least one of the compounds of the formula (III) has a structural formula

在一更佳的實施例中,光起始劑(C)包含如式(III)所示之結構的光起始劑(E-1),其中E1、E2、E3、E4、E5、E6、E7及E8分別獨立代表氫原子;或E1及E2、E3及E4或E5及E6分別獨立地共同代表 ,且至少一E1及E2、E3及E4或E5及E6 E2代表、COE16、NO2;或 E7代表或COE16;E9、E11及E12代表氫原子;E10代表氫原子、OE17或COE16;Z1代表CO或單鍵;E13代表碳數為1至20之烷基,其係未經取代或經如下所示之至少一基團取代,且至少一基團係選自鹵素原子、E17、OE17、SE18或PO(OCkH2k+1)2;或E13代表碳數為2至20之烷基,其係間雜至少一O;或E13代表苯基;k代表整數2;E14代表碳數為1至20之烷基或噻吩基;E15代表苯基或萘基,且其各未經取代或經至少一OE17或碳數為1至20之烷基取代;或E15代表噻吩基、氫原子或碳數為1至20之烷基,其中碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自OE17、SE18、碳數為3至8之環烷基、NE19E20或COOE17;或E15代表碳數為2至20之烷基,且碳數為2至20之烷基間雜有SO2;E16代表苯基或萘基,其各未經取代或經如下所示之至少一基團取代,且至少一基團係選自OE17、SE18、NE19E20或碳數為1 至20之烷基;或E16代表噻吩基;E17代表氫原子、碳數為1至8之烷醯基或碳數為1至20之烷基,碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素原子、O(CO)-(R1)、O(CO)-(R6),或者間雜至少一O且碳數為3至20之環烷基;或E17代表碳數為2至20之烷基,且碳數為2至20之烷基間雜至少一O;E18代表碳數為3至20之環烷基、碳數為1至20之烷基,其係未經取代或經至少一OH、O(CO)-(R6)或(CO)OE17取代;或E18代表苯基,其係未經取代或經至少一鹵素原子取代;E19及E20係分別獨立地代表碳數為1至8之烷醯基或碳數為1至8烷醯基氧基;或E19及E20係與所鍵結之氮原子一起形成間雜有O之五員或六員飽和環,但條件為如式(III)所示之結構的該光起始劑(E-1)具有 至少一個 In a more preferred embodiment, the photoinitiator (C) comprises a photoinitiator (E-1) of the structure shown in formula (III), wherein E 1 , E 2 , E 3 , E 4 , E 5 , E 6 , E 7 and E 8 each independently represent a hydrogen atom; or E 1 and E 2 , E 3 and E 4 or E 5 and E 6 are independently represented independently And at least one of E 1 and E 2 , E 3 and E 4 or E 5 and E 6 are E 2 represents , COE 16 , NO 2 or ; or E 7 represents Or COE 16 ; E 9 , E 11 and E 12 represent a hydrogen atom; E 10 represents a hydrogen atom, OE 17 or COE 16 ; Z 1 represents CO or a single bond; and E 13 represents an alkyl group having 1 to 20 carbon atoms; Is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, E 17 , OE 17 , SE 18 or PO(OC k H 2k+1 ) 2 ; or E 13 Represents an alkyl group having a carbon number of 2 to 20, the interstitial is at least one O; or E 13 represents a phenyl group; k represents an integer 2; E 14 represents an alkyl group having 1 to 20 carbon atoms or a thienyl group; and E 15 represents a benzene group. Or a naphthyl group, each of which is unsubstituted or substituted with at least one OE 17 or an alkyl group having 1 to 20 carbon atoms; or E 15 represents a thienyl group, a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, wherein The alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from OE 17 , SE 18 , a cycloalkyl group having 3 to 8 carbon atoms, NE 19 E 20 or COOE 17 ; or E 15 represents an alkyl group having 2 to 20 carbon atoms, and an alkyl group having a carbon number of 2 to 20 is interspersed with SO 2 ; E 16 represents a phenyl group or a naphthyl group, each of which is not Substituted or substituted with at least one group as shown below, and at least one Group selected from OE 17, SE 18, NE 19 E 20 carbon atoms or an alkyl group of 1 to 20; E 16, or on behalf of thienyl; E 17 represents a hydrogen atom, an alkyl carbon atoms or acyl of 1 to 8 carbon An alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, O(CO) -(R 1 ), O(CO)-(R 6 ), or a cycloalkyl group having at least one O and having a carbon number of 3 to 20; or E 17 representing an alkyl group having 2 to 20 carbon atoms, and having a carbon number Is an alkyl group of 2 to 20 at least one O; E 18 represents a cycloalkyl group having 3 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms which are unsubstituted or have at least one OH, O (CO) - (R 6 ) or (CO) OE 17 substituted; or E 18 represents a phenyl group which is unsubstituted or substituted with at least one halogen atom; the E 19 and E 20 systems independently represent a carbon number of 1 to 8 Alkanoyl or a carbon number of 1 to 8 alkyl fluorenyloxy; or E 19 and E 20 together with the bonded nitrogen atom to form a five or six member saturated ring interspersed with O, provided that The photoinitiator (E-1) having the structure shown in (III) has at least one

本發明之光起始劑(E-1)之具體例子係如上述所定義之式(IIIa)至(IIIg)之化合物,式(IIIa)、式(IIIb)、式(IIIc),尤其式(IIIa)或式(IIIc)、或式(IIIa)、式(IIIc)或式(IIId),尤其式(IIIa)之化合物令人關注。 Specific examples of the photoinitiator (E-1) of the present invention are compounds of the formulae (IIIa) to (IIIg) as defined above, formula (IIIa), formula (IIIb), formula (IIIc), especially formula ( IIIa) or formula (IIIc), or formula (IIIa), formula (IIIc) or formula (IIId), especially a compound of formula (IIIa) is of interest.

在一例子中,E1、E2、E3、E4、E5、E6、E7及E8分別獨 立代表氫原子、或COE16,或E1及E2、E2及E3、E3及 E4、E5及E6、E6及E7或E7及E8分別獨立地共同代表 In one example, E 1 , E 2 , E 3 , E 4 , E 5 , E 6 , E 7 and E 8 each independently represent a hydrogen atom, Or COE 16 , or E 1 and E 2 , E 2 and E 3 , E 3 and E 4 , E 5 and E 6 , E 6 and E 7 or E 7 and E 8 are respectively independently represented

在一例子中,E1及E2或E3及E4共同為 ,或E3及E4、E5及E6共同為;E3及 E4尤其共同為 In an example, E 1 and E 2 or E 3 and E 4 are , or E 3 and E 4 , E 5 and E 6 are ; E 3 and E 4 are especially common

在一例子中,E1、E5、E6及E8代表氫原子。較佳地, E7代表氫原子、或COE16,或E7代表或 COE16,然以E7代表為更佳。較佳地,E2代表 、COE16,或E2及E1共同為 ,然以E2代表COE16為更佳。Z1較佳為單鍵。 In one example, E 1 , E 5 , E 6 and E 8 represent a hydrogen atom. Preferably, E 7 represents a hydrogen atom, Or COE 16 or E 7 represents Or COE 16 , but with E 7 For better. Preferably, E 2 represents , COE 16 or , or E 2 and E 1 are However, it is better to use E 2 for COE 16 . Z 1 is preferably a single bond.

在一例子中,E9、E10、E11及E12分別獨立地代表氫原子、碳數為1至20之烷基、未經取代之苯基或經如下所示之至少一基團取代之苯基,且至少一基團係選自碳數為1至6之烷基、鹵素原子、OE17或SE18;或E9、E10、E11及E12分別獨立地代表鹵素原子、OE17、SE18、或NE19E20,其中取代基OE17、SE18或NE19E20係選擇性地經由基團E17、E18、E19及/或E20與式(III)中之萘環的一個碳原子形成五員環或六員環;或 E9、E10、E11及E12分別獨立地代表或COE16In one example, E 9 , E 10 , E 11 and E 12 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or substituted with at least one group as shown below. a phenyl group, and at least one group is selected from the group consisting of a C 1 to 6 alkyl group, a halogen atom, OE 17 or SE 18 ; or E 9 , E 10 , E 11 and E 12 each independently represent a halogen atom, OE 17 , SE 18 , or NE 19 E 20 , wherein the substituent OE 17 , SE 18 or NE 19 E 20 is selectively via the groups E 17 , E 18 , E 19 and/or E 20 and formula (III) One carbon atom of the naphthalene ring forms a five-membered ring or a six-membered ring; or E 9 , E 10 , E 11 and E 12 are independently represented Or COE 16 .

在一具體的例子中,E9、E10、E11及E12分別獨立地代 表氫原子、碳數為1至20之烷基、未經取代之苯基或經如下所示之至少一基團取代之苯基,且至少一基團係選自碳數為1至6之烷基、鹵素原子、OE17或SE18;或E9、E10、E11及E12分別獨立地代表鹵素原子、OE17、SE18或NE19E20;或 E9、E10、E11及E12分別獨立地代表或COE16In a specific example, E 9 , E 10 , E 11 and E 12 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or at least one group as shown below a group substituted with a phenyl group, and at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, OE 17 or SE 18 ; or E 9 , E 10 , E 11 and E 12 each independently representing a halogen Atom, OE 17 , SE 18 or NE 19 E 20 ; or E 9 , E 10 , E 11 and E 12 are independently represented Or COE 16 .

在一例子中,E9、E10、E11及E12分別獨立地代表氫原子、碳數為1至20之烷基、未經取代之苯基或經一或多個碳數為1至6之烷基取代之苯基;或E9、E10、E11及E12分別獨立地代表 或COE16In one example, E 9 , E 10 , E 11 and E 12 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or one or more carbon numbers of 1 to 6 alkyl substituted phenyl; or E 9 , E 10 , E 11 and E 12 are independently represented Or COE 16 .

在另一例子中,E9、E10、E11及E12分別獨立代表氫原子、碳數為1至20之烷基、未經取代之苯基或經如下所示之至少一基團取代之苯基,且至少一基團係選自碳數為1至6之烷基、鹵素原子、OE17或SE18;或E9、E10、E11及E12分別獨立代表鹵素原子、OE17、SE18或NE19E20,其中取代基OE17、SE18或NE19E20係選擇性地經由基團E17、E18、E19及/或E20與式(III)中之萘環的一個碳原子形成五員環或六員環。 In another example, E 9 , E 10 , E 11 and E 12 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or substituted with at least one group as shown below. a phenyl group, and at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, OE 17 or SE 18 ; or E 9 , E 10 , E 11 and E 12 each independently representing a halogen atom, OE 17. SE 18 or NE 19 E 20 wherein the substituent OE 17 , SE 18 or NE 19 E 20 is selectively via the groups E 17 , E 18 , E 19 and/or E 20 and in formula (III) One carbon atom of the naphthalene ring forms a five-membered ring or a six-membered ring.

此外,在一例子中,E9、E10、E11及E12分別獨立代表氫原子、碳數為1至20之烷基、未經取代之苯基或經如下所示之至少一基團取代之苯基,至少一基團係選自碳數為1至6之烷基、鹵素原子、OE17或SE18;或E9、E10、E11及E12分別獨立代表鹵素原子、OE17、SE18、NE19E20或COE16Further, in one example, E 9 , E 10 , E 11 and E 12 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or at least one group as shown below a substituted phenyl group, at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, OE 17 or SE 18 ; or E 9 , E 10 , E 11 and E 12 each independently representing a halogen atom, OE 17 , SE 18 , NE 19 E 20 or COE 16 .

或者,在一例子中,E9、E10、E11及E12分別獨立代表氫原子、碳數為1至20之烷基、未經取代之苯基或經如下所示之至少一基團取代之苯基,至少一基團係選自碳數為1至6之烷基、鹵素原子、OE17或SE18;或E9、E10、E11及E12分別獨立代表鹵素原子、OE17、COE16或NE19E20Or, in one example, E 9 , E 10 , E 11 and E 12 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or at least one group as shown below a substituted phenyl group, at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, OE 17 or SE 18 ; or E 9 , E 10 , E 11 and E 12 each independently representing a halogen atom, OE 17 , COE 16 or NE 19 E 20 .

較佳地,E9、E11及E12係氫原子,且E10為氫原子、OE17或COE16Preferably, E 9 , E 11 and E 12 are hydrogen atoms, and E 10 is a hydrogen atom, OE 17 or COE 16 .

E13係例如代表碳數為1至20之烷基,其係未經取代或經如下所示之至少一基團取代,其中上述之至少一基團係選自鹵素原子、COOE17或CONE19E20;或E13代表碳數為2至20之烷基,碳數為2至20之烷基係間雜有一或多個O、S、SO、SO2、NE26或CO;E13代表碳數為2至12之烯基,碳數為2至12之烯基係未間雜或間雜有一或多個O、CO或NE26;或E13代表碳數為3至10之環烷基,環烷基係未間雜或間雜有一或多個O、S、CO或NE26;或E13代表苯基或萘基,且其各為未經取代或經如下所示之至少一基團取代,其中至少一基團係選自OE17、SE18、NE19E20、COE16、NO2、鹵素原子、碳數為1至20之烷基、碳數為1至4之鹵代烷基,經至少一O間雜且碳數為2至20的烷基;或代表碳數為1至20之烷基,其係未經取代或經如下所示之至少一基團取代,其中上述之至少一基團係選自鹵素原子、E17、COOE17、OE17、SE18、CONE19E20或PO(OCkH2k+1)2;或代表碳數為2至20之烷基,其係間雜有一或多個O。 The E 13 group , for example, represents an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as described below, wherein at least one of the above groups is selected from a halogen atom, COOE 17 or CONE 19 E 20 ; or E 13 represents an alkyl group having 2 to 20 carbon atoms; an alkyl group having 2 to 20 carbon atoms; one or more O, S, SO, SO 2 , NE 26 or CO; E 13 represents carbon An alkenyl group having 2 to 12 alkenyl groups, an alkenyl group having 2 to 12 carbon atoms which is uninter or hetero-organic, having one or more O, CO or NE 26 ; or E 13 representing a cycloalkyl group having a carbon number of 3 to 10, The alkyl group is unintermixed or heterozygous with one or more O, S, CO or NE 26 ; or E 13 represents a phenyl or naphthyl group, and each of them is unsubstituted or substituted with at least one group as shown below, wherein At least one group is selected from the group consisting of OE 17 , SE 18 , NE 19 E 20 , , COE 16 , NO 2 , a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having at least one O and having a carbon number of 2 to 20; or a carbon number An alkyl group of 1 to 20 which is unsubstituted or substituted with at least one group as defined below, wherein at least one of the above groups is selected from the group consisting of a halogen atom, E 17 , COOE 17 , OE 17 , SE 18 , CONE 19 E 20 or PO(OC k H 2k +1) 2 ; or an alkyl group having a carbon number of 2 to 20, which has one or more O interphases.

此外,E13代表碳數為1至20之烷基,其係未經取代或 經如下所示之至少一基團取代,其中上述之至少一基團係選自鹵素原子、E17、COOE17、OE17、SE18、CONE19E20或PO(OCkH2k+1)2;或代表碳數為2至20之烷基,碳數為2至20之烷基係間雜有一個O;或代表碳數為2至12之烯基、碳數為3至10之環烷基;或E13代表苯基或萘基,且其各為未經取代或經如下所示之至少一基團取代,其中至少一基團 係選自OE17、SE18、NE19E20、COE16、NO2、鹵素原子、碳數為1至20之烷基、碳數為1至4之鹵代烷基、間雜有一或多個O之碳數為2至20的烷基。 Further, E 13 represents an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as shown below, wherein at least one of the above groups is selected from a halogen atom, E 17 , COOE 17 , OE 17 , SE 18 , CONE 19 E 20 or PO(OC k H 2k+1 ) 2 ; or an alkyl group having a carbon number of 2 to 20, and an alkyl group having a carbon number of 2 to 20 having an O; Or an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms; or E 13 representing a phenyl group or a naphthyl group, each of which is unsubstituted or at least one group as shown below Substituting at least one of the groups is selected from the group consisting of OE 17 , SE 18 , NE 19 E 20 , And COE 16 , NO 2 , a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 20 carbon atoms and having a carbon number of 2 to 20.

在另一實施例中,E13代表碳數為1至20之烷基,其係未經取代或經如下所示之至少一基團取代,其中上述之至少一基團係選自鹵素原子、E17、OE17、SE18、或PO(OCkH2k+1)2;或代表間雜有一或多個O且碳數為2至20之烷基;或代表碳數為2至12之烯基、碳數為3至10之環烷基、苯基或萘基。 In another embodiment, E 13 represents an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as defined below, wherein at least one of the above groups is selected from a halogen atom, E 17 , OE 17 , SE 18 , or PO(OC k H 2k+1 ) 2 ; or an alkyl group having one or more O and having a carbon number of 2 to 20; or an alkene having 2 to 12 carbon atoms A cycloalkyl group having a carbon number of 3 to 10, a phenyl group or a naphthyl group.

或者,E13例如可代表碳數為1至20之烷基,其係未經取代或經如下所示之至少一基團取代,其中上述之至少一基團係選自鹵素原子、E17、OE17、SE18或PO(OCkH2k+1)2;或代表至少一O間雜且碳數為2至20之烷基;或代表苯基、碳數為2至12之烯基或碳數為3至10之環烷基。 Alternatively, E 13 may, for example, represent an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as defined below, wherein at least one of the above groups is selected from a halogen atom, E 17 , OE 17 , SE 18 or PO(OC k H 2k+1 ) 2 ; or an alkyl group having at least one O and having a carbon number of 2 to 20; or an alkenyl group or a carbon having a phenyl group and a carbon number of 2 to 12 The number is from 3 to 10 cycloalkyl groups.

或者,E13可代表碳數為1至20之烷基、苯基、碳數為2至12之烯基或碳數為3至10之環烷基。或E13係碳數為1至20之烷基、碳數為2至12之烯基或碳數為3至10之環烷基。較佳地,E13可代表碳數為1至20之烷基,尤其是碳數為1至8之烷基,例如2-乙基己基。 Alternatively, E 13 may represent an alkyl group having 1 to 20 carbon atoms, a phenyl group, an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. Or E 13 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. Preferably, E 13 may represent an alkyl group having from 1 to 20 carbon atoms, especially an alkyl group having from 1 to 8 carbon atoms, such as 2-ethylhexyl.

E14可例如代表氫原子、碳數為3至8之環烷基、碳數為2至5之烯基、碳數為1至20之烷氧基或碳數為1至20之烷基,其係未經取代或經至少一鹵素原子或苯基取代;或 E14代表苯基或萘基,其各係未經取代或經如下所示之至少一基團取代,且至少一基團係選自碳數為1至6之烷基、碳數為1至4之鹵代烷基、鹵素原子、OE17、SE18及/或NE19E20;或E14代表碳數為3至5之雜芳基,例如噻吩基,或代表碳數為1至8之烷氧基、芐氧基或苯氧基。 E 14 may, for example, represent a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. It is unsubstituted or substituted with at least one halogen atom or phenyl group; or E 14 represents a phenyl or naphthyl group, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group It is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a halogen atom, OE 17 , SE 18 and/or NE 19 E 20 ; or E 14 representing a carbon number of 3 to 5 An aryl group such as a thienyl group, or an alkoxy group having a carbon number of 1 to 8, a benzyloxy group or a phenoxy group.

或者,E14可例如代表碳數為1至20之烷基,且碳數為1至20之烷基係經至少一鹵素原子或苯基取代;或E14代表碳數為3至5之雜芳基(例如噻吩基)或代表未經取代或經如下所示之至少一基團取代之苯基,且至少一基團係選自碳數為1至6之烷基、碳數為1至4之鹵代烷基、鹵素原子、OE17、SE18及/或NE19E20;或E14代表碳數為1至8之烷氧基、芐氧基或苯氧基。 Alternatively, E14 may, for example, represent an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms may be substituted with at least one halogen atom or a phenyl group; or E 14 represents a heteroaryl group having a carbon number of 3 to 5. a group (for example, thienyl) or a phenyl group which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from an alkyl group having 1 to 6 carbon atoms and a carbon number of 1 to 4 The haloalkyl group, the halogen atom, OE 17 , SE 18 and/or NE 19 E 20 ; or E 14 represents an alkoxy group having a carbon number of 1 to 8, a benzyloxy group or a phenoxy group.

在另一實施例中,E14代表碳數1至20之烷基,且碳數1至20之烷基係未經取代或經苯基取代;或E14係苯基,且苯基未經取代或經至少一碳數為1至6之烷基取代。 In another embodiment, E 14 represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with a phenyl group; or E 14 is a phenyl group, and the phenyl group is not Substituted or substituted with at least one alkyl group having 1 to 6 carbon atoms.

較佳地,E14係碳數為1至20之烷基、碳數為3至5之雜芳基(例如噻吩基),或係苯基,尤其為碳數為1至20之烷基或噻吩基,更佳為碳數為1至8之烷基。 Preferably, E 14 is an alkyl group having 1 to 20 carbon atoms, a heteroaryl group having 3 to 5 carbon atoms (for example, thienyl group), or a phenyl group, especially an alkyl group having 1 to 20 carbon atoms or The thienyl group is more preferably an alkyl group having 1 to 8 carbon atoms.

E15可例如為碳數為6至20之芳基或碳數為5至20之雜芳基,其各未經取代或經如下所示之至少一基團取代,且至少一基團係選自於苯基、鹵素原子、碳數為1至4之鹵代烷基、CN、NO2、OE17、SE18、NE19E20、碳數為1至20之烷基;或E15係氫原子、碳數為3至8之環烷基,其中碳數為3至8之環烷基係未經間雜或間雜有一或多個O、CO或NE26;或E15係碳數為1至20之烷基,碳數為1至20之烷基未經取代或 經如下所示之至少一基團取代,且至少一基團係選自於鹵素原子、OE17、碳數為3至8之環烷基、碳數為5至20之雜芳基、碳數為8至20之苯氧基羰基、碳數為5至20之雜芳氧基-羰基、 NE19E20、COOE17、CONE19E20、PO(OCkH2k+1)2苯基或經以下基團取代之苯基,上述基團係選自於鹵素原子、碳數為1至20之烷基、碳數為1至4之鹵代烷基、OE17或NE19E20;或E15係碳數為2至20之烷基,且碳數為2至20之烷基間雜有至少一O、S或SO2;或E15係碳數為2至20之烷醯基、苯甲醯基、碳數為2至12之烷氧基羰基、苯氧基羰基、CONE19E20、NO2或碳數為1至4之鹵代烷基。 E 15 may, for example, be an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 5 to 20 carbon atoms, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected From a phenyl group, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, CN, NO 2 , OE 17 , SE 18 , NE 19 E 20 , an alkyl group having 1 to 20 carbon atoms; or an E 15 hydrogen atom a cycloalkyl group having 3 to 8 carbon atoms, wherein the cycloalkyl group having 3 to 8 carbon atoms is undoped or inter-hetero-doped with one or more O, CO or NE 26 ; or the E 15 carbon number is 1 to 20 The alkyl group, the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, OE 17 and a carbon number of 3 to 8. a cycloalkyl group, a heteroaryl group having 5 to 20 carbon atoms, a phenoxycarbonyl group having 8 to 20 carbon atoms, a heteroaryloxy-carbonyl group having 5 to 20 carbon atoms, NE 19 E 20 , COOE 17 , CONE 19 E 20 , PO(OC k H 2k+1 ) 2 , a phenyl group or a phenyl group substituted by a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, OE 17 or NE 19 E 20 ; Or E 15 is an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is at least one O, S or SO 2 ; or E 15 is an alkyl 2 group having 2 to 20 carbon atoms; a benzamidine group, an alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group, CONE 19 E 20 , NO 2 or a halogenated alkyl group having 1 to 4 carbon atoms.

此外,E15可例如為氫原子、碳數為6至20之芳基,尤其為苯基或萘基,苯基或萘基係各未經取代或經碳數為1至12之烷基取代;或係碳數為3至5之雜芳基,例如噻吩基;或係碳數為3至8之環烷基、碳數為1至20之烷基,其係未經取代或經如下所示之至少一基團取代,且至少一基團係選自於OE17、SE17、碳數為3至8之環烷基、NE19E20或COOE17;或E15係碳數為2至20之烷基,且碳數為2至20之烷基間雜有至少一O或SO2Further, E 15 may, for example, be a hydrogen atom, an aryl group having 6 to 20 carbon atoms, especially a phenyl group or a naphthyl group, each of which is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms. Or a heteroaryl group having a carbon number of 3 to 5, such as a thienyl group; or a cycloalkyl group having a carbon number of 3 to 8, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or as follows At least one group is substituted, and at least one group is selected from OE 17 , SE 17 , a cycloalkyl group having a carbon number of 3 to 8, NE 19 E 20 or COOE 17 ; or an E 15 carbon number of 2 An alkyl group of 20, and an alkyl group having 2 to 20 carbon atoms is interspersed with at least one O or SO 2 .

在如式(III)所示之化合物中,E15可例如為氫原子、苯基、萘基,其各未經取代或經碳數為1至8之烷基取代;或E15係噻吩基、碳數為1至20之烷基,其未經取代或經如下所示之至少一基團取代,且至少一基團係選自於OE17、SE17、碳數為3至8之環烷基、NE19E20或COOE17;或 E15係碳數為2至20之烷基,且碳數為2至20之烷基間雜有至少一O或SO2In the compound of the formula (III), E 15 may, for example, be a hydrogen atom, a phenyl group or a naphthyl group, each of which is unsubstituted or substituted with an alkyl group having 1 to 8 carbon atoms; or an E 15 -based thienyl group. An alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of OE 17 and SE 17 and having a carbon number of 3 to 8. An alkyl group, NE 19 E 20 or COOE 17 ; or E 15 is an alkyl group having 2 to 20 carbon atoms, and an alkyl group having 2 to 20 carbon atoms is interspersed with at least one O or SO 2 .

E15尤其為(例如)碳數為3至8之環烷基或碳數為1至20之烷基,較佳為碳數為1至20之烷基,更佳為碳數為1至12之烷基。 E 15 is especially, for example, a cycloalkyl group having 3 to 8 carbon atoms or an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. Alkyl group.

E'14及E'15之較佳者分別具有如上文針對E14及E15所定義中的其中一者。 The preferred ones of E' 14 and E' 15 respectively have one of the definitions defined above for E 14 and E 15 .

Z2係(例如)O、S或SO,例如O或S,尤其為O。 Z 2 is, for example, O, S or SO, such as O or S, especially O.

E16可例如為碳數為6至20之芳基(尤其苯基或萘基、尤其苯基)或碳數為5至20之雜芳基(尤其噻吩基),其各未經取代或經如下所示之至少一基團取代,且至少一基團係選自於苯基、鹵素原子、碳數為1至4之鹵代烷基、CN、NO2、OE17、SE18、NE19E20或間雜至少一O之碳數為1至20之烷基;或其各經至少一碳數為1至20之烷基取代,碳數為1至20之烷基未經取代或經如下所示之至少一基團取代,且至少一基團係選自於鹵素原子、COOE17、CONE19E20、苯基、碳數為3至8之環烷基、碳數為5至20之雜芳基、碳數為6至20之芳氧基羰基、碳數為5至20之雜芳氧基羰基、OE17、SE18或NE19E20;或E16係氫原子、碳數為1至20之烷基,且碳數為1至20之烷基未經取代或經如下所示之至少一基團取代,且至少一基團係選自於鹵素原子、苯基、OH、SH、碳數為3至6之烯氧基、OCH2CH2(CO)O(R1)、O(CO)-(R1)、O(CO)-苯基、(CO)OH或(CO)O(R1);或E16係碳數為2至12之烷基,且碳數為2至12之烷基間雜有至少一O;或E16係(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4)、碳數為2至12之烯基或碳數為3至8之環烷基,且n係1至20,例如1至12或1至8,尤其為1或2。 E 16 may, for example, be an aryl group having 6 to 20 carbon atoms (especially a phenyl or naphthyl group, especially a phenyl group) or a heteroaryl group having a carbon number of 5 to 20 (especially a thienyl group), each of which is unsubstituted or Substituting at least one group as shown below, and at least one group is selected from the group consisting of a phenyl group, a halogen atom, a halogenated alkyl group having a carbon number of 1 to 4, CN, NO 2 , OE 17 , SE 18 , NE 19 E 20 Or an alkyl group having at least one carbon number of 1 to 20; or each of which is substituted with at least one alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms unsubstituted or as shown below Substituting at least one group, and at least one group is selected from the group consisting of a halogen atom, COOE 17 , CONE 19 E 20 , a phenyl group, a cycloalkyl group having a carbon number of 3 to 8, and a heteroaryl group having a carbon number of 5 to 20. a aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 5 to 20 carbon atoms, OE 17 , SE 18 or NE 19 E 20 ; or an E 16 -based hydrogen atom having a carbon number of 1 to An alkyl group of 20, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of a halogen atom, a phenyl group, an OH group, an SH group, and a carbon group. Number 3 to 6 alkenyloxy, OCH 2 CH 2 (CO)O(R 1 ), O (CO)-(R 1 ), O(CO)-phenyl, (CO)OH or (CO)O(R 1 ); or an E 16 alkyl group having 2 to 12 carbon atoms and having a carbon number of 2 Between the alkyl groups of 12, at least one O; or E 16 (CH 2 CH 2 O) n+1 H, (CH 2 CH 2 O) n (CO)-(R 4 ), carbon number 2 to 12 The alkenyl group or a cycloalkyl group having a carbon number of 3 to 8 and n is 1 to 20, for example 1 to 12 or 1 to 8, especially 1 or 2.

此外,E16可例如為苯基或萘基,尤其為苯基、噻吩基或咔唑,其各未經取代或經如下所示之至少一基團取代,且至少一基團係選自於苯基、鹵素原子、碳數為1至4之鹵代烷基、OE17、SE18、NE19E20或碳數為1至20之烷基;或E16係碳數為1至20之烷基,碳數為1至20之烷基未經取代或經如下所示之至少一基團取代,且至少一基團係選自於鹵素原子、苯基、OH、SH、碳數為3至6之烯氧基、OCH2CH2(CO)O(R1)、O(CO)-(R1)、O(CO)-苯基、(CO)OH或(CO)O(R1);或E16係碳數為2至12之烷基,且碳數為2至12之烷基係間雜有至少一O;或E16係(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4)、碳數為2至12之烯基或碳數為3至8之環烷基,且n係1至20,例如1至12或1至8,尤其為1或2。 Furthermore, E 16 may, for example, be phenyl or naphthyl, especially phenyl, thienyl or oxazole, each unsubstituted or substituted by at least one group as shown below, and at least one group selected from a phenyl group, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, OE 17 , SE 18 , NE 19 E 20 or an alkyl group having 1 to 20 carbon atoms; or an E 16 alkyl group having 1 to 20 carbon atoms An alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, a phenyl group, an OH group, and an SH group having a carbon number of 3 to 6 Alkenyloxy, OCH 2 CH 2 (CO)O(R 1 ), O(CO)-(R 1 ), O(CO)-phenyl, (CO)OH or (CO)O(R 1 ); Or an E 16 alkyl group having 2 to 12 carbon atoms, and an alkyl group having 2 to 12 carbon atoms having at least one O; or an E 16 system (CH 2 CH 2 O) n+1 H, (CH 2 CH 2 O) n (CO)-(R 4 ), an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, and n is 1 to 20, for example 1 to 12 or 1 to 8 Especially 1 or 2.

此外,E16可例如為苯基或萘基,尤其為苯基,其各未經取代或經如下所示之至少一基團取代,且至少一基團係選自於苯基、鹵素原子、碳數為1至4之鹵代烷基、OE17、SE18、NE19E20或碳數為1至20之烷基;或E16係碳數為3至5之雜芳基,尤其為噻吩基。 Furthermore, E 16 may, for example, be phenyl or naphthyl, especially phenyl, each unsubstituted or substituted by at least one group as shown below, and at least one group selected from phenyl, halogen atom, a haloalkyl group having 1 to 4 carbon atoms, OE 17 , SE 18 , NE 19 E 20 or an alkyl group having 1 to 20 carbon atoms; or an E 16 group heteroaryl group having 3 to 5 carbon atoms, especially a thienyl group .

E16尤其為(例如)苯基,苯基未經取代或經如下所示之至少一基團取代,且至少一基團係選自於OE17、SE18、NE19E20或碳數為1至20之烷基,或E16係噻吩基。 E 16 is especially, for example, a phenyl group which is unsubstituted or substituted with at least one group as shown below, and at least one group selected from OE 17 , SE 18 , NE 19 E 20 or a carbon number of An alkyl group of 1 to 20, or an E 16 system thienyl group.

較佳地,E16係(例如)苯基或萘基,其各未經取代或經至少一碳數為1至20之烷基取代。 Preferably, E 16 is, for example, phenyl or naphthyl, each unsubstituted or substituted with at least one alkyl group having from 1 to 20 carbon atoms.

E16尤其為苯基,且苯基經至少一碳數為1至20之烷基取代。 E 16 is especially a phenyl group, and the phenyl group is substituted with at least one alkyl group having 1 to 20 carbon atoms.

E17可例如為氫原子、苯基-R5、碳數為1至20之烷基,其係未經取代或經如下所示之至少一基團取代,且至少一基團係選自於鹵素原子、OH、OCH2CH2(CO)O(R1)、O(CO)-(R1)、O(CO)-(R6)、O(CO)-苯基、(CO)OH、(CO)O(R1)、碳數為3至20之環烷基或間雜有至少一O之碳數為3至20之環烷基;或E17係碳數為2至20之烷基,且碳數為2至20之烷基間雜有至少一O;或E17係(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4)、碳數為1至8之烷醯基、碳數為2至12之烯基、碳數為3至6之烯醯基或碳數為3至20之環烷基,其係未經間雜或間雜有至少一O;或E17係苯甲醯基,且苯甲醯基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自於碳數為1至6之烷基、鹵素原子、OH或碳數為1至3之烷氧基取代;或E17係苯基、萘基或碳數為5至20之雜芳基,其各未經取代或經如下所示之至少一基團取代,且至少一基團係選自於鹵素原子、OH、碳數為1至12之烷基、碳數為1至12之烷氧基、CN、NO2、苯基-R8、苯氧基、碳數為1至12之烷基硫基、苯基硫基、 N(R9)2、二苯基-胺基或 E 17 may, for example, be a hydrogen atom, a phenyl-R 5 group, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from Halogen atom, OH, OCH 2 CH 2 (CO)O(R 1 ), O(CO)-(R 1 ), O(CO)-(R 6 ), O(CO)-phenyl, (CO)OH , (CO)O(R 1 ), a cycloalkyl group having 3 to 20 carbon atoms or a cycloalkyl group having a carbon number of 3 to 20 intermixed with at least one O; or an E 17 alkyl group having 2 to 20 carbon atoms And the alkyl group having a carbon number of 2 to 20 is interspersed with at least one O; or E 17 (CH 2 CH 2 O) n+1 H, (CH 2 CH 2 O) n (CO)-(R 4 ) An alkanoyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an olefinic group having 3 to 6 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, which is unintercalated or Between at least one O; or E 17 benzyl fluorenyl, and the benzyl group is unsubstituted or substituted by at least one group as shown below, and at least one group is selected from a carbon number of 1 to An alkyl group, a halogen atom, an OH group or an alkoxy group having a carbon number of 1 to 3; or an E 17 group phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 5 to 20, each of which is unsubstituted or Substituting at least one group as shown below, and Less in a group selected from a halogen atom, OH, an alkyl group having a carbon number of 1-12, an alkoxy group having a carbon number of 1 to 12, CN, NO 2, phenyl -R 8, a phenoxy group, C a number of 1 to 12 alkylthio, phenylthio, N(R 9 ) 2 , diphenyl-amine or

在另一實施例中,E17係(例如)氫原子、苯基-R5、碳數為1至20之烷基,其係未經取代或經如下所示之至少一基團取代,且至少一基團係選自於鹵素原子、O(CO)-(R1)、O(CO)-(R6)或間雜有至少一O之碳數為2至20之烷基;或E17係碳數為1至8之烷醯基、碳數為2至12之烯基、碳數為3至6之烯醯基、間雜有至少一O之碳數為2至20之烷基、未經間雜或間雜有至少一O之碳數為3至20之環烷基;或 E17係苯甲醯基,苯甲醯基係未經取代或經如下所示之至少一基團取代,且至少一基團係選自於碳數為1至6之烷基、鹵素原子、OH或碳數為1至3之烷氧基;或E17係苯基或萘基,其各未經取代或經如下所示之至少一基團取代,且至少一基團係選自於鹵素原子、碳數為1至12之烷基或碳數為1至12之烷氧基。 In another embodiment, E 17 is, for example, a hydrogen atom, a phenyl-R 5 , an alkyl group having from 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group as shown below, and At least one group is selected from a halogen atom, O(CO)-(R 1 ), O(CO)-(R 6 ) or an alkyl group having at least one O and having a carbon number of 2 to 20; or E 17 And an alkylene group having 1 to 8 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an olefinic group having 3 to 6 carbon atoms, an alkyl group having 2 to 20 carbon atoms and at least one O, and not a heterocyclic or intervening heterocyclic alkyl group having at least one carbon number of 3 to 20; or an E 17 benzhydryl group, which is unsubstituted or substituted with at least one group as shown below, and At least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, OH or an alkoxy group having 1 to 3 carbon atoms; or an E 17 phenyl group or a naphthyl group, each of which is unsubstituted or Substituted by at least one group as shown below, and at least one group is selected from a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.

E17亦為(例如)氫原子、苯基-R5、碳數為1至8之烷醯基、碳數為1至20之烷基,其係未經取代或經如下所示之至少一基團取代,且至少一基團係選自於鹵素原子、碳數為3至20之環烷基、O(CO)-(R1)、O(CO)-(R6)或間雜有至少一O之碳數為2至20之烷基,或E17係碳數為2至20之烷基,其間雜有至少一O。 E 17 is also, for example, a hydrogen atom, a phenyl-R 5 group, an alkanoyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or at least one as shown below. a group substituted, and at least one group is selected from a halogen atom, a cycloalkyl group having 3 to 20 carbon atoms, O(CO)-(R 1 ), O(CO)-(R 6 ) or at least O is an alkyl group of a carbon number of 2 to 20, E 17, or based carbon atoms of the alkyl group of 2 to 20, between at least one heteroatom O.

E17尤其為氫原子、碳數為1至8之烷醯基、碳數為1至20之烷基,其係未經取代或經如下所示之至少一基團取代,且至少一基團係選自於O(CO)-(R1)、O(CO)-(R6)或間雜有至少一O之碳數為2至20之烷基,或E17係碳數為2至20之烷基,其間雜有至少一O。 E 17 is especially a hydrogen atom, an alkanoyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group as shown below, and at least one group Is selected from O(CO)-(R 1 ), O(CO)-(R 6 ) or an alkyl group having at least one O carbon number of 2 to 20, or an E 17 carbon number of 2 to 20 An alkyl group having at least one O intermixed therebetween.

E18係(例如)碳數為3至20之環烷基,其未經間雜或間雜有至少一O;或E18係碳數為1至20之烷基,其未經取代或經如下所示之至少一基團取代,且至少一基團係選自於OH、O(CO)-(R6)、O(CO)-(R1)或(CO)OE17;或E18係碳數為2至20之烷基,其間雜有至少一O、S、CO、NE26或COOE17;或E18係碳數為2至8之烷醯基或碳數為3至6之烯醯基、苯甲醯基;或E18係苯基、萘基或碳數為3至20之雜芳基,其各未經取代或經如下所示之至少一基團取代,且至少一基團係選自於鹵素 原子、碳數為1至12之烷基、碳數為1至4之鹵代烷基、碳數為1至12之烷氧基或NO2E 18 is, for example, a cycloalkyl group having 3 to 20 carbon atoms which is undoped or inter-heteromeric with at least one O; or an E 18 alkyl group having 1 to 20 carbon atoms which is unsubstituted or as follows At least one group is substituted, and at least one group is selected from OH, O(CO)-(R 6 ), O(CO)-(R 1 ) or (CO)OE 17 ; or E 18 -based carbon a number of 2 to 20 alkyl groups interspersed with at least one O, S, CO, NE 26 or COOE 17 ; or an E 18 alkylene group having 2 to 8 carbon atoms or an olefin having 3 to 6 carbon atoms a phenyl fluorenyl group; or an E 18 phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group It is selected from a halogen atom, an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or NO 2 .

在另一實施例中,E18係(例如)碳數為3至20之環烷基、碳數為1至20之烷基,其係未經取代或經如下所示之至少一基團取代,且至少一基團係選自於OH、O(CO)-(R6)、O(CO)-(R1)或(CO)OE17;或E18係苯基或萘基,其各未經取代或經至少一鹵素原子或碳數為1至12之烷基,尤其鹵素原子取代。 In another embodiment, E 18 is, for example, a cycloalkyl group having from 3 to 20 carbon atoms, an alkyl group having from 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group as shown below And at least one group is selected from the group consisting of OH, O(CO)-(R 6 ), O(CO)-(R 1 ) or (CO)OE 17 ; or E 18 phenyl or naphthyl, each of which Unsubstituted or substituted with at least one halogen atom or an alkyl group having 1 to 12 carbon atoms, especially a halogen atom.

E18係(例如)碳數為1至20之烷基、碳數為2至12之烯基、碳數為3至20之環烷基、苯基-R5、碳數為2至8之烷醯基、苯甲醯基、苯基或萘基。 E 18 is, for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a phenyl group - R 5 and a carbon number of 2 to 8 Alkyl, benzylidene, phenyl or naphthyl.

舉例而言,E18係碳數為1至20之烷基,其經如下所示之至少一基團取代,且至少一基團係選自於OH、O(CO)-(R6)、O(CO)-(R1)或(CO)OE17,或E18係苯基,其經至少一鹵素原子取代。 For example, E 18 is an alkyl group having 1 to 20 carbon atoms which is substituted with at least one group as shown below, and at least one group is selected from OH, O(CO)-(R 6 ), O(CO)-(R 1 ) or (CO)OE 17 , or an E 18 -based phenyl group substituted with at least one halogen atom.

較佳地,E18係碳數為1至8之烷基,其如上文所定義經取代。 Preferably, E 18 is an alkyl group having 1 to 8 carbon atoms which is substituted as defined above.

舉例而言,E19及E20分別獨立地為氫原子、碳數為1至20之烷基、碳數為2至4之羥基烷基、碳數為3至20之環烷基、苯基-R5、苯基或萘基、碳數為1至8之烷醯基、碳數為1至8之烷醯基氧基、碳數為3至12之烯醯基或苯甲醯基;或E19及E20係與所鍵結之氮原子一起形成未經間雜或間雜有O、S或NE17之五員或六員飽和或不飽和環;或E19及E20係與所鍵結之氮原子一起形成雜芳香族環系統,雜芳香族環系統未經取代或經如下所示之至少一基團取代,且至少一基團係選自於碳數為1至20之烷基、碳數為1至4之鹵代烷 基、或 For example, E 19 and E 20 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a phenyl group. a -R 5 , phenyl or naphthyl group, an alkanoyl group having 1 to 8 carbon atoms, an alkyl fluorenyloxy group having 1 to 8 carbon atoms, an olefinic group having a carbon number of 3 to 12 or a benzamidine group; Or the E 19 and E 20 systems together with the bonded nitrogen atom form a five- or six-membered saturated or unsaturated ring without interstitial or interstitial O, S or NE 17 ; or E 19 and E 20 and the bond The nitrogen atoms of the knot together form a heteroaromatic ring system, the heteroaromatic ring system is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from an alkyl group having 1 to 20 carbon atoms. a halogenated alkyl group having 1 to 4 carbon atoms, or

此外,舉例而言,E19及E20分別獨立地為氫原子、碳數為1至20之烷基、碳數為2至4之羥基烷基、碳數為3至20之環烷基、苯基-R5、碳數為1至8之烷醯基、碳數為1至8之烷醯基氧基、碳數為3至12之烯醯基或苯甲醯基;或E19及E20係與所鍵結之氮原子一起形成未經間雜或間雜有O或NE17之五員或六員飽和環;或E19及E20係與所鍵結之氮原子一起形成咔唑環。 Further, for example, E 19 and E 20 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, Phenyl-R 5 , an alkanoyl group having a carbon number of 1 to 8, an alkanoyloxy group having 1 to 8 carbon atoms, an olefinic group having a carbon number of 3 to 12 or a benzhydryl group; or E 19 and The E 20 system together with the bonded nitrogen atom forms a five- or six-membered saturated ring which is unintermixed or intermixed with O or NE17; or the E 19 and E 20 systems together with the bonded nitrogen atom form an indazole ring.

舉例而言,E19及E20分別獨立地為氫原子、碳數為1至20之烷基、碳數為2至4之羥基烷基、碳數為3至20之環烷基、苯基-R5、碳數為1至8之烷醯基、碳數為1至8之烷醯基氧基、碳數為3至12之烯醯基或苯甲醯基;或E19及E20係與所鍵結之氮原子一起形成未經間雜或間雜有O或NE17之五員或六員飽和環。 For example, E 19 and E 20 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a phenyl group. -R 5 , an alkanoyl group having 1 to 8 carbon atoms, an alkenyloxy group having 1 to 8 carbon atoms, an olefinic group having a carbon number of 3 to 12 or a benzamidine group; or E 19 and E 20 Together with the nitrogen atom to which it is bonded, it forms a five- or six-membered saturated ring that is either inter- or hetero-organized with O or NE 17 .

較佳地,E19及E20分別獨立地為碳數為1至8之烷醯基、碳數為1至8之烷醯基氧基;或E19及E20係與所鍵結之氮原子形成嗎啉環。 Preferably, E 19 and E 20 are each independently an alkanoyl group having 1 to 8 carbon atoms, an alkyl fluorenyl group having 1 to 8 carbon atoms, or an E 19 and E 20 system bonded to a nitrogen atom; The atom forms a morpholine ring.

舉例而言,E21及E22分別獨立地為氫原子、碳數為1至20之烷基、碳數為1至4之鹵代烷基、碳數為3至10之環烷基或苯基;或E21及E22係與所鍵結之氮原子形成嗎啉環。E21及E22尤其分別獨立地為氫原子或碳數為1至20之烷基。 For example, E 21 and E 22 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group; Or the E 21 and E 22 systems form a morpholine ring with the bonded nitrogen atom. In particular, E 21 and E 22 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

E23係(例如)氫原子、OH、苯基或碳數為1至20之烷基。E23尤其為氫原子、OH或碳數為1至4之烷基。 E 23 is, for example, a hydrogen atom, an OH group, a phenyl group or an alkyl group having 1 to 20 carbon atoms. E 23 is especially a hydrogen atom, OH or an alkyl group having 1 to 4 carbon atoms.

E24之較佳者係如針對E19及E20所定義之其中一者。E25 之較佳者係如針對E17所定義之其中一者。 The preferred of E 24 is as defined for E 19 and E 20 . The preferred of E 25 is one of those defined for E 17 .

E26係(例如)氫原子、碳數為1至20之烷基、碳數為1至4之鹵代烷基、碳數為2至20之烷基,其間雜有至少一O或CO;或E26係苯基-R1、碳數為3至8之環烷基,且碳數為3至8之環烷基係未經間雜或間雜一或多個O或CO;或E26係(CO)E19或苯基,且苯基係未經取代或經以下至少一基團取代,至少一基團可為碳數為1至20之烷基、鹵素原子、碳數為1至4之鹵代烷基、OE17、SE18、NE19E20E 26 is, for example, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having 2 to 20 carbon atoms, and at least one O or CO intermixed therebetween; or E 26 series phenyl-R 1 , cycloalkyl having 3 to 8 carbon atoms, and a cycloalkyl group having 3 to 8 carbon atoms without inter- or hetero- or one or more O or CO; or E 26 (CO) E 19 or a phenyl group, and the phenyl group is unsubstituted or substituted by at least one of the following groups, and at least one group may be an alkyl group having 1 to 20 carbon atoms, a halogen atom, and an alkyl halide having 1 to 4 carbon atoms. Base, OE 17 , SE 18 , NE 19 E 20 .

或E26表示(例如)氫原子、碳數為1至20之烷基、碳數為1至4之鹵代烷基;係苯基-R1、碳數為3至8之環烷基、(CO)E19或苯基,且苯基係未經取代或經至少一碳數為1至20之烷基取代。此外,E26係(例如)氫或碳數為1至20之烷基、尤其為碳數為1至4之烷基。 Or E 26 represents, for example, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group-R 1 , a cycloalkyl group having 3 to 8 carbon atoms, (CO) E 19 or a phenyl group, and the phenyl group is unsubstituted or substituted with at least one alkyl group having 1 to 20 carbon atoms. Further, E 26 is, for example, hydrogen or an alkyl group having 1 to 20 carbon atoms, particularly an alkyl group having 1 to 4 carbon atoms.

前述具有如式(III)所示之結構的光起始劑(E-1)之具體例可包含具有如下式(III-1)至式(III-86)所示之結構的光起始劑。 Specific examples of the photoinitiator (E-1) having the structure represented by the formula (III) may include a photoinitiator having a structure represented by the following formula (III-1) to formula (III-86). .

基於鹼可溶性樹脂(C)之使用量為100重量份,光起始劑(E-1)之使用量為0.1重量份至15重量份,較佳為1重量份至12重量份,且更佳為3重量份至10重量份。當使用該光起始劑(E-1)時,該感光性樹脂組成物所形成之彩色濾光片其熱溶劑膜厚變化率更佳。 The photoinitiator (E-1) is used in an amount of from 0.1 part by weight to 15 parts by weight, preferably from 1 part by weight to 12 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C), and more preferably It is from 3 parts by weight to 10 parts by weight. When the photoinitiator (E-1) is used, the color filter formed of the photosensitive resin composition has a higher change rate of the thermal solvent film thickness.

根據本發明之光起始劑(E)可進一步包含其它自由基型光起始劑(E-2)。 The photoinitiator (E) according to the invention may further comprise other radical type photoinitiators (E-2).

該其它自由基型光起始劑(E-2)可選自於苯乙酮系化合物(acetophenone)、二咪唑系化合物(biimidazole)、醯肟系化合物(acyl oxime)或此等之一組合。 The other radical type photoinitiator (E-2) may be selected from the group consisting of an acetophenone compound, a biimidazole compound, an acyl oxime compound, or a combination thereof.

上述的苯乙酮系化合物是選自於對二甲胺苯乙酮(p-dimethylamino-acetophenone)、α,α’-二甲氧基氧化偶氮苯乙酮(α,α’-dimethoxyazoxy-acetophenone)、2,2’-二甲基-2-苯基苯乙酮(2,2’-dimethyl-2-phenyl-acetophenone)、對甲氧基苯乙酮(p-methoxy-acetophenone)、2-甲基-1-(4-甲基硫代苯基)-2-嗎啉代-1-丙酮〔2-methyl-1-(4-methylthio phenyl)-2-morpholino-1-propanone〕、2-苄基-2-氮,氮-二甲胺-1-(4-嗎啉代苯基)-1-丁酮〔2-benzyl-2-N,N-di-methylamino-1-(4-morpholinophenyl)-1-butanone〕。 The above acetophenone-based compound is selected from the group consisting of p-dimethylamino-acetophenone, α , α '-dimethoxy azo acetophenone (α, α'-dimethoxyazoxy-acetophenone). , 2,2'-dimethyl-2-phenyl-acetophenone, p-methoxy-acetophenone, 2- Methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2- Benzyl-2-nitrogen, nitrogen-dimethylamine-1-(4-morpholinophenyl)-1-butanone [2-benzyl-2-N,N-di-methylamino-1-(4-morpholinophenyl) )-1-butanone].

上述的二咪唑系化合物是選自於2,2’-雙(鄰-氯苯基)-4,4’,5,5’-四苯基二咪唑〔2,2’-bis(o-chlorophenyl)-4,4’,5,5’-tetraphenyl-biimidazole〕、2,2’-雙(鄰-氟苯基)-4,4,5,5’-四苯基二咪唑〔2,2’-bis(o-fluorophenyl)-4,4’,5,5’-tetraphenyl-biimidazole〕、2,2’-雙 (鄰-甲基苯基)-4,4’,5,5’-四苯基二咪唑〔2,2’-bis(o-methyl phenyl)-4,4’,5,5’-tetraphenyl-biimidazole〕、2,2’-雙(鄰-甲氧基苯基)-4,4’,5,5’-四苯基二咪唑〔2,2’-bis(o-methoxyphenyl)-4,4’,5,5’-tetraphenyl-biimidazole〕、2,2’-雙(鄰-乙基苯基)-4,4’,5,5’-四苯基二咪唑〔2,2’-bis(o-ethylphenyl)-4,4’,5,5’-tetraphenyl-biimidazole〕、2,2’-雙(對甲氧基苯基)-4,4’,5,5’-四苯基二咪唑〔2,2’-bis(p-methoxyphenyl)-4,4’,5,5’-tetraphenyl-biimidazole〕、2,2’-雙(2,2’,4,4’-四甲氧基苯基)-4,4’,5,5’-四苯基二咪唑〔2,2’-bis(2,2’,4,4’-tetramethoxyphenyl)-4,4’,5,5’-tetraphenyl-biimidazole〕、2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基二咪唑〔2,2’-bis(2-chlorophenyl)-4,4’,5,5’-tetraphenyl-biimidazole〕、2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基二咪唑〔2,2’-bis(2,4-dichlorophenyl)-4,4’,5,5’-tetraphenyl-biimidazole〕。 The above diimidazole compound is selected from 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis (o-chlorophenyl) )-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-fluorophenyl)-4,4,5,5'-tetraphenyldiimidazole [2,2' -bis(o-fluorophenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-double (o-methylphenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(o-methyl phenyl)-4,4',5,5'-tetraphenyl- Biimidazole], 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(o-methoxyphenyl)-4,4 ',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-ethylphenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis ( O-ethylphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(2,2',4,4'-tetramethoxybenzene 4,4',5,5'-tetraphenyldiimide [2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyl -biimidazole], 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(2-chlorophenyl)-4,4' ,5,5'-tetraphenyl-biimidazole], 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis (2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole].

上述的醯肟系化合物是選自於乙烷酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9氫-咔唑-3-取代基]-,1-(氧-乙醯肟)〔Ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime),例如Ciba Specialty Chemicals製之品名為CGI-242者,其結構如下式(E-2-1)所示〕、1-[4-(苯基硫代)苯基]-辛烷-1,2-二酮2-(O-苯醯基肟)〔1-[4-(benzoyl)phenyl]-heptane-1,2-dione 2-(O-benzoyloxime),例如Ciba Specialty Chemicals製造之商品名為CGI-124之商品,其結構如下式(E-2-2)所示〕、乙烷酮,1-[9-乙基-6-(2-氯-4-苯甲基-硫代-苯甲醯基)-9氫-咔唑-3-取代基]-,1-(氧-乙醯肟)〔Ethanone,1-[9-ethyl-6-(2-cholro-4-benzyl-thio-benzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime),例如旭電化公司製,其結構如下式(E-2-3)所示〕: The above lanthanide compound is selected from the group consisting of ethane ketone, 1-[9-ethyl-6-(2-methylbenzylidenyl)-9hydro-oxazol-3- substituent]-, 1- (Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), for example, manufactured by Ciba Specialty Chemicals The product name is CGI-242, and its structure is as shown in the following formula (E-2-1)], 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O -1-[4-(benzoyl)phenyl]-heptane-1,2-dione 2-(O-benzoyloxime), for example, a product of the trade name CGI-124 manufactured by Ciba Specialty Chemicals, the structure of which As shown in the following formula (E-2-2), ethane ketone, 1-[9-ethyl-6-(2-chloro-4-benzyl-thio-benzhydryl)-9-hydrogen- Ethanone, 1-[9-ethyl-6-(2-cholro-4-benzyl-thio-benzoyl)-9H-carbazole-3 -yl]-, 1-(O-acetyl oxime), for example, manufactured by Asahi Kasei Co., Ltd., whose structure is as shown in the following formula (E-2-3):

較佳地,該其它自由基型光起始劑(E-2)為2-甲基-1-(4-甲基硫代苯基)-2-嗎啉代-1-丙酮、2-苄基-2-氮,氮-二甲胺-1-(4-嗎啉代苯基)-1-丁酮、2,2’-雙(鄰-氯苯基)-4,4’,5,5’-四苯基二咪唑、乙烷酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9氫-咔唑-3-取代基]-,1-(氧-乙醯肟)或此等之一組合。 Preferably, the other radical photoinitiator (E-2) is 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl Base-2-nitrogen, nitrogen-dimethylamine-1-(4-morpholinophenyl)-1-butanone, 2,2'-bis(o-chlorophenyl)-4,4',5, 5'-tetraphenyldiimidazole, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidenyl)-9hydro-oxazol-3-substituted group]-, 1-( Oxygen-acetamidine) or a combination of these.

本發明之其它自由基型光起始劑(E-2)可進一步添加下列之化合物:噻噸酮(thioxanthone)、2,4-二乙基噻噸酮(2,4-diethyl-thioxanthanone)、噻噸酮-4-碸(thioxanthone-4-sulfone)、二苯甲酮(benzophenone)、4,4’-雙(二甲胺)二苯甲酮〔4,4’-bis(dimethylamino)benzophenone〕、4,4’-雙(二乙胺)二苯甲酮〔4,4’- bis(diethylamino)benzophenone〕等之二苯甲酮(benzophenone)類化合物;苯偶醯(benzil)、乙醯基(acetyl)等之α-二酮(α-diketone)類化合物;二苯乙醇酮(benzoin)等之酮醇(acyloin)類化合物;二苯乙醇酮甲醚(benzoin methylether)、二苯乙醇酮乙醚(benzoin ethylether)、二苯乙醇酮異丙醚(benzoin isopropyl ether)等之酮醇醚(acyloin ether)類化合物;2,4,6-三甲基苯醯二苯基膦氧化物(2,4,6-trimethyl-benzoyl-diphenyl-phosphineoxide)、雙-(2,6-二甲氧基苯醯)-2,4,4-三甲基苯基膦氧化物〔bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethyl-benzyl-phosphineoxide〕等之醯膦氧化物(acylphosphineoxide)類化合物;蒽醌(anthraquinone)、1,4-萘醌(1,4-naphthoquinone)等之醌(quinone)類化合物;苯醯甲基氯(phenacyl chloride)、三溴甲基苯碸(tribromomethyl-phenylsulfone)、三(三氯甲基)-s-三嗪〔tris(trichloromethyl)-s-triazine〕等之鹵化物;以及二-第三丁基過氧化物(di-tertbutylperoxide)等之過氧化物。其中,以二苯甲酮(benzophenone)類化合物較佳,尤以4,4’-雙(二乙胺)二苯甲酮為最佳。 The other radical type photoinitiator (E-2) of the present invention may further contain the following compounds: thioxanthone, 2,4-diethyl-thioxanthanone, Thioxanthone-4-sulfone, benzophenone, 4,4'-bis(dimethylamino)benzophenone a benzophenone compound such as 4,4'-bis(diethylamino)benzophenone; benzil or acetamidine (Acetyl), etc. α - dione (α-diketone) compound; benzoin-based compound (Benzoin) etc. ketol (acyloin); Benzoin methyl ether (benzoin methylether), benzoin ethyl ether (benzoin ethylether), benzoin isopropyl ether and other acyloin ether compounds; 2,4,6-trimethylphenylhydrazine diphenylphosphine oxide (2,4 ,6-trimethyl-benzoyl-diphenyl-phosphineoxide), bis-(2,6-dimethoxybenzoquinone)-2,4,4-trimethylphenylphosphine oxide [bis-(2,6-dimethoxy) -benzoyl)-2,4,4-trimethyl-benzyl-phosphineoxide] (acylphosphineoxide) compounds; quinone compounds such as anthraquinone, 1,4-naphthoquinone, etc.; phenacyl chloride, tribromomethylphenylhydrazine a halide such as tribromomethyl-phenylsulfone, tris(trichloromethyl)-s-triazine or the like; and di-tertbutylperoxide peroxide. Among them, a benzophenone-based compound is preferred, and 4,4'-bis(diethylamine)benzophenone is particularly preferred.

上述其它自由基型光起始劑(E-2)可單獨一種或混合複數種使用。 The above other radical type photoinitiators (E-2) may be used singly or in combination of plural kinds.

於本發明之具體例中,基於該鹼可溶性樹脂(C)之使用量為100重量份,該其它自由基型光起始劑(E-2)之使用量為9.9重量份至85重量份;較佳為14重量份至78重量份;更佳為17重量份至70重量份。 In a specific example of the present invention, the amount of the other radical-type photoinitiator (E-2) used is 9.9 parts by weight to 85 parts by weight based on 100 parts by weight of the alkali-soluble resin (C); It is preferably from 14 parts by weight to 78 parts by weight; more preferably from 17 parts by weight to 70 parts by weight.

基於該鹼可溶性樹脂(C)之使用量為100重量份,該光起始劑(E)之使用量為10重量份至100重量份;較佳為15重量份至90重量份;更佳為20重量份至80重量份。 The photoinitiator (E) is used in an amount of 10 parts by weight to 100 parts by weight based on 100 parts by weight of the alkali-soluble resin (C); preferably 15 parts by weight to 90 parts by weight; more preferably 20 parts by weight to 80 parts by weight.

根據本發明之熱酸發生劑(F)具有式(I)所示結構:R1f(SO3R2f)a 式(I) The thermal acid generator (F) according to the present invention has a structure represented by the formula (I): R 1f (SO 3 R 2f ) a formula (I)

於式(I)中,R1f及R2f各自獨立地表示任意的取代基,該取代基並無特別限制,例如:烴基(烷基、烯基、苯基、芐基、甲苯基、二甲苯基、萘基、烷基萘基等)及全氟烷基等,其中,R2f較佳為(C6H5)COCH(C6H5)O-;及a表示1以上之整數;較佳為1至4之整數;更佳為1至2之整數。 In the formula (I), R 1f and R 2f each independently represent an arbitrary substituent, and the substituent is not particularly limited, and examples thereof include a hydrocarbon group (alkyl group, alkenyl group, phenyl group, benzyl group, tolyl group, xylene group). And a perfluoroalkyl group, wherein R 2f is preferably (C 6 H 5 )COCH(C 6 H 5 )O-; and a represents an integer of 1 or more; Preferably, it is an integer of 1 to 4; more preferably an integer of 1 to 2.

該具有式(I)所示結構之熱酸發生劑(F)較佳係選自由芳香族磺酸酯、脂肪族磺酸酯及全氟烷基磺酸酯所組合之群。 The thermal acid generator (F) having the structure represented by the formula (I) is preferably selected from the group consisting of an aromatic sulfonate, an aliphatic sulfonate and a perfluoroalkyl sulfonate.

於本發明之具體例中,前述之芳香族磺酸酯為p-甲苯磺酸甲酯、p-甲苯磺酸乙酯、p-甲苯磺酸丁酯、1,2,3-三(p-甲苯磺醯氧基)苯〔1,2,3-tri(p-toluenesulfonyloxy)benzene〕、p-甲苯磺酸安息香酯(p-toluene sulfonic acid benzoin ester)、十二烷基苯磺酸甲酯、十二烷基苯磺酸乙酯(例如king Industries社製造,型號為K-PURE TAG 2507之商品)、萘二磺酸二甲酯、萘二磺酸二乙酯、萘磺酸甲酯、萘磺酸乙酯、二壬基萘磺酸甲酯、二壬基萘磺酸乙酯(例如king Industries社製造,型號為K-PURE CXC1762之商品)、二壬基萘二磺酸乙酯(例如king Industries社製造,型號為K-PURE CXC1764之商品)或下述式(I-1)至式(I-3)所示之結構等。 In a specific example of the present invention, the aromatic sulfonate is methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, 1,2,3-tris (p- 1,2,3-tri(p-toluenesulfonyloxy)benzene, p-toluene sulfonic acid benzoin ester, methyl dodecylbenzenesulfonate, Ethyl dodecylbenzenesulfonate (for example, manufactured by King Industries, K-PURE TAG 2507), dimethyl naphthalene disulfonate, diethyl naphthalene disulfonate, methyl naphthalenesulfonate, naphthalene Ethyl sulfonate, methyl dinonylnaphthalenesulfonate, ethyl dinonylnaphthalenesulfonate (for example, manufactured by King Industries, K-PURE CXC1762), ethyl dinonylnaphthalene disulfonate (for example) The product shown by King Industries Co., Ltd., model K-PURE CXC1764) or the structure shown by the following formula (I-1) to formula (I-3).

其中,m表示1至3之整數 Where m represents an integer from 1 to 3

於本發明之具體例中,前述之脂肪族磺酸酯為甲烷磺 酸甲酯、甲烷磺酸乙酯、甲烷磺酸丁酯、1,2,3-三(甲烷磺醯氧基)苯〔1,2,3-tri(methanesulfonyloxy)benzene〕、甲烷磺酸苯酯、甲烷磺酸安息香酯(methane sulfonic acid benzoin ester)等。 In a specific example of the present invention, the aforementioned aliphatic sulfonate is methane sulfonate. Methyl ester, ethyl methanesulfonate, butyl methanesulfonate, 1,2,3-tri(methanesulfonyloxy)benzene, phenyl methanesulfonate , methane sulfonic acid benzoin ester (methane sulfonic acid benzoin ester).

於本發明之具體例中,前述之全氟烷基磺酸酯為三氟甲烷磺酸甲酯、三氟甲烷磺酸乙酯、三氟甲烷磺酸丁酯、1,2,3-(三氟甲烷磺醯氧基)苯〔1,2,3-(trifluoromethanesulfonyloxy)benzene〕、三氟甲烷磺酸苯酯、三氟甲烷磺酸安息香酯(trifluoromethanesulfonic acid benzoin ester)等。 In a specific example of the present invention, the above perfluoroalkyl sulfonate is methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, butyl trifluoromethanesulfonate, 1,2,3-(three Trifluoromethanesulfonyl benzene, trifluoromethanesulfonic acid benzoin ester, and the like.

上述之磺酸酯可單獨一種使用或混合多種使用。 The above sulfonic acid esters may be used singly or in combination of two or more.

基於該鹼可溶性樹脂(C)之使用量為100重量份,該熱酸發生劑(F)之使用量範圍為0.1重量份至10重量份;較佳為0.6重量份至8重量份;更佳為1重量份至6重量份。當未使用該熱酸發生劑(F)時,該感光性樹脂組成物所形成之彩色濾光片具有熱溶劑膜厚變化率不佳之問題。當使用該芳香族磺酸酯之熱酸發生劑(F)時,該感光性樹脂組成物所形成之彩色濾光片其熱溶劑膜厚變化率更佳。 The thermal acid generator (F) is used in an amount ranging from 0.1 part by weight to 10 parts by weight, based on the amount of the alkali-soluble resin (C), preferably from 0.6 part by weight to 8 parts by weight; more preferably from 0.6 part by weight to 8 parts by weight; more preferably It is from 1 part by weight to 6 parts by weight. When the thermal acid generator (F) is not used, the color filter formed of the photosensitive resin composition has a problem that the rate of change in the thickness of the thermal solvent film is not good. When the thermal acid generator (F) of the aromatic sulfonate is used, the color filter formed of the photosensitive resin composition has a higher change rate of the thermal solvent film thickness.

本發明該感光性樹脂組成物的製備,通常是先將該顏料(A)以外的各成份溶解於溶劑(G)中,調製成液狀組成物,再加入顏料(A)均勻混合。溶劑(G)需選擇可溶解染料(B)、鹼可溶性樹脂(C)、具有乙烯性不飽和基之化合物(D)、光起始劑(E)以及熱酸發生劑(F),且需不與該等成份相互反應並具有適當揮發性者。 In the preparation of the photosensitive resin composition of the present invention, usually, each component other than the pigment (A) is dissolved in a solvent (G) to prepare a liquid composition, and then the pigment (A) is uniformly mixed. The solvent (G) is selected from a soluble dye (B), an alkali-soluble resin (C), a compound having an ethylenically unsaturated group (D), a photoinitiator (E), and a thermal acid generator (F). Do not react with these components and have appropriate volatility.

基於該鹼可溶性樹脂(C)之使用量為100重量份,該溶劑(G)之使用量為500重量份至5000重量份;較佳為800重量份至4500重量份;更佳為1000重量份至4000重量份。 The solvent (G) is used in an amount of 500 parts by weight to 5000 parts by weight, based on the amount of the alkali-soluble resin (C) used, preferably from 800 parts by weight to 4,500 parts by weight; more preferably 1,000 parts by weight. Up to 4000 parts by weight.

此外,溶劑(G)可與製備鹼可溶性樹脂(C)所使用的溶劑相同,在此不再贅述。較佳地,該溶劑(G)是擇自於丙二醇甲醚醋酸酯、環己酮或3-乙氧基丙酸乙酯。 Further, the solvent (G) may be the same as the solvent used to prepare the alkali-soluble resin (C), and will not be described herein. Preferably, the solvent (G) is selected from the group consisting of propylene glycol methyl ether acetate, cyclohexanone or ethyl 3-ethoxypropionate.

於本發明之較佳具體例中,該感光性樹脂組成物還包括添加劑(H),例如:填充劑、鹼可溶性樹脂(C)以外的高分子化合物、密著促進劑、抗氧化劑、紫外線吸收劑、防凝集劑等。 In a preferred embodiment of the present invention, the photosensitive resin composition further includes an additive (H) such as a filler, a polymer compound other than the alkali-soluble resin (C), an adhesion promoter, an antioxidant, and ultraviolet absorption. Agent, anti-aggregation agent, etc.

該添加劑(H)可單獨或混合使用,且該添加劑(H)包含但不限於玻璃、鋁等填充劑;聚乙烯醇、聚乙二醇單烷基醚、聚氟丙烯酸烷酯等鹼可溶性樹脂(C)以外的高分子化合物;乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧乙氧基)矽烷、氮-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、氮-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-環氧丙醇丙基三甲氧基矽烷、3-環氧丙醇丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯氧基丙基三甲氧基矽烷、3-硫醇基丙基三甲氧基矽烷等密著促進劑;2,2-硫代雙(4-甲基-6-第三丁基苯酚)、2,6-二-第三丁基苯酚等抗氧化劑;2-(3-第三丁基-5-甲基-2-羥基苯基)-5-氯苯基疊氮、烷氧基苯酮等紫外線吸收劑;及聚丙烯酸鈉等防凝集劑。 The additive (H) may be used singly or in combination, and the additive (H) includes, but is not limited to, a filler such as glass or aluminum; an alkali-soluble resin such as polyvinyl alcohol, polyethylene glycol monoalkyl ether or polyfluoroalkyl acrylate. Polymer compound other than (C); vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, nitrogen-(2-aminoethyl)-3 -Aminopropylmethyldimethoxydecane, nitrogen-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-ring Oxypropanol propyl trimethoxy decane, 3-glycidyl propyl methyl dimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 3-chloropropyl a adhesion promoter such as methyl dimethoxy decane, 3-chloropropyl trimethoxy decane, 3-methyl propylene oxypropyl trimethoxy decane, 3-thiol propyl trimethoxy decane; , an antioxidant such as 2-thiobis(4-methyl-6-tert-butylphenol) or 2,6-di-tert-butylphenol; 2-(3-tert-butyl-5-methyl Ultraviolet absorbers such as 2-hydroxyphenyl)-5-chlorophenyl azide and alkoxyphenone; and sodium polyacrylate Anti-agglomerating agent.

基於該鹼可溶性樹脂(C)之使用量為100重量份,該添加劑(H)之使用量為0.1重量份至10重量份;較佳為0.3重量份至7重量份;更佳為0.5重量份至4重量份。 The additive (H) is used in an amount of from 0.1 part by weight to 10 parts by weight, based on the amount of the alkali-soluble resin (C), preferably from 0.3 part by weight to 7 parts by weight; more preferably 0.5 part by weight. Up to 4 parts by weight.

本發明亦提供一種彩色濾光片之製造方法,其係使用前述之彩色濾光片用感光性樹脂組成物,以於基板上形成一畫素層。 The present invention also provides a method of producing a color filter using the above-described photosensitive resin composition for a color filter to form a pixel layer on a substrate.

本發明又提供一種彩色濾光片,其係由前述之方法所製得。 The present invention further provides a color filter which is produced by the aforementioned method.

本發明之彩色濾光片之製造方法,主要係藉由迴轉塗佈、流延塗佈、噴墨塗佈(ink-jet)或輥式塗佈等塗佈方式,將混合成溶液狀態之前述彩色濾光片用感光性組成物塗佈在基板上。塗佈後,先以減壓乾燥之方式,去除大部分之溶劑,再以預烤(pre-bake)方式 將溶劑去除而形成一預烤塗膜。其中,減壓乾燥及預烤之條件,依各成份之種類,配合比率而異,通常,減壓乾燥乃是在0至200mmHg之壓力下進行1秒鐘至60秒鐘,而預烤乃是在70至110℃溫度下進行1分鐘至15分鐘。預烤後,該預烤塗膜於所指定之光罩(mask)下曝光,於23±2℃溫度下浸漬於顯影液15秒至5分鐘進行顯影,除去不要之部分而形成圖案。曝光使用之光線,以g線、h線、i線等之紫外線為佳,而紫外線裝置可為(超)高壓水銀燈或金屬鹵素燈。 The method for producing a color filter of the present invention is mainly a method of mixing into a solution state by a coating method such as rotary coating, cast coating, ink-jet coating or roll coating. The color filter is coated on the substrate with a photosensitive composition. After coating, remove most of the solvent by drying under reduced pressure, and then pre-bake. The solvent is removed to form a prebaked coating film. The conditions for drying under reduced pressure and pre-baking vary depending on the type of each component and the blending ratio. Usually, the drying under reduced pressure is carried out at a pressure of 0 to 200 mmHg for 1 second to 60 seconds, and the pre-baking is It is carried out at a temperature of 70 to 110 ° C for 1 minute to 15 minutes. After prebaking, the prebaked coating film is exposed to a designated mask, immersed in a developing solution at a temperature of 23 ± 2 ° C for 15 seconds to 5 minutes for development, and the unnecessary portion is removed to form a pattern. The light used for exposure is preferably ultraviolet rays such as g-line, h-line, and i-line, and the ultraviolet device may be a (super) high-pressure mercury lamp or a metal halide lamp.

前述基板之具體例如:用於液晶顯示裝置之無鹼玻璃、鈉鈣玻璃、硬質玻璃(派勒斯玻璃)、石英玻璃、鈉玻璃以及於此等玻璃上所附著的透明導電膜;或用於固體攝影裝置等之光電變換裝置基板(如:矽基板)等等。此等基板一般係先形成隔離各畫素著色層之黑色矩陣(black matrix)。 Specific examples of the substrate include: alkali-free glass, soda-lime glass, hard glass (Pyrus glass), quartz glass, soda glass, and a transparent conductive film attached to the glass for use in a liquid crystal display device; or A photoelectric conversion device substrate (such as a germanium substrate) of a solid-state imaging device or the like. These substrates generally form a black matrix that separates the colored layers of each pixel.

再者,顯影液之具體例如:氫氧化鈉,氫氧化鉀,碳酸鈉,碳酸氫鈉,碳酸鉀,碳酸氫鉀,矽酸鈉,甲基矽酸鈉,氨水,乙胺,二乙胺,二甲基乙醇胺,氫氧化四甲銨,氫氧化四乙銨,膽鹼,吡咯,呱啶,1,8-二氮雜二環-(5,4,0)-7-十一烯等鹼性化合物所構成之鹼性水溶液,其濃度一般為0.001至10重量%,較佳為0.005至5重量%,更佳為0.01至1重量%。 Further, specific examples of the developer include: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, ammonia, ethylamine, diethylamine, Dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, acridine, 1,8-diazabicyclo-(5,4,0)-7-undecene The alkaline aqueous solution of the compound is generally present in a concentration of from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight, more preferably from 0.01 to 1% by weight.

使用前述鹼性水溶液所構成之顯影液時,一般係於顯影後再以水洗淨,其次以壓縮空氣或壓縮氮氣將圖案風乾。 When the developer composed of the alkaline aqueous solution is used, it is usually washed with water after development, and then air-dried with compressed air or compressed nitrogen.

風乾後之具有光硬化塗膜層的基板,利用熱板或烘箱等加熱裝置,在溫度100至280℃下加熱1至15分鐘,將塗膜中的揮發性成分去除,並且使塗膜中未反應的乙烯性不飽和雙鍵進行熱硬化反應。使用各色(主要包括紅、綠、藍三色)之感光性樹脂組成物在預定的畫素上以同樣的步驟重複操作三次,即可得到紅、綠、藍三色之畫素著色層。 After drying, the substrate having the photo-curing coating layer is heated by a heating means such as a hot plate or an oven at a temperature of 100 to 280 ° C for 1 to 15 minutes to remove volatile components in the coating film, and the coating film is not The reacted ethylenically unsaturated double bond undergoes a thermosetting reaction. A photosensitive resin composition of each color (mainly including red, green, and blue colors) is repeatedly operated in the same step three times on a predetermined pixel to obtain a pixel coloring layer of three colors of red, green, and blue.

其次,在畫素著色層上,以220℃至250℃溫度於真空下形成ITO(氧化銦錫)蒸鍍膜,必要時,對ITO蒸鍍膜施行蝕刻暨佈線之後,再塗佈液晶配向膜用聚醯亞胺,進而燒成之,即可作為液晶顯示器用之彩色濾光片。 Next, on the pixel colored layer, an ITO (indium tin oxide) deposited film is formed under vacuum at a temperature of 220 ° C to 250 ° C, and if necessary, after etching and wiring the ITO deposited film, the liquid crystal alignment film is coated. The quinone imine, which is then fired, can be used as a color filter for liquid crystal displays.

再者,前述使用的液晶配向膜,係用於限制液晶分子之配向,此處並未特別限定,舉凡無機物或有機物任一者均可。至於形成液晶配向膜之技術為本發明所屬技術領域中任何具有通常知識者所熟知,且非為本發明的重點,故不另贅述。 Further, the liquid crystal alignment film used as described above is used to restrict the alignment of liquid crystal molecules, and is not particularly limited herein, and any of an inorganic substance or an organic substance may be used. The technique for forming a liquid crystal alignment film is well known to those of ordinary skill in the art to which the present invention pertains, and is not the focus of the present invention, and therefore will not be further described.

本發明又一目的在於提供一種液晶顯示元件,該液晶顯示元件包含前述彩色濾光片。 It is still another object of the present invention to provide a liquid crystal display element comprising the aforementioned color filter.

本發明之液晶顯示元件,主要係藉由上述彩色濾光片形成方法所形成之彩色濾光片基板,以及設置有薄膜電晶體(TFT,Thin Film Transistor)之驅動基板所構成,其中,在2片基板間介入間隙(晶胞間隔;cell gap)作對向配置,2片基板的周圍部位用封止劑貼合,在基板表面以及封止劑所區分出的間隙內充填注入液晶,封住注入孔而構成液晶晶胞(cell)。然後,在液晶晶胞的外表面,亦即構成液晶晶胞的各個基板的其他側面上,貼合偏光板而製得液晶顯示元件。 The liquid crystal display device of the present invention is mainly composed of a color filter substrate formed by the above-described color filter forming method and a driving substrate provided with a thin film transistor (TFT), wherein The inter-substrate gap (cell gap) is arranged in the opposite direction, and the peripheral portions of the two substrates are bonded together with a sealing agent, and the liquid crystal is filled in the gap between the surface of the substrate and the sealing agent to seal the injection. The holes constitute a liquid crystal cell. Then, a polarizing plate is bonded to the outer surface of the liquid crystal cell, that is, the other side surface of each of the substrates constituting the liquid crystal cell, to obtain a liquid crystal display element.

至於前述使用的液晶,亦即液晶化合物或液晶組成物,此處並未特別限定,惟可使用任何一種液晶化合物及液晶組成物。 The liquid crystal used in the above, that is, the liquid crystal compound or the liquid crystal composition is not particularly limited herein, and any liquid crystal compound and liquid crystal composition can be used.

茲以下列實例予以詳細說明本發明,唯並不意謂本發明僅侷限於此等實例所揭示之內容。 The invention is illustrated by the following examples, which are not intended to be limited to the scope of the invention.

<合成例> <Synthesis Example>

製備第一鹼可溶性樹脂(C) Preparation of first alkali soluble resin (C)

合成例C-1-1 Synthesis Example C-1-1

將100重量份的芴環氧化合物(型號ESF-300,新日鐵化學製;環氧當量231)、30重量份的丙烯酸、0.3重量份的氯化苄基三乙基銨、0.1重量份的2,6-二第三丁基對甲酚及130重量份的丙二醇甲醚醋酸酯連續添加至500mL的四口燒瓶中,且入料速度控制在25重量份/分鐘,將溫度維持在100℃至110℃的範圍內,反應15小時後,即可獲得固體成分濃度為50wt%之淡黃色透明混合液。 100 parts by weight of an antimony epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 part by weight 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500-mL four-necked flask, and the feed rate was controlled at 25 parts by weight/min, and the temperature was maintained at 100 ° C. After reacting for 15 hours in the range of 110 ° C, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

接著,將100重量份的上述混合液溶於25重量份的乙二醇乙醚醋酸酯中,同時添加6重量份的四氫鄰苯二甲酸酐及13重量份的二苯甲酮四甲酸二酐,並加熱至110℃至115℃,反應2小時後,即可獲得酸價為98.0mgKOH/g,且數目平均分子量為1,623之第一鹼可溶性樹脂(C-1-1)。 Next, 100 parts by weight of the above mixture was dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate, while 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of benzophenone tetracarboxylic dianhydride were added. And heating to 110 ° C to 115 ° C, after reacting for 2 hours, a first alkali-soluble resin (C-1-1) having an acid value of 98.0 mgKOH/g and a number average molecular weight of 1,623 was obtained.

合成例C-1-2 Synthesis Example C-1-2

將100重量份的芴環氧化合物(型號ESF-300,新日鐵化學製;環氧當量231)、30重量份的丙烯酸、0.3重量份的氯化苄基三乙基銨、0.1重量份的2,6-二第三丁基對甲酚及130重量份的丙二醇甲醚醋酸酯連續添加至500mL的四口燒瓶中,且入料速度控制在25重量份/分鐘,將溫度維持在100℃至110℃的範圍內,反應15小時後,即可獲得固體成分濃度為50wt%之淡黃色透明混合液。 100 parts by weight of an antimony epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 part by weight 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500-mL four-necked flask, and the feed rate was controlled at 25 parts by weight/min, and the temperature was maintained at 100 ° C. After reacting for 15 hours in the range of 110 ° C, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

接著,將100重量份的上述混合液溶於25重量份的乙二醇乙醚醋酸酯中,同時添加13重量份的二苯甲酮四甲酸二酐,在90℃至95℃下反應2小時,接著,添加6重量份的四氫鄰苯二甲酸酐,並於90℃至95℃下反應4小時,即可獲得酸價為99.0mgKOH/g,且數目平均分子量為2,162之第一鹼可溶性樹脂(C-1-2)。 Next, 100 parts by weight of the above mixture was dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate, while 13 parts by weight of benzophenone tetracarboxylic dianhydride was added, and the reaction was carried out at 90 ° C to 95 ° C for 2 hours. Next, 6 parts by weight of tetrahydrophthalic anhydride is added and reacted at 90 ° C to 95 ° C for 4 hours to obtain a first alkali-soluble resin having an acid value of 99.0 mgKOH/g and a number average molecular weight of 2,162. (C-1-2).

合成例C-1-3 Synthesis Example C-1-3

將400重量份的環氧化合物(型號NC-3000,日本化藥(株)製;環氧當量288)、102重量份的丙烯酸、0.3重量份的甲氧基酚 (methoxyphenol)、5重量份的三苯基膦及264重量份的丙二醇甲醚醋酸酯置於反應瓶中,將溫度維持在95℃,反應9小時後,即可獲得酸價為2.2mgKOH/g之中間產物。接著,加入151重量份的四氫鄰苯二甲酸酐(tetrahydrophthalic anhydride),在95℃下反應4小時,即可獲得酸價為102mgKOH/g,且數目平均分子量為2,589之第一鹼可溶性樹脂(C-1-3)。 400 parts by weight of an epoxy compound (Model NC-3000, manufactured by Nippon Kayaku Co., Ltd.; epoxy equivalent 288), 102 parts by weight of acrylic acid, and 0.3 parts by weight of methoxyphenol (methoxyphenol), 5 parts by weight of triphenylphosphine and 264 parts by weight of propylene glycol methyl ether acetate were placed in a reaction flask, and the temperature was maintained at 95 ° C. After 9 hours of reaction, an acid value of 2.2 mgKOH/g was obtained. Intermediate product. Next, 151 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain a first alkali-soluble resin having an acid value of 102 mgKOH/g and a number average molecular weight of 2,589 ( C-1-3).

合成例C-1-4 Synthesis Example C-1-4

將200重量份的環氧化合物(型號NC-3000,日本化藥(株)製;環氧當量288)、60重量份的丙烯酸、0.15重量份的甲氧基酚(methoxyphenol)、2.5重量份的三苯基膦及200重量份的丙二醇甲醚醋酸酯置於反應瓶中,將溫度維持在95℃,反應9小時後,即可獲得酸價為2.5mgKOH/g之中間產物。接著,加入85重量份的四氫鄰苯二甲酸酐(tetrahydrophthalic anhydride),在95℃下反應4小時,即可獲得酸價為105mgKOH/g,且數目平均分子量為3,410之第一鹼可溶性樹脂(C-1-4)。 200 parts by weight of an epoxy compound (Model NC-3000, manufactured by Nippon Kayaku Co., Ltd.; epoxy equivalent 288), 60 parts by weight of acrylic acid, 0.15 parts by weight of methoxyphenol, and 2.5 parts by weight Triphenylphosphine and 200 parts by weight of propylene glycol methyl ether acetate were placed in a reaction flask, and the temperature was maintained at 95 ° C. After 9 hours of reaction, an intermediate product having an acid value of 2.5 mg KOH / g was obtained. Next, 85 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain a first alkali-soluble resin having an acid value of 105 mgKOH/g and a number average molecular weight of 3,410 ( C-1-4).

製備第二鹼可溶性樹脂(C-2) Preparation of a second alkali soluble resin (C-2)

合成例C-2-1 Synthesis Example C-2-1

在一四頸錐瓶上設置攪拌器、溫度計、冷凝管及氮氣入口,並導入氮氣。然後,加入100重量份之丙二醇甲醚醋酸酯(簡稱為PGMEA),並將溫度升溫至100℃。接著,將25重量份之2-甲基丙烯醯乙氧基丁二酸酯(簡稱為HOMS)、70重量份之甲基丙烯酸2-羥基乙酯(簡稱為HEMA)、15重量份之甲基丙烯酸3,4-環氧環己基甲酯(ECMMA)、10重量份之鄰-乙烯基苯甲基環氧丙醚(簡稱為VBGE),以及4.5重量份之2,2’-偶氮雙-2-甲基丁腈(簡稱為AMBN)溶於100重量份之丙二醇甲醚醋酸酯中,並將此混合溶液於2小時內逐滴滴入上述四頸錐瓶中。於100℃反應6.5小時後,將5重量份之丙烯酸(簡稱為AA) 加至充滿氮氣之四頸錐瓶中,並將溫度上升至110℃。反應6小時後,即可製得合成例C-2-1之第二鹼可溶性樹脂。 A stirrer, thermometer, condenser, and nitrogen inlet were placed on a four-necked flask and nitrogen was introduced. Then, 100 parts by weight of propylene glycol methyl ether acetate (abbreviated as PGMEA) was added, and the temperature was raised to 100 °C. Next, 25 parts by weight of 2-methylpropenyl ethoxy succinate (abbreviated as HOMS), 70 parts by weight of 2-hydroxyethyl methacrylate (abbreviated as HEMA), and 15 parts by weight of methyl group 3,4-epoxycyclohexylmethyl acrylate (ECMMA), 10 parts by weight of o-vinylbenzyl glycidyl ether (abbreviated as VBGE), and 4.5 parts by weight of 2,2'-azobis- 2-methylbutyronitrile (abbreviated as AMBN) was dissolved in 100 parts by weight of propylene glycol methyl ether acetate, and the mixed solution was dropwise added to the above four-necked flask in 2 hours. After reacting at 100 ° C for 6.5 hours, 5 parts by weight of acrylic acid (abbreviated as AA) Add to a four-necked flask filled with nitrogen and raise the temperature to 110 °C. After reacting for 6 hours, a second alkali-soluble resin of Synthesis Example C-2-1 was obtained.

合成例C-2-2至C-2-6之製造方法 Production method of Synthesis Example C-2-2 to C-2-6

合成例C-2-2至C-2-6是以與合成例C-2-1相同的步驟來製備第二鹼可溶性樹脂(C-2),不同的地方在於:改變反應溫度、聚合時間、成份的種類及使用量,且詳載於表1。 Synthesis Examples C-2-2 to C-2-6 The second alkali-soluble resin (C-2) was prepared in the same manner as in Synthesis Example C-2-1 except that the reaction temperature and the polymerization time were changed. The types and amounts of ingredients are detailed in Table 1.

<實施例> <Example>

製備感光性樹脂組成物 Preparation of photosensitive resin composition

實施例1 Example 1

將前述合成例所得之100重量份的第二鹼可溶性樹脂(C-2-1)、50重量份的C.I.顏料紅254(以下簡稱A-1)、10重量份的C.I.溶劑紅24(以下簡稱B-1)、30重量份的二季戊四醇六丙烯酸酯(以下簡稱D-2)、50重量份的1-[4-(苯基硫代)苯基]-辛烷-1,2-二酮2-(O-苯醯基肟)(以下簡稱E-2-1)、5重量份的2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基二咪唑(以下簡稱E-2-2)、0.9重量份之甲烷磺酸乙酯(F-1),加入1500重量份的3-乙氧基丙酸乙酯(以下簡稱G-1)後,以搖動式攪拌器,加以溶解混合,即可調製而得感光性樹脂組成物,該感光性樹脂組成物以下述之各測定評價方式進行評價,所得結果如表2所示。 100 parts by weight of the second alkali-soluble resin (C-2-1) obtained in the above Synthesis Example, 50 parts by weight of CI Pigment Red 254 (hereinafter abbreviated as A-1), and 10 parts by weight of CI Solvent Red 24 (hereinafter referred to as B-1), 30 parts by weight of dipentaerythritol hexaacrylate (hereinafter referred to as D-2), 50 parts by weight of 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoinhydrazide) (hereinafter referred to as E-2-1), 5 parts by weight of 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5' -tetraphenyldiimidazole (hereinafter referred to as E-2-2), 0.9 parts by weight of ethyl methanesulfonate (F-1), and 1500 parts by weight of ethyl 3-ethoxypropionate (hereinafter referred to as G-) After the first step, the photosensitive resin composition was prepared by dissolving and mixing with a stirring stirrer. The photosensitive resin composition was evaluated by the following measurement evaluation methods, and the results are shown in Table 2.

實施例2至14及比較例1至6 Examples 2 to 14 and Comparative Examples 1 to 6

實施例2至14及比較例1至6係使用與實施例1之感光性樹脂組成物的製作方法相同之製備方法,不同之處在於實施例2至14及比較例1至6係改變感光性樹脂組成物中原料的種類及使用量,且其配方及評價結果分別如表2所示,在此不另贅述。 In Examples 2 to 14 and Comparative Examples 1 to 6, the same production method as that of the photosensitive resin composition of Example 1 was used, except that Examples 2 to 14 and Comparative Examples 1 to 6 were used to change the photosensitivity. The type and amount of the raw materials in the resin composition, and the formulations and evaluation results thereof are shown in Table 2, and are not described here.

A-1 C.I.顏料紅254 A-1 C.I. Pigment Red 254

A-2 C.I.顏料綠36 A-2 C.I. Pigment Green 36

A-3 C.I.顏料藍15:6 A-3 C.I. Pigment Blue 15:6

A-4 C.I.顏料藍66 A-4 C.I. Pigment Blue 66

A-5 C.I.顏料紅177 A-5 C.I. Pigment Red 177

B-1 C.I.溶劑紅24 B-1 C.I. Solvent Red 24

B-2 C.I.溶劑紅49 B-2 C.I. Solvent Red 49

B-3 C.I.酸性紅289 B-3 C.I. Acid Red 289

D-1 EO改質之三甲基丙烯酸三羥甲基丙酯 D-1 EO modified trimethylolpropyl methacrylate

D-2 二季戊四醇六丙烯酸酯 D-2 dipentaerythritol hexaacrylate

D-3 己內酯改質之二季戊四醇六丙烯酸酯 D-3 caprolactone modified dipentaerythritol hexaacrylate

E-1-1 式(III-1)所示之化合物 E-1-1 a compound of the formula (III-1)

E-1-2 式(III-8)所示之化合物 E-1-2 A compound of the formula (III-8)

E-1-3 式(III-27)所示之化合物 E-1-3 A compound of the formula (III-27)

E-2-1 1-[4-(苯基硫代)苯基]-辛烷-1,2-二酮2-(O-苯醯基肟) E-2-1 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-phenylhydrazinium)

E-2-2 2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基二咪唑 E-2-2 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole

2,2’-bis(2,4-dichloro phenyl)-4,4’,5,5’-tetraphenyl-biimidazole 2,2'-bis(2,4-dichloro phenyl)-4,4',5,5'-tetraphenyl-biimidazole

E-2-3 4,4’-雙(二乙胺)二苯甲酮4,4’-bis(diethylamino)benzophenone E-2-3 4,4'-bis(diethylamine)benzophenone 4,4'-bis(diethylamino)benzophenone

E-2-4 2-苄基-2-氮,氮-二甲胺-1-(4-嗎啉代苯基)-1-丁酮 E-2-4 2-benzyl-2-nitrogen, nitrogen-dimethylamine-1-(4-morpholinophenyl)-1-butanone

2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone

F-1 甲烷磺酸乙酯 F-1 ethyl methanesulfonate

F-2 三氟甲烷磺酸甲酯 F-2 methyl trifluoromethanesulfonate

F-3 二壬基萘磺酸乙酯 F-3 ethyl dinonylnaphthalenesulfonate

(例如king Industries社製造,型號為K-PURE CXC1762之商品) (for example, manufactured by King Industries, model K-PURE CXC1762)

十二烷基苯磺酸乙酯 Ethyl dodecylbenzenesulfonate

F-4 (例如king Industries社製造,型號為K-PURE TAG 2507之商品) F-4 (for example, manufactured by King Industries, model K-PURE TAG 2507)

G-1 3-乙氧基丙酸乙酯 G-1 3-ethoxypropionate ethyl ester

G-2 丙二醇甲醚酯酸酯 G-2 propylene glycol methyl ether ester

G-3 環己酮 G-3 cyclohexanone

H-1 3-硫醇基丙基三甲氧基矽烷 H-1 3-thiolpropyltrimethoxydecane

H-2 2,2-硫代雙(4-甲基-6-第三丁基苯酚) H-2 2,2-thiobis(4-methyl-6-tert-butylphenol)

H-3 2-羥基-4-甲氧基二苯甲酮 H-3 2-hydroxy-4-methoxybenzophenone

<評價方式> <Evaluation method>

熱溶劑膜厚變化率 Thermal solvent film thickness change rate

將實施例1至14及比較例1至6所製得之感光性樹脂組成物以旋轉塗佈的方式,塗佈在尺寸為100mm×100mm之玻璃基板上。然後,進行減壓乾燥,其壓力為100mmHg且時間為30秒鐘。接著,進行預烤製程,其溫度為80℃且時間為2分鐘,而可形成一膜厚為2.5μm之預烤塗膜。進行預烤製程後,以能量為60mJ/cm2的紫外光(曝光 機Canon PLA-501F)照射該預烤塗膜,並將曝光後之預烤塗膜浸漬於23℃之顯影液中。經過1分鐘後,以純水洗淨該塗膜,並以230℃進行後烤製程。進行後烤處理後,量測塗膜之厚度(Ti)。之後,將塗膜浸置於60℃之丙二醇甲醚酯酸酯溶劑。經過6分鐘後,量測塗膜之厚度(Tf),以下式計算膜厚變化率,並依據以下基準進行評價: The photosensitive resin compositions obtained in Examples 1 to 14 and Comparative Examples 1 to 6 were applied by spin coating to a glass substrate having a size of 100 mm × 100 mm. Then, it was dried under reduced pressure at a pressure of 100 mmHg for 30 seconds. Next, a pre-bake process was carried out at a temperature of 80 ° C for 2 minutes to form a pre-baked film having a film thickness of 2.5 μm. After the prebaking process, the prebaked coating film was irradiated with ultraviolet light (exposure machine Canon PLA-501F) having an energy of 60 mJ/cm 2 , and the exposed prebaked coating film was immersed in a developing solution at 23 ° C. After 1 minute, the coating film was washed with pure water and subjected to a post-baking process at 230 °C. After the post-baking treatment, the thickness (T i ) of the coating film was measured. Thereafter, the coating film was immersed in a propylene glycol methyl ether ester solvent at 60 °C. After 6 minutes, the thickness (T f ) of the coating film was measured, and the rate of change in film thickness was calculated by the following formula and evaluated according to the following criteria:

◎:膜厚變化率<1%。 ◎: The film thickness change rate was <1%.

○:1%≦膜厚變化率<3%。 ○: 1% ≦ film thickness change rate <3%.

△:3%≦膜厚變化率<5%。 △: 3% ≦ film thickness change rate <5%.

×:5%≦膜厚變化率。 ×: 5% film thickness change rate.

上述實施例僅為說明本發明之原理及其功效,而非限制本發明。習於此技術之人士對上述實施例所做之修改及變化仍不違背本發明之精神。本發明之權利範圍應如後述之申請專利範圍所列。 The above-described embodiments are merely illustrative of the principles and effects of the invention, and are not intended to limit the invention. Modifications and variations of the embodiments described above will be apparent to those skilled in the art without departing from the spirit of the invention. The scope of the invention should be as set forth in the appended claims.

Claims (13)

一種感光性樹脂組成物,其包含:顏料(A);染料(B);鹼可溶性樹脂(C);具有乙烯性不飽和基之化合物(D);光起始劑(E);具有式(I)所示結構之熱酸發生劑(F);及溶劑(G);R1f(SO3R2f)a 式(I)於式(I)中,R1f及R2f各自獨立地表示任意的取代基;及a表示1以上之整數。 A photosensitive resin composition comprising: a pigment (A); a dye (B); an alkali-soluble resin (C); a compound (D) having an ethylenically unsaturated group; a photoinitiator (E); I) thermal acid generator (F) of the structure shown; and solvent (G); R 1f (SO 3 R 2f ) a Formula (I) In the formula (I), R 1f and R 2f each independently represent any a substituent; and a represents an integer of 1 or more. 根據請求項1之感光性樹脂組成物,其中該鹼可溶性樹脂(C)包含一第一鹼可溶性樹脂(C-1),該第一鹼可溶性樹脂(C-1)係由一混合物進行聚合反應所製得,且該混合物包含一具有至少二個環氧基之環氧化合物(c-1-1)及一具有至少一個羧酸基及至少一個乙烯性不飽和基之化合物(c-1-2)。 The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (C) comprises a first alkali-soluble resin (C-1), and the first alkali-soluble resin (C-1) is polymerized by a mixture And the mixture comprises an epoxy compound (c-1-1) having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (c-1- 2). 根據請求項2之感光性樹脂組成物,其中該具有至少二個環氧基之環氧化合物(c-1-1)具有如式(II-1)或式(II-2)所示之結構; 於式(II-1)中,R1c、R2c、R3c及R4c分別為相同或不同,且表示氫原子、鹵素原子、碳數為1至5之烷基、碳數為1至5之烷氧 基、碳數為6至12之芳香基或碳數為6至12之芳烷基; 於式(II-2)中,R5c至R18c各自獨立表示氫原子、鹵素原子、碳數為1至8之烷基或碳數為6至15之芳香基;及g表示0至10的整數。 The photosensitive resin composition of claim 2, wherein the epoxy compound (c-1-1) having at least two epoxy groups has a structure represented by formula (II-1) or formula (II-2) ; In the formula (II-1), R 1c , R 2c , R 3c and R 4c are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and a carbon number of 1 to 5. An alkoxy group, an aromatic group having 6 to 12 carbon atoms or an aralkyl group having 6 to 12 carbon atoms; In the formula (II-2), R 5c to R 18c each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms; and g represents 0 to 10 Integer. 根據請求項1之感光性樹脂組成物,其中該光起始劑(E)包含具有如式(III)所示結構之一光起始劑(E-1): 於式(III)中,E1、E2、E3、E4、E5、E6、E7及E8分別獨立代 表氫原子、碳數為1至20之烷基、、COE16、 OE17、鹵素原子、NO2;或E1及E2、E2及E3、E3及E4、E5及E6、E6及E7或E7及E8分別獨 立代表經取代之碳數為2至10之烯基;或E1及E2、E2及E3、E3及E4、E5及E6、E6及E7或E7及E8分別獨立地共同代表-(CH2)p-W-(CH2)q-;或 E1及E2、E2及E3、E3及E4、E5及E6、E6及E7或E7及E8分別獨 立地共同代表,其中至少一E1及E2、E2及E3、 E3及E4、E5及E6、E6及E7或E7及E8E9、E10、E11及E12分別獨立代表氫原子、碳數為1至20之烷基,該碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自苯基、鹵素原子、CN、OH、SH、碳數為1至4之烷氧基、(CO)OH或(CO)O(R1),其中R1代表碳數為1至4之烷基;或E9、E10、E11及E12分別獨立地代表未經取代之苯基或經如下所示之至少一基團取代之苯基,該至少一基團係選自碳數為1至6之烷基、鹵素原子、CN、OE17、SE18或NE19E20;或E9、E10、E11及E12分別獨立地代表鹵素原子、CN、OE17、SE18、SOE18、SO2E18或NE19E20,其中該等取代基OE17、SE18或NE19E20係未經或經由該等基團E17、E18、E19及/或E20與萘環的一個碳原子形成五員環或六員環;或 E9、E10、E11及E12分別獨立地代表、COE16或NO2;W代表O、S、NE26或單鍵,p代表0至3之整數,q代表1至3之整數,Z1代表CO或單鍵;E13代表碳數為1至20之烷基,該碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,其中該至少一基團係選自鹵素原子、E17、COOE17、OE17、SE18、CONE19E20、 NE19E20、PO(OCkH2k+1)2;或 E13代表碳數為2至20之烷基,該碳數為2至20之烷基其間雜有一或多個O、S、SO、SO2、NE26或CO;或E13代表碳數為2至12之烯基,該碳數為2至12之烯基其係未經間雜或間雜有一或多個O、CO或NE26,其中該經間雜且碳數為2至20之烷基及該未經間雜或經間雜之碳數為2至12之烯基係未經取代或經至少一鹵素原子取代;或E13代表碳數為4至8之環烯基、碳數為2至12之炔基、或未經間雜或間雜有一或多個O、S、CO或NE26之碳數為3至10之環烷基;或E13代表苯基或萘基,且該苯基或該萘基各未經取代或經如下所示之至少一基團取代,其中該至少一基團係選自OE17、 SE18、NE19E20、COE16、CN、NO2、鹵素原子、碳數為1至20之烷基、碳數為1至4之鹵代烷基,間雜有一或多個O、S、CO或NE26且碳數為2至20的烷基;或該苯基或該萘基各經碳數為3至10之環烷基取代或各經間雜有一或多個O、S、CO或NE26且碳數為3至10之環烷基取代;k代表1至10之整數;E14代表氫原子、碳數為3至8之環烷基、碳數為2至5之烯基、碳數為1至20之烷氧基或未經取代或經如下所示之至少一基團取代之碳數為1至20之烷基,且該至少一基團係選自鹵素原子、苯基、碳數為1至20之烷基苯基或CN;或E14代表苯基或萘基,其各未經取代或經如下所示之至少一基團取代,且該至少一基團係選自碳數為1至6之烷基、碳數為1至4之鹵代烷基、鹵素原子、CN、OE17、SE18及/或NE19E20;或E14代表碳數為3至20之雜芳基、碳數為1至8之烷氧基、苄 氧基或苯氧基,該苄氧基及該苯氧基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自碳數為1至6之烷基、碳數為1至4之鹵代烷基及/或鹵素原子;E15代表碳數為6至20之芳香基或碳數為3至20之雜芳基,其各未經取代或經如下所示之至少一基團取代,且該至少一基團係選自苯基、鹵素原子、碳數為1至4之鹵代烷基、CN、NO2、OE17、SE18、NE19E20、PO(OCkH2k+1)2、與SO鍵結且碳數為1至10之烷基、與SO2鍵結且碳數為1至10之烷基、間雜有一或多個O、S或NE26且碳數為2至20之烷基;或其各經碳數為1至20之烷基取代,其中該碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素原子、COOE17、CONE19E20、苯基、碳數為3至8之環烷基、碳數為3至20之雜芳基、碳數為6至20之芳氧基羰基、碳數為3至20之雜芳氧基羰基、OE17、SE18或NE19E20;或E15代表氫原子、碳數為2至12之烯基、未經間雜或間雜有一或多個O、CO或NE26且碳數為3至8之環烷基;或E15代表碳數為1至20之烷基,該碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素原子、OE17、SE18、碳數為3至8之環烷基、碳數為3至20之雜芳基、碳數為6至20之芳氧基羰基、碳數為3至20之雜芳氧基羰基、NE19E20、COOE17、CONE19E20、PO(OCkH2k+1)2、苯基,其中該碳數為1至20之烷基係經苯基取代,且該苯基係經鹵素原子、碳數為1至20之烷基、碳數為1至4之鹵代烷基、OE17、SE18或NE19E20取代;或E15代表碳數為2至20之烷基,該碳數為2至20之烷基係間雜 有一或多個O、SO或SO2,該經間雜且碳數為2至20之烷基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素原子、OE17、COOE17、CONE19E20、苯基或經OE17、SE18或NE19E20取代之苯基;或E15代表碳數為2至20之烷醯基或苯甲醯基,其係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自碳數為1至6之烷基、鹵素原子、苯基、OE17、SE18或NE19E20;或E15代表未經取代或經至少一OE17取代之萘甲醯基或係碳數為3至14之雜芳基羰基;或E15代表碳數為2至12之烷氧基羰基,該碳數為2至12之烷氧基羰基係未經間雜或經至少一O間雜,其中該經間雜或未經間雜且碳數為2至12之烷氧基羰基係未經取代或經至少一羥基取代;或E15代表苯氧基羰基,該苯氧基羰基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自碳數為1至6之烷基、鹵素原子、碳數為1至4之鹵代烷基、苯基、OE17、SE18或NE19E20;或E15代表CN、CONE19E20、NO2、碳數為1至4之鹵代烷基、S(O)r-R2、與S(O)r鍵結之苯基,其中該與S(O)r鍵結之苯基係未經取代或經碳數為1至12之烷基或SO2-R2取代,且R2代表碳數為1至6之烷基;或E15代表與SO2O鍵結之苯基、二苯基膦醯基或二(R3)-膦醯基,其中該與SO2O鍵結之苯基係未經取代或經碳數為1至12之烷基取代,且R3代表碳數為1至4之烷氧基;r表示1至2之整數;E'14代表具有針對E14定義中其中之一者; E'15代表具有針對E15定義中其中之一者;Z2代表O、S、SO或SO2;Z3代表O、CO、S或單鍵;E16代表碳數為6至20之芳基或碳數為3至20之雜芳基,其各未經取代或經如下所示之至少一基團取代,且該至少一基團係選自苯基、鹵素原子、碳數為1至4之鹵代烷基、CN、NO2、OE17、SE18、NE19E20、間雜有一或多個O、S或NE26且碳數為1至20之烷基,或者碳數為1至20之烷基,其中該碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,其中該至少一基團係選自鹵素原子、COOE17、CONE19E20、苯基、碳數為3至8之環烷基、碳數為3至20之雜芳基、碳數為6至20之芳氧基羰基、碳數為3至20之雜芳氧基羰基、OE17、SE18或NE19E20;或E16代表氫原子或碳數為1至20之烷基,其中該碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素原子、苯基、OH、SH、CN、碳數為3至6之烯氧基、OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R1)、O(CO)-苯基或(CO)OH或(CO)O(R1);或E16代表碳數為2至12之烷基,該2至12之烷基係間雜有一或多個O、S或NE26;或E16代表(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4)、碳數為2至12之烯基或碳數為3至8之環烷基,其中R4代表碳數為1至8之烷基;或E16代表經SE18取代之苯基,其中E18代表鍵結至該COE16所附接之該咔唑部份之該苯基或該萘基環的單鍵;n代表1至20之整數;E17代表氫原子、苯基-R5、碳數為1至20之烷基,其係未經 取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素原子、OH、SH、CN、碳數為3至6之烯氧基、OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R1)、O(CO)-(R6)、與O(CO)鍵結之苯基、(CO)OH、(CO)O(R1)、碳數為3至20之環烷基、SO2-(R7)、O(R7)或經至少一O間雜且碳數為3至20之環烷基,其中R6代表碳數為2至4之烯基,且R7代表碳數為1至4之鹵代烷基;或E17代表碳數為2至20之烷基,且該碳數為2至20之烷基係間雜有一或多個O、S或NE26;或E17代表(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4)、碳數為1至8之烷醯基、碳數為2至12之烯基、碳數為3至6之烯醯基或碳數為3至20之環烷基,其係未經間雜或間雜有一或多個O、S、CO或NE26;或E17代表碳數為1至8之烷基與碳數為3至10之環烷基鍵結所形成之基團,且該基團係未經間雜或經至少一O間雜;或E17代表苯甲醯基,該苯甲醯基係未取代或經如下所示之至少一基團取代,且該至少一基團係選自碳數為1至6之烷基、鹵素原子、OH或碳數為1至3之烷氧基;或E17代表苯基、萘基或碳數為3至20之雜芳基,其各未經取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素原子、OH、碳數為1至12之烷基、碳數為1至12之烷氧基、CN、NO2、苯基-R8、苯氧基、碳數為1至12之烷基硫基、苯基硫 基、N(R9)2、二苯基-胺基或,其中R8代表碳數為1至3之烷氧基,且R9代表碳數為1至12之烷基;或 E17與具有之苯基或萘基環之其中一個碳原子形成單鍵;E18代表氫原子、碳數為2至12之烯基、碳數為3至20之環烷基或苯基-R5,其中該碳數為2至12之烯基、該碳數為3至20之環烷基及該苯基-R5係未經間雜或間雜有一或多個O、S、CO、NE26或COOE17;或E18代表碳數為1至20之烷基,該碳數為1至20之烷基係未取代或經如下所式之至少一基團取代,且該至少一基團係選自OH、SH、CN、碳數為3至6之烯氧基、OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R6)、O(CO)-(R1)、O(CO)-苯基或(CO)OE17;或E18代表碳數為2至20之烷基,該碳數為2至20之烷基係間雜有一或多個O、S、CO、NE26或COOE17;或E18代表(CH2CH2O)nH、(CH2CH2O)n(CO)-(R4)、碳數為2至8之烷醯基或碳數為3至6之烯醯基;或E18代表苯甲醯基,該苯甲醯基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自碳數為1至6之烷基、鹵素原子、OH、碳數為1至4之烷氧基或碳數為1至4之烷基硫基;或E18代表苯基、萘基或碳數為3至20之雜芳基,其各係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素原子、碳數為1至12之烷基、碳數為1至4之鹵代烷基、碳數為1至12之烷氧基、CN、NO2、苯基-R8、苯氧基、碳數為1至12之烷基硫基、苯基硫基、N(R9)2、二苯基胺基、(CO)O(R4)、 (CO)-R4、(CO)N(R4)2E19及E20分別獨立地代表氫原子、碳數為1至20之烷基、碳數為2至4之羥基烷基、碳數為2至10之烷氧基烷基、碳數為2至5之烯基、碳數為3至20之環烷基、苯基-R5、碳數為1至8之烷醯基、碳數為1至8之烷醯基氧基、碳數為3至12之烯醯基、SO2-R7或苯甲醯基;或E19及E20代表苯基、萘基或碳數為3至20之雜芳基,其各未經取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素原子、碳數為1至4之鹵代烷基、碳數為1至20之烷氧基、碳數為1至12之烷基、苯甲醯基或碳數為1至12之烷氧基;或E19及E20係與所鍵結之氮原子一起形成未經間雜或間雜有O、S或NE17之五員或六員飽和或不飽和環,且該五員或六員飽和或不飽和環係未經取代或經如下所示之至少一基團取代,其中該至少一基團係選自碳數為1至20之烷基、碳數為1至20之烷氧基、=O、OE17、SE18、NE21E22、(CO)E23、NO2、鹵素原子、 碳數為1至4之鹵代烷基、CN、苯基、,或者未經間雜或間雜有一或多個O、S、CO或NE17且碳數為3至20之環烷基;或E19及E20係與所附接之氮原子一起形成雜芳香族環系統,該雜芳香族環系統係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自碳數為1至20之烷基、碳數為1至4之鹵代烷基、碳數為1至20之烷氧基、=O、OE17、SE18、NE21E22、 (CO)E23、鹵素原子、NO2、CN、苯基,或者未經間雜或間雜有一或多個O、S、CO或NE17且碳數為3至20的環烷基; E21及E22分別獨立地代表氫原子、碳數為1至20之烷基、碳數為1至4之鹵代烷基、碳數為3至10之環烷基或苯基;E21及E22與其所鍵接之氮原子一起形成未經間雜或間雜有O、S或NE26之五員或六員飽和或不飽和環,其中該五員或六員飽和或不飽和環係未稠合或與苯環稠合;E23代表氫原子、OH、碳數為1至20之烷基、碳數為1至4之鹵代烷基、間雜有至少一O、CO或NE26且碳數為2至20的烷基、未經間雜或間雜有O、S、CO或NE26且碳數為3至20之環烷基;或E23代表苯基、萘基、苯基-R1、OE17、SE18或NE21E22;E24代表(CO)OE17、CONE19E20、(CO)E17或具有針對E19及E20定義中其中之一者;E25代表COOE17、CONE19E20、(CO)E17;或E25具有針對E17定義中其中之一者;E26代表氫原子、碳數為1至20之烷基、碳數為1至4之鹵代烷基、間雜有至少一O或CO且碳數為2至20之烷基;或E26代表苯基-R1、未經間雜或經至少一O或CO間雜且碳數為3至8之環烷基;或E26代表(CO)E19;或E26代表苯基,E26係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自碳數為1至20之烷基、鹵素原子、碳數為1至4之鹵代烷基、OE17、SE18、 NE19E20,但條件為如該式(III)所示結構之該 光起始劑(E-1)具有至少一 The photosensitive resin composition according to claim 1, wherein the photoinitiator (E) comprises a photoinitiator (E-1) having a structure represented by the formula (III): In the formula (III), E 1 , E 2 , E 3 , E 4 , E 5 , E 6 , E 7 and E 8 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, , COE 16 , OE 17 , halogen atom, NO 2 or ; Or E 1 and E 2, E 2, and E 3, E 3 and E 4, E 5 and E 6, E 6 or E 7 and E 7 and E 8 each independently represent by Alternate carbon number is 2 to 10 alkenyl; or E 1 and E 2 , E 2 and E 3 , E 3 and E 4 , E 5 and E 6 , E 6 and E 7 or E 7 and E 8 are respectively independent Commonly represented by -(CH 2 ) p -W-(CH 2 ) q -; or E 1 and E 2 , E 2 and E 3 , E 3 and E 4 , E 5 and E 6 , E 6 and E 7 or E 7 and E 8 are independently represented Wherein at least one of E 1 and E 2 , E 2 and E 3 , E 3 and E 4 , E 5 and E 6 , E 6 and E 7 or E 7 and E 8 are E 9 , E 10 , E 11 and E 12 each independently represent a hydrogen atom and an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or at least one group as shown below. Substituted, and the at least one group is selected from the group consisting of a phenyl group, a halogen atom, CN, OH, SH, an alkoxy group having a carbon number of 1 to 4, (CO)OH or (CO)O(R 1 ), wherein R 1 represents an alkyl group having 1 to 4 carbon atoms; or E 9 , E 10 , E 11 and E 12 each independently represent an unsubstituted phenyl group or a phenyl group substituted with at least one group as shown below, The at least one group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, CN, OE 17 , SE 18 or NE 19 E 20 ; or E 9 , E 10 , E 11 and E 12 are independently represented a halogen atom, CN, OE 17 , SE 18 , SOE 18 , SO 2 E 18 or NE 19 E 20 , wherein the substituents OE 17 , SE 18 or NE 19 E 20 are not or via such groups E 17 , E 18 , E 19 and/or E 20 form a five-membered or six-membered ring with one carbon atom of the naphthalene ring; or E 9 , E 10 , E 11 and E 12 respectively represent independently , COE 16 or NO 2 ; W represents O, S, NE 26 or a single bond, p represents an integer from 0 to 3, q represents an integer from 1 to 3, Z 1 represents CO or a single bond; and E 13 represents a carbon number of 1. The alkyl group having a carbon number of from 1 to 20 is unsubstituted or substituted with at least one group as shown below, wherein the at least one group is selected from a halogen atom, E 17 , COOE 17 , OE 17 , SE 18 , CONE 19 E 20 , NE 19 E 20 , PO(OC k H 2k+1 ) 2 or Or E 13 represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is interspersed with one or more of O, S, SO, SO 2 , NE 26 or CO; or E 13 represents carbon The number of alkenyl groups of 2 to 12, the alkenyl group having 2 to 12 carbon atoms which is undoped or inter-hetero-doped with one or more O, CO or NE 26 , wherein the inter- and hetero-carbon number is 2 to 20 And the alkenyl group having 2 to 12 carbon atoms without undoped or intervening is unsubstituted or substituted with at least one halogen atom; or E 13 represents a cycloalkenyl group having 4 to 8 carbon atoms and having a carbon number of 2 An alkynyl group of 12, or a cycloalkyl group having 3 or 10 carbon atoms without an inter or hetero or hetero or O, S, CO or NE 26 ; or E 13 representing a phenyl or naphthyl group, and the phenyl group Or the naphthyl group is unsubstituted or substituted with at least one group as shown below, wherein the at least one group is selected from the group consisting of OE 17 , SE 18 , NE 19 E 20 , , COE 16 , CN, NO 2 , a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, intermixed with one or more O, S, CO or NE 26 and having a carbon number of 2 An alkyl group of up to 20; or the phenyl group or the naphthyl group is each substituted with a cycloalkyl group having a carbon number of 3 to 10 or each interstitial having one or more O, S, CO or NE 26 and having a carbon number of 3 to 10 Cycloalkyl substituted; k represents an integer from 1 to 10; E 14 represents a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. An alkyl group having 1 to 20 carbon atoms which is substituted with or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, a phenyl group, and an alkyl group having 1 to 20 carbon atoms. Phenylphenyl or CN; or E 14 represents phenyl or naphthyl, each unsubstituted or substituted by at least one group as shown below, and the at least one group is selected from the group consisting of a C 1 to 6 alkane a halogenated alkyl group having 1 to 4 carbon atoms, a halogen atom, CN, OE 17 , SE 18 and/or NE 19 E 20 ; or E 14 representing a heteroaryl group having 3 to 20 carbon atoms and having a carbon number of 1 to Alkoxy, benzyloxy or phenoxy group, the benzyloxy group and the phenoxy group are not taken Or the group substituted with at least one of the following, and the at least one group selected from an alkyl group having a carbon number of 1 to 6 carbon atoms, a haloalkyl group of 1 to 4 and / or a halogen atom; E 15 represents a carbon An aryl group having 6 to 20 or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of a phenyl group and a halogen group. Atom, haloalkyl having 1 to 4 carbon atoms, CN, NO 2 , OE 17 , SE 18 , NE 19 E 20 , PO(OC k H 2k+1 ) 2 , bonded to SO and having a carbon number of 1 to 10 An alkyl group, an alkyl group bonded to SO 2 and having a carbon number of 1 to 10, an intervening one or more O, S or NE 26 and an alkyl group having 2 to 20 carbon atoms; or each carbon number thereof is 1 An alkyl group substituted to 20, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, COOE 17 , CONE 19 E 20 , phenyl, cycloalkyl having 3 to 8 carbon atoms, heteroaryl having 3 to 20 carbon atoms, aryloxycarbonyl having 6 to 20 carbon atoms, heteroaryl having 3 to 20 carbon atoms Oxycarbonyl, OE 17 , SE 18 or NE 19 E 20 ; or E 15 represents a hydrogen atom, carbon An alkenyl group having 2 to 12 alkenyl groups, having no or hetero or one or more O, CO or NE 26 and having a carbon number of 3 to 8; or E 15 representing an alkyl group having 1 to 20 carbon atoms; The alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, OE 17 , SE 18 , and a carbon number of 3 to 8. a cycloalkyl group, a heteroaryl group having 3 to 20 carbon atoms, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 3 to 20 carbon atoms, NE 19 E 20 , COOE 17 , CONE 19 E 20 , PO(OC k H 2k+1 ) 2 , , a phenyl group, wherein the alkyl group having 1 to 20 carbon atoms is substituted with a phenyl group, and the phenyl group is a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, OE 17 , SE18 or NE 19 E 20 substituted; or E 15 represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is one or more O, SO or SO 2 The alkyl group having a carbon number of 2 to 20 is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, OE 17 , COOE 17 , CONE 19 E 20 , a phenyl group or a phenyl group substituted with OE 17 , SE 18 or NE 19 E 20 ; or E 15 represents an alkanoyl group or a benzamidine group having a carbon number of 2 to 20, which is unsubstituted or as shown below Substituting at least one group, and the at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, a phenyl group, OE 17 , SE 18 or NE 19 E 20 ; or E 15 represents unsubstituted or a naphthylmethyl group substituted with at least one OE 17 or a heteroarylcarbonyl group having a carbon number of 3 to 14; or E 15 representing an alkoxycarbonyl group having a carbon number of 2 to 12, the carbon number of 2 to 12 The oxycarbonyl group is unintercalated or at least one miscellaneous Wherein the alkoxycarbonyl group which is inter- or hetero-doped and has a carbon number of 2 to 12 is unsubstituted or substituted with at least one hydroxyl group; or E 15 represents a phenoxycarbonyl group which is unsubstituted Or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, OE 17 , SE 18 or NE 19 E 20 ; or E 15 represents CN, CONE 19 E 20 , NO 2 , haloalkyl having a carbon number of 1 to 4, S(O) r -R 2 , bonded to S(O) r a phenyl group, wherein the phenyl group bonded to S(O) r is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms or SO 2 -R 2 , and R 2 represents a carbon number of 1 to 6 alkyl; or E 15 represents a phenyl group bonded to the SO 2 O, diphenylphosphino acyl or di (R 3) - phosphino acyl, SO 2 O wherein the bond with the phenyl unsubstituted or lines Substituted by an alkyl group having 1 to 12 carbon atoms, and R 3 represents an alkoxy group having 1 to 4 carbon atoms; r represents an integer of 1 to 2; and E' 14 represents one of the definitions for E 14 ; E '15 represents a 15 for one of those defined in E; Z 2 representative of O, S, SO, or SO 2; Z 3 Table O, CO, S or a single bond; E 16 represents a carbon atoms or an aryl group of 6 to 20 carbon atoms of the 3 to 20 hetero aryl group, each of which is unsubstituted or is at least as shown by a substituted And the at least one group is selected from the group consisting of a phenyl group, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, CN, NO 2 , OE 17 , SE 18 , NE 19 E 20 , one or more O, S Or NE 26 and an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or at least one group as shown below And wherein the at least one group is selected from the group consisting of a halogen atom, COOE 17 , CONE 19 E 20 , a phenyl group, a cycloalkyl group having a carbon number of 3 to 8, a heteroaryl group having a carbon number of 3 to 20, and a carbon number of An aryloxycarbonyl group of 6 to 20, a heteroaryloxycarbonyl group having 3 to 20 carbon atoms, OE 17 , SE 18 or NE 19 E 20 ; or E 16 representing a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; Wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of a halogen atom, a phenyl group, an OH group, a SH group, a CN group, and a carbon number. 3 to 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO O(R 1 ), O(CO)-(R 1 ), O(CO)-phenyl or (CO)OH or (CO)O(R 1 ); or E 16 represents a carbon number of 2 to 12 An alkyl group having 2 to 12 alkyl interstitials having one or more O, S or NE 26 ; or E 16 representing (CH 2 CH 2 O) n+1 H, (CH 2 CH 2 O) n (CO) -(R 4 ), an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, wherein R 4 represents an alkyl group having 1 to 8 carbon atoms; or E 16 represents a substitution with SE 18 a phenyl group, wherein E 18 represents a single bond to the phenyl group or the naphthyl ring to which the carbazole moiety is attached to the COE 16 ; n represents an integer from 1 to 20; and E 17 represents a hydrogen atom, benzene group -R 5, an alkyl group having a carbon number of 1 to 20, which system the at least one substituent group is unsubstituted or illustrated by the following, and the at least one group selected from a halogen atom, OH, SH, CN, Alkenyloxy group having 3 to 6 carbon atoms, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(R 1 ), O(CO)-(R 1 ), O(CO)-(R 6 ), a phenyl group bonded to O(CO), (CO)OH, (CO)O(R 1 ), a cycloalkyl group having a carbon number of 3 to 20, SO 2 -(R 7 ), O(R 7 ) or interrupted by O and at least one cycloalkyl group having a carbon number of 3 to 20, wherein R 6 represents an alkenyl group having a carbon number of 2-4, and R 7 represents from 1 to 4 carbon atoms Haloalkyl; or E 17 represents a carbon atoms of an alkyl group of 2 to 20, carbon atoms and the alkyl group of 2 to 20 based interrupted by one or more O, S or NE 26; E 17, or on behalf of (CH 2 CH 2 O) n+1 H, (CH 2 CH 2 O) n (CO)-(R 4 ), an alkanoyl group having a carbon number of 1 to 8, an alkenyl group having 2 to 12 carbon atoms, and a carbon number of 3 to An olefinic group of 6 or a cycloalkyl group having 3 to 20 carbon atoms which is undoped or inter-hetero-doped with one or more O, S, CO or NE 26 ; or E 17 represents an alkyl group having 1 to 8 carbon atoms a group formed by bonding a cycloalkyl group having a carbon number of 3 to 10, and the group is unintermixed or at least one impurity; or E 17 represents a benzamidine group, and the benzamidine group is not Substituted or substituted with at least one group as shown below, and the at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, OH or an alkoxy group having 1 to 3 carbon atoms; or E 17 represents a phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, OH, An alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, CN, NO 2 , phenyl-R 8 , phenoxy group, and carbon number 1 to 12 alkylthio, phenylthio, N(R 9 ) 2 , diphenyl-amine or Wherein R 8 represents an alkoxy group having a carbon number of 1 to 3, and R 9 represents an alkyl group having a carbon number of 1 to 12; or E 17 and has or One of the carbon atoms of the phenyl or naphthyl ring forms a single bond; E 18 represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or a phenyl-R 5 group, wherein The alkenyl group having 2 to 12 carbon atoms, the cycloalkyl group having 3 to 20 carbon atoms, and the phenyl-R 5 group having no or hetero or one or more O, S, CO, NE 26 or COOE 17 Or E 18 represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group of the formula: wherein the at least one group is selected from OH , SH, CN, alkoxy groups having a carbon number of 3 to 6, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(R 1 ), O(CO)-(R 6 ), O(CO)- (R 1 ), O(CO)-phenyl or (CO)OE 17 ; or E 18 represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms has one or more O , S, CO, NE 26 or COOE 17 ; or E 18 represents (CH 2 CH 2 O) n H, (CH 2 CH 2 O) n (CO)-(R 4 ), alkane having 2 to 8 carbon atoms a mercapto group or an olefin group having a carbon number of 3 to 6; or E 18 represents a benzamidine group which is unsubstituted or substituted with at least one group as shown below, and the at least one group Is selected from a carbon number of 1 to 6 a group, a halogen atom, an OH group, an alkoxy group having 1 to 4 carbon atoms or an alkylthio group having 1 to 4 carbon atoms; or E 18 represents a phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 3 to 20 Each of which is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a halogenated alkyl group having 1 to 4 carbon atoms. Alkoxy group having a carbon number of 1 to 12, CN, NO 2 , phenyl-R 8 , phenoxy group, alkylthio group having 1 to 12 carbon atoms, phenylthio group, N(R 9 ) 2 , diphenylamino, (CO)O(R 4 ), (CO)-R 4 , (CO)N(R 4 ) 2 or E 19 and E 20 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, and a carbon number of 2 Alkenyl group to 5, cycloalkyl group having 3 to 20 carbon atoms, phenyl-R 5 , alkanoyl group having 1 to 8 carbon atoms, alkyl alkoxy group having 1 to 8 carbon atoms, carbon number 3 to 12 olefinic groups, SO 2 -R 7 or benzamidine groups; or E 19 and E 20 represent a phenyl group, a naphthyl group or a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or Substituting at least one group as shown below, and the at least one group is selected from the group consisting of a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number of 1 to 12 An alkyl group, a benzamidine group or an alkoxy group having a carbon number of 1 to 12; or an E 19 and E 20 group together with a bonded nitrogen atom to form a five-membered member having no inter or heterogeneous O, S or NE 17 Or a six-membered saturated or unsaturated ring, and the five or six member saturated or unsaturated ring system is unsubstituted or substituted with at least one group as shown below, wherein the at least one group is selected from the group consisting of 1 carbon number to an alkyl group having a carbon number of 20 is alkyl group of 1 to 20, = O, OE 17, SE 18, NE 21 E 22 (CO) E 23, NO 2 , a halogen atom, a haloalkyl group having a carbon number of 1 to 4, CN, phenyl, Or a cycloalkyl group having one or more O, S, CO or NE 17 and having a carbon number of 3 to 20 without interstitial or heterogeneous; or E 19 and E 20 together with the attached nitrogen atom to form a heteroaromatic a ring system, the heteroaromatic ring system being unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and having a carbon number of 1 to 4 Haloalkyl, alkoxy with 1 to 20 carbon atoms, =0, OE 17 , SE 18 , NE 21 E 22 , (CO) E 23 , a halogen atom, NO 2 , CN, phenyl, or a cycloalkyl group having one or more O, S, CO or NE 17 and having a carbon number of 3 to 20 without interstitial or heterogeneous; E 21 and E 22 are independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group; and a nitrogen atom to which E 21 and E 22 are bonded thereto Forming a five- or six-membered saturated or unsaturated ring having no or interstitial or O, S or NE 26 , wherein the five or six member saturated or unsaturated ring system is not fused or fused to the benzene ring; 23 represents a hydrogen atom, OH, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having at least one O, CO or NE 26 and having a carbon number of 2 to 20, which is not a cycloalkyl group having an O, S, CO or NE 26 and having a carbon number of 3 to 20; or E 23 representing a phenyl group, a naphthyl group, a phenyl-R 1 , OE 17 , SE 18 or NE 21 E 22 E 24 stands for (CO) OE 17 , CONE 19 E 20 , (CO) E 17 or has one of the definitions for E 19 and E 20 ; E 25 stands for COOE 17 , CONE 19 E 20 , (CO) E 17 ; or E 25 has one of the definitions for E 17 ; E 26 represents a hydrogen atom An alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having at least one O or CO and having a carbon number of 2 to 20; or E 26 representing a phenyl-R 1 group; a cycloalkyl group which is heterozygous or has at least one O or CO and a carbon number of 3 to 8; or E 26 represents (CO)E 19 ; or E 26 represents a phenyl group, and the E 26 system is unsubstituted or as shown below Substituting at least one group, and the at least one group is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, OE 17 , SE 18 , NE 19 E 20 or , the photoinitiator (E-1) having the structure of the formula (III) has at least one or 根據請求項4之感光性樹脂組成物,其中該式(III)所示結構之一光起始劑(E-1)中,E1、E2、E3、E4、E5、E6、E7及E8分別獨立代 表氫原子、碳數為1至20之烷基、、COE16或NO2;或E1及E2、E2及E3、E3及E4、E5及E6、E6及E7或E7及E8分別獨 立地共同代表,其中至少一E1及E2、E2及E3、 E3及E4、E5及E6、E6及E7或E7及E8;Z1代表CO或單鍵;E13代表碳數為1至20之烷基,該碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素原子、OE17、SE18、COOE17、CONE19E20或PO(OCkH2k+1)2;或E13代表碳數為2至20之烷基,該碳數為2至20之烷基係間雜有一或多個O、S、NE26或CO;或E13代表苯基或萘基,且其各未經取代或經至少一 或COE16取代;E14代表碳數為1至20之烷基、苯基或碳數為1至8之烷氧基;E15代表苯基、萘基、碳數為3至20之雜芳基,其各未經取代或經如下所示之至少一基團取代,且該至少一基團係選自苯基、鹵素原子、碳數為1至4之鹵代烷基、OE17、SE18、間雜有至少一O或S且碳數為2至20之烷基,或其各經一或多個碳數為1至20之烷基取代,該碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素原子、COOE17、CONE19E20、苯基、碳數為3至8之環烷基、碳數為3至20之雜芳基、碳數為6至20之芳氧基羰基、碳數為4至20之雜芳 氧基羰基、OE17、SE18、NE19E20或PO(OCkH2k+1)2;或E15代表碳數為1至20之烷基,該碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自OE17、SE18、碳數為3至8之環烷基、碳數為3至20之雜芳基、NE19E20、COOE17、CONE19E20或PO(OCkH2k+1)2;E'14代表具有針對E14定義中其中之一者;E'15代表具有針對E15定義中其中之一者;E16代表苯基,E16係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自OE17、SE18、NE19E20、間雜至少一O、S或NE26且碳數為2至20之烷基;或E16代表苯基,且該苯基係經至少一碳數為1至20之烷基取代,其中該碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素原子、COOE17、CONE19E20、苯基、碳數為3至8之環烷基、碳數為3至20之雜芳基、碳數為6至20之芳氧基羰基、碳數為4至20之雜芳氧基羰基、OE17、SE18或NE19E20;或E16代表碳數為1至20之烷基,該代表碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素原子、苯基、OH、SH、CN、碳數為3至6之烯氧基、OCH2CH2(CO)O(R1)、O(CO)-(R1)或(CO)O(R1);E17代表碳數為1至20之烷基,該碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素原子、OCH2CH2(CO)O(R1)、O(R1)、(CO)O(R1)、碳數為3至20之環烷基,其中該碳數為3至20之環烷基係未間雜或間雜至少一O;或E17代表碳數為2至20之烷基,該碳數為2至20之烷基係間雜 至少一O;E18代表經(CO)OE17取代之甲基;E19及E20分別獨立代表氫原子、苯基、碳數為1至20之烷基、碳數為1至8之烷醯基或碳數為1至8之烷醯基氧基;或E19及E20係與所鍵結之氮原子一起形成雜芳香族環系統,該 雜芳香族環系統係未經取代或經取代,但條件為如該式(III)所示結構之該光起始劑(E-1)具有至少一個 The photosensitive resin composition of claim 4, wherein in the photoinitiator (E-1) of the structure represented by the formula (III), E 1 , E 2 , E 3 , E 4 , E 5 , E 6 And E 7 and E 8 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, , COE 16 or NO 2 ; or E 1 and E 2 , E 2 and E 3 , E 3 and E 4 , E 5 and E 6 , E 6 and E 7 or E 7 and E 8 are respectively independently represented Wherein at least one of E 1 and E 2 , E 2 and E 3 , E 3 and E 4 , E 5 and E 6 , E 6 and E 7 or E 7 and E 8 are Z 1 represents CO or a single bond; E 13 represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and At least one group is selected from a halogen atom, OE 17 , SE 18 , COOE 17 , CONE 19 E 20 or PO(OC k H 2k+1 ) 2 ; or E 13 represents an alkyl group having a carbon number of 2 to 20, An alkyl group having 2 to 20 carbon atoms having one or more O, S, NE 26 or CO; or E 13 representing a phenyl or naphthyl group, each of which is unsubstituted or at least one Or COE 16 substituted; E 14 represents an alkyl group having 1 to 20 carbon atoms, a phenyl group or an alkoxy group having 1 to 8 carbon atoms; and E 15 represents a phenyl group, a naphthyl group, and a heteroaryl group having a carbon number of 3 to 20. a group, each of which is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of a phenyl group, a halogen atom, a halogenated alkyl group having a carbon number of 1 to 4, OE 17 , SE 18 , An alkyl group having at least one O or S and having a carbon number of 2 to 20, or each of which is substituted with one or more alkyl groups having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is not Substituting or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of a halogen atom, COOE 17 , CONE 19 E 20 , a phenyl group, a cycloalkyl group having a carbon number of 3 to 8, and a carbon number of a heteroaryl group of 3 to 20, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 4 to 20 carbon atoms, OE 17 , SE 18 , NE 19 E 20 or PO (OC k H 2k +1 ) 2 ; or E 15 represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and the at least one group The group is selected from OE 17 , SE 18 , a cycloalkyl group having a carbon number of 3 to 8, and a carbon number of 3 to 20 heteroaryl, NE 19 E 20 , COOE 17 , CONE 19 E 20 or PO(OC k H 2k+1 ) 2 ; E' 14 represents one of the definitions for E 14 ; E' 15 represents One of the definitions of E 15 ; E 16 represents a phenyl group, E 16 is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from OE 17 , SE 18 , NE 19 E 20 , an alkyl group having at least one O, S or NE 26 and having a carbon number of 2 to 20; or E 16 representing a phenyl group, and the phenyl group is substituted with at least one alkyl group having 1 to 20 carbon atoms, Wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of a halogen atom, COOE 17 , CONE 19 E 20 , phenyl group, a cycloalkyl group having 3 to 8 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 4 to 20 carbon atoms, OE 17 , SE 18 or NE 19 E 20 ; or E 16 represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and The at least one group is selected from a halogen atom, a phenyl group, and an OH group. , SH, CN, alkoxy groups having a carbon number of 3 to 6, OCH 2 CH 2 (CO)O(R 1 ), O(CO)-(R 1 ) or (CO)O(R 1 ); E 17 An alkyl group having a carbon number of 1 to 20, the alkyl group having 1 to 20 carbon atoms being unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, OCH 2 CH 2 (CO)O(R 1 ), O(R 1 ), (CO)O(R 1 ), a cycloalkyl group having 3 to 20 carbon atoms, wherein the carbon number is 3 to 20 cycloalkyl groups Is not hetero or heterozygous at least one O; or E 17 represents an alkyl group having 2 to 20 carbon atoms, the alkyl group having a carbon number of 2 to 20 is at least one O; and E 18 is substituted by (CO)OE 17 Methyl; E 19 and E 20 each independently represent a hydrogen atom, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms or an alkanoyloxy group having 1 to 8 carbon atoms. Or the E 19 and E 20 systems together with the bonded nitrogen atom form a heteroaromatic ring system that is unsubstituted or Substituting, but the photoinitiator (E-1) having the structure of the formula (III) has at least one 根據請求項4之感光性樹脂組成物,其中該式(III)所示結構之一光起始劑(E-1)中,E1、E2、E3、E4、E5、E6、E7及E8分別獨立代表氫原子;或E1及E2、E3及E4或E5及E6分別獨立地共同代表 ,且至少一E1及E2、E3及E4或E5及E6 E2代表、COE16、NO2;或 E7代表或COE16;E9、E11及E12代表氫原子;E10代表氫原子、OE17或COE16;Z1代表CO或單鍵;E13代表碳數為1至20之烷基,該碳數為1至20之烷基係未經 取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素原子、E17、OE17、SE18或PO(OCkH2k+1)2;或E13代表碳數為2至20之烷基,該碳數為2至20之烷基間雜至少一O;或E13代表苯基;k代表整數2;E14代表碳數為1至20之烷基或噻吩基;E15代表苯基或萘基,且其各未經取代或經至少一OE17或碳數為1至20之烷基取代;或E15代表噻吩基、氫原子或碳數為1至20之烷基,其中該碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自OE17、SE18、碳數為3至8之環烷基、NE19E20或COOE17;或E15代表碳數為2至20之烷基,且該碳數為2至20之烷基間雜有SO2;E16代表苯基或萘基,其各未經取代或經如下所示之至少一基團取代,且該至少一基團係選自OE17、SE18、NE19E20或碳數為1至20之烷基;或E16代表噻吩基;E17代表氫原子、碳數為1至8之烷醯基或碳數為1至20之烷基,該碳數為1至20之烷基係未經取代或經如下所示之至少一基團取代,且該至少一基團係選自鹵素原子、O(CO)-(R1)、O(CO)-(R6),或者間雜至少一O且碳數為3至20之環烷基;或E17代表碳數為2至20之烷基,且該碳數為2至20之烷基間雜至少一O;E18代表碳數為3至20之環烷基、碳數為1至20之烷基,且該 碳數為1至20之烷基係未經取代或經至少一OH、O(CO)-(R6)或(CO)OE17取代;或E18代表苯基,該苯基係未經取代或經至少一鹵素原子取代;E19及E20係分別獨立地代表碳數為1至8之烷醯基或碳數為1至8烷醯基氧基;或E19及E20係與所鍵結之氮原子一起形成間雜有O之五員或六員飽和環,但條件為如該式(III)所示結構之該光起始劑(E-1)具有 至少一 The photosensitive resin composition of claim 4, wherein in the photoinitiator (E-1) of the structure represented by the formula (III), E 1 , E 2 , E 3 , E 4 , E 5 , E 6 , E 7 and E 8 each independently represent a hydrogen atom; or E 1 and E 2 , E 3 and E 4 or E 5 and E 6 are independently represented independently And at least one of E 1 and E 2 , E 3 and E 4 or E 5 and E 6 are E 2 represents , COE 16 , NO 2 or ; or E 7 represents Or COE16; E 9 , E 11 and E 12 represent a hydrogen atom; E 10 represents a hydrogen atom, OE 17 or COE 16 ; Z 1 represents CO or a single bond; and E 13 represents an alkyl group having a carbon number of 1 to 20, the carbon The alkyl group of 1 to 20 is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom, E 17 , OE 17 , SE 18 or PO (OC k H 2k + 1) 2; or E 13 represents a carbon atoms of an alkyl group of 2 to 20, the carbon number of 2 to 20 alkyl interrupted by at least one O; or E 13 represents phenyl; K represents an integer of 2; E 14 representatives An alkyl group or a thienyl group having 1 to 20 carbon atoms; E 15 represents a phenyl group or a naphthyl group, and each of them is unsubstituted or substituted with at least one OE 17 or an alkyl group having 1 to 20 carbon atoms; or E 15 represents a thienyl group, a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and the at least one group is It is selected from OE 17 , SE 18 , a cycloalkyl group having a carbon number of 3 to 8, NE 19 E 20 or COOE 17 ; or E 15 represents an alkyl group having 2 to 20 carbon atoms, and the carbon number is 2 to 20 The alkyl group is interspersed with SO 2 ; E 16 represents a phenyl or naphthyl group, each of which is unsubstituted or Substituting at least one group as shown below, and the at least one group is selected from OE 17 , SE 18 , NE 19 E 20 or an alkyl group having a carbon number of 1 to 20; or E 16 represents a thienyl group; E 17 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below. And the at least one group is selected from a halogen atom, O(CO)-(R 1 ), O(CO)-(R 6 ), or a cycloalkyl group having at least one O and a carbon number of 3 to 20; E 17 represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is at least one O; E 18 represents a cycloalkyl group having 3 to 20 carbon atoms and a carbon number of 1 to 20 An alkyl group, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one OH, O(CO)-(R 6 ) or (CO)OE 17 ; or E 18 represents a phenyl group, the benzene The base is unsubstituted or substituted with at least one halogen atom; E 19 and E 20 each independently represent an alkanoyl group having a carbon number of 1 to 8 or a C 1 to 8 alkyl fluorenyloxy group; or E 19 and E 20 lines with the nitrogen atom are bonded together is interrupted by O of the five or six-membered saturated ring, but as the condition of formula (III) The structures shown photoinitiator (E-1) having at least one 根據請求項1之感光性樹脂組成物,其中該具有式(I)所示結構之熱酸發生劑(F)係選自由芳香族磺酸酯、脂肪族磺酸酯及全氟烷基磺酸酯所組合之群。 The photosensitive resin composition of claim 1, wherein the thermal acid generator (F) having the structure represented by the formula (I) is selected from the group consisting of an aromatic sulfonate, an aliphatic sulfonate, and a perfluoroalkyl sulfonic acid. a group of esters combined. 根據請求項1之感光性樹脂組成物,其中,基於該鹼可溶性樹脂(C)之使用量為100重量份,該顏料(A)之使用量為30重量份至300重量份;該染料(B)之使用量為5重量份至50重量份;該具有乙烯性不飽和基之化合物(D)之使用量為20重量份至200重量份;該光起始劑(E)之使用量為10重量份至100重量份;該具有式(I)所示結構之熱酸發生劑(F)之使用量為0.1重量份至10重量份;該溶劑(G)之使用量為500重量份至5000重量份。 The photosensitive resin composition of claim 1, wherein the pigment (A) is used in an amount of from 30 parts by weight to 300 parts by weight based on 100 parts by weight of the alkali-soluble resin (C); The amount used is 5 parts by weight to 50 parts by weight; the compound (D) having an ethylenically unsaturated group is used in an amount of 20 parts by weight to 200 parts by weight; and the photoinitiator (E) is used in an amount of 10 Parts by weight to 100 parts by weight; the thermal acid generator (F) having the structure of the formula (I) is used in an amount of from 0.1 part by weight to 10 parts by weight; the solvent (G) is used in an amount of from 500 parts by weight to 5,000 parts by weight Parts by weight. 根據請求項2之感光性樹脂組成物,其中,基於該鹼可溶性樹脂(C)之使用量為100重量份,該第一鹼可溶性樹脂(C-1)之使用量為0重量份至90重量份。 The photosensitive resin composition of claim 2, wherein the first alkali-soluble resin (C-1) is used in an amount of from 0 part by weight to 90% by weight based on 100 parts by weight of the alkali-soluble resin (C). Share. 根據請求項4之感光性樹脂組成物,其中,基於該鹼可溶性樹脂(C)之使用量為100重量份,該具有式(III)所示結構之光起始劑(E-1)之使用量為0.1重量份至15重量份 The photosensitive resin composition of claim 4, wherein the photoinitiator (E-1) having the structure represented by the formula (III) is used based on the amount of the alkali-soluble resin (C) used in an amount of 100 parts by weight. The amount is from 0.1 part by weight to 15 parts by weight 一種彩色濾光片之製造方法,其係使用根據請求項1至10任一項之感光性樹脂組成物形成一畫素層。 A method of producing a color filter, which comprises forming a pixel layer using the photosensitive resin composition according to any one of claims 1 to 10. 一種彩色濾光片,其係由根據請求項11之方法所製得。 A color filter produced by the method of claim 11. 一種液晶顯示裝置,其特徵在於包含根據請求項12之彩色濾光片。 A liquid crystal display device comprising a color filter according to claim 12.
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