TWI612386B - Photosensitive resin composition for color filter and application thereof - Google Patents
Photosensitive resin composition for color filter and application thereof Download PDFInfo
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- TWI612386B TWI612386B TW104129972A TW104129972A TWI612386B TW I612386 B TWI612386 B TW I612386B TW 104129972 A TW104129972 A TW 104129972A TW 104129972 A TW104129972 A TW 104129972A TW I612386 B TWI612386 B TW I612386B
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- 0 C*C(*)=NOC1OC1* Chemical compound C*C(*)=NOC1OC1* 0.000 description 12
- QWHNJUXXYKPLQM-UHFFFAOYSA-N CC1(C)CCCC1 Chemical compound CC1(C)CCCC1 QWHNJUXXYKPLQM-UHFFFAOYSA-N 0.000 description 1
- JPIKTTQEANJSEG-UHFFFAOYSA-N CCC1COCCC1 Chemical compound CCC1COCCC1 JPIKTTQEANJSEG-UHFFFAOYSA-N 0.000 description 1
- AHVQYHFYQWKUKB-UHFFFAOYSA-N NC1CCOCC1 Chemical compound NC1CCOCC1 AHVQYHFYQWKUKB-UHFFFAOYSA-N 0.000 description 1
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL 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
- G02F1/00—Devices 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
- G02F1/01—Devices 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
- G02F1/13—Devices 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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL 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
- G02F1/00—Devices 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
- G02F1/01—Devices 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
- G02F1/13—Devices 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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
- G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-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)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
Abstract
本發明有關一種彩色濾光片用感光性樹脂組成物及其應用。此彩色濾光片用感光性樹脂組成物包含顏料(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)及有機溶劑(F)。鹼可溶性樹脂(C)包含第一鹼可溶性樹脂(C-1)。所製得之彩色濾光片用感光性樹脂組成物具有較佳之圖案平滑性及對比度,且無泡狀之顯示缺陷。 The invention relates to a photosensitive resin composition for a color filter and an application thereof. The photosensitive resin composition for a color filter includes a pigment (A), a dye (B), an alkali-soluble resin (C), a compound (D) having an ethylenically unsaturated group, a photoinitiator (E), and an organic compound. Solvent (F). The alkali-soluble resin (C) includes a first alkali-soluble resin (C-1). The prepared photosensitive resin composition for a color filter has better pattern smoothness and contrast, and has no bubble-like display defects.
Description
本發明係有關一種彩色濾光片用感光性樹脂組成物,特別是提供一種具有較佳之圖案平滑性及對比度,並無泡狀之顯示缺陷。 The present invention relates to a photosensitive resin composition for a color filter, and in particular, to provide a pattern smoothness and contrast with good pattern, and no bubble-like display defects.
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。目前彩色濾光片之製造方法包含染色法、印刷法、電鍍法及分散法等,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, and color cameras. With the increasing market demand, the manufacturing technology of color filters also tends to diversify. At present, the manufacturing methods of color filters include dyeing method, printing method, electroplating method, and dispersion method, among which the dispersion method is the mainstream process.
分散法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。然後,經過曝光、顯像等步驟,即可製得特定圖案。經重複三次操作後,即可製得紅色(R)、綠色(G)及藍色(B)之畫素著色層之圖案。接著,視需要可施加保護膜於畫素著色層之圖案上。 The dispersion method is to disperse a colored pigment in a photosensitive resin, and then apply the photosensitive resin on a glass substrate. Then, through steps such as exposure and development, a specific pattern can be made. After repeating the operation three times, the pattern of the pixel colored layer of red (R), green (G) and blue (B) can be obtained. Then, if necessary, a protective film may be applied to the pattern of the pixel coloring layer.
用於分散法之感光性樹脂如日本專利特開第平6-95211號及特開第平8-183819號所揭示,所揭示之感光 性樹脂包含鹼可溶性樹脂,且此鹼可溶性樹脂係例如以(甲基)丙烯酸為共聚合單體成分所聚合而成之共聚物。 The photosensitive resin used in the dispersion method is disclosed in Japanese Patent Laid-Open No. 6-95211 and Japanese Patent Laid-Open No. 8-183819. The alkali-soluble resin includes an alkali-soluble resin, and the alkali-soluble resin is, for example, a copolymer obtained by polymerizing a (meth) acrylic acid as a comonomer component.
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℃條件下加熱1小時左右,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1至10μm),且該畫素著色層之耐熱性亦不佳。 However, during the manufacturing process of color filters, multiple heat treatment steps are required, such as red (R), green (G), and blue (B) pixel-colored layer patterns are formed and post-bake. Steps and formation steps of transparent conductive film (ITO film), etc. These steps generally need to be operated at a high temperature above 200 ° C, but if the conventional photosensitive resin is heated at 180 ° C for about 1 hour, it is easy to draw Pigment agglomerated particles are produced in the pigmented layer (generally, the particle size of the pigment agglomerated particles is between 1 and 10 μm), and the heat resistance of the pigmented layer is not good.
為改善上述之問題,日本專利特開第2001-075273號中揭示之感光性樹脂組成物,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作為感光性樹脂之鹼可溶性樹脂。然而,此習知技術之感光性樹脂組成物製得之彩色濾光片卻具有泡狀之顯示缺陷、圖案平滑性與對比度不佳的缺陷。 In order to improve the above problems, the photosensitive resin composition disclosed in Japanese Patent Laid-Open No. 2001-075273 includes a polymer obtained by polymerizing an unsaturated monomer containing a carboxylic acid group and a monomer containing an epoxy group. An alkali-soluble resin as a photosensitive resin. However, the color filter made of the photosensitive resin composition of this conventional technique has the defects of bubble-like display defects, poor pattern smoothness and poor contrast.
因此,如何同時克服泡狀之顯示缺陷、圖案平滑性與對比度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 problems of bubble-shaped display defects, poor pattern smoothness, and poor contrast at the same time to meet the current industry requirements is the goal of hard research in the technical field to which the present invention belongs.
因此,本發明之一態樣是在提供一種彩色濾光片用感光性樹脂組成物,此彩色濾光片用感光性樹脂組成物包含顏料(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)及有機溶劑(F),且此彩色濾光片用感光性樹脂組成物可提升圖案平滑性及對比度,且無泡狀之顯示缺陷。 Therefore, one aspect of the present invention is to provide a photosensitive resin composition for a color filter. The photosensitive resin composition for a color filter includes a pigment (A), a dye (B), and an alkali-soluble resin (C ), With ethylene Saturated compound (D), photoinitiator (E) and organic solvent (F). The photosensitive resin composition for a color filter can improve the smoothness and contrast of the pattern, and has no bubble-like display defects.
本發明之另一態樣是在提供一種彩色濾光片之製造方法,其包含利用前述之彩色濾光片用感光性樹脂組成物形成畫素層之步驟。 Another aspect of the present invention is to provide a method for manufacturing a color filter, which includes the step of forming a pixel layer using the aforementioned photosensitive resin composition for a color filter.
本發明之又一態樣是在提供一種彩色濾光片,其係利用前述之製造方法製得。 Another aspect of the present invention is to provide a color filter, which is manufactured by using the aforementioned manufacturing method.
本發明之再一態樣是在提供一種液晶顯示裝置,其包含前述之彩色濾光片。 Another aspect of the present invention is to provide a liquid crystal display device including the aforementioned color filter.
根據本發明之上述態樣,提出一種彩色濾光片用感光性樹脂組成物。此彩色濾光片用感光性樹脂組成物包含顏料(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)及有機溶劑(F),以下析述之。 According to the aspect of the present invention, a photosensitive resin composition for a color filter is proposed. The photosensitive resin composition for a color filter includes a pigment (A), a dye (B), an alkali-soluble resin (C), a compound (D) having an ethylenically unsaturated group, a photoinitiator (E), and an organic compound. The solvent (F) is described below.
本發明之顏料(A)可包含無機顏料、有機顏料或此等之一組合。 The pigment (A) of the present invention may include an inorganic pigment, an organic pigment, or a combination thereof.
上述之無機顏料可為金屬氧化物或金屬錯鹽等金屬化合物,其可選自於鐵、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、亞鉛或銻等金屬的氧化物以及前述金屬的複合氧化物。 The above-mentioned inorganic pigment may be a metal compound such as a metal oxide or a metal salt, and may be selected from oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, lead, or antimony, A composite oxide of the aforementioned metals.
上述之有機顏料係選自於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。該有機顏料可單獨一種使用或混合複數種使用。 The above organic pigments are 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, 224, 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. These organic pigments can be used alone or in combination.
該顏料(A)的一次粒子之平均粒子徑可為10nm至200nm,較佳為20nm至150nm,且更佳為30nm至130nm。 The average particle diameter of the primary particles of the pigment (A) may be 10 nm to 200 nm, preferably 20 nm to 150 nm, and more preferably 30 nm to 130 nm.
基於後述鹼可溶性樹脂(C)之總使用量為100重量份,該顏料(A)的使用量為30重量份至300重量份,較佳為35重量份至250重量份,且更佳為40重量份至200重量份。 Based on the total amount of the alkali-soluble resin (C) to be described later being 100 parts by weight, the amount of the pigment (A) used is 30 to 300 parts by weight, preferably 35 to 250 parts by weight, and more preferably 40 Part by weight 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、聚矽氧烷系或氟系等之界面活性劑。 If necessary, the pigment (A) can also selectively use a dispersant, for example, a cationic, anionic, nonionic, amphoteric, polysiloxane, or fluorine-based surfactant.
該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。該界面活性劑可單獨一種使用或混合複數種使用。 The surfactant may include, but is not limited to, polyethylene oxide alkyl ethers such as polyethylene oxide dodecyl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether, etc .; Polyethylene oxide alkyl phenyl ether surfactants such as ethylene oxide octyl phenyl ether, polyethylene oxide nonyl phenyl ether; polyethylene glycol dilaurate, polyethylene glycol distearate Ester surfactants such as polyethylene glycol diesters; sorbitan fatty acid ester surfactants; fatty acid modified polyester surfactants; tertiary amine modified polyurethane interface Active agent; manufactured by Shin-Etsu Chemical Co., Ltd., a product of model KP, manufactured by Toray Dow Corning Silicon, a product of model SF-8427, manufactured by Kyoeisha Oil Chemical Industry, a product of model Polyflow, Tochem Products Co. ., Ltd.), model F-Top, Dainippon Ink Chemical Industry, model Megafac, Sumitomo 3M, model Fluorad, Asahi Glass, model Asahi Guard and Surflon . The surfactant can be used singly or in combination.
本發明之染料(B)可包含呫噸(Xanthene)系染料(B-1)。其次,該染料(B)可選擇性地包含其他染料(B-2)。 The dye (B) of the present invention may include a xanthene dye (B-1). Second, the dye (B) may optionally contain other dyes (B-2).
呫噸系染料(B-1)Xanthene Dye (B-1)
該呫噸系染料(B-1)可具有如下式(V)所示之結構:
於式(V)中,D1至D4分別獨立地表示氫原子、-D6、碳數為6至10之芳香烴基,或著經鹵素原子、-D6、-OH、-OD6、-SO3 -、-SO3H、-SO3M、-COOH、-COOD6、-SO3D6、-SO2NHD8或-SO2ND8D9取代之碳數為6至10之芳香烴基;D5表示-SO3 -、-SO3H、-SO3M、-COOH、-COOD6、-SO3D6、-SO2NHD8或-SO2ND8D9;u表示0至5之整數;當u表示2至5時,複數個D5為相同或不同;Z表示鹵素原子;t表示0或1;D6表示碳數為1至10之烷基或經鹵素原子取代且碳數為1至10之烷基,其中該碳數為1至10之烷基或經鹵素原子取代且碳數為1至10之烷基中之-CH2-係未經置換或經置換為-O-、羰基或-ND7-; D7表示碳數為1至10之烷基或經鹵素原子取代且碳數為1至10之烷基;D8及D9各自獨立表示碳數為1至10之直鏈烷基、碳數為1至10之支鏈烷基、碳數為3至30之環烷基、或-Q;其中,碳數為1至10之直鏈烷基、碳數為1至10之支鏈烷基或碳數為3至30之環烷基中之氫原子係未經取代或經一取代基所取代,該取代基係選自由羥基、鹵素原子、-Q、-CH=CH2及-CH=CH-D6所組成之群;碳數為1至10之直鏈烷基、碳數為1至10之支鏈烷基或碳數為3至30之環烷基中之-CH2-係未經置換或經置換為-O-、羰基或-ND7-;或D8和D9結合形成碳數為1至10之雜環基,其中碳數為1至10之雜環基中之氫原子係未經取代或經D6、-OH、或-Q所取代;Q表示碳數為6至10之芳香烴基、碳數為5至10之雜芳香基、經鹵素原子、-D6、-OH、-OD6、-NO2、-CH=CH2或-CH=CH-D6取代之碳數為6至10之芳香烴基、或經鹵素原子、-D6、-OH、-OD6、-NO2、-CH=CH2及-CH=CH-D6取代且碳數為5至10之雜芳香基;及M表示鉀或鈉。 In formula (V), D 1 to D 4 each independently represent a hydrogen atom, -D 6 , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, -D 6 , -OH, -OD 6 , -SO 3 -, -SO 3 H, -SO 3 M, -COOH, -COOD 6, -SO 3 D 6, -SO 2 NHD 8 or -SO 2 ND 8 D 9 substituents to carbon atoms of 6 to 10 aromatic hydrocarbon group; D 5 represents -SO 3 -, -SO 3 H, -SO 3 M, -COOH, -COOD 6, -SO 3 D 6, -SO 2 NHD 8 or -SO 2 ND 8 D 9; u represents An integer from 0 to 5; when u represents 2 to 5, a plurality of D 5 are the same or different; Z represents a halogen atom; t represents 0 or 1; D 6 represents an alkyl group having 1 to 10 carbon atoms or a halogen atom A substituted alkyl group having 1 to 10 carbons, wherein -CH 2 -in the alkyl group having 1 to 10 carbons or the alkyl group substituted with a halogen atom and having 1 to 10 carbons is unsubstituted or Substituted by -O-, carbonyl or -ND 7- ; D 7 represents an alkyl group having 1 to 10 carbon atoms or an alkyl group substituted with a halogen atom and having 1 to 10 carbon atoms; D 8 and D 9 each independently represent carbon A linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q; wherein a linear alkyl group having 1 to 10 carbon atoms Base, carbon The hydrogen atom in a branched alkyl group having a number of 1 to 10 or a cycloalkyl group having a carbon number of 3 to 30 is unsubstituted or substituted with a substituent, and the substituent is selected from a hydroxyl group, a halogen atom, -Q Group consisting of -CH = CH 2 and -CH = CH-D 6 ; linear alkyl group having 1 to 10 carbon atoms, branched alkyl group having 1 to 10 carbon atoms or 3 to 30 carbon atoms -CH 2 -in a cycloalkyl group is unsubstituted or substituted with -O-, carbonyl, or -ND 7- ; or D 8 and D 9 combine to form a heterocyclic group having 1 to 10 carbon atoms, in which the carbon number The hydrogen atom in a heterocyclic group of 1 to 10 is unsubstituted or substituted with D 6 , -OH, or -Q; Q represents an aromatic hydrocarbon group having 6 to 10 carbons and a hetero group having 5 to 10 carbons Aromatic group, aromatic hydrocarbon group having 6 to 10 carbon atoms substituted with halogen atom, -D 6 , -OH, -OD 6 , -NO 2 , -CH = CH 2 or -CH = CH-D 6 , or halogen An atom, -D 6 , -OH, -OD 6 , -NO 2 , -CH = CH 2 and -CH = CH-D 6 substituted heteroaromatic group having 5 to 10 carbon atoms; and M represents potassium or sodium.
較佳地,前述之D6可包含但不限於甲基、乙基、丙基、異丙基、丁基、異丁基、戊基、異戊基、新戊基(neopentyl)、環戊基、己基、環己基、庚基、環庚烷、辛基、環辛基、2-乙基己基、壬基、癸基、三環[5.3.0.03,10]癸基[tricycle(5.3.0.03,10)decanyl]、甲氧基丙基、己氧基丙基、2-乙基己氧基丙基、甲氧基己基、或環氧基丙基。 Preferably, the aforementioned D 6 may include, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neoopentyl, cyclopentyl , Hexyl, cyclohexyl, heptyl, cycloheptane, octyl, cyclooctyl, 2-ethylhexyl, nonyl, decyl, tricyclo [5.3.0.0 3,10 ] decyl [tricycle (5.3.0.0 3,10 ) decanyl], methoxypropyl, hexyloxypropyl, 2-ethylhexyloxypropyl, methoxyhexyl, or epoxypropyl.
較佳地,碳數為6至10之芳香烴基可包含但不限於苯基或萘基等。 Preferably, the aromatic hydrocarbon group having 6 to 10 carbon atoms may include, but is not limited to, phenyl, naphthyl, and the like.
較佳地,前述之-SO3D6可包含但不限於甲基磺醯基(methanesulfonyl)、乙基磺醯基(ethanesulfonyl)、己基磺醯基(hexanesulfonyl)或癸基磺醯基(decanesulfonyl)。 Preferably, the aforementioned -SO 3 D 6 may include, but is not limited to, methanesulfonyl, ethanesulfonyl, hexanesulfonyl, or decanesulfonyl .
較佳地,前述之-COOD6可包含但不限於甲氧基羰基(methyloxycarbonyl)、乙氧基羰基(ethyloxycarbonyl)、丙氧基羰基、異丙氧基羰基、丁氧基羰基、異丁氧基羰基、戊氧基羰基、異戊氧基羰基、新戊氧基羰基、環戊氧基羰基、己氧基羰基、環己氧基羰基、庚氧基羰基、環庚氧基羰基、辛氧基羰基、環辛氧基羰基、2-乙基己氧基羰基、壬氧基羰基、癸氧基羰基、三環[5.3.0.03,10]癸基羰基、甲氧基丙氧基羰基、己氧基丙氧基羰基、2-乙基己氧基丙氧基羰基或甲氧基己氧基羰基。 Preferably, the aforementioned -COOD 6 may include, but is not limited to, methyloxycarbonyl, ethyloxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, and isobutoxy Carbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxy Carbonyl, cyclooctyloxycarbonyl, 2-ethylhexyloxycarbonyl, nonoxycarbonyl, decyloxycarbonyl, tricyclic [5.3.0.0 3,10 ] decylcarbonyl, methoxypropoxycarbonyl, hexane Oxypropoxycarbonyl, 2-ethylhexyloxypropoxycarbonyl or methoxyhexyloxycarbonyl.
較佳地,前述之-SO2NHD8可包含但不限於胺磺醯基(sulfamoyl)、甲基胺磺醯基、乙基胺磺醯基、丙基胺磺醯基、異丙基胺磺醯基、丁基胺磺醯基、異丁基胺磺醯基、戊基胺磺醯基、異戊基胺磺醯基、新戊基胺磺醯基、環戊基胺磺醯基、己基胺磺醯基、環己基胺磺醯基、庚基胺磺醯基、環庚烷胺磺醯基、辛基胺磺醯基、環辛基胺磺醯基、2-乙基己基胺磺醯基、壬基胺磺醯基、癸基胺磺醯基、三環[5.3.0.03,10]癸基胺磺醯基、甲氧基丙基胺磺醯基、己氧基
丙基胺磺醯基、2-乙基己氧基丙基胺磺醯基、甲氧基己基胺磺醯基、環氧基丙基胺磺醯基、1,5-二甲基己基胺磺醯基、丙氧基丙基胺磺醯基、異丙氧基丙基胺磺醯基、3-苯基-1-甲基丙基胺磺醯基、、、
較佳地,前述之-SO2ND8D9可包含但不限於
較佳地,呫噸系染料(B-1)可包含具有如下式(V-i)所示之結構:
於式(V-i)中,D11至D14各自獨立表示氫原子、-D6、碳數為6至10之芳香烴基,或者經鹵素原子、-D6、-OH、-OD6、-SO3 -、-SO3H、-SO3Na、-COOH、-COOD6、-SO3D6、-SO2NHD8或-SO2ND8D9取代且碳數為6至10之芳香烴基;D15表示氫原子、-SO3 -、-SO3H、-SO2NHD8或-SO2ND8D9;D16表示-SO3 -、-SO3H、-SO2NHD8或-SO2ND8D9;Z1表示鹵素原子;t1表示0或1。 In Formula (Vi), D 11 to D 14 each independently represent a hydrogen atom, -D 6 , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or via a halogen atom, -D 6 , -OH, -OD 6 , -SO 3 -, -SO 3 H, -SO 3 Na, -COOH, -COOD 6, -SO 3 D 6, -SO 2 NHD 8 or -SO 2 ND 8 D 9 carbon atoms and substituted with an aromatic hydrocarbon group having 6 to 10 of ; D 15 represents a hydrogen atom, -SO 3 -, -SO 3 H , -SO 2 NHD 8 or -SO 2 ND 8 D 9; D 16 represents -SO 3 -, -SO 3 H, -SO 2 NHD 8 or -SO 2 ND 8 D 9 ; Z 1 represents a halogen atom; t 1 represents 0 or 1.
較佳地,呫噸系染料(B-1)可包含具有如下式(V-ii)所示之結構:
於式(V-ii)中,D21至D24各自獨立表示氫原子、-D26、碳數為6至10之芳香烴基,或者經鹵素原子、-D26、-OH、 -OD26、-SO3 -、-SO3H、-SO3Na、-COOH、-COOD26、-SO3D26、或-SO2NHD28取代且碳數為6至10之芳香烴基;D25表示-SO3 -、-SO3Na、-COOH、-COOD26、-SO3H、或-SO2NHD28;u1表示0至5之整數;當u1表示2至5時,複數個D25為相同或不同;Z2表示鹵素原子;t2表示0或1;D26表示碳數為1至10之烷基,或者經鹵素原子或-OD27取代且碳數為1至10之烷基;D27表示碳數為1至10之烷基;及D28表示氫原子、-D26、-COOD26、碳數為6至10之芳香烴基,或著經-D26或-OD26取代且碳數為6至10之芳香烴基。 In the formula (V-ii), D 21 to D 24 each independently represent a hydrogen atom, -D 26 , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or via a halogen atom, -D 26 , -OH, -OD 26 , -SO 3 -, -SO 3 H, -SO 3 Na, -COOH, -COOD 26, -SO 3 D 26, or -SO 2 NHD 28 carbon atoms and substituted with an aromatic hydrocarbon group of 6 to 10; D 25 represents - SO 3 -, -SO 3 Na, -COOH, -COOD 26, -SO 3 H, or -SO 2 NHD 28; u 1 represents an integer of 0-5; when u 1 represents 2 to 5, a plurality of D 25 Are the same or different; Z 2 represents a halogen atom; t 2 represents 0 or 1; D 26 represents an alkyl group having 1 to 10 carbon atoms, or an alkyl group substituted with a halogen atom or -OD 27 and having 1 to 10 carbon atoms ; D 27 represents an alkyl group having a carbon number of 1 to 10; and D 28 represents a hydrogen atom, -D 26 , -COOD 26 , an aromatic hydrocarbon group having a carbon number of 6 to 10, or substituted by -D 26 or -OD 26 And an aromatic hydrocarbon group having 6 to 10 carbon atoms.
較佳地,呫噸系染料(B-1)可包含具有如下式(V-iii)所示之結構:
於式(V-iii)中,D31及D32各自獨立表示苯基,或者經鹵素原子、-D26、-OD26、-COOD26、-SO3D26或-SO2NHD28取代之苯基; D33表示-SO3 -、或-SO2NHD28;D34表示氫原子、-SO3 -、或-SO2NHD28;Z3表示鹵素原子;t3表示0或1;D26表示碳數為1至10之烷基,或者經鹵素原子或-OD27取代且碳數為1至10之烷基;D27表示碳數為1至10之烷基;及D28表示氫原子、-D26、-COOD26、碳數為6至10之芳香烴基,或者經-D26或-OD26取代且碳數為6至10之芳香烴基。 (V-iii) In the formula, D 31 and D 32 independently represent a phenyl group, or a halogen atom, -D 26, -OD 26, -COOD 26, the substituent -SO 3 D 26 or -SO 2 NHD 28 phenyl; D 33 represents -SO 3 -, or -SO 2 NHD 28; D 34 represents a hydrogen atom, -SO 3 -, or -SO 2 NHD 28; Z 3 represents a halogen atom; t 3 represents 0 or 1; D 26 represents an alkyl group having 1 to 10 carbon atoms, or an alkyl group substituted with a halogen atom or -OD 27 and having 1 to 10 carbon atoms; D 27 represents an alkyl group having 1 to 10 carbon atoms; and D 28 represents hydrogen An atom, -D 26 , -COOD 26 , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic hydrocarbon group substituted with -D 26 or -OD 26 and having 6 to 10 carbon atoms.
較佳地,呫噸系染料(B-1)可包含具有如下式(V-iv)所示之結構:
於式(V-4)中,D41及D42各自獨立表示苯基,或者經-D26或-SO2NHD28取代之苯基;D43表示-SO3 -、或-SO2NHD28;Z4表示鹵素原子;t4表示0或1;D26表示碳數為1至10之烷基,或者經鹵素原子或-OD27取代且碳數為1至10之烷基;D27表示碳數為1至10之烷基;及 D28表示氫原子、-D26、-COOD26、碳數為6至10之芳香烴基,或者經-D26或-OD26取代且碳數為6至10之芳香烴基。 In the formula (V-4), D 41 and D 42 independently represent a phenyl group, or by -D 26 -SO 2 NHD 28 or the substituted phenyl; D 43 represents -SO 3 -, or -SO 2 NHD 28 Z 4 represents a halogen atom; t 4 represents 0 or 1; D 26 represents an alkyl group having 1 to 10 carbon atoms, or an alkyl group substituted with a halogen atom or -OD 27 and having 1 to 10 carbon atoms; D 27 represents An alkyl group having 1 to 10 carbons; and D 28 represents a hydrogen atom, -D 26 , -COOD 26 , an aromatic hydrocarbon group having 6 to 10 carbons, or is substituted with -D 26 or -OD 26 and has a carbon number of 6 To 10 aromatic hydrocarbon groups.
於本發明之具體例中,染料(B)可包含但不限於如下式(V-1)至式(V-31)所示之化合物:
於式(V-1)中,Rc及Rd各自獨立表示氫原子、-SO3 -、-COOH或-SO2NHD81;D81表示2-乙基己基;Z表示鹵素原子;t表示0或1。 In the formula (V-1) in a, R c and R d each independently represent a hydrogen atom, -SO 3 -, -COOH, or -SO 2 NHD 81; D 81 represents a 2-ethylhexyl diyl; Z represents a halogen atom; T represents 0 or 1.
於式(V-2)中,Re表示氫原子、-SO3 -、-COOH或-SO2NHD81; D81表示2-乙基己基;Z表示鹵素原子;t表示0或1。 In the formula (V-2), R e represents a hydrogen atom, -SO 3 -, -COOH, or -SO 2 NHD 81; D 81 represents a 2-ethylhexyl diyl; Z represents a halogen atom; T represents 0 or 1.
於式(V-3)中,Re表示氫原子、-SO3 -、-COOH或-SO2NHD81;D81表示2-乙基己基;Z表示鹵素原子;t表示0或1。 In the formula (V-3), R e represents a hydrogen atom, -SO 3 -, -COOH, or -SO 2 NHD 81; D 81 represents a 2-ethylhexyl diyl; Z represents a halogen atom; T represents 0 or 1.
於式(V-4)中,Rf、Rg及Rh各自獨立表示-SO3 -、-SO3Na或-SO2NHD81;D81表示2-乙基己基。 In formula (V-4), R f , R g, and R h each independently represent —SO 3 — , —SO 3 Na, or —SO 2 NHD 81 ; D 81 represents 2-ethylhexyl.
於式(V-5)中,Rf、Rg及Rh各自獨立表示-SO3 -、-SO3Na或-SO2NHD81;D81表示2-乙基己基。 In the formula (V-5), R f , R g, and R h each independently represent —SO 3 — , —SO 3 Na, or —SO 2 NHD 81 ; D 81 represents 2-ethylhexyl.
於式(V-6)中,Ri、Rj及Rk各自獨立表示氫、-SO3 -、-SO3H或-SO2NHD81;D81表示2-乙基己基。 In the formula (V-6), R i , R j and R k each independently represent hydrogen, -SO 3 -, -SO 3 H or -SO 2 NHD 81; D 81 represents a 2-ethylhexyl group.
於式(V-7)中,Ri、Rj及Rk各自獨立表示氫、-SO3 -、-SO3H或-SO2NHD81;D81表示2-乙基己基。 In the formula (V-7), R i , R j and R k each independently represent hydrogen, -SO 3 -, -SO 3 H or -SO 2 NHD 81; D 81 represents a 2-ethylhexyl group.
於式(V-8)中,Rl、Rm及Rn各自獨立表示-SO3 -、-SO3Na或-SO2NHD81;D81表示2-乙基己基。 In the formula (V-8), R l , R m and R n each independently represent -SO 3 -, -SO 3 Na or -SO 2 NHD 81; D 81 represents a 2-ethylhexyl group.
於式(V-9)中,Rl、Rm及Rn各自獨立表示-SO3 -、-SO3Na或-SO2NHD81;D81表示2-乙基己基。 In the formula (V-9), R l , R m and R n each independently represent -SO 3 -, -SO 3 Na or -SO 2 NHD 81; D 81 represents a 2-ethylhexyl group.
於式(V-10)中,Rp、Rq及Rr各自獨立表示氫、-SO3 -、-SO3H或-SO2NHD81;D81表示2-乙基己基。 In the formula (V-10), R p , R q and R r each independently represent hydrogen, —SO 3 — , —SO 3 H, or —SO 2 NHD 81 ; D 81 represents 2-ethylhexyl.
於式(V-11)中,Rp、Rq及Rr各自獨立表示氫、-SO3 -、-SO3H或-SO2NHD81;D81表示2-乙基己基。 In the formula (V-11), R p , R q and R r independently represent hydrogen, -SO 3 -, -SO 3 H or -SO 2 NHD 81; D 81 represents a 2-ethylhexyl group.
較佳地,本發明呫噸系染料(B-1)之具體例可包含式(V-1)(Rc與Rd為-SO3 -且t為0;C.I.酸性紅色染料 52)、式(V-22)(C.I.酸性紅色染料289)、式(V-28)、式(V-31)或上述材料之任意組合。 Preferably, specific examples of the xanthene dye (B-1) of the present invention may include formula (V-1) (R c and Rd are -SO 3 - and t is 0; CI acid red dye 52), formula (V-22) (CI Acid Red Dye 289), Formula (V-28), Formula (V-31), or any combination of the above materials.
基於後述鹼可溶性樹脂(C)之總使用量為100重量份,呫噸系染料(B-1)之使用量為3重量份至50重量份,較佳為5重量份至45重量份,且更佳為10重量份至40重量份。 Based on the total amount of alkali-soluble resin (C) to be described later being 100 parts by weight, the amount of xanthene-based dye (B-1) to be used is 3 to 50 parts by weight, preferably 5 to 45 parts by weight, and More preferably, it is 10 to 40 parts by weight.
當本發明之染料(B)包含呫噸系染料(B-1)時,所製得之彩色濾光片用感光性樹脂組成物具有較佳之對比度。 When the dye (B) of the present invention contains a xanthene-based dye (B-1), the prepared photosensitive resin composition for a color filter has better contrast.
其他染料(B-2)Other dyes (B-2)
該其它染料(B-2)可包含但不限於偶氮系染料、蒽醌系染料、酞菁系染料、醌亞胺系染料、喹啉系染料或硝基系染料。 The other dye (B-2) may include, but is not limited to, an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinimine dye, a quinoline dye, or a nitro dye.
前述之偶氮系染料可包含但不限於C.I.酸性黃11、酸性橙7、酸性紅37、酸性紅180、酸性藍29、直接紅28、直接紅83、直接黃12、直接橙26、直接綠28、直接綠59、活性黃2、活性紅17、活性紅120、活性黑5、分散橙5、分散紅58、分散藍165、鹼性藍41、鹼性紅18、媒介紅7、媒介黃5或媒介黑7等。 The aforementioned azo dyes may include, but are not limited to, CI Acid Yellow 11, Acid Orange 7, Acid Red 37, Acid Red 180, Acid Blue 29, Direct Red 28, Direct Red 83, Direct Yellow 12, Direct Orange 26, Direct Green 28. Direct Green 59, Active Yellow 2, Active Red 17, Active Red 120, Active Black 5, Disperse Orange 5, Disperse Red 58, Disperse Blue 165, Basic Blue 41, Basic Red 18, Medium Red 7, Medium Yellow 5 or medium black 7.
該蒽醌系染料可包含但不限於C.I.巴德藍4(Batblue 4)、酸性藍40、酸性綠25、活性藍19、活性藍49、分散紅60、分散藍56或分散藍60等。 The anthraquinone-based dye may include, but is not limited to, C.I. Batblue 4, Acid Blue 40, Acid Green 25, Reactive Blue 19, Reactive Blue 49, Disperse Red 60, Disperse Blue 56 or Disperse Blue 60, and the like.
該酞菁系染料可包含但不限於C.I.鹼性藍5等。 The phthalocyanine dye may include, but is not limited to, C.I. Basic Blue 5 and the like.
該醌亞胺系染料可包含但不限於C.I.鹼性藍3或鹼性藍9等。 The quinoneimine-based dye may include, but is not limited to, C.I. Basic Blue 3 or Basic Blue 9 and the like.
該喹啉系染料可包含但不限於C.I.溶劑黃33、酸性黃3或分散黃64等。 The quinoline dye may include, but is not limited to, C.I. Solvent Yellow 33, Acid Yellow 3, or Disperse Yellow 64, and the like.
該硝基系染料可包含但不限於C.I.酸性黃1、酸性橙3或分散黃42等。上述其它染料(B-2)一般可單獨一種使用或混合複數種使用。 The nitro-based dye may include, but is not limited to, C.I. Acid Yellow 1, Acid Orange 3, or Disperse Yellow 42 and the like. The other dyes (B-2) described above can be used singly or in combination.
基於後述鹼可溶性樹脂(C)之總使用量為100重量份,其他染料(B-2)之使用量為0重量份至47重量份,較佳為0重量份至40重量份,且更佳為0重量份至30重量份。 Based on the total use amount of the alkali-soluble resin (C) to be described later, the use amount of the other dye (B-2) is 0 to 47 parts by weight, preferably 0 to 40 parts by weight, and more preferably It is 0 to 30 parts by weight.
基於後述鹼可溶性樹脂(C)之總使用量為100重量份,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,且更佳為15重量份至40重量份。 Based on the total amount of the alkali-soluble resin (C) described later being 100 parts by weight, the amount of the dye (B) used is 5 to 50 parts by weight, preferably 10 to 45 parts by weight, and more preferably 15 parts by weight Parts to 40 parts by weight.
本發明之鹼可溶性樹脂(C)可包含第一鹼可溶性樹脂(C-1)。其次,該鹼可溶性樹脂(C)可選擇性地包含第二鹼可溶性樹脂(C-2)。 The alkali-soluble resin (C) of the present invention may include the first alkali-soluble resin (C-1). Second, the alkali-soluble resin (C) may optionally include a second alkali-soluble resin (C-2).
第一鹼可溶性樹脂(C-1)First alkali-soluble resin (C-1)
該第一鹼可溶性樹脂(C-1)具有如下式(I)所示之結構:
於式(I)中,A1及A2分別獨立地代表氫原子、具有取代基或不具有取代基之碳數為1至25之烴基。 In Formula (I), A 1 and A 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms with or without a substituent.
在一實施例中,第一鹼可溶性樹脂(C-1)具有至少一個乙烯性不飽和基。 In one embodiment, the first alkali-soluble resin (C-1) has at least one ethylenically unsaturated group.
該第一鹼可溶性樹脂(C-1)可由第一混合物反應所製得,且該第一混合物係由具有如式(I-1)所示之結構之乙烯性不飽和單體(c-1-1)、具有至少一個羧酸或羧酸酐之乙烯性不飽和單體(c-1-2)及其他可共聚合之乙烯性不飽和單體(c-1-3)所共聚合而成之一共聚合物,再與具有環氧基之乙烯性不飽和單體(c-1-4)反應而得。 The first alkali-soluble resin (C-1) can be prepared by reacting a first mixture, and the first mixture is made of an ethylenically unsaturated monomer (c-1) having a structure represented by formula (I-1). -1), copolymerized by ethylenically unsaturated monomer (c-1-2) with at least one carboxylic acid or carboxylic anhydride and other copolymerizable ethylenically unsaturated monomer (c-1-3) A copolymer is obtained by reacting with an ethylenically unsaturated monomer (c-1-4) having an epoxy group.
具有如式(I-1)所示之結構之乙烯性不飽和單體(c-1-1)The ethylenically unsaturated monomer (c-1-1) having a structure represented by the formula (I-1)
該乙烯性不飽和單體具有如下式(I-1)所示之結構:
於式(I-1)中,A1及A2分別獨立地代表氫原子、具有取代基或不具有取代基之碳數為1至25之烴基。 In the formula (I-1), A 1 and A 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms with or without a substituent.
該乙烯性不飽和單體可具有如下式(I-2-1)及式(I-2-2)所示之結構:
於式(I-2-1)及式(I-2-2)中,A1及A2分別獨立地代表氫原子、具有取代基或不具有取代基之碳數為1至25之烴基。該乙烯性不飽和單體可為具有α-羥甲基丙烯酸或其酯化物經醚二聚化所形成之醚二聚體,亦即該乙烯性不飽和單體具有至少一個醚基。 In the formula (I-2-1) and the formula (I-2-2), A 1 and A 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms with or without a substituent. The ethylenically unsaturated monomer may be an ether dimer having α-hydroxymethacrylic acid or an esterified product thereof by ether dimerization, that is, the ethylenically unsaturated monomer has at least one ether group.
前述之醚二聚體藉由環化之聚合反應可形成具有如下式(I-3-1)或式(I-3-2)所示之結構的聚合物:
於式(I-3-1)或式(I-3-2)中,A1及A2分別獨立地代表氫原子、具有取代基或不具有取代基之碳數為1至25之烴基。 In the formula (I-3-1) or (I-3-2), A 1 and A 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms with or without a substituent.
該具有如式(I-3-1)或式(I-3-2)所示之結構的聚合物具有由醚二聚體所衍生之四氫吡喃環結構。 The polymer having a structure represented by Formula (I-3-1) or Formula (I-3-2) has a tetrahydropyran ring structure derived from an ether dimer.
於式(I-1)所示之結構中,A1及A2分別獨立地代表氫原子、具有取代基或不具有取代基之碳數為1至25之烴基,該A1及A2並沒有特別之限制,該A1及A2可例如為甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、第三戊基、硬脂基、月桂基或2-乙基己基等直鏈烷基或支鏈烷基;苯基等之芳香基;環己基、第三丁基環己基、二環戊二烯基、三環癸基、異冰片基、金剛烷基或2-甲基-2-金剛烷基等之脂環基;1-甲氧基乙基或1-乙氧基乙基等具有烷氧基取代之烷基;芐基等具有芳香基取代之烷基。該A1及A2 較佳可為甲基、乙基、環己基或芐基等。該A1及A2更佳可為甲基或乙基。 In the structure represented by formula (I-1), A 1 and A 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms with or without a substituent, and A 1 and A 2 are There is no particular limitation, and A 1 and A 2 may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, third butyl, third pentyl, stearyl, Linear or branched alkyl such as lauryl or 2-ethylhexyl; aromatic groups such as phenyl; cyclohexyl, third butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl Cycloaliphatic groups such as alkyl, adamantyl, or 2-methyl-2-adamantyl; alkoxy substituted alkyls such as 1-methoxyethyl or 1-ethoxyethyl; benzyl, etc. Alkyl substituted alkyl. The A 1 and A 2 may preferably be a methyl group, an ethyl group, a cyclohexyl group, a benzyl group, or the like. The A 1 and A 2 are more preferably a methyl group or an ethyl group.
前述之A1及A2可為相同之取代基或不同之取代基。基於提升聚合物之透明度及耐熱性的觀點,A1及A2較佳為相同之取代基,以形成對稱之醚二聚體。基於儲存安定性之觀點,A1及A2較佳為不同之取代基,以形成不對稱之醚二聚體。醚二聚體較佳可為例如:2,2’-[氧雙(亞甲基)]雙-丙烯酸或二烷基-2,2’[氧雙(亞甲基)]雙-2-丙烯酸酯。 The aforementioned A 1 and A 2 may be the same substituent or different substituents. From the viewpoint of improving the transparency and heat resistance of the polymer, A 1 and A 2 are preferably the same substituent to form a symmetrical ether dimer. From the standpoint of storage stability, A 1 and A 2 are preferably different substituents to form an asymmetric ether dimer. The ether dimer may preferably be, for example: 2,2 '-[oxybis (methylene)] bis-acrylic acid or dialkyl-2,2' [oxybis (methylene)] bis-2-acrylic acid ester.
前述對稱之醚二聚體的具體例可為2,2’-[氧雙(亞甲基)]雙-丙烯酸、二甲基-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二乙基-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二(正丙基)-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二(異丙基)-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二(正丁基)-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二(異丁基)-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二(第三丁基)-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二(第三戊基)-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二(硬脂基)-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二(十二烷基)-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸、二(2-乙基己基)-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二(1-甲氧基-乙基)-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二(1-乙氧基乙基)-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二芐基-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二苯基-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二環己基-2,2’-[氧雙(亞甲基)]雙-2-丙烯 酸酯、二(第三丁基環己基)-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二(二環戊二烯基)2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二(三環癸基)-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二(異冰片基)-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二金剛烷基-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯或二(2-甲基-2-金剛烷基)-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯等。 Specific examples of the symmetric ether dimer may be 2,2 '-[oxybis (methylene)] bis-acrylic acid, dimethyl-2,2'-[oxybis (methylene)] bis- 2-acrylate, diethyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (n-propyl) -2,2'-[oxybis (methylene) ] Bis-2-acrylate, bis (isopropyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (n-butyl) -2,2'-[oxy Bis (methylene)] bis-2-acrylate, bis (isobutyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (third butyl)- 2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (third pentyl) -2,2'-[oxybis (methylene)] bis-2-acrylate, Di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (dodecyl) -2,2'-[oxybis (methylene)] Bis-2-acrylic acid, bis (2-ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (1-methoxy-ethyl) -2, 2 '-[oxybis (methylene)] bis-2-acrylate, bis (1-ethoxyethyl) -2,2'-[oxybis (methylene)] bis-2-acrylate , Dibenzyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, diphenyl-2,2'-[oxybis (methylene )] Bis-2-propenoate, dicyclohexyl-2,2 '- [oxybis (methylene)] bis-2-propenyl Acid ester, bis (third butylcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (dicyclopentadienyl) 2,2'-[oxy Bis (methylene)] bis-2-acrylate, bis (tricyclodecyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate, bis (isobornyl)- 2,2 '-[oxybis (methylene)] bis-2-acrylate, diadamantyl-2,2'-[oxybis (methylene)] bis-2-acrylate, or di (2 -Methyl-2-adamantyl) -2,2 '-[oxybis (methylene)] bis-2-acrylate and the like.
較佳地,對稱之醚二聚體可為二甲基-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二乙基-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二環己基-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二芐基-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二苯基-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯或二(二環戊二烯基)2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯等。 Preferably, the symmetrical ether dimer may be dimethyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, diethyl-2,2'-[oxybis ( Methylene)] bis-2-acrylate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, dibenzyl-2,2'-[oxybis ( Methylene)] bis-2-acrylate, diphenyl-2,2 '-[oxybis (methylene)] bis-2-acrylate or bis (dicyclopentadienyl) 2,2' -[Oxybis (methylene)] bis-2-acrylate and the like.
更佳地,對稱之醚二聚體可為二甲基-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯、二苯基-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯或二芐基-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯等。 More preferably, the symmetric ether dimer may be dimethyl-2,2 '-[oxybis (methylene)] bis-2-acrylate, diphenyl-2,2'-[oxybis ( Methylene)] bis-2-acrylate or dibenzyl-2,2 '-[oxybis (methylene)] bis-2-acrylate and the like.
上述具有如式(I-1)所示之結構之乙烯性不飽和單體(c-1-1)可單獨一種使用或混合複數種使用。 The aforementioned ethylenically unsaturated monomer (c-1-1) having a structure represented by the formula (I-1) may be used singly or in combination.
若第一鹼可溶性樹脂(C-1)不包含具有如式(I-1)所示之結構之乙烯性不飽和單體(c-1-1)時,所製得之彩色濾光片用感光性樹脂組成物易具有泡狀之顯示缺陷。 If the first alkali-soluble resin (C-1) does not contain an ethylenically unsaturated monomer (c-1-1) having a structure represented by the formula (I-1), the obtained color filter is used The photosensitive resin composition is liable to have blistering display defects.
基於具有如式(I-1)所示之結構之乙烯性不飽和單體(c-1-1),以及後述具有至少一個羧酸或羧酸酐之乙烯性不飽和單體(c-1-2)與其他可共聚合之乙烯性不飽和單 體(c-1-3)之總使用量為100重量份,該具有如式(I-1)所示之結構之乙烯性不飽和單體(c-1-1)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,且更佳為15重量份至40重量份。 Based on an ethylenically unsaturated monomer (c-1-1) having a structure represented by the formula (I-1), and an ethylenically unsaturated monomer (c-1- 2) with other copolymerizable ethylenically unsaturated monomers The total amount of the compound (c-1-3) used is 100 parts by weight, and the amount of the ethylenically unsaturated monomer (c-1-1) having the structure shown by the formula (I-1) is 5 parts by weight Parts to 50 parts by weight, preferably 10 parts by weight to 45 parts by weight, and more preferably 15 parts by weight to 40 parts by weight.
當具有如式(I-1)所示之結構之乙烯性不飽和單體(c-1-1)之使用量為前述之範圍時,該感光性樹脂組成物經微影製程後,所形成之畫素著色層具有較佳之耐濺鍍性,且更不易具有泡狀之顯示缺陷。 When the use amount of the ethylenically unsaturated monomer (c-1-1) having the structure shown by the formula (I-1) is in the foregoing range, the photosensitive resin composition is formed after a lithography process. The pixel-colored layer has better splash resistance and is less likely to have blistering display defects.
具有至少一個羧酸或羧酸酐之乙烯性不飽和單體(c-1-2)Ethylene unsaturated monomer (c-1-2) having at least one carboxylic acid or carboxylic anhydride
該具有至少一個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 ethylenically unsaturated monomer having at least one carboxylic acid 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 one carboxylic acid group, or an unsaturated group And polycyclic compounds with multiple carboxylic acid groups.
前述之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-methacryloyloxyethyl 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且型號為ARONIX M-5300之商品。 The aforementioned unsaturated monocarboxylic acid compound may include, but is not limited to, (meth) acrylic acid, butenoic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, 2- (meth) acrylic acid and ethoxysuccinate (2-methacryloyloxyethyl succinate monoester), 2- (meth) acrylic acid ethoxy hexahydrophthalate, 2- (meth) acrylic acid ethoxy phthalate or omega-carboxylic acid polymer Caprolactone polyol monoacrylate and the like. The omega-carboxylic acid-based polycaprolactone polyol monoacrylate can be a product manufactured by East Asia Synthetic and 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, 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 aforementioned polycyclic compound having an unsaturated group and one carboxylic acid group may include, but is not limited to, 5-carboxylic acid bicyclo [2.2.1] hept-2-ene, 5-carboxylic acid-5-methylbicyclo [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-ene Ene 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。 Examples of the polycyclic compound having an unsaturated group and a plurality of carboxylic acid groups include 5,6-dicarboxylic acid bicyclo [2.2.1] hept-2-ene and the like.
較佳地,該具有至少一個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 ethylenically unsaturated monomer having at least one carboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid, 2-methacrylic acid, ethoxysuccinate, and 2-methacrylic acid. Hexahydrophthalate or any combination thereof.
該具有至少一個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 ethylenically unsaturated monomer having at least one carboxylic anhydride may include, but is not limited to, an unsaturated 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,且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, citraconic anhydride, and the like, and the aforementioned polycyclic compound having an unsaturated group and a carboxylic anhydride may include but It is not limited to 5,6-dicarboxylic anhydride bicyclo [2.2.1] hept-2-ene and the like.
較佳地,該具有至少一個羧酸酐之乙烯性不飽和單體可為馬來酸酐或甲基富馬酸酐。 Preferably, the ethylenically unsaturated monomer having at least one carboxylic anhydride may be maleic anhydride or methyl fumaric anhydride.
上述具有至少一個羧酸或羧酸酐之乙烯性不飽和單體(c-1-2)可單獨一種使用或混合複數種使用。 The aforementioned ethylenically unsaturated monomer (c-1-2) having at least one carboxylic acid or carboxylic anhydride may be used alone or in combination.
基於具有如式(I-1)所示之結構之乙烯性不飽和單體(c-1-1)與具有至少一個羧酸或羧酸酐之乙烯性不飽 和單體(c-1-2),以及後述其他可共聚合之乙烯性不飽和單體(c-1-3)之總使用量為100重量份,該具有至少一個羧酸或羧酸酐之乙烯性不飽和單體(c-1-2)之使用量為5重量份至40重量份,較佳為10重量份至35重量份,且更佳為15重量份至30重量份。 Based on an ethylenically unsaturated monomer (c-1-1) having a structure represented by the formula (I-1) and an ethylenically unsaturated monomer having at least one carboxylic acid or carboxylic anhydride And the monomer (c-1-2), and other copolymerizable ethylenically unsaturated monomers (c-1-3) described below are used in a total amount of 100 parts by weight, which has at least one carboxylic acid or carboxylic anhydride The use amount of the ethylenically unsaturated monomer (c-1-2) is 5 to 40 parts by weight, preferably 10 to 35 parts by weight, and more preferably 15 to 30 parts by weight.
其他可共聚合之乙烯性不飽和單體(c-1-3)Other copolymerizable ethylenically unsaturated monomers (c-1-3)
其他可共聚合之乙烯性不飽和單體(c-1-3)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之不飽和化合物。 Other copolymerizable ethylenically unsaturated monomers (c-1-3) may include, but are not limited to, alkyl (meth) acrylate, cycloaliphatic (meth) acrylate, and aryl (meth) acrylate , 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.
前述之(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 aforementioned 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 methacrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, and the like.
前述之(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 aforementioned alicyclic (meth) acrylate may include, but is not limited to, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and dicyclopentyl (meth) acrylate {or, Tricyclo [5.2.1.0 2,6 ] dec-8-yl (meth) acrylate}, dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate or (meth) acrylic acid Tetrahydrofuran ester.
前述之(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 aforementioned aryl (meth) acrylate may include, but is not limited to, phenyl (meth) acrylate, benzyl methacrylate, and the like.
前述之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, diethyl itaconic acid, and the like.
前述之(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, and the like.
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 is not limited to, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like.
前述之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 aforementioned styrenic compound may include, but is not limited to, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, or p-methoxystyrene.
前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。 Unsaturated compounds other than the aforementioned compounds may include, but are not limited to, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl ethyl ester, 1,3-butadiene, Isoprene, 2,3-dimethyl 1,3-butadiene, N-butanediimino-3-maleimide benzoate, N-butadiene imino- 4-maleimide iminobutyrate, N-butanediimide imino-6-maleimide iminohexanoate, N-butamidine imino-3-maleimide propionate , N- (9-acridyl) maleimide, N-octylmaleimide, N-cyclohexylmaleimide, or N-phenyl Maleimide (N-phenylmaleimide) and the like.
該其他可共聚合之乙烯性不飽和單體(c-1-3)可單獨一種使用或混合複數種使用。 The other copolymerizable ethylenically unsaturated monomers (c-1-3) may be used singly or in combination.
較佳地,該其他可共聚合之乙烯性不飽和單體(c-1-3)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-1-3) is selected from methyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, third butyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentyl (meth) acrylate, isobornyl methacrylate, (methyl ) Dicyclopentyloxyethyl acrylate, styrene, p-methoxystyrene, or any combination of the foregoing.
基於具有如式(I-1)所示之結構之乙烯性不飽和單體(c-1-1)、具有至少一個羧酸或羧酸酐之乙烯性不飽和單體(c-1-2)及其他可共聚合之乙烯性不飽和單體(c-1-3)之總使用量為100重量份,該其他可共聚合之乙烯性不飽和單體(c-1-3)之使用量為10重量份至90重量份,較佳為20重量份至80重量份,且更佳為30重量份至70重量份。 Based on an ethylenically unsaturated monomer (c-1-1) having a structure represented by the formula (I-1), an ethylenically unsaturated monomer (c-1-2) having at least one carboxylic acid or carboxylic anhydride And other copolymerizable ethylenically unsaturated monomers (c-1-3) are used in a total amount of 100 parts by weight, and the other copolymerizable ethylenically unsaturated monomers (c-1-3) are used in amounts It is 10 to 90 parts by weight, preferably 20 to 80 parts by weight, and more preferably 30 to 70 parts by weight.
具有環氧基之乙烯性不飽和單體(c-1-4)Ethylene unsaturated monomer with epoxy group (c-1-4)
該具有環氧基之乙烯性不飽和單體(c-1-4)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 ethylenically unsaturated monomer (c-1-4) having an epoxy group 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 Glycidyl ether compounds and 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 aforementioned (meth) acrylate compound having an epoxy group may include, but is not limited to, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and (meth) acrylic acid 3,4 -Butylene oxide, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate or 3,4-epoxycyclohexyl methyl (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 α-alkyl acrylate compound having an epoxy group may include, but is not limited to, α-ethyl acrylate, α-n-propyl propylene acrylate, α-n-butyl propylene acrylate, or α-ethylacrylic acid-6,7-epoxyheptyl ester and the like.
前述之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-vinylbenzylglycidyl ether)、間-乙烯基苯甲基環氧丙醚(m-vinylbenzyl glycidylether)或對-乙烯基苯甲基環氧丙醚(p-vinyl benzylglycidylether)等。 The aforementioned glycidyl ether compound may include, but is not limited to, o-vinylbenzylglycidyl ether, m-vinylbenzyl glycidylether, or p-vinylbenzyl glycidylether. Vinyl benzylglycidyl ether and the like.
該具有環氧基之乙烯性不飽和單體(c-1-4)可單獨一種使用或混合複數種使用。 The ethylenically unsaturated monomer (c-1-4) having an epoxy group may be used alone or in combination.
較佳地,該具有環氧基之乙烯性不飽和單體(c-1-4)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 ethylenically unsaturated monomer (c-1-4) having an epoxy group is selected from the group consisting of glycidyl methacrylate, 2-methylglycidyl methacrylate, and methacrylic acid 3,4-epoxycyclohexyl methyl ester, 6,7-epoxyheptyl methacrylate, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-ethylene Benzyl Glycidyl Ether or any combination thereof.
基於具有如式(I-1)所示之結構之乙烯性不飽和單體(c-1-1)、具有至少一個羧酸或羧酸酐之乙烯性不飽和單體(c-1-2)及其他可共聚合之乙烯性不飽和單體(c-1-3)之總使用量為100重量份,該具有環氧基之乙烯性不飽和單體(c-1-4)之使用量為1重量份至35重量份,較佳為3重量份至30重量份,且更佳為5重量份至25重量份。 Based on an ethylenically unsaturated monomer (c-1-1) having a structure represented by the formula (I-1), an ethylenically unsaturated monomer (c-1-2) having at least one carboxylic acid or carboxylic anhydride And other copolymerizable ethylenically unsaturated monomers (c-1-3) are used in a total amount of 100 parts by weight, and the amount of the epoxy-based ethylenically unsaturated monomers (c-1-4) is used It is 1 to 35 parts by weight, preferably 3 to 30 parts by weight, and more preferably 5 to 25 parts by weight.
在一實施例中,該第一鹼可溶性樹脂(C-1)係先將具有如式(I-1)所示之結構之乙烯性不飽和單體(c-1-1)、具有至少一個羧酸或羧酸酐之乙烯性不飽和單體(c-1-2)與其他可共聚合之乙烯性不飽和單體(c-1-3)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-1-4)進行加成反應,而製得該第一鹼可溶性樹脂(C-1)。 In one embodiment, the first alkali-soluble resin (C-1) is an ethylenically unsaturated monomer (c-1-1) having a structure as shown in Formula (I-1), having at least one The carboxylic acid or carboxylic anhydride ethylenically unsaturated monomer (c-1-2) and other copolymerizable ethylenically unsaturated monomer (c-1-3) undergo a double bond copolymerization reaction to form a polymer Where the side chain of this polymer has There are carboxylic acid groups. Then, the carboxylic acid group in the side chain of the polymer is subjected to an addition reaction with an ethylenically unsaturated monomer (c-1-4) having an epoxy group to prepare the first alkali-soluble resin (C-1 ).
在另一實施例中,該第一鹼可溶性樹脂(C-1)係先將具有如式(I-1)所示之結構之乙烯性不飽和單體(c-1-1)、其他可共聚合之乙烯性不飽和單體(c-1-3)與具有環氧基之乙烯性不飽和單體(c-1-4)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至少一個羧酸或羧酸酐之乙烯性不飽和單體(c-1-2)進行加成反應,而製得該第一鹼可溶性樹脂(C-1)。 In another embodiment, the first alkali-soluble resin (C-1) is an ethylenically unsaturated monomer (c-1-1) having a structure as shown in Formula (I-1), other The copolymerized ethylenically unsaturated monomer (c-1-3) and the ethylenically unsaturated monomer (c-1-4) having an epoxy group undergo a double bond copolymerization reaction to form a polymer, wherein The side chain of the polymer has an epoxy group. Then, an epoxy group in a side chain of the polymer is subjected to an addition reaction with an ethylenically unsaturated monomer (c-1-2) having at least one carboxylic acid or carboxylic anhydride to prepare the first alkali-soluble resin. (C-1).
在又一實施例中,該第一鹼可溶性樹脂(C-1)係先將具有如式(I-1)所示之結構之乙烯性不飽和單體(c-1-1)、其他可共聚合之乙烯性不飽和單體(c-1-3)與具有環氧基之乙烯性不飽和單體(c-1-4)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至少一個羧酸或羧酸酐之乙烯性不飽和單體(c-1-2)進行加成反應後,進一步與酸酐類化合物進行半酯化反應,而製得該第一鹼可溶性樹脂(C-1)。 In yet another embodiment, the first alkali-soluble resin (C-1) is an ethylenically unsaturated monomer (c-1-1) having a structure as shown in Formula (I-1), other The copolymerized ethylenically unsaturated monomer (c-1-3) and the ethylenically unsaturated monomer (c-1-4) having an epoxy group undergo a double bond copolymerization reaction to form a polymer, wherein The side chain of the polymer has an epoxy group. Then, an epoxy group in a side chain of the polymer is subjected to an addition reaction with an ethylenically unsaturated monomer (c-1-2) having at least one carboxylic acid or carboxylic anhydride, and then half-esterified with an acid anhydride compound Chemical reaction to obtain the first alkali-soluble resin (C-1).
所製得之第一鹼可溶性樹脂(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重量平均分子量一般為1000至35000,較佳為3000至30000,且更佳為5000至25000。 The weight average molecular weight of the obtained first alkali-soluble resin (C-1) measured by a gel permeation chromatography (GPC) in terms of polystyrene is generally 1,000 to 35,000, preferably 3,000 to 30,000 And more preferably 5,000 to 25,000.
基於鹼可溶性樹脂(C)之總使用量為100重量份,第一鹼可溶性樹脂(C-1)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,且更佳為20重量份至80重量份。 Based on the total use amount of the alkali-soluble resin (C) being 100 parts by weight, the use amount of the first alkali-soluble resin (C-1) is 10 to 100 parts by weight, preferably 15 to 90 parts by weight, and More preferably, it is 20 parts by weight to 80 parts by weight.
第二鹼可溶性樹脂(C-2)Second alkali soluble resin (C-2)
本發明之鹼可溶性樹脂(C)可選擇性地包含第二鹼可溶性樹脂(C-2)。該第二鹼可溶性樹脂(C-2)可由第二混合物進行聚合反應所製得,且第二混合物包含具有至少二個環氧基之環氧化合物(c-2-1)及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-2-2)。此外,該第二混合物可選擇性地包含羧酸酐化合物(c-2-3)及/或具有環氧基的化合物(c-2-4)。 The alkali-soluble resin (C) of the present invention may optionally include a second alkali-soluble resin (C-2). The second alkali-soluble resin (C-2) can be prepared by polymerizing a second mixture, and the second mixture includes an epoxy compound (c-2-1) having at least two epoxy groups and at least one carboxyl group. Compound (c-2-2) having an acid group and at least one ethylenically unsaturated group. In addition, the second mixture may optionally include a carboxylic anhydride compound (c-2-3) and / or a compound (c-2-4) having an epoxy group.
具有至少二個環氧基之環氧化合物(c-2-1)Epoxy compound (c-2-1) having at least two epoxy groups
該具有至少二個環氧基之環氧化合物(c-2-1)可具有如下式(III)或式(IV)所示之結構。其中,「環氧化合物(c-2-1)可具有如下式(III)或式(IV)所示之結構」的敘述亦涵蓋了具有如下式(III)所示之結構的化合物及具有如下式(IV)所示之結構的化合物同時存在而作為環氧化合物(c-2-1)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-2-1),例如是具有如下式(III)所示之結構:
於式(III)中,B1、B2、B3及B4分別為相同或不同,且B1、B2、B3及B4分別表示氫原子、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 formula (III), B 1 , B 2 , B 3, and B 4 are the same or different, and B 1 , B 2 , B 3, and B 4 each represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 5 An alkyl group, an alkoxy group having 1 to 5 carbons, an aromatic group having 6 to 12 carbons, or an aralkyl group having 6 to 12 carbons.
如式(III)所示之結構之具有至少二個環氧基的環氧化合物(c-2-1)可包含由雙酚芴型化合物(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-2-1) having at least two epoxy groups having a structure as shown in formula (III) may include reacting a bisphenol fluorene compound with an epihalohydrin The obtained epoxy-containing bisphenol amidine type compound is not limited thereto.
前述雙酚芴型化合物之具體例可包含但不限於9,9-雙(4-羥基苯基)芴[9,9-bis(4-hydroxyphenyl)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]或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 hydrazone compound may include, but are not limited to, 9,9-bis (4-hydroxyphenyl) fluorene [9,9-bis (4-hydroxyphenyl) fluorene], 9,9-bis (4-hydroxy -3-methylphenyl) fluorene [9,9-bis (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-bromophenyl) fluorene], 9,9 -Bis (4-hydroxy-3-fluorophenyl) fluorene [9,9-bis (4-hydroxy-3-fluorophenyl) fluorene], 9,9-bis (4-hydroxy-3-methoxyphenyl)芴 [9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene], 9,9-bis (4-hydroxy-3,5-dimethylphenyl) 芴 [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) fluorene] or 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene [9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene] and other compounds.
前述鹵化環氧丙烷(epihalohydrin)之具體例可包含但不限於3-氯-1,2-環氧丙烷(epichlorohydrin)或3-溴-1,2-環氧丙烷(epibromohydrin)等。 Specific examples of the aforementioned halogenated propylene oxide (epihalohydrin) may include, but are not limited to, 3-chloro-1,2-propylene oxide (epichlorohydrin) or 3-bromo-1,2-propylene oxide (epibromohydrin).
該由雙酚芴型化合物與鹵化環氧丙烷反應所製得之具有環氧基之雙酚芴型化合物可包含但不限於:(1)新日鐵化學(Nippon Steel Chemical Co.,Ltd)所製造之商品,且其型號為ESF-300等;(2)大阪瓦斯(Osaka Gas Co.,Ltd)所製造之商品,且其型號為PG-100或EG-210等;(3)短信科技(S.M.S Technology Co.,Ltd)所製造之商品,且其型號為SMS-F9PhPG、SMS-F9CrG或SMS-F914PG等。 The epoxy-containing bisphenol fluorene type compound prepared by the reaction of a bisphenol fluorene type compound and a halogenated propylene oxide may include, but is not limited to: (1) Nippon Steel Chemical Co., Ltd. Manufactured goods, and its model is ESF-300, etc .; (2) Goods manufactured by Osaka Gas Co., Ltd, and its model is PG-100 or EG-210, etc .; (3) SMS technology ( SMS Technology Co., Ltd), and its model is SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, etc.
於式(IV)中,B5至B18分別為相同或不同,B5至B18分別氫原子、鹵素原子、碳數為1至8之烷基或碳數為6至15之芳香基,且a代表0至10之整數。 In formula (IV), B 5 to B 18 are the same or different, B 5 to B 18 are 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 a represents an integer from 0 to 10.
如式(IV)所示之具有至少二個環氧基的環氧化合物(c-2-1)可例如是藉由在鹼金屬氫氧化物存在下,使具有如下式(IV-1)所示之結構之化合物與鹵化環氧丙烷進行反應而得:
於式(IV-1)中,B5至B18之定義如前所述,在此不另贅述。 In formula (IV-1), the definitions of B 5 to B 18 are as described above, and will not be repeated here.
再者,前述如式(IV)所示之具有至少二個環氧基的環氧化合物(c-2-1)可例如是在酸觸媒存在下,使用具有如下式(IV-2)所示之結構之化合物與酚(phenol)類進行縮合反應,以形成具有如式(IV-1)所示之結構之化合物。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(IV)所示之結構之具有至少二個環氧基的環氧化合物(c-2-1):
於式(IV-2)中,B7至B10之定義如前所述,在此不另贅述。B19及B20分別獨立地代表鹵原子、碳數為1至6的烷基或碳數為1至6的烷氧基。 In formula (IV-2), the definitions of B 7 to B 10 are as described above, and are not repeated here. B 19 and B 20 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
較佳地,該鹵素原子可例如為氯原子或溴原子;該烷基可例如為甲基、乙基或第三丁基;且該烷氧基可例如為甲氧基或乙氧基。 Preferably, the halogen atom may be, for example, a chlorine atom or a bromine atom; the alkyl group may be, for example, a methyl group, an ethyl group, or a third butyl group; and the alkoxy group may be, for example, a methoxy group or an ethoxy group.
前述酚類之具體例可包含但不限於酚(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(methyl butylphenol)、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(cyclohexyl cresol)等。上述酚類可單獨一種使用或混合複數種使用。 Specific examples of the aforementioned phenols may include, but are not limited to, phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, and t-butylphenol (t-butylphenol), octylphenol, nonylphenol, xylenol, methyl butylphenol, di-t-butylphenol, ethylene Phenol (vinylphenol), propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol or cyclohexyl cresol, etc. These phenols may be used alone or in combination.
基於前述具有如式(IV-2)所示之結構的化合物之使用量為1莫耳,酚類之使用量為0.5莫耳至20莫耳,且較佳為2莫耳至15莫耳。 The amount of the compound based on the aforementioned structure having the formula (IV-2) is 1 mole, and the amount of the phenols is 0.5 to 20 moles, and preferably 2 to 15 moles.
該酸觸媒之具體例可包含鹽酸、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(aluminium chloride anhydrous)或氯化鋅(zinc chloride)等。該酸觸媒較佳可為對甲苯磺酸、硫酸、鹽酸或上述化合物之任意組合。該酸觸媒可單獨一種使用或混合複數種使用。 Specific examples of the acid catalyst may include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, aluminum chloride anhydrous, or chlorine. Zinc chloride, etc. The acid catalyst may preferably be p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, or any combination thereof. The acid catalyst may be used alone or in combination.
該酸觸媒之使用量雖無特別之限制,惟基於前述具有如式(IV-2)所示之結構的化合物之使用量為100重量百分比,酸觸媒之使用量較佳可為0.1重量百分比至30重量百分比。 Although the use amount of the acid catalyst is not particularly limited, based on the use amount of the compound having the structure represented by the formula (IV-2) is 100% by weight, the use amount of the acid catalyst is preferably 0.1% by weight. Percent to 30 weight percent.
前述之縮合反應可在無溶劑或在有機溶劑之存在下進行。該有機溶劑之具體例可包含但不限於甲苯(toluene)、二甲苯(xylene)或甲基異丁基酮(methyl isobutyl ketone)等。上述的有機溶劑可單獨一種使用或混合複數種使用。 The aforementioned condensation reaction can be performed without a solvent or in the presence of an organic solvent. Specific examples of the organic solvent may include, but are not limited to, toluene, xylene, or methyl isobutyl ketone. isobutyl ketone) and so on. These organic solvents may be used singly or in combination.
基於前述具有如式(IV-2)所示之結構的化合物及酚類之總使用量為100重量百分比,該有機溶劑之使用量為50重量百分比至300重量百分比,且較佳為100重量百分比至250重量百分比。前述縮合反應之操作溫度可為40℃至180℃,且操作時間可為1小時至8小時。 Based on the foregoing, the total amount of the compound and phenols having the structure represented by the formula (IV-2) is 100% by weight, and the amount of the organic solvent is 50% to 300% by weight, and preferably 100% by weight To 250 weight percent. The operation temperature of the aforementioned condensation reaction may be 40 ° C to 180 ° C, and the operation time may be 1 hour to 8 hours.
進行前述之縮合反應後,可進一步進行中和處理或水洗處理。 After the condensation reaction is performed, a neutralization treatment or a water washing treatment may be further performed.
該中和處理係將反應後之溶液的pH值調整為3至7,且較佳為5至7。 The neutralization treatment adjusts the pH value of the solution after the reaction to 3 to 7, and preferably 5 to 7.
該水洗處理可使用中和劑進行,且此中和劑為鹼性物質。該中和劑之具體例可包含但不限於氫氧化鈉(sodium hydroxide)或氫氧化鉀(potassium hydroxide)等之鹼金屬氫氧化物;氫氧化鈣(calcium hydroxide)或氫氧化鎂(magnesium hydroxide)等之鹼土類金屬氫氧化物;二伸乙三胺(diethylene triamine)、三伸乙四胺(triethylenetetramine)、苯胺(aniline)或苯二胺(phenylene diamine)等之有機胺;氨(ammonia)、磷酸二氫鈉(sodium dihydrogen phosphate)或上述化合物之任意組合。該中和劑可單獨一種使用或混合複數種使用。 The water washing treatment can be performed using a neutralizing agent, and the neutralizing agent is an alkaline substance. Specific examples of the neutralizing agent may include, but are not limited to, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide; calcium hydroxide or magnesium hydroxide Alkaline earth metal hydroxides, etc .; organic amines such as diethylene triamine, triethylenetetramine, aniline or phenylene diamine; ammonia (ammonia), Sodium dihydrogen phosphate or any combination thereof. This neutralizing agent can be used individually or in mixture of multiple types.
該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具有中和劑的水溶液,並且反覆進行萃取。經中和處理或水洗處理後,可藉由減壓加熱處理去除未 反應的酚類及溶劑,並進行濃縮,而可獲得具有如式(IV-1)所示之結構的化合物。 This water washing treatment can be performed by a conventional method. For example, an aqueous solution with a neutralizing agent is added to the solution after the reaction, and extraction is performed repeatedly. After neutralization treatment or water washing treatment, The reacted phenols and solvents are concentrated to obtain a compound having a structure represented by formula (IV-1).
前述鹵化環氧丙烷的具體例可包含但不限於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)或上述化合物之任意組合。 Specific examples of the halogenated propylene oxide may include, but are not limited to, 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane (3- bromo-1,2-epoxypropane) or any combination thereof.
進行上述的脫鹵化氫反應前,可預先添加或於反應過程中添加氫氧化鈉或氫氧化鉀等之鹼金屬氫氧化物。 Before carrying out the above-mentioned dehydrohalogenation reaction, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or during the reaction.
上述脫鹵化氫反應的操作溫度可為20℃至120℃,且其操作時間可為1小時至10小時。 The operation temperature of the above-mentioned dehydrohalogenation reaction may be 20 ° C to 120 ° C, and the operation time thereof may be 1 hour to 10 hours.
前述脫鹵化氫反應所添加之鹼金屬氫氧化物可為鹼金屬氫氧化物水溶液。在此實施例中,將該鹼金屬氫氧化物水溶液連續地添加至脫鹵化氫反應系統內,並於減壓或常壓下,連續蒸餾出水及鹵化環氧丙烷,以分離並除去水。鹵化環氧丙烷係連續地回流至反應系統內。 The alkali metal hydroxide added in the dehydrohalogenation reaction may be an alkali metal hydroxide aqueous solution. In this embodiment, the alkali metal hydroxide aqueous solution is continuously added to the dehydrohalogenation reaction system, and water and halogenated propylene oxide are continuously distilled off under reduced or normal pressure to separate and remove water. The halogenated propylene oxide system was continuously refluxed into the reaction system.
進行上述的脫鹵化氫反應前,反應系統可添加氯化四甲銨(tetramethyl ammonium chloride)、溴化四甲銨(tetramethyl ammonium bromide)或三甲基苄基氯化銨(trimethyl benzyl ammonium chloride)等之四級銨鹽作為觸媒。在50℃至150℃下,反應1小時至5小時後,加入鹼金屬氫氧化物或其水溶液。接著,於20℃至120℃的溫度下,進行脫鹵化氫反應1小時至10小時。 Before carrying out the above-mentioned dehydrohalogenation reaction, tetramethyl ammonium chloride, tetramethyl ammonium bromide or trimethyl benzyl ammonium chloride can be added to the reaction system. The quaternary ammonium salt acts as a catalyst. After reacting at 50 ° C to 150 ° C for 1 hour to 5 hours, an alkali metal hydroxide or an aqueous solution thereof is added. Next, a dehydrohalogenation reaction is performed at a temperature of 20 ° C to 120 ° C for 1 hour to 10 hours.
基於前述具有如式(IV-1)所示之結構的化合物中之羥基總當量為1當量,該鹵化環氧丙烷的使用量可為1當量至20當量,且較佳可為2當量至10當量。 Based on the total equivalents of hydroxyl groups in the aforementioned compound having the structure represented by formula (IV-1) is 1 equivalent, the amount of the halogenated propylene oxide used may be 1 to 20 equivalents, and preferably 2 to 10 equivalents equivalent.
基於前述具有如式(IV-1)所示之結構的化合物中之羥基總當量為1當量,脫鹵化氫反應中所添加的鹼金屬氫氧化物的使用量可為0.8當量至15當量,且較佳可為0.9當量至11當量。 Based on the total equivalents of the hydroxyl groups in the aforementioned compound having the structure represented by the formula (IV-1) is 1 equivalent, the use amount of the alkali metal hydroxide added in the dehydrohalogenation reaction may be 0.8 equivalent to 15 equivalents, and It may preferably be 0.9 to 11 equivalents.
此外,為了使脫鹵化氫反應順利進行,反應系統可添加甲醇或乙醇等之醇類。其次,反應系統亦可添加二甲碸(dimethyl sulfone)或二甲亞碸(dimethyl sulfoxide)等之非質子性(aprotic)極性溶媒進行反應。 In addition, in order to make the dehydrohalogenation reaction proceed smoothly, an alcohol such as methanol or ethanol may be added to the reaction system. Second, the reaction system can also add aprotic polar solvents such as dimethyl sulfone or dimethyl sulfoxide for reaction.
在使用醇類的情況下,基於前述鹵化環氧丙烷之總使用量為100重量百分比,該醇類的使用量可為2重量百分比至20重量百分比,且較佳可為4重量百分比至15重量百分比。 In the case of using alcohols, based on the total usage of the aforementioned halogenated propylene oxide is 100% by weight, the usage of the alcohols may be 2 to 20% by weight, and preferably 4 to 15% by weight percentage.
在使用非質子性極性溶媒的情況下,基於鹵化環氧丙烷的總使用量為100重量百分比,非質子性極性溶媒的使用量為5重量百分比至100重量百分比,且較佳為10重量百分比至90重量百分比。 In the case of using an aprotic polar solvent, based on the total amount of halogenated propylene oxide used, 100% by weight, the amount of aprotic polar solvent used is 5 to 100% by weight, and preferably 10 to 100% by weight 90 weight percent.
進行脫鹵化氫反應後,產物可選擇性地進行水洗處理,並利用減壓蒸餾的方式除去鹵化環氧丙烷、醇類及非質子性極性溶媒。該減壓蒸餾可於溫度為110℃至250℃且壓力為1.3kPa[10毫米汞柱(mmHg)]以下進行。 After the dehydrohalogenation reaction, the product can be optionally washed with water, and halogenated propylene oxide, alcohols, and aprotic polar solvents can be removed by distillation under reduced pressure. This vacuum distillation can be performed at a temperature of 110 ° C to 250 ° C and a pressure of 1.3 kPa [10 millimeters of mercury (mmHg)] or less.
為了避免所製得之環氧樹脂具有加水分解性的鹵素,進行脫鹵化氫反應後之溶液可加至甲苯或甲基異丁基酮(methyl isobutyl ketone)等之溶劑以及氫氧化鈉或氫氧化鉀等之鹼金屬氫氧化物水溶液中,並再次進行脫鹵化氫反應。 In order to avoid the hydrolyzable halogen of the prepared epoxy resin, the solution after the dehydrohalogenation reaction can be added to a solvent such as toluene or methyl isobutyl ketone, and sodium hydroxide or hydroxide In an aqueous alkali metal hydroxide solution such as potassium, dehydrohalogenation is performed again.
於該脫鹵化氫反應中,基於前述具有如式(IV-1)所示之結構的化合物中之羥基總當量為1當量,鹼金屬氫氧化物之使用量可為0.01莫耳至0.3莫耳,且較佳可為0.05莫耳至0.2莫耳。其次,前述脫鹵化氫反應之操作溫度可為50℃至120℃,且其操作時間可為0.5小時至2小時。 In the dehydrohalogenation reaction, based on the total equivalents of the hydroxyl groups in the compound having the structure represented by the formula (IV-1) is 1 equivalent, the amount of the alkali metal hydroxide used may be 0.01 mol to 0.3 mol And, preferably, it is 0.05 mol to 0.2 mol. Secondly, the operation temperature of the aforementioned dehydrohalogenation reaction may be 50 ° C to 120 ° C, and the operation time thereof may be 0.5 hour to 2 hours.
完成脫鹵化氫反應後,鹽類可藉由過濾及水洗等步驟去除,並利用減壓蒸餾的方式除去甲苯或甲基異丁基酮等之溶劑,即可製得具有如式(IV)所示之結構的化合物。 After the dehydrohalogenation reaction is completed, the salts can be removed by steps such as filtration and water washing, and the solvent such as toluene or methyl isobutyl ketone can be removed by means of distillation under reduced pressure to obtain a compound having the formula (IV) The compound of the structure shown.
前述如式(IV)所示之具有至少二個環氧基的環氧化合物(c-2-1)可包含但不限於日本化藥(Nippon Kayaku Co.Ltd.)所製造之商品,且其型號為NC-3000、NC-3000H、NC-3000S或NC-3000P等。 The aforementioned epoxy compound (c-2-1) having at least two epoxy groups as shown in the formula (IV) may include, but is not limited to, products manufactured by Nippon Kayaku Co. Ltd., and Models are NC-3000, NC-3000H, NC-3000S or NC-3000P.
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-2-2)Compound (c-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group
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-2-2)可選自於由以下(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)由具有羥基之(甲基)丙烯酸酯與二元羧酸化合物反應而製得之化合物,其中二元羧酸化合物可包含但不限於己二酸、丁二酸、馬來酸或鄰苯二甲酸;(3)由具有羥基之(甲基)丙烯酸酯與羧酸酐化合物反應而製得之半酯化合物,其中具有羥基之(甲基)丙烯酸酯可包含但不限於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。其中,該羧酸酐化合物可與後述第二混合物所含之羧酸酐化合物(c-2-3)相同,故在此不再贅述。 The aforementioned compound (c-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group may be selected from the group consisting of (1) to (3): (1) acrylic acid, methyl Acrylic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methacryloyloxyethyl adipic acid base Acrylic acid oxybutyl adipic acid, 2-methacrylic acid oxyethyl hexahydrophthalic acid, 2-methacrylic acid oxyethyl maleic acid, 2-methacrylic acid oxypropyl maleic acid , 2-methacrylic acid oxobutyl maleic acid, 2-methacrylic acid oxopropyl succinic acid, 2-methacrylic acid oxypropyl adipic acid, 2-methacrylic acid oxypropyl tetracarboxylic acid Hydrophthalic acid, 2-methacrylic acid oxypropyl phthalic acid, 2-methacrylic acid oxybutyl phthalic acid, or 2-methacrylic acid oxybutyl phthalic acid; (2) A compound prepared by reacting a (meth) acrylate having a hydroxyl group with a dicarboxylic acid compound, wherein the dicarboxylic acid compound may include, but is not limited to, adipic acid, succinic acid, maleic acid, or Phthalic acid; (3) a half-ester compound prepared by reacting a (meth) acrylate having a hydroxyl group with a carboxylic anhydride compound, wherein the (meth) acrylate having a hydroxyl group may include, but is not limited to, 2-hydroxyethyl Acrylate [(2-hydroxyethyl) acrylate], 2-hydroxyethyl methacrylate [(2-hydroxyethyl) methacrylate], 2-hydroxypropyl acrylate [(2-hydroxypropyl) acrylate], 2-hydroxy [(2-hydroxypropyl) methacrylate], 4-hydroxybutyl acrylate [(4-hydroxybutyl) acrylate], 4-hydroxybutyl methacrylate [(4-hydroxybutyl) methacrylate], or pentaerythritol trimethyl Acrylate, etc. The carboxylic acid anhydride compound may be the same as the carboxylic acid anhydride compound (c-2-3) contained in the second mixture described later, so it will not be repeated here.
羧酸酐化合物(c-2-3)Carboxylic anhydride compound (c-2-3)
前述第二之混合物可選擇性地包含羧酸酐化合物(-c-2-3)及/或具有環氧基的化合物(c-2-4)。 The aforementioned second mixture may optionally include a carboxylic anhydride compound (-c-2-3) and / or a compound (c-2-4) having an epoxy group.
上述羧酸酐化合物(c-2-3)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 above carboxylic anhydride compound (c-2-3) may be selected from the group consisting of (1) to (2): (1) succinic anhydride (butanedioic anhydride), maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride (hexahydrophthalic anhydride), methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl endo-methylene tetrahydro phthalic anhydride, chloramphenicol Dicarboxylic acid anhydride compounds such as chlorendic anhydride, glutaric anhydride or 1,3-dioxoisobenzofuran-5-carboxylic anhydride; and (2) benzophenone tetracarboxylic dianhydride , Abbreviated as BTDA), tetracarboxylic dianhydride or diphenyltetracarboxylic dianhydride and other tetracarboxylic carboxylic anhydride compounds.
具有環氧基的化合物(c-2-4)Compound with epoxy group (c-2-4)
上述具有環氧基的化合物(c-2-4)可例如是選自於甲基丙烯酸環氧丙酯、3,4-環氧基環己基甲基丙烯酸酯、具有不飽和基的縮水甘油醚化合物、具有環氧基的不飽和化合物或上述化合物之任意組合所組成的群組。 The compound (c-2-4) having an epoxy group may be, for example, selected from glycidyl methacrylate, 3,4-epoxy cyclohexyl methacrylate, and glycidyl ether having an unsaturated group. A group of compounds, unsaturated compounds having epoxy groups, or any combination of the foregoing.
前述具有不飽和基的縮水甘油醚化合物可包含但不限於長瀨化成工業株式會社製造之商品,且其型號為Denacol EX-111、EX-121 Denacol、Denacol EX-141、Denacol EX-145、Denacol EX-146、Denacol EX-171或Denacol EX-192等。 The aforementioned glycidyl ether compound having an unsaturated group may include, but is not limited to, products manufactured by Nagase Chemical Industry Co., Ltd. and the models are Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171 or Denacol EX-192, etc.
在一實施例中,該第二鹼可溶性樹脂(C-2)可由如式(III)所示之具有至少二個環氧基的環氧化合物(c-2-1)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-2-2)進行聚合反應,以形成具有羥基的反應產物。接著,添加羧酸酐化合物(c-2-3)進行反應。基於該具有羥基的反應產物之羥基總當量為1當量,羧酸酐化合物(c-2-3)所含有之酸酐基的當量較佳為0.4當量至1當量,且更佳為0.75當量至1當量。當使用多個羧酸酐化合物(c-2-3)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-2-3)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,且更佳為5/95至80/20。其次,上述反應之操作溫度可例如為50℃至130℃。 In one embodiment, the second alkali-soluble resin (C-2) may be an epoxy compound (c-2-1) having at least two epoxy groups and at least one carboxylic acid as shown in formula (III). Group and at least one ethylenically unsaturated compound (c-2-2) are polymerized to form a reaction product having a hydroxyl group. Next, a carboxylic anhydride compound (c-2-3) was added and reacted. Based on the total hydroxyl equivalent of the reaction product having a hydroxyl group, the equivalent is 1 equivalent, and the equivalent of the acid anhydride group contained in the carboxylic anhydride compound (c-2-3) is preferably 0.4 equivalent to 1 equivalent, and more preferably 0.75 equivalent to 1 equivalent. . When a plurality of carboxylic anhydride compounds (c-2-3) are used, they can be added sequentially or simultaneously during the reaction. When a dicarboxylic acid anhydride compound and a tetracarboxylic acid anhydride compound are used as the carboxylic acid anhydride compound (c-2-3), the molar ratio of the dicarboxylic acid anhydride compound and the tetracarboxylic acid anhydride compound is preferably 1/99 to 90 / 10, and more preferably 5/95 to 80/20. Second, the operating temperature of the above reaction may be, for example, 50 ° C to 130 ° C.
在另一實施例中,該第二鹼可溶性樹脂(C-2)可由如式(IV)所示之具有至少二個環氧基的環氧化合物(c-2-1)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-2-2)進行反應,以形成含羥基的反應產物。接著,藉由添加羧酸酐化合物(c-2-3)及/或具有環氧基的化合物(c-2-4)進行聚合反應。基於如式(IV)所示之具有至少二個環氧基的環氧化合物(c-2-1)的環氧基總當量為1當量,該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-2-2)的酸價當量較佳為0.8當量至1.5當量,且更佳為0.9當量至1.1當量。基於上述具有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-2-3)的使用量 為10莫耳%至100莫耳%,較佳為20莫耳%至100莫耳%,且更佳為30莫耳%至100莫耳%。 In another embodiment, the second alkali-soluble resin (C-2) may be an epoxy compound (c-2-1) having at least two epoxy groups and at least one carboxyl group as shown in formula (IV). The acid group and at least one ethylenically unsaturated compound (c-2-2) are reacted to form a hydroxyl-containing reaction product. Next, a polymerization reaction is performed by adding a carboxylic anhydride compound (c-2-3) and / or a compound (c-2-4) having an epoxy group. Based on the total epoxy group equivalent of the epoxy compound (c-2-1) having at least two epoxy groups as shown in formula (IV) is 1 equivalent, the epoxy compound having at least one carboxylic acid group and at least one ethylenic compound The acid value equivalent of the saturated compound (c-2-2) is preferably 0.8 equivalents to 1.5 equivalents, and more preferably 0.9 equivalents to 1.1 equivalents. The total amount of hydroxyl groups based on the above-mentioned reaction product having hydroxyl groups is 100 mole percent (mole%), and the amount of carboxylic anhydride compound (c-2-3) used It is 10 mol% to 100 mol%, preferably 20 mol% to 100 mol%, and more preferably 30 mol% to 100 mol%.
在製備前述之第二鹼可溶性樹脂(C-2)時,為了加速反應,於反應溶液中通常會添加鹼性化合物作為反應觸媒。該反應觸媒可單獨一種使用或混合複數種使用,且該反應觸媒可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(tetramethylammonium chloride)或氯化苄基三乙基銨(benzyltriethylammonium chloride)等。基於該具有至少二個環氧基的環氧化合物(c-2-1)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-2-2)之總使用量為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,且更佳為0.3重量份至5重量份。 When preparing the aforementioned second alkali-soluble resin (C-2), in order to accelerate the reaction, a basic compound is usually added to the reaction solution as a reaction catalyst. The reaction catalyst may be used singly or in combination. The reaction catalyst may include, but is not limited to, triphenyl phosphine, triphenyl stibine, triethylamine, triethylamine. Ethanolamine (triethanolamine), tetramethylammonium chloride (benzyltriethylammonium chloride) and the like. The total amount of the epoxy compound (c-2-1) having at least two epoxy groups and the compound (c-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100. The use amount of the reaction catalyst is preferably 0.01 to 10 parts by weight, and more preferably 0.3 to 5 parts by weight.
此外,為了控制聚合度,於反應溶液中通常還會添加聚合抑制劑(polymerization inhibitor)。該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一種使用或混合複數種使用。基於上述具有至少二個環氧基的環氧化合物(c-2-1)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-2-2)之總使用量為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,且更佳為0.1重量份至5重量份。 In addition, in order to control the degree of polymerization, a polymerization inhibitor is usually added to the reaction solution. The polymerization inhibitor may include, but is not limited to, methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol (2,6-di- t-butyl-p-cresol) or phenothiazine. In general, the above-mentioned polymerization inhibitors can be used singly or in combination. Based on the total amount of the epoxy compound (c-2-1) having at least two epoxy groups and the compound (c-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group, 100 is used. Parts by weight, poly The combined inhibitor is preferably used in an amount of 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight.
當製備該第二鹼可溶性樹脂(C-2)時,必要時可添加聚合反應溶劑。該聚合反應溶劑之具體例可包含但不限於乙醇、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***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。該聚合反應溶劑可單獨一種使用或混合複數種使用。另外,該第二鹼可溶性樹脂(C-2)的酸價較佳為50mgKOH/g至200mgKOH/g,且更佳為60mgKOH/g至150mgKOH/g。 When the second alkali-soluble resin (C-2) is prepared, a polymerization reaction solvent may be added if necessary. Specific examples of the polymerization reaction solvent may include, but are not limited to, alcohol compounds such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, or ethylene glycol; methyl ethyl ketone or cyclohexanone, and the like Ketones; aromatic hydrocarbons such as toluene or xylene; cellosolve or butyl cellosolve; carbitol or butyl carbitol (butyl carbitol) and other carbitol compounds; propylene glycol monomethyl ether (propylene glycol monomethyl ether) and other propylene glycol alkyl ether compounds; dipropylene glycol monomethyl ether [di (propylene glycol) methyl ether] and other propylene glycol alkyl ethers [ poly (propylene glycol) alkyl ether]; acetate compounds such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, or propylene glycol methyl ether acetate ; Alkyl lactate compounds such as ethyl lactate or butyl lactate; or dialkyl glycol ethers. This polymerization reaction solvent may be used individually or in mixture of multiple types. In addition, the acid value of the second alkali-soluble resin (C-2) is preferably 50 mgKOH / g to 200 mgKOH / g, and more preferably 60 mgKOH / g to 150 mgKOH / g.
前述之第二鹼可溶性樹脂(C-2)藉由膠體滲透層析儀測定之聚苯乙烯換算的數目平均分子量一般為500至10000,較佳為800至8000,且更佳為1000至6000。 The polystyrene-equivalent number average molecular weight of the aforementioned second alkali-soluble resin (C-2) measured by a colloidal permeation chromatography is generally 500 to 10,000, preferably 800 to 8000, and more preferably 1000 to 6000.
基於鹼可溶性樹脂(C)之總使用量為100重量份,第二鹼可溶性樹脂(C-2)之使用量為0重量份至90重量份,較佳為10重量份至85重量份,且更佳為20重量份至80重量份。 Based on the total use amount of the alkali-soluble resin (C) is 100 parts by weight, and the use amount of the second alkali-soluble resin (C-2) is 0 to 90 parts by weight, preferably 10 to 85 parts by weight, and More preferably, it is 20 parts by weight to 80 parts by weight.
當鹼可溶性樹脂(C)包含第二鹼可溶性樹脂(C-2)時,所製得之彩色濾光片用感光性樹脂組成物更不具有泡狀之顯示缺陷。 When the alkali-soluble resin (C) contains the second alkali-soluble resin (C-2), the obtained photosensitive resin composition for a color filter is less likely to have bubble-like display defects.
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 of the present invention may include an unsaturated compound having at least one ethylenically unsaturated group and an unsaturated compound having at least two ethylenically unsaturated groups.
該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 unsaturated compound having at least one ethylenically unsaturated group may include, but are not limited to, acrylamide, acrylamidomorpholine, methacrylamidomorpholine, acrylic-7-amino-3,7-dimethyl Octyl ester, methacrylic acid 7-amino-3,7-dimethyloctyl ester, isobutoxymethacrylamide, isobutoxymethylmethacrylamide, isobornyl acrylate Ethyl ester, isobornyloxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, ethyldiethylene glycol Acrylate, Ethyl Diethylene Glycol Methacrylate, Third Octyl Acrylamidoxamine, Third Octyl Methacrylamidine, Diacetone Acrylamidine, Diacetone Methacrylamidine, Dimethyamine Acrylate Ester, dimethylamino methacrylate, dodecyl acrylate, dodecyl methacrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyl ethyl methacrylate, dicyclopentyl acrylate Pentenyl, dicyclopentenyl methacrylate, nitrogen, nitrogen-dimethylacrylamide, nitrogen, nitrogen-dimethyl Methacrylamide, tetrachlorophenyl acrylate, tetrachlorophenyl methacrylate, 2-tetrachlorophenoxyethyl acrylate, 2-tetrachlorophenoxyethyl methacrylate, tetrahydrofurfuryl acrylate Ester, tetrahydrofurfuryl methacrylate, tetrabromophenyl acrylate, tetrabromophenyl methacrylate, 2-tetrabromophenoxyethyl acrylate, 2-tetrabromophenoxyethyl methacrylate, 2-trichlorophenoxyethyl acrylate, 2-trichlorophenoxyethyl methacrylate, tribromophenyl acrylate, tribromophenyl methacrylate, 2-tribromophenoxyethyl acrylate Ester, 2-tribromophenoxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate Esters, vinyl caprolactam, nitrogen-vinyl sheathinones, phenoxyethyl acrylate, phenoxyethyl methacrylate, pentachlorophenyl acrylate, pentachlorophenyl methacrylate, pentachloroacrylate Bromophenyl, Pentabromophenyl methacrylate, Polyethylene glycol monoacrylate, Polyethylene glycol monomethacrylate, Polypropylene glycol monoacrylate, Polypropylene dimethacrylate Alcohol esters, norbornyl acrylate, or bornyl methacrylate. The unsaturated compound having at least one ethylenically unsaturated group may be used alone or in combination.
該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 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 Modification of triacrylate and caprolactone three (2-hydroxyethyl) isocyanate trimethacrylate, trimethylol propyl triacrylate, trimethylol propyl trimethacrylate, ethylene oxide (hereinafter referred to as EO) modified trihydroxy triacrylate Methyl propyl, EO modified trimethylol propyl trimethacrylate, propylene oxide (hereinafter referred to as PO) modified trimethylol propyl triacrylate, PO modified trimethyl methacrylate Methyl propyl ester, triethylene glycol diacrylate, triethylene glycol dimethacrylate, neopentyl glycol diacrylate, 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, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipentaerythritol hexaacrylate hexaacrylate (DPHA), dipentaerythritol hexamethacrylate, dipentaerythritol Pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, caprolactone modified dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexamethacrylic acid Esters, dipentaerythritol pentaacrylate modified by caprolactone, dipentaerythritol pentamethacrylate modified by caprolactone, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, EO modified bisphenol A diacrylate, EO modified bisphenol A dimethacrylate, PO modified bisphenol A diacrylate, PO modified bisphenol A dimethacrylate, EO modified 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 glycerin Tripropionate, EO-modified bisphenol F diacrylate, EO-modified bisphenol F dimethacrylate, phenolic polyglycidyl ether acrylate, phenolic polyglycidyl ether methacrylate, Japan East Asia Synthesis A product manufactured by Japan Co., Ltd. under the model number TO-1382, or a product manufactured by Nippon Kayaku Co., Ltd. and having the model numbers KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, or KAYARAD DPCA-120. The unsaturated compound having at least two ethylenically unsaturated groups may be used alone or in combination.
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 the group consisting of trimethylolpropyl triacrylate, trimethylolpropyl triacrylate modified by EO, and trihydroxymethyltriacrylate modified by PO. Methylpropyl ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate, tetraacrylate ditrihydroxyol Methylpropyl ester, PO modified glycerol tripropionate, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 or KAYARAD DPCA-120 or any combination of the above compounds.
該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 compound (D) having an ethylenically unsaturated group may be used alone or in combination.
基於鹼可溶性樹脂(C)之總使用量為100重量份,該具有乙烯性不飽和基之化合物(D)的使用量為20重量份至200重量份,較佳為30重量份至180重量份,且更佳為50重量份至150重量份。 Based on the total amount of the alkali-soluble resin (C) used, 100 parts by weight, the amount of the ethylenically unsaturated compound (D) used is 20 to 200 parts by weight, preferably 30 to 180 parts by weight And more preferably 50 parts by weight to 150 parts by weight.
本發明之光起始劑(E)可包含具有如下式(II)所示之結構的光起始劑(E-1)。其次,該光起始劑(E)可選擇性地包含其他自由基型光起始劑(E-2)。 The photoinitiator (E) of the present invention may include a photoinitiator (E-1) having a structure represented by the following formula (II). Second, the photo-initiator (E) may optionally include other free-radical photo-initiators (E-2).
光起始劑(E-1)Photoinitiator (E-1)
該光起始劑(E-1)可具有如下式(II)所示之結構:
其中R1、R2、R3、R4、R5、R6、R7及R8彼此獨立地為氫、C1-C20烷基、、COR16、OR17、鹵素、 NO2或,或R1及R2、R2及R3、R3及R4、R5 及R6、R6及R7或R7及R8彼此獨立地為經取代之C2-C10烯基或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此獨立地共同為-(CH2)P-Y-(CH2)q-;或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7 及R8彼此獨立地共同為;但條件為R1及R2、R2及R3、R3及R4、R5及R6、R6及 R7或R7及R8中至少一對係 R9、R10、R11及R12彼此獨立地為氫、C1-C20烷基,該C1-C20烷基未經取代或經一或多個以下基團取代:鹵素、 苯基、CN、OH、SH、C1-C4-烷氧基、(CO)OH或(CO)O(C1-C4烷基);或R9、R10、R11及R12彼此獨立地為未經取代之苯基或經一或多個以下基團取代之苯基:C1-C6烷基、鹵素、CN、OR17、SR18或NR19R20;或R9、R10、R11及R12彼此獨立地為鹵素、CN、OR17、SR18、SOR18、SO2R18或NR19R20,其中該等取代基OR17、SR18或NR19R20視情況經由基團R17、R18、R19及/或R20與萘基環中一個碳原子形成5員或6員環; 或R9、R10、R11及R12彼此獨立地為、COR16或NO2;Y係O、S、NR26或直接鍵;p係整數0、1、2或3;q係整數1、2或3;X係CO或直接鍵;R13係C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、R17、COOR17、OR17、SR18、CONR19R20、NR19R20、PO(OCkH2k+1)2或;或R13係C2-C20烷基,其間雜有一或多個O、S、SO、SO2、NR26或CO,或係C2-C12烯基,其未經間雜或間雜有一或多個O、CO或NR26,其中經間雜之C2-C20烷基及未經間雜或經間雜之C2-C12烯基未經取代或經一或多個鹵素取代;或R13係C4-C8環烯基、C2-C12炔基或未經間雜或間雜有一或多個O、S、CO或NR26之C3-C10環烷基; 或R13係苯基或萘基,其各未經取代或經一或多個以下基團取代:OR17、SR18、NR19R20、、COR16、CN、NO2、鹵素、C1-C20烷基、C1-C4鹵代烷基、間雜有一或多個O、S、CO或NR26之C2-C20烷基;或其各經C3-C10環烷基或間雜有一或多個O、S、CO或NR26之C3-C10環烷基取代;k係整數1至10;R14係氫、C3-C8環烷基、C2-C5烯基、C1-C20烷氧基或C1-C20烷基,其未經取代或經一或多個鹵素、苯基、C1-C20烷基苯基或CN取代;或R14係苯基或萘基,其各未經取代或經一或多個以下基團取代:C1-C6烷基、C1-C4鹵代烷基、鹵素、CN、OR17、SR18及/或NR19R20;或R14係C3-C20雜芳基、C1-C8烷氧基、苄氧基或苯氧基,該苄氧基及苯氧基未經取代或經一或多個C1-C6烷基、C1-C4鹵代烷基及/或鹵素取代;R15係C6-C20芳基或C3-C20雜芳基,其各未經取代或經一或多個以下基團取代:苯基、鹵素、C1-C4鹵代烷基、CN、NO2、OR17、SR18、NR19R20、PO(OCkH2k+1)2、SO-C1-C10烷基、SO2-C1-C10烷基、間雜有一或多個O、S或NR26之C2-C20烷基;或其各經C1-C20烷基取代,該C1-C20烷基未經取代或經一或多個以下基團取代:鹵素、COOR17、CONR19R20、苯基、C3-C8環烷基、C3-C20雜芳基、C6-C20芳氧基羰基、C3-C20雜芳氧基羰基、OR17、SR18或NR19R20;或R15係氫、C2-C12烯基、未經間雜或間雜有一或多個O、CO或NR26之C3-C8環烷基; 或R15係C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、OR17、SR18、C3-C8環烷基、C3-C20雜芳基、C6-C20芳氧基羰基、C3-C20雜芳氧基羰基、NR19R20、COOR17、CONR19R20、PO(OCkH2k+1)2、、 、苯基;或該C1-C20烷基經苯基取代,該苯基經鹵素、C1-C20烷基、C1-C4鹵代烷基、OR17、SR18或NR19R20取代;或R15係C2-C20烷基,其間雜有一或多個O、SO或SO2,且該經間雜之C2-C20烷基未經取代或經一或多個以下基團取代:鹵素、OR17、COOR17、CONR19R20、苯基或經OR17、SR18或NR19R20取代之苯基;或R15係C2-C20烷醯基或苯甲醯基,其未經取代或經一或多個以下基團取代:C1-C6烷基、鹵素、苯基、OR17、SR18或NR19R20;或R15係未經取代或經一或多個OR17取代之萘甲醯基或係C3-C14雜芳基羰基;或R15係C2-C12烷氧基羰基,其未經間雜或間雜有一或多個O且該經間雜或未經間雜之C2-C12烷氧基羰基未經取代或經一或多個羥基取代;或R15係苯氧基羰基,其未經取代或經一或多個以下基團取代:C1-C6烷基、鹵素、C1-C4鹵代烷基、苯基、OR17、SR18或NR19R20;或R15係CN、CONR19R20、NO2、C1-C4鹵代烷基、S(O)m-C1-C6烷基、未經取代或經C1-C12烷基或SO2-C1-C6烷基取代之S(O)m-苯基; 或R15係SO2O-苯基,其未經取代或經C1-C12烷基取代;或係二苯基膦醯基或二(C1-C4烷氧基)-膦醯基;m係1或2;R’14具有針對R14所給出含義中之一者;R’15具有針對R15所給出含義中之一者;X1係O、S、SO或SO2;X2係O、CO、S或直接鍵;R16係C6-C20芳基或C3-C20雜芳基,其各未經取代或經一或多個以下基團取代:苯基、鹵素、C1-C4鹵代烷基、CN、NO2、OR17、SR18、NR19R20或間雜有一或多個O、S或NR26之C1-C20烷基;或其各經一或多個C1-C20烷基取代,該C1-C20烷基未經取代或經一或多個以下基團取代:鹵素、COOR17、CONR19R20、苯基、C3-C8環烷基、C3-C20雜芳基、C6-C20芳氧基羰基、C3-C20雜芳氧基羰基、OR17、SR18或NR19R20;或R16係氫、C1-C20烷基,該C1-C20烷基未經取代或經一或多個以下基團取代:鹵素、苯基、OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)、O(CO)-苯基、(CO)OH或(CO)O(C1-C4烷基);或R16係C2-C12烷基,其間雜有一或多個O、S或NR26;或R16係(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C2-C12烯基或C3-C8環烷基; 或R16係經SR18取代之苯基,其中基團R18表示鍵結至其中附接有COR16之咔唑部分之苯基或萘基環的直接鍵;n係1至20;R17係氫、苯基-C1-C3烷基、C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)、O(CO)-(C2-C4烯基)、O(CO)-苯基、(CO)OH、(CO)O(C1-C4烷基)、C3-C20環烷基、SO2-(C1-C4鹵代烷基)、O(C1-C4鹵代烷基)或間雜有一或多個O之C3-C20環烷基;或R17係C2-C20烷基,其間雜有一或多個O、S或NR26;或R17係(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C1-C8烷醯基、C2-C12烯基、C3-C6烯醯基或未經間雜或間雜有一或多個O、S、CO或NR26之C3-C20環烷基;或R17係C1-C8烷基-C3-C10環烷基,其未經間雜或間雜有一或多個O;或R17係苯甲醯基,其未經取代或經一或多個C1-C6烷基、鹵素、OH或C1-C3烷氧基取代;或R17係苯基、萘基或C3-C20雜芳基,其各未經取代或經一或多個以下基團取代:鹵素、OH、C1-C12烷基、C1-C12烷氧基、CN、NO2、苯基-C1-C3烷氧基、苯氧基、C1-C12烷基硫基、苯基硫基、N(C1-C12烷基)2、二苯基-胺基或 ; 或R17形成鍵結至其上具有基團或 之苯基或萘基環之一個碳原子之直接鍵; R18係氫、C2-C12烯基、C3-C20環烷基或苯基-C1-C3烷基,其中C2-C12烯基、C3-C20環烷基或苯基-C1-C3烷基未經間雜或間雜有一或多個O、S、CO、NR26或COOR17;或R18係C1-C20烷基,其未經取代或經一或多個以下基團取代:OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C2-C4烯基)、O(CO)-(C1-C4烷基)、O(CO)-苯基或(CO)OR17;或R18係C2-C20烷基,其間雜有一或多個O、S、CO、NR26或COOR17;或R18係(CH2CH2O)nH、(CH2CH2O)n(CO)-(C1-C8烷基)、C2-C8烷醯基或C3-C6烯醯基;或R18係苯甲醯基,其未經取代或經一或多個以下基團取代:C1-C6烷基、鹵素、OH、C1-C4烷氧基或C1-C4烷基硫基;或R18係苯基、萘基或C3-C20雜芳基,其各未經取代或經一或多個以下基團取代:鹵素、C1-C12烷基、C1-C4鹵代烷基、C1-C12烷氧基、CN、NO2、苯基-C1-C3烷氧基、苯氧基、C1-C12烷基硫基、苯基硫基、N(C1-C12烷基)2、二苯基胺基、(CO)O(C1-C8烷基)、(CO)-C1-C8烷基、 (CO)N(C1-C8烷基)2或;R19及R20彼此獨立地為氫、C1-C20烷基、C2-C4羥基烷基、C2-C10烷氧基烷基、C2-C5烯基、C3-C20環烷基、苯基-C1-C3烷基、C1-C8烷醯基、C1-C8烷醯基氧基、C3-C12烯醯基、SO2-(C1-C4鹵代烷基)或苯甲醯基; 或R19及R20係苯基、萘基或C3-C20雜芳基,其各未經取代或經一或多個以下基團取代:鹵素、C1-C4鹵代烷基、C1-C20烷氧基、C1-C12烷基、苯甲醯基或C1-C12烷氧基;或R19及R20與其所附接之N原子一起形成未經間雜或間雜有O、S或NR17之5員或6員飽和或不飽和環,且該5員或6員飽和或不飽和環未經取代或經一或多個以下基團取代:C1-C20烷基、C1-C20烷氧基、=O、OR17、SR18、NR21R22、(CO)R23、NO2、鹵素、C1-C4-鹵代烷基、CN、 苯基、或C3-C20環烷基,該C3-C20環烷基未經間雜或間雜有一或多個O、S、CO或NR17;或R19及R20與其所附接之N原子一起形成雜芳香族環系統,該環系統未經取代或經一或多個以下基團取代:C1-C20烷基、C1-C4鹵代烷基、C1-C20烷氧基、=O、OR17、 SR18、NR21R22、(CO)R23、、鹵素、NO2、CN、苯基或C3-C20環烷基,該C3-C20環烷基未經間雜或間雜有一或多個O、S、CO或NR17;R21及R22彼此獨立地為氫、C1-C20烷基、C1-C4鹵代烷基、C3-C10環烷基或苯基;或R21及R22與其所附接之N原子一起形成未經間雜或間雜有O、S或NR26之5員或6員飽和或不飽和環,且該5員或6員飽和或不飽和環未稠合或該5員或6員飽和或不飽和環係與苯環稠合;R23係氫、OH、C1-C20烷基、C1-C4鹵代烷基、間雜有一或多個O、CO或NR26之C2-C20烷基、未經間雜或間雜有O、S、CO或NR26之C3-C20環烷基,或R23係苯基、萘基、苯基-C1-C4烷基、OR17、SR18或NR21R22;R24係(CO)OR17、CONR19R20、(CO)R17;或R24具有針對R19及R20所給出含義中之一者; R25係COOR17、CONR19R20、(CO)R17;或R25具有針對R17所給出含義中之一者;R26係氫、C1-C20烷基、C1-C4鹵代烷基、間雜有一或多個O或CO之C2-C20烷基;或係苯基-C1-C4烷基、未經間雜或間雜有一或多個O或CO之C3-C8環烷基;或係(CO)R19;或係苯基,其未經取代或經一或多個以下基團取代:C1-C20烷基、鹵素、C1-C4鹵代烷基、OR17、SR18、NR19R20或; 但條件為在該分子中存在至少一個基團 或。 Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently hydrogen, C 1 -C 20 alkyl, , COR 16 , OR 17 , halogen, NO 2 or , Or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are independent of each other. Substituted C 2 -C 10 alkenyl or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 independently of one another are -(CH 2 ) P -Y- (CH 2 ) q- ; or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 independently of each other is But provided that at least one of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 R 9 , R 10 , R 11 and R 12 are independently of each other hydrogen, C 1 -C 20 alkyl, the C 1 -C 20 alkyl is unsubstituted or substituted with one or more of the following groups: halogen, benzene Group, CN, OH, SH, C 1 -C 4 -alkoxy, (CO) OH or (CO) O (C 1 -C 4 alkyl); or R 9 , R 10 , R 11 and R 12 each other Independently unsubstituted phenyl or phenyl substituted with one or more of the following: C 1 -C 6 alkyl, halogen, CN, OR 17 , SR 18 or NR 19 R 20 ; or R 9 , R 10 , R 11 and R 12 are each independently halogen, CN, OR 17 , SR 18 , SOR 18 , SO 2 R 18 or NR 19 R 20 , wherein the substituents OR 17 , SR 18 or NR 19 R 20 Optionally a 5- or 6-membered ring with a carbon atom in the naphthyl ring via the groups R 17 , R 18 , R 19 and / or R 20 ; or R 9 , R 10 , R 11 and R 12 are independently of each other as , COR 16 or NO 2 ; Y is O, S, NR 26 or direct bond; p is integer 0, 1, 2 or 3; q is integer 1, 2 or 3; X is CO or direct bond; R 13 is C 1- C 20 alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, R 17 , COOR 17 , OR 17 , SR 18 , CONR 19 R 20 , NR 19 R 20 , PO (OC k H 2k + 1 ) 2 or ; Or R 13 is a C 2 -C 20 alkyl group, which is interspersed with one or more O, S, SO, SO 2 , NR 26 or CO, or C 2 -C 12 alkenyl group, which is not interspersed or interspersed with one Or more O, CO or NR 26 in which the interspersed C 2 -C 20 alkyl and unsaturated or interspersed C 2 -C 12 alkenyl are unsubstituted or substituted with one or more halogens; or R 13 is C 4 -C 8 cycloalkenyl, C 2 -C 12 alkynyl or C 3 -C 10 cycloalkyl without one or more O, S, CO or NR 26 ; or R 13 Phenyl or naphthyl, each unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 , , COR 16, CN, NO 2 , halogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, interrupted by one or more O, S, CO or NR C 26 of 2 -C 20 alkyl group; or via their respective C 3 -C 10 cycloalkyl, or interrupted by one or more O, S, CO or NR 26 of the C 3 -C 10 cycloalkyl; based integer k 1 to 10; R 14 type hydrogen, C 3 -C 8 cycloalkyl, C 2 -C 5 alkenyl, C 1 -C 20 alkoxy, or C 1 -C 20 alkyl, which are unsubstituted or substituted by one or more halogen, phenyl, C 1- C 20 alkylphenyl or CN substituted; or R 14 is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following: C 1 -C 6 alkyl, C 1 -C 4 haloalkane Group, halogen, CN, OR 17 , SR 18 and / or NR 19 R 20 ; or R 14 is a C 3 -C 20 heteroaryl group, C 1 -C 8 alkoxy group, benzyloxy group or phenoxy group, the Benzyloxy and phenoxy are unsubstituted or substituted with one or more C 1 -C 6 alkyl, C 1 -C 4 haloalkyl and / or halogen; R 15 is C 6 -C 20 aryl or C 3 -C 20 heteroaryl, each unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, CN, NO 2 , OR 17 , SR 18 , NR 19 R 20 、 PO (OC k H 2k + 1 ) 2 , SO-C 1 -C 10 alkyl, SO 2 -C 1 -C 10 alkyl, C 2 -C 20 alkyl interspersed with one or more O, S or NR 26 ; or each C 1- C 20 alkyl substitution, the C 1 -C 20 alkyl group is unsubstituted or substituted with one or more of the following groups: halogen, COOR 17 , CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 3 -C 20 heteroaryloxycarbonyl, OR 17 , SR 18 or NR 19 R 20 ; or R 15 is hydrogen, C 2- C 12 alkenyl, C 3 -C 8 cycloalkyl without one or more O, CO or NR 26 ; or R 15 is C 1 -C 20 alkyl, which is unsubstituted or Multiple substitutions of the following groups: halogen, OR 17 , SR 18 , C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 3 -C 20 heteroaryl Oxycarbonyl, NR 19 R 20 , COOR 17 , CONR 19 R 20 , PO (OC k H 2k + 1 ) 2 , , , Phenyl; or the C 1 -C 20 alkyl group is substituted with a phenyl group, the phenyl group is halogen, C 1 -C 20 alkyl group, C 1 -C 4 haloalkyl group, OR 17 , SR 18 or NR 19 R 20 Substituted; or R 15 is a C 2 -C 20 alkyl group, in which one or more O, SO, or SO 2 is interspersed, and the interspersed C 2 -C 20 alkyl group is unsubstituted or substituted by one or more of the following groups Group substitution: halogen, OR 17 , COOR 17 , CONR 19 R 20 , phenyl or phenyl substituted with OR 17 , SR 18 or NR 19 R 20 ; or R 15 is a C 2 -C 20 alkylfluorenyl or benzyl Fluorenyl, which is unsubstituted or substituted with one or more of the following: C 1 -C 6 alkyl, halogen, phenyl, OR 17 , SR 18 or NR 19 R 20 ; or R 15 is unsubstituted or A naphthylmethyl group substituted with one or more OR 17 or a C 3 -C 14 heteroarylcarbonyl group; or R 15 is a C 2 -C 12 alkoxycarbonyl group, which is not interspersed or has one or more O And the C 2 -C 12 alkoxycarbonyl group is unsubstituted or substituted with one or more hydroxyl groups; or R 15 is a phenoxycarbonyl group which is unsubstituted or substituted with one or more Group substitution: C 1 -C 6 alkyl, halogen, C 1 -C 4 haloalkyl, phenyl, OR 17 , SR 18 or NR 19 R 20 ; or R 15 is CN, CONR 19 R 20 , NO 2 , C 1 -C 4 haloalkyl, S (O) m -C 1 -C 6 alkyl, unsubstituted or C 1 -C 12 alkyl or SO 2 -C 1 -C 6 alkyl substituted S (O) m -phenyl; or R 15 is SO 2 O-phenyl, which is unsubstituted or C 1 -C 12 alkyl Group substitution; or diphenylphosphinofluorenyl or bis (C 1 -C 4 alkoxy) -phosphinofluorenyl; m is 1 or 2; R '14 has one of the meanings given for R 14 ; R '15 has one of the meanings given for R 15 ; X 1 is O, S, SO or SO 2 ; X 2 is O, CO, S or a direct bond; R 16 is C 6 -C 20 aryl Or C 3 -C 20 heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, CN, NO 2 , OR 17 , SR 18 , NR 19 R 20 or one or more C 1 -C 20 alkyl groups with one or more O, S or NR 26 ; or each substituted with one or more C 1 -C 20 alkyl groups, the C 1 -C 20 alkyl group Unsubstituted or substituted with one or more of the following groups: halogen, COOR 17 , CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 Aryloxycarbonyl, C 3 -C 20 heteroaryloxycarbonyl, OR 17 , SR 18 or NR 19 R 20 ; or R 16 is hydrogen, C 1 -C 20 alkyl, the C 1 -C 20 alkyl is unsubstituted or substituted with one or more of the following groups: halogen, phenyl , OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO) O (C 1 -C 4 alkyl), O (CO)-(C 1 -C 4 alkyl), O (CO) -phenyl, (CO) OH or (CO) O (C 1 -C 4 alkyl); or R 16 is C 2 -C 12 alkyl, with one or more intervening in between O, S or NR 26 ; or R 16 series (CH 2 CH 2 O) n + 1 H, (CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl), C 2 -C 12 Alkenyl or C 3 -C 8 cycloalkyl; or R 16 is a phenyl substituted with SR 18 , where the group R 18 represents a phenyl or naphthyl ring bonded to the carbazole moiety to which COR 16 is attached N is 1 to 20; R 17 is hydrogen, phenyl-C 1 -C 3 alkyl, C 1 -C 20 alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen , OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO) O (C 1 -C 4 alkyl), O (CO)-(C 1 -C (4 alkyl), O (CO)-(C 2 -C 4 alkenyl), O (CO) -phenyl, (CO) OH, (CO) O (C 1 -C 4 alkyl), C 3- C 20 cycloalkyl, SO 2- (C 1 -C 4 haloalkyl), O (C 1 -C 4 haloalkyl) or a C 3 -C 20 cycloalkyl group interspersed with one or more O; or R 17 is a C 2 -C 20 alkyl group interspersed with one or more O, S or NR 26 ; or R 17 series (CH 2 CH 2 O) n + 1 H, (CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl), C 1 -C 8 alkyl, C 2 -C 12 Alkenyl, C 3 -C 6 alkenyl or C 3 -C 20 cycloalkyl without one or more O, S, CO or NR 26 ; or R 17 is C 1 -C 8 alkyl -C 3 -C 10 cycloalkyl, which has one or more O unsubstituted or interspersed; or R 17 is benzamyl, which is unsubstituted or has one or more C 1 -C 6 alkyl, halogen , OH or C 1 -C 3 alkoxy substitution; or R 17 is phenyl, naphthyl or C 3 -C 20 heteroaryl, each unsubstituted or substituted with one or more of the following groups: halogen, OH, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, CN, NO 2 , phenyl-C 1 -C 3 alkoxy, phenoxy, C 1 -C 12 alkylthio, Phenylthio, N (C 1 -C 12 alkyl) 2 , diphenyl-amino or ; Or R 17 forms a bond to a group having or Direct bond of one carbon atom of phenyl or naphthyl ring; R 18 is hydrogen, C 2 -C 12 alkenyl, C 3 -C 20 cycloalkyl or phenyl-C 1 -C 3 alkyl, where C 2- C 12 alkenyl, C 3 -C 20 cycloalkyl or phenyl-C 1 -C 3 alkyl without one or more O, S, CO, NR 26 or COOR 17 ; or R 18 Is a C 1 -C 20 alkyl group, which is unsubstituted or substituted with one or more of the following groups: OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 ( CO) O (C 1 -C 4 alkyl), O (CO)-(C 2 -C 4 alkenyl), O (CO)-(C 1 -C 4 alkyl), O (CO) -phenyl Or (CO) OR 17 ; or R 18 is a C 2 -C 20 alkyl group, which is interspersed with one or more O, S, CO, NR 26 or COOR 17 ; or R 18 (CH 2 CH 2 O) n H , (CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl), C 2 -C 8 alkylfluorenyl or C 3 -C 6 alkenyl; or R 18 benzamyl, It is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, OH, C 1 -C 4 alkoxy, or C 1 -C 4 alkylthio; or R 18 series phenyl, naphthyl or C 3 -C 20 heteroaryl, each of which is unsubstituted or substituted with one or more of the following radicals: halogen, C 1 -C 12 alkyl, C 1 -C 4 Substituted alkyl, C 1 -C 12 alkoxy, CN, NO 2, phenyl -C 1 -C 3 alkoxy, phenoxy, C 1 -C 12 alkylthio, phenylthio, N (C 1 -C 12 alkyl) 2 , diphenylamino, (CO) O (C 1 -C 8 alkyl), (CO) -C 1 -C 8 alkyl, (CO) N (C 1 -C 8 alkyl) 2 or ; R 19 and R 20 are each independently hydrogen, C 1 -C 20 alkyl, C 2 -C 4 hydroxyalkyl, C 2 -C 10 alkoxyalkyl, C 2 -C 5 alkenyl, C 3 -C 20 cycloalkyl, phenyl-C 1 -C 3 alkyl, C 1 -C 8 alkylfluorenyl, C 1 -C 8 alkylfluorenyloxy, C 3 -C 12 alkenyl, SO 2- (C 1 -C 4 haloalkyl) or benzamidine; or R 19 and R 20 are phenyl, naphthyl or C 3 -C 20 heteroaryl, each of which is unsubstituted or substituted by one or more of the following groups Group substitution: halogen, C 1 -C 4 haloalkyl, C 1 -C 20 alkoxy, C 1 -C 12 alkyl, benzamidine or C 1 -C 12 alkoxy; or R 19 and R 20 With its attached N atom to form a 5- or 6-membered saturated or unsaturated ring that is not interspersed or interspersed with O, S, or NR 17 , and the 5- or 6-membered saturated or unsaturated ring is unsubstituted or One or more of the following groups substituted: C 1 -C 20 alkyl, C 1 -C 20 alkoxy, = O, OR 17 , SR 18 , NR 21 R 22 , (CO) R 23 , NO 2 , halogen , C 1 -C 4 -haloalkyl, CN, phenyl, Or C 3 -C 20 cycloalkyl, the C 3 -C 20 cycloalkyl has one or more O, S, CO, or NR 17 without interspersed or interspersed; or R 19 and R 20 with the N atom to which it is attached Together form a heteroaromatic ring system that is unsubstituted or substituted with one or more of the following groups: C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 1 -C 20 alkoxy, = O, OR 17 , SR 18 , NR 21 R 22 , (CO) R 23 , , Halogen, NO 2 , CN, phenyl, or C 3 -C 20 cycloalkyl, the C 3 -C 20 cycloalkyl has one or more O, S, CO, or NR 17 uninterspersed or interspersed; R 21 and R 22 is independently of each other hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 3 -C 10 cycloalkyl or phenyl; or R 21 and R 22 together with the N atom to which they are attached Forms a 5- or 6-membered saturated or unsaturated ring without interspersed or interspersed O, S, or NR 26 , and the 5- or 6-membered saturated or unsaturated ring is not fused or the 5- or 6-membered saturated or unsaturated ring saturated ring system is fused with a benzene ring; R 23 type hydrogen, OH, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, interrupted by one or more O, cO or NR C 26 alkoxy of 2 -C 20 , C 3 -C 20 cycloalkyl without meta or hetero, O, S, CO or NR 26 , or R 23 phenyl, naphthyl, phenyl-C 1 -C 4 alkyl, OR 17 , SR 18 or NR 21 R 22 ; R 24 is (CO) OR 17 , CONR 19 R 20 , (CO) R 17 ; or R 24 has one of the meanings given for R 19 and R 20 ; R 25 is COOR 17 , CONR 19 R 20 , (CO) R 17 ; or R 25 has one of the meanings given for R 17 ; R 26 is hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl , Heteroaryl having one or more O or CO of C 2 -C 20 alkyl group; or a phenyl-based -C 1 -C 4 alkyl, interrupted or not interrupted by one or more O or CO of C 3 -C 8 cycloalkyl Or (CO) R 19 ; or phenyl, which is unsubstituted or substituted with one or more of the following groups: C 1 -C 20 alkyl, halogen, C 1 -C 4 haloalkyl, OR 17 , SR 18 , NR 19 R 20 or ; Provided that at least one group is present in the molecule or .
式(II)化合物之特徵在於其在咔唑部分上包含一或多個成環(annelated)不飽和環。換言之,R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8中至少一對係。 The compound of formula (II) is characterized in that it contains one or more annelated unsaturated rings on the carbazole moiety. In other words, at least one of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7, or R 7 and R 8 .
C1-C20烷基係直鏈或支鏈且係(例如)C1-C18-、C1-C4-、C1-C12-、C1-C8-、C1-C8-或C1-C4烷基或C4-C12-或C4-C8烷基。實例係甲基、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。C1-C6烷基具有與上文針對C1-C20烷基所給出相同之含義且具有最高相應C原子數。 C 1 -C 20 alkyl is straight or branched and is, for example, C 1 -C 18- , C 1 -C 4- , C 1 -C 12- , C 1 -C 8- , C 1 -C 8- or C 1 -C 4 alkyl or C 4 -C 12 -or C 4 -C 8 alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, isobutyl, third butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl Amyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and icosyl. C 1 -C 6 alkyl has the same meaning as given above for C 1 -C 20 alkyl and has the highest corresponding number of C atoms.
含有一或多個C-C多重鍵之未經取代或經取代之C1-C20烷基係指如下文所解釋之烯基。 It contains one or more CC multiple bonds of a substituted or non-substituted alkyl group of C 1 -C 20 as explained herein refers to the alkenyl group.
C1-C4鹵代烷基係如下文所定義經鹵素取代之如上文所定義C1-C4烷基。烷基基團係(例如)單-或多鹵化,直至所有H-原子替換為鹵素。其係(例如)CnHxHaly,其中x+y=2n+1且Hal係鹵素,較佳為F。具體實例係氯甲基、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。C2-C4羥基烷基意指經一或兩個O原子取代之C2-C4烷基。烷基基團係直鏈或支鏈。實例係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。C2-C10烷氧基烷基係間雜有一個O原子之C2-C10烷基。C2-C10烷基具有與上文針對C1-C20烷基所給出相同之含義且具有最高相應C原子數。實例係甲氧基甲基、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。 C 1 -C 4 haloalkyl is a halogen substituted C 1 -C 4 alkyl group as defined above, as defined below. Alkyl groups are, for example, mono- or polyhalogenated until all H-atoms are replaced with halogen. It is, for example, C n H x Hal y , where x + y = 2n + 1 and Hal is halogen, preferably F. Specific examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl. C 2 -C 4 hydroxyalkyl means C 2 -C 4 alkyl substituted with one or two O atoms. Alkyl groups are straight or branched. 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. C 2 -C 10 alkoxyalkyl lines interrupted by O atoms of a C 2 -C 10 alkyl. C 2 -C 10 alkyl has the same meaning as given above for C 1 -C 20 alkyl and has the highest corresponding number of C atoms. Examples are methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, Propoxypropyl.
間雜有一或多個O、S、NR26或CO之C2-C20烷基經O、S、NR26或CO間雜(例如)1至9次、1至5次、1至3次或1次或2次。若存在一個以上間雜基團,則其為相同種類或不同。兩個O原子由至少一個亞甲基、較佳至少兩個亞甲基(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)-NR26-CH2-CH3、-CH2-CH2-COO-CH2CH3或-CH2-CH(CH3)-OCO-CH2-CH2CH3。 C 2 -C 20 alkyl interspersed with one or more O, S, NR 26 or CO via O, S, NR 26 or CO (for example) 1 to 9 times, 1 to 5 times, 1 to 3 times or 1 Times or 2 times. If more than one meta group is present, they are the same kind or different. The two O atoms are separated by at least one methylene group, preferably at least two methylene groups (ie, ethylidene). These alkyl groups are straight or branched. For example, the following structural units will exist: -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 ) -NR 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 .
C3-C10環烷基、C3-C10環烷基及C3-C8環烷基在本申請案上下文中應理解為至少包含一個環之烷基。其係(例如)環丙基、環丁基、環戊基、環己基、環辛基、戊基環戊基及環己基。C3-C10環烷基在本發明上下文中亦意欲涵 蓋二環,換言之,橋聯環,例如、、 及相應環。其他實例係諸如、 、(例如)或 等結構、以及橋聯或稠合環系統,舉例而 言,該術語亦意欲涵蓋、等。 C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl and C 3 -C 8 cycloalkyl are to be understood in the context of this application as alkyl groups containing at least one ring. It is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, pentylcyclopentyl and cyclohexyl. C 3 -C 10 cycloalkyl is also intended to encompass bicyclics in the context of the present invention, in other words, bridged rings such as , , And the corresponding ring. Other examples are such as , , (E.g )or Isostructure, and bridged or fused ring systems, the term is also intended to cover, for example , Wait.
間雜有O、S、CO、NR26之C3-C20環烷基具有上文給出之含義,其中烷基中至少一個CH2-基團替換為
O、S、CO或NR26。實例係諸如、
、(例如)、
C1-C8烷基-C3-C10環烷基係經一或多個具有最多8個碳原子之烷基取代的如上文所定義之C3-C10環烷基。實例係、等。 C 1 -C 8 alkyl-C 3 -C 10 cycloalkyl is a C 3 -C 10 cycloalkyl group, as defined above, substituted with one or more alkyl groups having up to 8 carbon atoms. Instance system , Wait.
間雜有一或多個O之C1-C8烷基-C3-C10環烷基係經一或多個具有最多8個碳原子之烷基取代的如上文所定義之O間雜C3-C10環烷基。實例係、等。 C 1 -C 8 alkyl-C 3 -C 10 cycloalkyl interspersed with one or more O is an O interspersed C 3 -as defined above substituted with one or more alkyl groups having up to 8 carbon atoms C 10 cycloalkyl. Instance system , Wait.
C1-C12烷氧基係經一個O原子取代之C1-C12烷基。C1-C12烷基具有與上文針對C1-C20烷基所給出相同之含義且具有最高相應C原子數。C1-C4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。C1-C8烷氧基及C1-C4-烷氧基具有與上文所述相同之含義且具有最高相應C原子數。 C 1 -C 12 alkoxy substituted with the system via a O atom C 1 -C 12 alkyl. C 1 -C 12 alkyl has the same meaning as given above for C 1 -C 20 alkyl and has the highest corresponding number of C atoms. C 1 -C 4 alkoxy is straight or branched, such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, second butoxy, isobutoxy, or Tributoxy. C 1 -C 8 alkoxy and C 1 -C 4 -alkoxy have the same meaning as described above and have the highest corresponding number of C atoms.
C1-C12烷基硫基係經一個S原子取代之C1-C12烷基。C1-C20烷基具有與上文針對C1-C20烷基所給出相同之含義且具有最高相應C原子數。C1-C4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。 C 1 -C 12 alkylthio is a C 1 -C 12 alkyl substituted with one S atom. C 1 -C 20 alkyl has the same meaning as given above for C 1 -C 20 alkyl and has the highest corresponding number of C atoms. C 1 -C 4 alkylthio is linear or branched, such as methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, second butylthio , Isobutylthio, third butylthio.
苯基-C1-C3烷基係(例如)苄基、苯基乙基、α-甲基苄基或α,α-二甲基-苄基,尤其為苄基。 Phenyl-C 1 -C 3 alkyl is, for example, benzyl, phenylethyl, α-methylbenzyl or α, α-dimethyl-benzyl, especially benzyl.
苯基-C1-C3烷氧基係(例如)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。 Phenyl-C 1 -C 3 alkoxy is, for example, benzyloxy, phenylethoxy, α-methylbenzyloxy or α, α-dimethylbenzyloxy, especially benzyloxy.
C2-C12烯基係單-或多不飽和且係(例如)C2-C10-、C2-C8-、C2-C5-烯基,例如乙烯基、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。C2-C5烯基具有與上文針對C2-C12烯基所給出相同之含義且具有最高相應C原子數。 C 2 -C 12 alkenyl is mono- or polyunsaturated and is, for example, C 2 -C 10- , C 2 -C 8- , C 2 -C 5 -alkenyl, such as vinyl, allyl, Methylallyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentadienyl, 5-hexenyl, 7-octenyl or dodecenyl, especially allyl. C 2 -C 5 alkenyl has the same meaning as given above for C 2 -C 12 alkenyl and has the highest corresponding number of C atoms.
間雜有一或多個O、CO或NR26之C2-C12烯基經O、S、NR26或CO間雜(例如)1至9次、1至5次、1至3次或1次或2次。若存在一個以上間雜基團,則其為相同種類或不同。兩個O原子由至少一個亞甲基、較佳至少兩個亞甲基(即伸乙基)隔開。烯基係直鏈或支鏈且如上文所定義。舉例而言,可形成以下結構單元:-CH=CH-O-CH2CH3、-CH=CH-O-CH=CH2等。 C 2 -C 12 alkenyl interspersed with one or more O, CO or NR 26 via O, S, NR 26 or CO interspersed (for example) 1 to 9 times, 1 to 5 times, 1 to 3 times or 1 time or 2 times. If more than one meta group is present, they are the same kind or different. The two O atoms are separated by at least one methylene group, preferably at least two methylene groups (ie, ethylidene). Alkenyl is straight or branched and is as defined above. For example, the following structural units may be formed: -CH = CH-O-CH 2 CH 3 , -CH = CH-O-CH = CH 2 and the like.
C4-C8環烯基具有一或多個雙鍵且係(例如)C4-C6-環烯基或C6-C8-環烯基。實例係環丁烯基、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。 C 4 -C 8 cycloalkenyl has one or more double bonds and is, for example, C 4 -C 6 -cycloalkenyl or C 6 -C 8 -cycloalkenyl. Examples are cyclobutenyl, cyclopentenyl, cyclohexenyl or cyclooctenyl, especially cyclopentenyl and cyclohexenyl, and preferably cyclohexenyl.
C3-C6烯氧基係單或多不飽和且具有上文針對烯基所給出含義中之一者,且附接氧基具有最高相應C原子數。實例係烯丙氧基、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。 C 3 -C 6 alkenyloxy is mono- or polyunsaturated and has one of the meanings given above for alkenyl, and the attached oxygen group has the highest corresponding number of C atoms. Examples are allyloxy, methallyloxy, butenyloxy, pentenyloxy, 1,3-pentadienyloxy, 5-hexenyloxy.
C2-C12炔基係單或多不飽和直鏈或支鏈且係(例如)C2-C8-、C2-C6-或C2-C4炔基。實例係乙炔基、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。 C 2 -C 12 alkynyl is a mono- or polyunsaturated straight or branched chain and is, for example, C 2 -C 8- , C 2 -C 6 -or C 2 -C 4 alkynyl. Examples are ethynyl, propynyl, butynyl, 1-butynyl, 3-butynyl, 2-butynyl, pentynylhexynyl, 2-hexynyl, 5-hexynyl, Octynyl and others.
C2-C20烷醯基係直鏈或支鏈且係(例如)C2-C18-、C2-C14-、C2-C12-、C2-C8-、C2-C6-或C2-C4烷醯基或C4-C12-或C4-C8烷醯基。實例係乙醯基、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。C1-C8烷醯基具有與上文針對C2-C20烷醯基所給出相同之含義且具有最高相應C原子數。 C 2 -C 20 alkylfluorenyl is straight or branched and is, for example, C 2 -C 18- , C 2 -C 14- , C 2 -C 12- , C 2 -C 8- , C 2- C 6 -or C 2 -C 4 alkylfluorenyl or C 4 -C 12 -or C 4 -C 8 alkylfluorenyl. Examples are ethenyl, propionyl, butyryl, isobutyryl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl Base, hexadecyl, octadecyl, and icosyl, preferably ethenyl. C 1 -C 8 alkylfluorenyl has the same meaning as given above for C 2 -C 20 alkylfluorenyl and has the highest corresponding number of C atoms.
C2-C12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。 C 2 -C 12 alkoxycarbonyl is straight or branched and is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, 1,1 -Dimethylpropoxycarbonyl, pentoxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonoxycarbonyl, decoxycarbonyl or dodecyloxycarbonyl, especially methoxy The carbonyl, ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl or isobutoxycarbonyl group is preferably a methoxycarbonyl group.
間雜有一或多個O之C2-C12烷氧基羰基係直鏈或支鏈。兩個O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。C6-C20芳氧基羰基係(例如)苯基氧基羰基[=苯基-O-(CO)-]、萘氧基羰基、蒽氧基羰基等。C5-C20雜芳氧基羰基係C5-C20雜芳基-O-CO-。 The C 2 -C 12 alkoxycarbonyl group interspersed with one or more O is linear or branched. The two O atoms are separated by at least two methylene (ie, ethylene). The meta heteroalkoxycarbonyl group is unsubstituted or substituted with one or more hydroxyl groups. C 6 -C 20 aryloxycarbonyl is, for example, phenyloxycarbonyl [= phenyl-O- (CO)-], naphthyloxycarbonyl, anthracenoxycarbonyl, and the like. C 5 -C 20 heteroaryloxycarbonyl is C 5 -C 20 heteroaryl-O-CO-.
C3-C10環烷基羰基係C3-C10環烷基-CO-,其中環烷基具有上文所示含義中之一者且具有最高相應C原子數。間雜有一或多個O、S、CO、NR26之C3-C10環烷基羰基係指經間雜環烷基-CO-,其中經間雜環烷基係如上文所述所定義。 C 3 -C 10 cycloalkylcarbonyl is C 3 -C 10 cycloalkyl-CO-, wherein cycloalkyl has one of the meanings indicated above and has the highest corresponding number of C atoms. The C 3 -C 10 cycloalkylcarbonyl group interspersed with one or more O, S, CO, NR 26 refers to a metacycloalkyl-CO- group, wherein the metacycloalkyl group is as defined above.
C3-C10環烷氧基羰基係C3-C10環烷基-O-(CO)-,其中環烷基具有上文所示含義中之一者且具有最高相應C原子數。間雜有一或多個O、S、CO、NR26之C3-C10環烷氧基羰基係指經間雜環烷基-O-(CO)-,其中經間雜環烷基係如上文所述所定義。 C 3 -C 10 cycloalkoxycarbonyl is C 3 -C 10 cycloalkyl-O- (CO)-, wherein cycloalkyl has one of the meanings indicated above and has the highest corresponding number of C atoms. The C 3 -C 10 cycloalkoxycarbonyl group interspersed with one or more O, S, CO, NR 26 refers to metacycloalkyl-O- (CO)-, wherein the metacycloalkyl group is as described above As defined.
C1-C20烷基苯基係指經一或多個烷基取代之苯基,其中C原子之總和最多為20。 C 1 -C 20 alkylphenyl refers to a phenyl substituted with one or more alkyl groups, where the total of C atoms is at most 20.
C6-C20芳基係(例如)苯基、萘基、蒽基、菲基、芘基、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。 C 6 -C 20 aryl is, for example, phenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, Phenyl, tetracrylphenyl, triphenylene, etc., especially phenyl or naphthyl, preferably phenyl. Naphthyl is 1-naphthyl or 2-naphthyl.
在本發明上下文中,C3-C20雜芳基意欲包含單環或多環系統,例如稠合環系統。實例係噻吩基、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、吩噻基、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 present invention, a C 3 -C 20 heteroaryl is intended to include a monocyclic or polycyclic system, such as a fused ring system. Examples are thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, thienyl, furanyl, dibenzofuranyl, Fluorenyl, xanthenyl, thioxanthenyl, phenoxathiol, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, midindenyl, isoindolyl, indolyl , Indazolyl, purinyl, quinazinyl, isoquinolinyl, quinolinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, Porphyrinyl, pyridinyl, carbazolyl, β-fluorinyl, phenanthridyl, acridinyl, naphthylazine, phenanthroline, phenothiyl, isothiazolyl, phenothiazyl , Isoxazolyl, furfuryl, phenoxal, 7-phenanthryl, anthraquinone-2-yl (= 9,10-dioxo-9,10-dihydroanthracen-2-yl), 3 -Benzo [b] thienyl, 5-benzo [b] thienyl, 2-benzo [b] thienyl, 4-dibenzofuryl, 4,7-dibenzofuryl, 4-methyl -7-dibenzofuranyl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl, 2-phenoxanthenyl, 2,7-phenoxanthenyl, 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-indolyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indolyl, 1-methyl-3-indazolyl, 2 , 7-dimethyl-8-purinyl, 2-methoxy-7-methyl-8-purine , 2-quinazinyl, 3-isoquinolinyl, 6-isoquinolinyl, 7-isoquinolinyl, 3-methoxy-6-isoquinolinyl, 2-quinolinyl, 6- Quinolinyl, 7-quinolinyl, 2-methoxy-3-quinolinyl, 2-methoxy-6-quinolinyl, 6-phthalazinyl, 7-phthalazinyl, 1-methoxy -6-phthalazinyl, 1,4-dimethoxy-6-phthalazinyl, 1,8-naphthyridin-2-yl, 2-quinoxalinyl, 6-quinoxalinyl, 2, 3-dimethyl-6-quinoxaline group, 2,3-dimethoxy-6-quinoxaline group, 2-quinazolinyl group, 7-quinazolinyl group, 2-dimethylamino group -6-quinazolinyl, 3- Phenyl, 6- Phenyl, 7- Phenyl, 3-methoxy-7- Phenyl, 2-pyridinyl, 6-pyridinyl, 7-pyridinyl, 6,7-dimethoxy-2-pyridinyl, 2-carbazolyl, 3-carbazolyl, 9- Methyl-2-carbazolyl, 9-methyl-3-carbazolyl, β-fluorin-3-yl, 1-methyl-β-fluorin-3-yl, 1-methyl-β- Perylene-6-yl, 3-phenanthridyl, 2-acridyl, 3-acridyl, 2-naphthylazine, 1-methyl-5-naphthylazine, 5-phenanthroline, 6-phenanthroline, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenthiazinyl , 3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isooxazolyl, 4-isooxazolyl, 5-isooxazolyl, 4-methyl-3-furanyl Group, 2-phenoxa group, 10-methyl-2-phenoxa group and the like.
C3-C20雜芳基尤其為噻吩基、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;尤其為噻吩基。 C 3 -C 20 heteroaryl is especially thienyl, benzo [b] thienyl, thiathranyl, thioxantyl, 1-methyl-2-indolyl or 1-methyl-3-indolyl ; Especially thienyl.
C4-C20雜芳基羰基係經由CO基團連接至分子其餘部分之如上文所定義C3-C20雜芳基。 C 4 -C 20 heteroarylcarbonyl is a C 3 -C 20 heteroaryl group, as defined above, attached to the rest of the molecule via a CO group.
經取代之芳基(苯基、萘基、C6-C20芳基或C5-C20雜芳基)係分別經1至7次、1至6次或1至4次、尤其1次、2次或3次取代。顯而易見,所定義芳基不能具有比芳基環處之自由位置為多之取代基。 Substituted aryl groups (phenyl, naphthyl, C 6 -C 20 aryl or C 5 -C 20 heteroaryl) are 1 to 7 times, 1 to 6 times or 1 to 4 times, especially 1 times, respectively. , 2 or 3 substitutions. Obviously, the defined aryl group cannot have more substituents than there are free positions at the aryl ring.
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 in a 3,4-, 3,4,5-, 2,6-, 2,4-, or 2,4,6-configuration .
間雜1次或多次之經間雜基團間雜(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(顯而易見,間雜原子數取決於擬間雜之C原子數)。經1次或多次取代之經取代基團具有 (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。 Interstitial groups that are interspersed one or more times (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 times or 1 or 2 times (obviously, the number of inter-hetero atoms depends on the number of C atoms to be inter-hetero-hetero). A substituted group substituted 1 or more times has For example, 1 to 7, 1 to 5, 1 to 4, 1 to 3, or 1 or 2 of the same or different substituents.
經一或多個所定義取代基取代之基團意欲具有一個取代基或多個如所給出相同或不同定義之取代基。鹵素係氟、氯、溴及碘,尤其為氟、氯及溴,較佳為氟及氯。若R1及R2、R2及R3、R3及R4或R5及Re、R6及R7、R7及R8彼此獨立地共同為;則形成(例如)以下式(II-a)至式(II-i):
較佳者係式(II-a)。 The preferred formula is (II-a).
式(II)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。亦即上述結構中之一者係以式(II)給出。 Compounds of formula (II) are characterized in that at least one phenyl ring is fused with a carbazole moiety to form a "naphthyl" ring. That is, one of the above structures is given by formula (II).
若R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此獨立地共同為-(CH2)P-Y-(CH2)q-,則形成(例如)諸如、等結構。 If R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7, or R 7 and R 8 independently of each other are-(CH 2 ) P -Y- (CH 2 ) q- , then forming (for example) such as , And other structures.
若苯基或萘基環上之取代基OR17、SR18、SOR18、SO2R18或NR19R20經由基團R17、R18、R19及/或R20與萘基環之一個碳原子形成5員或6員環,則獲得包含3
個或更多個環(包括萘基環)之結構。實例係
若R17形成鍵結至其上具有基團或之苯基或萘基環之一個碳原子之直接鍵,則形成(例如)諸如、結構。 If R 17 forms a bond to a group or A direct bond to a carbon atom of a phenyl or naphthyl ring forms, for example, such as , structure.
若R16係經SR18取代之苯基,其中基團R19表示鍵結至其中附接有COR16基團之咔唑部分之苯基或萘基環的直接鍵,則形成(例如)諸如、
若R19及R20與其所附接之N原子一起形成視情況間雜有O、S或NR17之5員或6員飽和或不飽和環,則形成飽和或不飽和環,例如氮丙啶、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R19及R20與其所附接之N原子一起形成視情況間雜有O、S或NR17之5員或6員飽和或不飽和環,則形成未經間雜或間雜有O或NR17、尤其O之5員或6員飽和環。 If R 19 and R 20 together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring optionally mixed with O, S or NR 17 , then a saturated or unsaturated ring is formed, such as aziridine, Pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, hexahydropyridine or morpholine. Preferably, R 19 and R 20 when appended thereto together with the N atom to which optionally is interrupted by O, S or NR 5, or 6 of 17 membered saturated or unsaturated ring, is formed without interrupted or is interrupted by O Or NR 17 , especially O's 5 or 6 member saturated ring.
若R21及R22與其所附接之N原子一起形成視情況間雜有O、S或NR26之5員或6員飽和或不飽和環,且苯環視情況與該飽和或不飽和環稠合,則形成飽和或不飽和環,例如氮丙啶、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)等。 If R 21 and R 22 together with the attached N atom form a 5- or 6-membered saturated or unsaturated ring optionally mixed with O, S or NR 26 , and the benzene ring is fused with the saturated or unsaturated ring as appropriate , Then form a saturated or unsaturated ring, such as aziridine, pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, hexahydropyridine or morpholine or the corresponding ring (E.g )Wait.
若R19及R20與其所附接之N原子一起形成雜芳香族環系統,則該環系統意欲包含一個以上環(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。適宜雜原子係(例如)N、S、O或P、尤其N、S或O。實例係咔唑、吲哚、異吲哚、吲唑、嘌呤、異喹啉、喹啉、哢啉、吩噻嗪等。 If R 19 and R 20 together with the N atom to which they are attached form a heteroaromatic ring system, the ring system is intended to include more than one ring (e.g., 2 or 3 rings) and one or one from the same species or different species Above heteroatoms. Suitable heteroatom systems are, for example, N, S, O or P, especially N, S or O. Examples are carbazole, indole, isoindole, indazole, purine, isoquinoline, quinoline, oxoline, phenothiazine, and the like.
術語「及/或」或「或/及」在本發明上下文中意欲表達不僅可存在所定義替代物(取代基)中之一者,而且可存在總共若干所定義替代物(取代基),即不同替代物(取代基)之混合物。 The term "and / or" or "or / and" in the context of the present invention is intended to express that not only one of the defined substitutions (substituents) may exist, but also a total of several defined substitutions (substituents), that Mixture of different substitutes (substituents).
術語「至少」意欲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。 The term "at least" is intended to define one or more, such as one or both or three, preferably one or both.
術語「視情況經取代」意指其提及之基團未經取代或經取代。 The term "optionally substituted" means that the group to which it refers is unsubstituted or substituted.
術語「視情況經間雜」意指其提及之基團未經雜或經間雜。 The term "as the case may be" means that the group to which it refers is not or is not.
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。術語「(甲基)丙烯酸酯」在本申請案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 scope of patent applications below, unless the context requires otherwise, the word "comprise" or variations (e.g., "comprises" or "comprising") shall be understood to imply the inclusion of the stated integer or Step or integer group or step group, but does not exclude any other integer or step or integer group or step group. The term "(meth) acrylate" in the context of this application is intended to refer to acrylates and corresponding methacrylates.
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 ones shown in the text used for the compounds of the present invention in the context of the present invention are intended to refer to all categories of patent application scope, that is, to the patent application scope of compositions, uses, methods, color filters, and the like.
式(II)肟酯係藉由文獻中所述方法來製備,例如藉由在以下條件下使相應肟與醯鹵、尤其氯化物或酸酐反應: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。在下文中作為實例,闡述式(II-a)化合物之製備,其中R7係肟酯基團且X係直接鍵係[自適當肟開始實施化合物(II-b)-(II-h)之反應]:
R1、R2、R5、R6、R8、R13、R14及R15係如上文所定義,Hal意指鹵素原子、尤其Cl。 R 1 , R 2 , R 5 , R 6 , R 8 , R 13 , R 14 and R 15 are as defined above, and Hal means a halogen atom, especially Cl.
R14較佳為甲基。 R 14 is preferably methyl.
此等反應為彼等熟習此項技術者所熟知,且通常在-15℃至+50℃、較佳0至25℃之溫度下實施。 These reactions are well known to those skilled in the art and are usually carried out at a temperature of -15 ° C to + 50 ° C, preferably 0 to 25 ° C.
當X係CO時,相應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,酯化係在與上文所述相同之條件下實施:
因此,本發明之標的亦係藉由在鹼或鹼之混合物存在下使相應肟化合物與之醯鹵或之酸酐反應來製備如上文所定義式(IV)化合物之方法,其中Hal係鹵素、尤其Cl,且R14係如上文所定義。 Therefore, the object of the present invention is also to make the corresponding oxime compound and the corresponding oxime compound in the presence of a base or a mixture of bases. Zhi Ling or A method for the reaction of an acid anhydride to prepare a compound of formula (IV) as defined above, wherein Hal is halogen, especially Cl, and R 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 oxime required as a starting material can be obtained through standard chemistry textbooks (such as J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992) or monographs (such as SRSandler & W. Karo, Organic functional group preparations, Section 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 ketone with hydroxylamine or a salt thereof in a polar solvent such as dimethylacetamide (DMA), aqueous DMA, ethanol or aqueous ethanol. 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. It is also possible to use a basic solvent such as pyridine 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 generally 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 intermediates are prepared, for example, by methods described in the literature (e.g. standard chemistry textbooks, e.g. J. March, Advanced Organic Chemistry, 4th edition, Wiley Interscience, 1992). In addition, the continuous Friedel-Crafts reaction can be effectively used for the synthesis of intermediates. These 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 oximes is the use of nitrous acid or alkyl nitrite to "active" methylene 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 (as, for example, Organic Synthesis coll (Vol. V, pages 32 and 373, coll. Vol. III, pages 191 and 513, coll. Vol. II, pages 202, 204 and 363) Suitable for the preparation of oximes used as starting materials in the present invention. Nitrite is generally produced from sodium nitrite. The alkyl nitrite may be, for example, methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite, or isoamyl nitrite.
本發明另一實施例係游離式(IIa)肟化合物:
其中R1、R2、R3、R4、R5、R6、R7及R8彼此獨立地為氫、C1-C20烷基、、COR16、OR17、鹵素、NO2 或;或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7 及R8彼此獨立地為經取代之C2-C10烯基;或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此獨立地共同為-(CH2)P-Y-(CH2)q-;或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7 及R8彼此獨立地共同為;但條件為R1及R2、R2及R3、R3及R4、R5及R6、R6及 R7或R7及R8中至少一對係,R9、R10、R11及R12彼此獨立地為氫、C1-C20烷基,該C1-C20烷基未經取代或經一或多個以下基團取代:鹵素、苯基、CN、OH、SH、C1-C4-烷氧基、(CO)OH或(CO)O(C1-C4烷基); 或R9、R10、R11及R12彼此獨立地為未經取代之苯基或經一或多個以下基團取代之苯基:C1-C6烷基、鹵素、CN、OR17、SR18或NR19R20;或R9、R10、R11及R12彼此獨立地為鹵素、CN、OR17、SR18、SOR18、SO2R18或NR19R20,其中該等取代基OR17、SR18或NR19R20視情況經由基團R17、R18、R19及/或R20與萘基環中一個碳原子形成5員或6員環; 或R9、R10、R11及R12彼此獨立地為、COR16或NO2;Y係O、S、NR26或直接鍵;p係整數0、1、2或3;q係整數1、2或3;X係CO或直接鍵;R13係C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、R17、COOR17、OR17、SR18、CONR19R20、 NR19R20、PO(OCkH2k+1)2或;或R13係C2-C20烷基,其間雜有一或多個O、S、SO、SO2、NR26或CO,或係C2-C12烯基,其未經間雜或間雜有一或多個O、CO或NR26,其中經間雜之C2-C20烷基及未經間雜或經間雜之C2-C12烯基未經取代或經一或多個鹵素取代;或R13係C4-C8環烯基、C2-C12炔基或C3-C10環烷基,其未經間雜或間雜有一或多個O、S、CO或NR26;或R13係苯基或萘基,其各未經取代或經一或多個以下 基團取代:OR17、SR18、NR19R20、、COR16、CN、NO2、鹵素、C1-C20烷基、C1-C4鹵代烷基、C2-C20 烷基,其間雜有一或多個O、S、CO或NR26;或其各經C3-C10環烷基或間雜有一或多個O、S、CO或NR26之C3-C10環烷基取代;k係整數1至10;R15係C6-C20芳基或C3-C20雜芳基,其各未經取代或經一或多個以下基團取代:苯基、鹵素、C1-C4鹵代烷基、CN、NO2、OR17、SR18、NR19R20、PO(OCkH2k+1)2、SO-C1-C10烷基、SO2-C1-C10烷基、間雜有一或多個O、S或NR26之C2-C20烷基;或其各經C1-C20烷基取代,該C1-C20烷基未經取代或經一或多個以下基團取代:鹵素、COOR17、CONR19R20、苯基、C3-C8環烷基、C3-C20雜芳基、C6-C20芳氧基羰基、C3-C20雜芳氧基羰基、OR17、SR18或NR19R20;或R15係氫、C2-C12烯基、C3-C8環烷基,其未經間雜或間雜有一或多個O、CO或NR26;或R15係C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、OR17、SR18、C3-C8環烷基、C3-C20雜芳基、C6-C20芳氧基羰基、C3-C20雜芳氧基羰基、NR19R20、 COOR17、CONR19R20、PO(OCkH2k+1)2、、 、苯基;或該C1-C20烷基經苯基取代,該苯基經鹵素、C1-C20烷基、C1-C4鹵代烷基、OR17、SR18或NR19R20取代;或R15係C2-C20烷基,其間雜有一或多個O、SO或SO2,且該經間雜之C2-C20烷基未經取代或經一或多個以下基團取代:鹵素、OR17、COOR17、CONR19R20、苯基或經OR17、SR18或NR19R20取代之苯基;或R15係C2-C20烷醯基或苯甲醯基,其未經取代或經一或多個以下基團取代:C1-C6烷基、鹵素、苯基、OR17、SR18或NR19R20; 或R15係未經取代或經一或多個OR17取代之萘甲醯基或係C3-C14雜芳基羰基;或R15係C2-C12烷氧基羰基,其未經間雜或間雜有一或多個O且該經間雜或未經間雜之C2-C12烷氧基羰基未經取代或經一或多個羥基取代;或R15係苯氧基羰基,其未經取代或經一或多個以下基團取代:C1-C6烷基、鹵素、C1-C4鹵代烷基、苯基、OR17、SR18或NR19R20;或R15係CN、CONR19R20、NO2、C1-C4鹵代烷基、S(O)m-C1-C6烷基、未經取代或經C1-C12烷基或SO2-C1-C6烷基取代之S(O)m-苯基;或R15係SO2O-苯基,其未經取代或經C1-C12烷基取代;或係二苯基膦醯基或二(C1-C4烷氧基)-膦醯基;m係1或2;R’15具有針對R15所給出含義中之一者;X1係O、S、SO或SO2;X2係O、CO、S或直接鍵;R16係C6-C20芳基或C3-C20雜芳基,其每一者未經取代或經一或多個以下基團取代:苯基、鹵素、C1-C4鹵代烷基、CN、NO2、OR17、SR18、NR19R20或間雜有一或多個O、S或NR26之C1-C20烷基;或其每一者經一或多個C1-C20烷基取代,該C1-C20烷基未經取代或經一或多個以下基團取代:鹵素、COOR17、CONR19R20、苯基、C3-C8環烷基、C3-C20雜芳基、C6-C20芳氧基羰基、C3-C20雜芳氧基羰基、OR17、SR18或NR19R20;或R16係氫、未經取代或經一或多 個以下基團取代之C1-C20烷基:鹵素、苯基、OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)、O(CO)-苯基、(CO)OH或(CO)O(C1-C4烷基);或R16係間雜有一或多個O、S或NR26之C2-C12烷基;或R16係(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C2-C12烯基或C3-C8環烷基;或R16係經SR18取代之苯基,其中基團R18表示鍵結至其中附接有COR16基團之咔唑部分之苯基或萘基環的直接鍵;n係1至20;R17係氫、苯基-C1-C3烷基、C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)、O(CO)-(C2-C4烯基)、O(CO)-苯基、(CO)OH、(CO)O(C1-C4烷基)、SO2-(C1-C4鹵代烷基)、O(C1-C4鹵代烷基)、C3-C20環烷基或間雜有一或多個O之C3-C20環烷基;或R17係C2-C20烷基,其間雜有一或多個O、S或NR26;或R17係(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C1-C8烷醯基、C2-C12烯基、C3-C6烯醯基或C3-C20環烷基,其未經間雜或間雜有一或多個O、S、CO或NR26;或R17係C1-C8烷基-C3-C10環烷基,其未經間雜或間雜有一或多個O; 或R17係苯甲醯基,其未經取代或經一或多個C1-C6烷基、鹵素、OH或C1-C3烷氧基取代;或R17係苯基、萘基或C3-C20雜芳基,其各未經取代或經一或多個以下基團取代:鹵素、OH、C1-C12烷基、C1-C12烷氧基、CN、NO2、苯基-C1-C3烷氧基、苯氧基、C1-C12烷基硫基、苯基硫基、N(C1-C12烷基)2、二苯基-胺基或 ; 或R17形成鍵結至其上具有基團或之苯基或萘基環之一個碳原子之直接鍵;R18係氫、C2-C12烯基、C3-C20環烷基或苯基-C1-C3烷基,其中C2-C12烯基、C3-C20環烷基或苯基-C1-C3烷基未經間雜或間雜有一或多個O、S、CO、NR26或COOR17;或R18係C1-C20烷基,其未經取代或經一或多個以下基團取代:OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C2-C4烯基)、O(CO)-(C1-C4烷基)、O(CO)-苯基或(CO)OR17;或R18係C2-C20烷基,其間雜有一或多個O、S、CO、NR26或COOR17;或R18係(CH2CH2O)nH、(CH2CH2O)n(CO)-(C1-C8烷基)、C2-C8烷醯基或C3-C6烯醯基;或R18係苯甲醯基,其未經取代或經一或多個以下基團取代:C1-C6烷基、鹵素、OH、C1-C4烷氧基或C1-C4烷基硫基;或R18係苯基、萘基或C3-C20雜芳基,其各未經取代或經一或多個以下基團取代:鹵素、C1-C12烷基、C1-C4鹵代烷基、C1-C12烷氧基、CN、NO2、苯基-C1-C3烷氧基、苯氧基、C1-C12烷基硫基、苯基硫基、N(C1-C12烷基)2、二 苯基胺基、(CO)O(C1-C8烷基)、(CO)-C1-C8烷基、 (CO)N(C1-C8烷基)2或。 Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently hydrogen, C 1 -C 20 alkyl, , COR 16 , OR 17 , halogen, NO 2 or ; Or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are independent of each other. Substituted C 2 -C 10 alkenyl; or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7, or R 7 and R 8 are independently common with each other Is-(CH 2 ) P -Y- (CH 2 ) q- ; or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 And R 8 independently of each other are But provided that at least one of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 , R 9 , R 10 , R 11 and R 12 are independently of each other hydrogen, C 1 -C 20 alkyl, the C 1 -C 20 alkyl is unsubstituted or substituted with one or more of the following groups: halogen, Phenyl, CN, OH, SH, C 1 -C 4 -alkoxy, (CO) OH or (CO) O (C 1 -C 4 alkyl); or R 9 , R 10 , R 11 and R 12 Independently of each other are unsubstituted phenyl or phenyl substituted with one or more of the following: C 1 -C 6 alkyl, halogen, CN, OR 17 , SR 18 or NR 19 R 20 ; or R 9 , R 10 , R 11 and R 12 are independently of each other halogen, CN, OR 17 , SR 18 , SOR 18 , SO 2 R 18 or NR 19 R 20 , wherein the substituents OR 17 , SR 18 or NR 19 R 20 optionally forms a 5- or 6-membered ring with one carbon atom in the naphthyl ring via the groups R 17 , R 18 , R 19 and / or R 20 ; or R 9 , R 10 , R 11 and R 12 are independent of each other for , COR 16 or NO 2 ; Y is O, S, NR 26 or direct bond; p is integer 0, 1, 2 or 3; q is integer 1, 2 or 3; X is CO or direct bond; R 13 is C 1- C 20 alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, R 17 , COOR 17 , OR 17 , SR 18 , CONR 19 R 20 , NR 19 R 20 , PO (OC k H 2k + 1 ) 2 or ; Or R 13 is a C 2 -C 20 alkyl group, which is interspersed with one or more O, S, SO, SO 2 , NR 26 or CO, or C 2 -C 12 alkenyl group, which is not interspersed or interspersed with one Or more O, CO or NR 26 in which the interspersed C 2 -C 20 alkyl and unsaturated or interspersed C 2 -C 12 alkenyl are unsubstituted or substituted with one or more halogens; or R 13 is a C 4 -C 8 cycloalkenyl, C 2 -C 12 alkynyl, or C 3 -C 10 cycloalkyl group, which is not interspersed or interspersed with one or more O, S, CO, or NR 26 ; or R 13 Phenyl or naphthyl, each unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 , COR 16 , CN, NO 2 , halogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 2 -C 20 alkyl, interposed with one or more O, S, CO or NR 26 ; each warp or C 3 -C 10 cycloalkyl, or interrupted by one or more O, S, CO or NR 26 of the C 3 -C 10 cycloalkyl; K-based integer from 1 to 10; R 15 lines C 6 - C 20 aryl or C 3 -C 20 heteroaryl, each unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, CN, NO 2 , OR 17 , SR 18 , NR 19 R 20 , PO (OC k H 2k + 1 ) 2 , SO-C 1 -C 10 alkyl, SO 2 -C 1 -C 10 alkyl, interspersed with one or more O, S or C 2 -C 20 alkyl group of NR 26 ; or each C 1 -C 20 alkyl group substituted, the C 1 -C 20 alkyl group is unsubstituted or substituted with one or more of the following groups: halogen, COOR 17 , CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 3 -C 20 heteroaryloxycarbonyl, OR 17 , SR 18 or NR 19 R 20 ; or R 15 is hydrogen, C 2 -C 12 alkenyl, C 3 -C 8 cycloalkyl, which is not interspersed or interspersed with one or more O, CO or NR 26 ; or R 15 C 1 -C 20 alkyl-based, which was used without A substituted or by one or more of the following groups: halo, OR 17, SR 18, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl group, C 3 -C 20 heteroaryloxycarbonyl, NR 19 R 20 , COOR 17 , CONR 19 R 20 , PO (OC k H 2k + 1 ) 2 , , , Phenyl; or the C 1 -C 20 alkyl group is substituted with a phenyl group, the phenyl group is halogen, C 1 -C 20 alkyl group, C 1 -C 4 haloalkyl group, OR 17 , SR 18 or NR 19 R 20 Substituted; or R 15 is a C 2 -C 20 alkyl group, in which one or more O, SO, or SO 2 is interspersed, and the interspersed C 2 -C 20 alkyl group is unsubstituted or substituted by one or more groups Group substitution: halogen, OR 17 , COOR 17 , CONR 19 R 20 , phenyl or phenyl substituted with OR 17 , SR 18 or NR 19 R 20 ; or R 15 is a C 2 -C 20 alkylfluorenyl or benzyl Fluorenyl, which is unsubstituted or substituted with one or more of the following: C 1 -C 6 alkyl, halogen, phenyl, OR 17 , SR 18, or NR 19 R 20 ; or R 15 is unsubstituted or A naphthylmethyl group substituted with one or more OR 17 or a C 3 -C 14 heteroarylcarbonyl group; or R 15 is a C 2 -C 12 alkoxycarbonyl group, which is not interspersed or interspersed with one or more O And the C 2 -C 12 alkoxycarbonyl group is unsubstituted or substituted with one or more hydroxyl groups; or R 15 is a phenoxycarbonyl group which is unsubstituted or substituted with one or more Group substitution: C 1 -C 6 alkyl, halogen, C 1 -C 4 haloalkyl, phenyl, OR 17 , SR 18 or NR 19 R 20 ; or R 15 is CN, CONR 19 R 20 , NO 2 , C 1 -C 4 haloalkyl, S (O) m -C 1 -C 6 alkyl, unsubstituted or C 1 -C 12 alkyl or SO 2 -C 1 -C 6 alkyl substituted S (O) m -phenyl; or R 15 is SO 2 O-phenyl, which is unsubstituted or substituted by C 1 -C 12 Group substitution; or is diphenylphosphinofluorenyl or bis (C 1 -C 4 alkoxy) -phosphinofluorenyl; m is 1 or 2; R '15 has one of the meanings given for R 15 ; X 1 is O, S, SO or SO 2 ; X 2 is O, CO, S or a direct bond; R 16 is C 6 -C 20 aryl or C 3 -C 20 heteroaryl, each of which is not Substituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, CN, NO 2 , OR 17 , SR 18 , NR 19 R 20 or interspersed with one or more O, S or C 1 -C 20 alkyl of NR 26 ; or each of them is substituted by one or more C 1 -C 20 alkyl, the C 1 -C 20 alkyl is unsubstituted or substituted by one or more of the following Substitution: halogen, COOR 17 , CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 3 -C 20 heteroaryl butoxycarbonyl, oR 17, SR 18 or NR 19 R 20; or R 16 lines , Unsubstituted or substituted with one or more of the following radicals C 1 -C 20 alkyl group: halogen, phenyl, OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO) O (C 1 -C 4 alkyl), O (CO)-(C 1 -C 4 alkyl), O (CO) -phenyl, (CO) OH or (CO) O ( (C 1 -C 4 alkyl); or R 16 is a C 2 -C 12 alkyl mixed with one or more O, S or NR 26 ; or R 16 is (CH 2 CH 2 O) n + 1 H, ( CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl), C 2 -C 12 alkenyl or C 3 -C 8 cycloalkyl; or R 16 is phenyl substituted with SR 18 , Where the group R 18 represents a direct bond to a phenyl or naphthyl ring bonded to the carbazole moiety to which the COR 16 group is attached; n is 1 to 20; R 17 is hydrogen, phenyl-C 1 -C 3 alkyl, C 1 -C 20 alkyl, unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO) O (C 1 -C 4 alkyl), O (CO)-(C 1 -C 4 alkyl), O (CO)-(C 2 -C 4 alkenyl), O ( CO) -phenyl, (CO) OH, (CO) O (C 1 -C 4 alkyl), SO 2- (C 1 -C 4 haloalkyl), O (C 1 -C 4 haloalkyl), C or 3 -C 20 cycloalkyl interrupted by one or more of C 3 -C 20 O Alkyl group; R 17, or C 2 -C 20 alkyl-based, have therebetween one or more heteroatoms O, S or NR 26; or R 17 lines (CH 2 CH 2 O) n + 1 H, (CH 2 CH 2 O ) n (CO)-(C 1 -C 8 alkyl), C 1 -C 8 alkyl, C 2 -C 12 alkenyl, C 3 -C 6 alkenyl or C 3 -C 20 cycloalkyl , Which is not interspersed or interspersed with one or more O, S, CO or NR 26 ; or R 17 is a C 1 -C 8 alkyl-C 3 -C 10 cycloalkyl group, which is unstrained or interspersed with one or more O; or R 17 is benzamidine, which is unsubstituted or substituted with one or more C 1 -C 6 alkyl, halogen, OH or C 1 -C 3 alkoxy; or R 17 is phenyl , Naphthyl or C 3 -C 20 heteroaryl, each unsubstituted or substituted with one or more of the following groups: halogen, OH, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, CN, NO 2 , phenyl-C 1 -C 3 alkoxy, phenoxy, C 1 -C 12 alkylthio, phenylthio, N (C 1 -C 12 alkyl) 2 , diphenyl Amino-amino ; Or R 17 forms a bond to a group having or Direct bond of one carbon atom of phenyl or naphthyl ring; R 18 is hydrogen, C 2 -C 12 alkenyl, C 3 -C 20 cycloalkyl or phenyl-C 1 -C 3 alkyl, where C 2- C 12 alkenyl, C 3 -C 20 cycloalkyl or phenyl-C 1 -C 3 alkyl without one or more O, S, CO, NR 26 or COOR 17 ; or R 18 Is a C 1 -C 20 alkyl group, which is unsubstituted or substituted with one or more of the following groups: OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 ( CO) O (C 1 -C 4 alkyl), O (CO)-(C 2 -C 4 alkenyl), O (CO)-(C 1 -C 4 alkyl), O (CO) -phenyl Or (CO) OR 17 ; or R 18 is a C 2 -C 20 alkyl group, which is interspersed with one or more O, S, CO, NR 26 or COOR 17 ; or R 18 (CH 2 CH 2 O) n H , (CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl), C 2 -C 8 alkylfluorenyl or C 3 -C 6 alkenyl; or R 18 benzamyl, It is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, OH, C 1 -C 4 alkoxy, or C 1 -C 4 alkylthio; or R 18 series phenyl, naphthyl or C 3 -C 20 heteroaryl, each of which is unsubstituted or substituted with one or more of the following radicals: halogen, C 1 -C 12 alkyl, C 1 -C 4 Substituted alkyl, C 1 -C 12 alkoxy, CN, NO 2, phenyl -C 1 -C 3 alkoxy, phenoxy, C 1 -C 12 alkylthio, phenylthio, N (C 1 -C 12 alkyl) 2 , diphenylamino, (CO) O (C 1 -C 8 alkyl), (CO) -C 1 -C 8 alkyl, (CO) N (C 1 -C 8 alkyl) 2 or .
R19及R20彼此獨立地為氫、C1-C20烷基、C2-C4羥基烷基、C2-C10烷氧基烷基、C2-C5烯基、C3-C20環烷基、苯基-C1-C3烷基、SO2-(C1-C4鹵代烷基)、C1-C8烷醯基、C1-C8烷醯基氧基、C3-C12烯醯基或苯甲醯基;或R19及R20係苯基、萘基或C3-C20雜芳基,其各未經取代或經一或多個以下基團取代:鹵素、C1-C4鹵代烷基、C1-C20烷氧基、C1-C12烷基、苯甲醯基或C1-C12烷氧基;或R19及R20與其所附接之N原子一起形成未經間雜或間雜有O、S或NR17之5員或6員飽和或不飽和環,且該5員或6員飽和或不飽和環未經取代或經一或多個以下基團取代:C1-C20烷基、C1-C20烷氧基、=O、OR17、SR18、NR21R22、(CO)R23、NO2、鹵素、C1-C4-鹵代烷基、CN、 苯基、或C3-C20環烷基,該C3-C20環烷基未經間雜或間雜有一或多個O、S、CO或NR17;或R19及R20與其所附接之N原子一起形成雜芳香族環系統,該環系統未經取代或經一或多個以下基團取代:C1-C20烷基、C1-C4鹵代烷基、C1-C20烷氧基、=O、OR17、SR18、NR21R22、(CO)R23、 、鹵素、NO2、CN、苯基或C3-C20環烷基,該C3-C20環烷基未經間雜或間雜有一或多個O、S、CO或NR17;R21及R22彼此獨立地為氫、C1-C20烷基、C1-C4鹵代烷基、C3-C10環烷基或苯基;或R21及R22與其所附接之N原子一起形成未經間雜或間雜有O、S或NR26之5員或6員飽和或不飽和環,且該5員或6員飽和或不飽和環未稠合或該5員或6員飽和或不飽和環係與苯環稠合; R23係氫、OH、C1-C20烷基、C1-C4鹵代烷基、間雜有一或多個O、CO或NR26之C2-C20烷基、未經間雜或間雜有O、S、CO或NR26之C3-C20環烷基,或R23係苯基、萘基、苯基-C1-C4烷基、OR17、SR18或NR21R22;R24係(CO)OR17、CONR19R20、(CO)R17;或R24具有針對R19及R20所給出含義中之一者;R25係COOR17、CONR19R20、(CO)R17;或R25具有針對R17所給出含義中之一者;R26係氫、C1-C20烷基、C1-C4鹵代烷基、C2-C20烷基,其間雜有一或多個O或CO;或係苯基-C1-C4烷基、C3-C8環烷基,其未經間雜或間雜有一或多個O或CO;或係(CO)R19;或係苯基,其未經取代或經一或多個以下基團取代:C1-C20烷基、鹵素、C1-C4鹵代烷 基、OR17、SR18、NR19R20或; 但條件為在該分子中存在至少一個基團或 。 R 19 and R 20 are each independently hydrogen, C 1 -C 20 alkyl, C 2 -C 4 hydroxyalkyl, C 2 -C 10 alkoxyalkyl, C 2 -C 5 alkenyl, C 3- C 20 cycloalkyl, phenyl-C 1 -C 3 alkyl, SO 2- (C 1 -C 4 haloalkyl), C 1 -C 8 alkylfluorenyl, C 1 -C 8 alkylfluorenyloxy, C 3 -C 12 alkenyl or benzamidine; or R 19 and R 20 are phenyl, naphthyl, or C 3 -C 20 heteroaryl, each of which is unsubstituted or has one or more of the following groups Substitution: halogen, C 1 -C 4 haloalkyl, C 1 -C 20 alkoxy, C 1 -C 12 alkyl, benzamyl or C 1 -C 12 alkoxy; or R 19 and R 20 with The attached N atoms together form a 5- or 6-membered saturated or unsaturated ring that is not interspersed or interspersed with O, S, or NR 17 , and the 5- or 6-membered saturated or unsaturated ring is unsubstituted or Or more of the following groups substituted: C 1 -C 20 alkyl, C 1 -C 20 alkoxy, = O, OR 17 , SR 18 , NR 21 R 22 , (CO) R 23 , NO 2 , halogen, C 1 -C 4 -haloalkyl, CN, phenyl, Or C 3 -C 20 cycloalkyl, the C 3 -C 20 cycloalkyl has one or more O, S, CO, or NR 17 without interspersed or interspersed; or R 19 and R 20 with the N atom to which it is attached Together form a heteroaromatic ring system that is unsubstituted or substituted with one or more of the following groups: C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 1 -C 20 alkoxy, = O, OR 17 , SR 18 , NR 21 R 22 , (CO) R 23 , , Halogen, NO 2 , CN, phenyl, or C 3 -C 20 cycloalkyl, the C 3 -C 20 cycloalkyl has one or more O, S, CO, or NR 17 uninterspersed or interspersed; R 21 and R 22 is independently of each other hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 3 -C 10 cycloalkyl or phenyl; or R 21 and R 22 together with the N atom to which they are attached Forms a 5- or 6-membered saturated or unsaturated ring without interspersed or interspersed O, S, or NR 26 , and the 5- or 6-membered saturated or unsaturated ring is not fused or the 5- or 6-membered saturated or unsaturated ring saturated ring system is fused with a benzene ring; R 23 type hydrogen, OH, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, interrupted by one or more O, cO or NR C 26 alkoxy of 2 -C 20 , C 3 -C 20 cycloalkyl without meta or hetero, O, S, CO or NR 26 , or R 23 phenyl, naphthyl, phenyl-C 1 -C 4 alkyl, OR 17 , SR 18 or NR 21 R 22 ; R 24 is (CO) OR 17 , CONR 19 R 20 , (CO) R 17 ; or R 24 has one of the meanings given for R 19 and R 20 ; R 25 is COOR 17 , CONR 19 R 20 , (CO) R 17 ; or R 25 has one of the meanings given for R 17 ; R 26 is hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl , C 2 -C 20 alkyl, with one or more O or CO interspersed between them; or phenyl-C 1 -C 4 alkyl, C 3 -C 8 cycloalkyl, without interspersed or interspersed with one or more O Or CO; or (CO) R 19 ; or phenyl, which is unsubstituted or substituted with one or more of the following groups: C 1 -C 20 alkyl, halogen, C 1 -C 4 haloalkyl, OR 17 , SR 18 , NR 19 R 20 or ; Provided that at least one group is present in the molecule or .
針對式(IIa)化合物所定義基團之較佳者對應於如針對如下文所給出式(II)化合物給出者,只是每一所定 義肟酯基團(例如)皆替換為相應游離肟基團 。 Preferred groups defined for compounds of formula (IIa) correspond to those given for compounds of formula (II) as given below, except that each defined oxime ester group (e.g. ) Are replaced by the corresponding free oxime group .
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,本發明亦係關於式(II)化合物之構型異構體之混合物。 Each oxime ester group can exist in two configurations (Z) or (E). Isomers can be separated by conventional methods, but it is also possible to use a mixture of isomers as, for example, a photoinitiator. Accordingly, the present invention also relates to a mixture of configurational isomers of a compound of formula (II).
較佳者係如上文所定義之式(II)化合物,其中R1、R2、R3、R4、R5、R6、R7及R8彼此獨立地為氫、C1-C20烷基、、COR16或NO2,或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7 及R8彼此獨立地共同為;但條件為R1及R2、R2及R3、R3及R4、R5及R6、R6及 R7或R7及R8中至少一對係,X係CO或直接鍵;R13係C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、OR17、SR18、COOR17、CONR19R20或PO(OCkH2k+1)2;或R13係C2-C20烷基,其間雜有一或多個O、S、NR26或CO;或R13係苯基或萘基,此二者未經取代或經一或多個 或COR16取代;R14係C1-C20烷基、苯基或C1-C8烷氧基;R15係苯基、萘基、C3-C20雜芳基,其各未經取代或經一或多個以下基團取代:苯基、鹵素、C1-C4鹵代烷基、OR17、SR18或C2-C20烷基,其間雜有一或多個O或S;或其各經一或多個C1-C20烷基取代,該C1-C20烷基未經取代或經一或多個以下基團取代:鹵素、COOR17、CONR19R20、苯基、C3-C8環烷基、C3-C20雜芳基、C6-C20芳氧基羰基、 C4-C20雜芳氧基羰基、OR17、SR18、NR19R20或PO(OCkH2k+1)2;或R15係C1-C20烷基,其未經取代或經一或多個以下基團取代:OR17、SR18、C3-C8環烷基、C3-C20雜芳基、NR19R20、COOR17、CONR19R20或PO(OCkH2k+1)2;R’14具有針對R14所給出含義中之一者;R’15具有針對R15所給出含義中之一者;R16係苯基,其未經取代或經一或多個以下基團取代:OR17、SR18、NR19R20或間雜有一或多個O、S或NR26之C2-C20烷基,或R16係苯基,其經一或多個C1-C20烷基取代,該C1-C20烷基未經取代或經一或多個以下基團取代:鹵素、COOR17、CONR19R20、苯基、C3-C8環烷基、C3-C20雜芳基、C6-C20芳氧基羰基、C4-C20雜芳氧基羰基、OR17、SR18或NR19R20;或R16係C1-C20烷基,其未經取代或經以下基團取代:鹵素、苯基、OH、SH、CN、C3-C6烯氧基、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)或(CO)O(C1-C4烷基);R17係C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、OCH2CH2(CO)O(C1-C4烷基)、O(C1-C4烷基)、(CO)O(C1-C4烷基)、C3-C20環烷基或間雜有一或多個O之C3-C20環烷基;或R17係C2-C20烷基,其間雜有一或多個O; R18係經(CO)OR17取代之甲基;R19及R20彼此獨立地為氫、苯基、C1-C20烷基、C1-C8烷醯基或C1-C8烷醯基氧基;或R19及R20與其所附接之N原子一起形成雜芳香族環 系統,該環系統未經取代或經取代; 但條件為在該分子中存在至少一個基團 或。 Preferred are compounds of formula (II) as defined above, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently hydrogen, C 1 -C 20 alkyl, , COR 16 or NO 2 , or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 independently of one another are But provided that at least one of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 , X is CO or a direct bond; R 13 is a C 1 -C 20 alkyl group, which is unsubstituted or substituted with one or more of the following groups: halogen, OR 17 , SR 18 , COOR 17 , CONR 19 R 20 or PO (OC k H 2k + 1 ) 2 ; or R 13 is a C 2 -C 20 alkyl group with one or more O, S, NR 26 or CO interposed therebetween; or R 13 is phenyl or naphthyl, both Unsubstituted or one or more Or COR 16 substitution; R 14 is C 1 -C 20 alkyl, phenyl or C 1 -C 8 alkoxy; R 15 is phenyl, naphthyl, C 3 -C 20 heteroaryl, each without Substituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, OR 17 , SR 18 or C 2 -C 20 alkyl, interspersed with one or more O or S; or They are each substituted with one or more C 1 -C 20 alkyl groups, the C 1 -C 20 alkyl group being unsubstituted or substituted with one or more of the following groups: halogen, COOR 17 , CONR 19 R 20 , phenyl , C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 4 -C 20 heteroaryloxycarbonyl, OR 17 , SR 18 , NR 19 R 20 Or PO (OC k H 2k + 1 ) 2 ; or R 15 is a C 1 -C 20 alkyl group, which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , C 3 -C 8 Cycloalkyl, C 3 -C 20 heteroaryl, NR 19 R 20 , COOR 17 , CONR 19 R 20 or PO (OC k H 2k + 1 ) 2 ; R '14 has one of the meanings given for R 14 One; R '15 has one of the meanings given for R 15 ; R 16 is phenyl, which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 Or interspersed with one or more O, S or NR 26 C 2 -C 20 alkyl groups, or R 16 series phenyl, which is substituted with one or more C 1 -C 20 alkyl groups, the C 1 -C 20 alkyl groups Is unsubstituted or substituted with one or more of the following groups: halogen, COOR 17 , CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 4 -C 20 heteroaryloxycarbonyl, OR 17 , SR 18 or NR 19 R 20 ; or R 16 is C 1 -C 20 alkyl, which is unsubstituted or substituted with : Halogen, phenyl, OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 (CO) O (C 1 -C 4 alkyl), O (CO)-(C 1 -C 4 Alkyl) or (CO) O (C 1 -C 4 alkyl); R 17 is C 1 -C 20 alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, OCH 2 CH 2 (CO) O (C 1 -C 4 alkyl), O (C 1 -C 4 alkyl), (CO) O (C 1 -C 4 alkyl), C 3 -C 20 cycloalkyl or interspersed Or C 3 -C 20 cycloalkyl of O; or R 17 is C 2 -C 20 alkyl with one or more O interposed therebetween; R 18 is methyl substituted with (CO) OR 17 ; R 19 and R 20 independently of one another hydrogen, phenyl, C 1 -C 20 alkyl, C 1 -C 8 alkanoyl group or a C 1 -C 8 alkanoyl-yloxy ; Or R 19 and R 20 appended thereto the N atom to form a heteroaromatic ring system with the ring system is unsubstituted or Substitution; provided that at least one group is present in the molecule or .
必須重視如上文所定義之式(II)化合物,其中R1、R2、R5、R6、R7及R8彼此獨立地為氫、、COR16或NO2, R3及R4一起為;R9、R10、R11及R12係氫;X係直接鍵;R13係C1-C20烷基;R14係C1-C20烷基;R15係C1-C20烷基或苯基,其經一或多個OR17或C1-C20烷基取代;R16係苯基,其經一或多個C1-C20烷基或OR17取代;且R17係未經取代或經一或多個鹵素取代之C1-C20烷基或係間雜有一或多個O之C2-C20烷基。 Attention must be paid to compounds of formula (II) as defined above, wherein R 1 , R 2 , R 5 , R 6 , R 7 and R 8 are independently hydrogen, , COR 16 or NO 2 , R 3 and R 4 together are ; R 9 , R 10 , R 11 and R 12 are hydrogen; X is a direct bond; R 13 is C 1 -C 20 alkyl; R 14 is C 1 -C 20 alkyl; R 15 is C 1 -C 20 Alkyl or phenyl substituted with one or more OR 17 or C 1 -C 20 alkyl; R 16 is phenyl substituted with one or more C 1 -C 20 alkyl or OR 17 ; and R 17 based unsubstituted or substituted with one or more of halogen or C 1 -C 20 alkyl interrupted by one or more lines of C 2 -C 20 O-alkyl.
但條件為在該分子中存在至少一個基團。 Provided that at least one group is present in the molecule .
本發明之標的進一步係如上文所定義之式(II)化合物,其中R1、R2、R3、R4、R5、R6、R7及R8彼此獨立地為氫,或R1及R2、R3及R4或R5及R6彼此獨立地共同為 ;但條件為R1及R2、R3及R4或R5及R6中至少一對為 ; 或R2係、COR16、NO2或 或R7係或COR16;R9、R11及R12係氫;R10係氫、OR17或COR16;X係CO或直接鍵;R13係C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、R17、OR17、SR18或PO(OCkH2k+1)2;或R13係C2-C20烷基,其間雜有一或多個O;或R13係苯基;k係整數2;R14係C1-C20烷基或噻吩基;R15係苯基或萘基,其各未經取代或經一或多個OR17或C1-C20烷基取代;或R15係噻吩基、氫、C1-C20烷基,該 C1-C20烷基未經取代或經一或多個以下基團取代:OR17、SR18、C3-C8環烷基、NR19R20或COOR17;或R15係C2-C20烷基,其間雜有SO2;R16係苯基或萘基,其各未經取代或經一或多個以下基團取代:OR17、SR18、NR19R20或C1-C20烷基;或R16係噻吩基;R17係氫、C1-C8烷醯基、C1-C20烷基,其未經取代或經一或多個以下基團:鹵素、O(CO)-(C1-C4烷基)、O(CO)-(C2-C4烯基)或間雜有一或多個O之C3-C20環烷基;或R17係C2-C20烷基,其間雜有一或多個O;R18係C3-C20環烷基、C1-C20烷基,其未經取代或經一或多個OH、O(CO)-(C2-C4烯基)或(CO)OR17取代;或R18係苯基,其未經取代或經一或多個鹵素取代;R19及R20彼此獨立地為C1-C8烷醯基或C1-C8烷醯基氧基;或R19及R20與其所附接之N原子一起形成間雜有O之5員或6員飽和環;但條件為在該分子中存在至少一個基團 。 The subject of the present invention is further a compound of formula (II) as defined above, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently hydrogen, or R 1 And R 2 , R 3 and R 4 or R 5 and R 6 independently of one another are ; Provided that at least one of R 1 and R 2 , R 3 and R 4 or R 5 and R 6 is ; Or R 2 series , COR 16 , NO 2 or Or R 7 series Or COR 16 ; R 9 , R 11 and R 12 are hydrogen; R 10 is hydrogen, OR 17 or COR 16 ; X is CO or a direct bond; R 13 is C 1 -C 20 alkyl, which is unsubstituted or One or more of the following groups are substituted: halogen, R 17 , OR 17 , SR 18 or PO (OC k H 2k + 1 ) 2 ; or R 13 is a C 2 -C 20 alkyl group with one or more O in between Or R 13 is phenyl; k is an integer 2; R 14 is C 1 -C 20 alkyl or thienyl; R 15 is phenyl or naphthyl, each of which is unsubstituted or via one or more OR 17 or C 1 -C 20 alkyl substitution; or R 15 is thienyl, hydrogen, C 1 -C 20 alkyl, which C 1 -C 20 alkyl is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , C 3 -C 8 cycloalkyl, NR 19 R 20 or COOR 17 ; or R 15 is a C 2 -C 20 alkyl with SO 2 interposed therebetween; R 16 is phenyl or naphthyl, each Unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 or C 1 -C 20 alkyl; or R 16 is thienyl; R 17 is hydrogen, C 1 -C 8 Alkyl, C 1 -C 20 alkyl, unsubstituted or via one or more of the following groups: halogen, O (CO)-(C 1 -C 4 alkyl), O (CO)-(C 2- C 4 alkenyl) or interspersed with one or more O 3 C 3 -C 20 cycloalkyl; or R 17 is C 2 -C 20 alkyl with one or more O interposed therebetween; R 18 is C 3 -C 20 cycloalkyl, C 1 -C 20 alkyl Group, which is unsubstituted or substituted with one or more OH, O (CO)-(C 2 -C 4 alkenyl) or (CO) OR 17 ; or R 18 is phenyl, which is unsubstituted or substituted Or more than one halogen substitution; R 19 and R 20 are independently C 1 -C 8 alkylfluorenyl or C 1 -C 8 alkylfluorenyloxy; or R 19 and R 20 are formed together with the N atom to which they are attached 5- or 6-membered saturated rings mixed with O; provided that at least one group is present in the molecule .
本發明化合物之實例係如上文所定義之式(II-a)至式(II-g)化合物。式(II-a)、(II-b)、(II-c)、尤其式(II-a)或(II-c)、或式(II-a)、(II-c)或(II-d)、尤其式(II-a)之化合物令人關注。 Examples of compounds of the invention are compounds of formula (II-a) to formula (II-g) as defined above. Formula (II-a), (II-b), (II-c), especially formula (II-a) or (II-c), or formula (II-a), (II-c) or (II- d) Compounds of formula (II-a) are of particular interest.
舉例而言,R1、R2、R3、R4、R5、R6、R7及R8彼此獨立地為氫、或COR16,或R1及R2、R2及R3、R3及R4或R5及R6、R6及R7、R7及R8彼此獨立地共同為。 For example, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently hydrogen, Or COR 16 or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 or R 5 and R 6 , R 6 and R 7 , R 7 and R 8 independently of one another are .
舉例而言,R3及R4或R1及R2共同為或R3及R4及R5及R6共同為;R3及R4尤其共同為。 For example, R 3 and R 4 or R 1 and R 2 together are Or R 3 and R 4 and R 5 and R 6 together are ; R 3 and R 4 are particularly common .
舉例而言,R1、R5、R6及R8係氫。 For example, R 1 , R 5 , R 6 and R 8 are hydrogen.
R7尤其為氫、或COR16。或R7係或COR16、尤其為。 R 7 is especially hydrogen, Or COR 16 . Or R 7 series Or COR 16 , especially .
R2尤其為,COR16或或R2與R1一起為。R2尤其為COR16。 R 2 is especially , COR 16 or Or R 2 together with R 1 is . R 2 is especially COR 16 .
X較佳為直接鍵。 X is preferably a direct bond.
舉例而言,R9、R10、R11及R12彼此獨立地為氫、C1-C20烷基、未經取代之苯基或經一或多個以下基團取代之苯基:C1-C6烷基、鹵素、OR17或SR18;或R9、R10、R11及R12彼此獨立地為鹵素、OR17、SR18或NR19R20,其中取代基OR17、SR18或NR19R20視情況經由基團R17、R18、R19及/或R20與萘基環之一個碳原子形成5員或6員環;或R9、R10、R11及R12彼此獨立地為或COR16。 For example, R 9 , R 10 , R 11, and R 12 are each independently hydrogen, C 1 -C 20 alkyl, unsubstituted phenyl, or phenyl substituted with one or more of the following groups: C 1- C 6 alkyl, halogen, OR 17 or SR 18 ; or R 9 , R 10 , R 11 and R 12 are independently of each other halogen, OR 17 , SR 18 or NR 19 R 20 , wherein the substituents OR 17 , SR 18 or NR 19 R 20 optionally forms a 5- or 6-membered ring with one carbon atom of the naphthyl ring via the groups R 17 , R 18 , R 19 and / or R 20 ; or R 9 , R 10 , R 11 And R 12 are independent of each other Or COR 16 .
具體而言,舉例而言,R9、R10、R11及R12彼此獨立地為氫、C1-C20烷基、未經取代之苯基或經一或多個以下基團取代之苯基:C1-C6烷基、鹵素、OR17或SR18;或R9、R10、R11及R12彼此獨立地為鹵素、OR17、SR18或NR19R20;或R9、R10、R11及R12彼此獨立地為或COR16。 Specifically, for example, R 9 , R 10 , R 11, and R 12 are each independently hydrogen, C 1 -C 20 alkyl, unsubstituted phenyl, or one substituted with one or more of the following groups Phenyl: C 1 -C 6 alkyl, halogen, OR 17 or SR 18 ; or R 9 , R 10 , R 11 and R 12 are each independently halogen, OR 17 , SR 18 or NR 19 R 20 ; or R 9 , R 10 , R 11 and R 12 are independently of each other Or COR 16 .
舉例而言,R9、R10、R11及R12彼此獨立地為氫、C1-C20烷基、未經取代之苯基或經一或多個C1-C6烷基取代之苯基;或R9、R10、R11及R12彼此獨立地為或COR16。 For example, R 9 , R 10 , R 11, and R 12 are each independently hydrogen, C 1 -C 20 alkyl, unsubstituted phenyl, or one substituted with one or more C 1 -C 6 alkyl. Phenyl; or R 9 , R 10 , R 11 and R 12 are each independently Or COR 16 .
在另一實施例中,舉例而言,R9、R10、R11及R12彼此獨立地為氫、C1-C20烷基、未經取代之苯基或經一 或多個以下基團取代之苯基:C1-C6烷基、鹵素、OR17或SR18;或R9、R10、R11及R12彼此獨立地為鹵素、OR17、SR18或NR19R20,其中取代基OR17、SR18或NR19R20視情況經由基團R17、R18、R19及/或R20與萘基環之一個碳原子形成5員或6員環。 In another embodiment, for example, R 9 , R 10 , R 11, and R 12 are independently of each other hydrogen, C 1 -C 20 alkyl, unsubstituted phenyl, or via one or more of the following groups Group substituted phenyl: C 1 -C 6 alkyl, halogen, OR 17 or SR 18 ; or R 9 , R 10 , R 11 and R 12 are independently halogen, OR 17 , SR 18 or NR 19 R 20 Wherein the substituents OR 17 , SR 18 or NR 19 R 20 optionally form a 5- or 6-membered ring with one carbon atom of the naphthyl ring via the groups R 17 , R 18 , R 19 and / or R 20 .
此外,舉例而言,R9、R10、R11及R12彼此獨立地為氫、C1-C20烷基、未經取代之苯基或經一或多個以下基團取代之苯基:C1-C6烷基、鹵素、OR17或SR18,或R9、R10、R11及R12彼此獨立地為鹵素、OR17、SR18、NR19R20或COR16。 In addition, for example, R 9 , R 10 , R 11, and R 12 are each independently hydrogen, C 1 -C 20 alkyl, unsubstituted phenyl, or phenyl substituted with one or more of the following groups : C 1 -C 6 alkyl, halogen, OR 17 or SR 18 , or R 9 , R 10 , R 11 and R 12 are each independently halogen, OR 17 , SR 18 , NR 19 R 20 or COR 16 .
或舉例而言,R9、R10、R11及R12彼此獨立地為氫、C1-C20烷基、未經取代之苯基或經一或多個以下基團取代之苯基:C1-C6烷基、鹵素、OR17或SR18,或R9、R10、R11及R12彼此獨立地為鹵素、OR17、COR16或NR19R20。 Or, for example, R 9 , R 10 , R 11 and R 12 are independently of each other hydrogen, C 1 -C 20 alkyl, unsubstituted phenyl, or phenyl substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, OR 17 or SR 18 , or R 9 , R 10 , R 11 and R 12 are each independently halogen, OR 17 , COR 16 or NR 19 R 20 .
較佳地,R9、R11及R12係氫且R10係氫、OR17或COR16。 Preferably, R 9 , R 11 and R 12 are hydrogen and R 10 is hydrogen, OR 17 or COR 16 .
R13係(例如)C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、COOR17或CONR19R20;或R13係C2-C20烷基,其間雜有一或多個O、S、SO、SO2、NR26或CO,或係C2-C12烯基,其視情況間雜有一或多個O、CO或NR26,或R13係C3-C10環烷基,其視情況間雜有一或多個O、S、CO、NR26, 或R13係苯基或萘基,此二者未經取代或經一或多個以 下基團取代:OR17、sR18、NR19R20、、COR16、NO2、鹵素、C1-C20烷基、C1-C4鹵代烷基、C2-C20烷基,其間雜有一或多個O;或係C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、R17、COOR17、OR17、SR18、CONR19R20或PO(OCkH2k+1)2;或係C2-C20烷基,其間雜有一或多個O。 R 13 is, for example, a C 1 -C 20 alkyl group, which is unsubstituted or substituted with one or more of the following groups: halogen, COOR 17 or CONR 19 R 20 ; or R 13 is a C 2 -C 20 alkyl group , Interspersed with one or more O, S, SO, SO 2 , NR 26 or CO, or C 2 -C 12 alkenyl, optionally interspersed with one or more O, CO or NR 26 , or R 13 series C 3 -C 10 cycloalkyl, optionally mixed with one or more O, S, CO, NR 26 , or R 13 phenyl or naphthyl, both of which are unsubstituted or have one or more of the following groups Group substitution: OR 17 , sR 18 , NR 19 R 20 , , COR 16 , NO 2 , halogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 2 -C 20 alkyl with one or more O interposed therebetween; or C 1 -C 20 alkyl , Which is unsubstituted or substituted with one or more of the following groups: halogen, R 17 , COOR 17 , OR 17 , SR 18 , CONR 19 R 20 or PO (OC k H 2k + 1 ) 2 ; or C 2 -C 20 alkyl with one or more O interposed therebetween.
此外,R13係(例如)C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、R17、COOR17、OR17、SR18、CONR19R20或PO(OCkH2k+1)2;或係C2-C20烷基,其間雜有一或多個O;或係C2-C12烯基、C3-C10環烷基;或R13係苯基或萘基,此二者未經取代或經一或多個以下基團取代:OR17、SR18、NR19R20、、COR16、NO2、鹵素、C1-C20烷基、C1-C4鹵代烷基、C2-C20烷基,其間雜有一或多個O。 In addition, R 13 is, for example, a C 1 -C 20 alkyl group, which is unsubstituted or substituted with one or more of the following groups: halogen, R 17 , COOR 17 , OR 17 , SR 18 , CONR 19 R 20 or PO (OC k H 2k + 1 ) 2 ; or a C 2 -C 20 alkyl group with one or more O interposed therebetween; or a C 2 -C 12 alkenyl group, a C 3 -C 10 cycloalkyl group; or R 13 based phenyl or naphthyl, both of which unsubstituted or substituted with one or more of the following groups: oR 17, SR 18, NR 19 R 20, , COR 16 , NO 2 , halogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 2 -C 20 alkyl, with one or more O interposed therebetween.
在另一實施例中,R13係(例如)C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、R17、OR17、SR18或PO(OCkH2k+1)2;或係C2-C20烷基,其間雜有一或多個O;或係C2-C12烯基、C3-C10環烷基、苯基或萘基;或R13係(例如)C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、R17、OR17、SR18或PO(OCkH2k+1)2;或係C2-C20烷基,其間雜有一或多個O;或係苯基、C2-C12烯基或C3-C10環烷基;或R13係(例如)C1-C20烷基、苯基、C2-C12烯基或C3-C10環烷基; 或R13係(例如)C1-C20烷基、C2-C12烯基或C3-C10環烷基。 In another embodiment, R 13 is, for example, a C 1 -C 20 alkyl group, which is unsubstituted or substituted with one or more of the following groups: halogen, R 17 , OR 17 , SR 18, or PO (OC k H 2k + 1 ) 2 ; or C 2 -C 20 alkyl with one or more O interposed therebetween; or C 2 -C 12 alkenyl, C 3 -C 10 cycloalkyl, phenyl or naphthyl ; Or R 13 is, for example, a C 1 -C 20 alkyl group, which is unsubstituted or substituted with one or more of the following groups: halogen, R 17 , OR 17 , SR 18, or PO (OC k H2 k + 1 ) 2; or C 2- C 20 alkyl-based, have therebetween one or more O heteroatom; or a phenyl-based, C 2 -C 12 alkenyl or C 3 -C 10 cycloalkyl; or R 13 lines (e.g.) C 1 -C 20 alkyl, phenyl, C 2 -C 12 alkenyl or C 3 -C 10 cycloalkyl; or R 13 series (for example) C 1 -C 20 alkyl, C 2 -C 12 alkenyl Or C 3 -C 10 cycloalkyl.
較佳地,R13係C1-C20烷基,尤其為C1-C8烷基,例如2-乙基己基。 Preferably, R 13 is a C 1 -C 20 alkyl group, especially a C 1 -C 8 alkyl group, such as 2-ethylhexyl.
R14係(例如)氫、C3-C8環烷基、C2-C5烯基、C1-C20烷氧基或C1-C20烷基,其未經取代或經一或多個鹵素或苯基取代;或R14係苯基或萘基,此二者未經取代或經一或多個以下基團取代:C1-C6烷基、C1-C4鹵代烷基、鹵素、OR17、SR18及/或NR19R20;或R14係C3-C5雜芳基,例如噻吩基,或係C1-C8烷氧基、苄氧基或苯氧基。 R 14 is, for example, hydrogen, C 3 -C 8 cycloalkyl, C 2 -C 5 alkenyl, C 1 -C 20 alkoxy, or C 1 -C 20 alkyl, which are unsubstituted or Multiple halogen or phenyl substitution; or R 14 is phenyl or naphthyl, both of which are unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, C 1 -C 4 haloalkyl , Halogen, OR 17 , SR 18 and / or NR 19 R 20 ; or R 14 is a C 3 -C 5 heteroaryl group, such as thienyl, or C 1 -C 8 alkoxy, benzyloxy or phenoxy base.
或R14係(例如)C1-C20烷基,其未經取代或經一或多個鹵素或苯基取代;或R14係C3-C5雜芳基(例如噻吩基)或係未經取代或經取代一或多個以下基團取代之苯基:C1-C6烷基、C1-C4鹵代烷基、鹵素、OR17、SR18及/或NR19R20;或R14係C1-C8烷氧基、苄氧基或苯氧基。 Or R 14 is, for example, a C 1 -C 20 alkyl group, which is unsubstituted or substituted with one or more halogen or phenyl groups; or R 14 is a C 3 -C 5 heteroaryl group (for example, thienyl) or Phenyl, unsubstituted or substituted with one or more of the following: C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, halogen, OR 17 , SR 18 and / or NR 19 R 20 ; or R 14 is C 1 -C 8 alkoxy, benzyloxy or phenoxy.
在另一實施例中,R14表示C1-C20烷基,其未經取代或經苯基取代;或R14係苯基,其未經取代或經一或多個C1-C6烷基取代。 In another embodiment, R 14 represents C 1 -C 20 alkyl, which is unsubstituted or substituted with phenyl; or R 14 is phenyl, which is unsubstituted or substituted with one or more C 1 -C 6 Alkyl substituted.
較佳地,R14係C1-C20烷基、C3-C5雜芳基(例如噻吩基),或係苯基,尤其為C1-C20烷基或噻吩基,尤其為C1-C8烷基。 Preferably, R 14 is C 1 -C 20 alkyl, C 3 -C 5 heteroaryl (such as thienyl), or is phenyl, especially C 1 -C 20 alkyl or thienyl, especially C 1- C 8 alkyl.
R15係(例如)C6-C20芳基或C5-C20雜芳基,其各未經取代或經一或多個以下基團取代:苯基、鹵素、C1-C4鹵代烷基、CN、NO2、OR17、SR18、NR19R20、C1-C20烷基;或R15係氫、C3-C8環烷基,該C3-C8環烷基視情況間雜有一或多個O、CO或NR26;或R15係C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、OR17、C3-C8環烷基、C5-C20雜芳基、C8-C20苯氧基羰基、C5-C20雜芳氧基-羰基、NR19R20、COOR17、 CONR19R20、PO(OCkH2k+1)2、、苯基或經以下基團取代之苯基:鹵素、C1-C20烷基、C1-C4鹵代烷基、OR17或NR19R20;或R15係C2-C20烷基,其間雜有一或多個O、S或SO2,或R15係C2-C20烷醯基、苯甲醯基、C2-C12烷氧基羰基、苯氧基羰基、CONR19R20、NO2或C1-C4鹵代烷基。 R 15 is, for example, a C 6 -C 20 aryl group or a C 5 -C 20 heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkane Group, CN, NO 2 , OR 17 , SR 18 , NR 19 R 20 , C 1 -C 20 alkyl group; or R 15 series hydrogen, C 3 -C 8 cycloalkyl group, the C 3 -C 8 cycloalkyl group Optionally mixed with one or more O, CO or NR 26 ; or R 15 is a C 1 -C 20 alkyl group, which is unsubstituted or substituted with one or more of the following groups: halogen, OR 17 , C 3 -C 8 cycloalkyl, C 5 -C 20 heteroaryl, C 8 -C 20 phenoxycarbonyl, C 5 -C 20 heteroaryloxy-carbonyl, NR 19 R 20 , COOR 17 , CONR 19 R 20 , PO (OC k H 2k + 1 ) 2 , , Phenyl or phenyl substituted by: halogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, OR 17 or NR 19 R 20 ; or R 15 is C 2 -C 20 alkyl , Interspersed with one or more O, S or SO 2 , or R 15 is C 2 -C 20 alkylfluorenyl, benzamidine, C 2 -C 12 alkoxycarbonyl, phenoxycarbonyl, CONR 19 R 20 , NO 2 or C 1 -C 4 haloalkyl.
此外,R15係(例如)氫、C6-C20芳基,尤其為苯基或萘基,其各未經取代或經C1-C12烷基取代;或係C3-C5雜芳基,例如噻吩基;或係C3-C8環烷基、C1-C20烷基,其未經取代或經一或多個以下基團取代:OR17、SR17、C3-C8-環烷基、NR19R20或COOR17;或R15係C2-C20烷基,其間雜有一或多個O或SO2。 In addition, R 15 is, for example, hydrogen, C 6 -C 20 aryl, especially phenyl or naphthyl, each of which is unsubstituted or substituted with C 1 -C 12 alkyl; or is C 3 -C 5 hetero Aryl, such as thienyl; or C 3 -C 8 cycloalkyl, C 1 -C 20 alkyl, which are unsubstituted or substituted with one or more of the following groups: OR 17 , SR 17 , C 3- C 8 - cycloalkyl, NR 19 R 20 or COOR 17; R 15, or C 2 -C 20 alkyl-based, have therebetween one or more heteroatoms O or SO 2.
式(II)化合物令人關注,其中R15係(例如)氫、苯基、萘基,其各未經取代或經C1-C8烷基取代;或R15係噻吩基、C1-C20烷基,其未經取代或經一或多個以下基團取代:OR17、SR17、C3-C8-環烷基、NR19R20或COOR17;或R15係C2-C20烷基,其間雜有一或多個O或SO2。 Compounds of formula (II) are of interest, in which R 15 is, for example, hydrogen, phenyl, naphthyl, each of which is unsubstituted or substituted with C 1 -C 8 alkyl; or R 15 is thienyl, C 1- C 20 alkyl, which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 17 , C 3 -C 8 -cycloalkyl, NR 19 R 20 or COOR 17 ; or R 15 is C 2 -C 20 alkyl with one or more O or SO 2 interspersed therebetween.
R15尤其為(例如)C3-C8環烷基或C1-C20烷基,尤其為C1-C20烷基,尤其為C1-C12烷基。 R 15 is, for example, a C 3 -C 8 cycloalkyl group or a C 1 -C 20 alkyl group, especially a C 1 -C 20 alkyl group, especially a C 1 -C 12 alkyl group.
R’14及R’15之較佳者分別係如上文針對R14及R15所給出者。 R '14 and R' 15 are the preferred lines are as described above for R 14 and R 15 are given.
X1係(例如)O、S或SO,例如O或S,尤其為O。 X 1 is, for example, O, S or SO, such as O or S, especially O.
R16係(例如)C6-C20芳基(尤其苯基或萘基、尤其苯基)或C5-C20雜芳基(尤其噻吩基),其各未經取代或經一或多個以下基團取代:苯基、鹵素、C1-C4鹵代烷基、CN、NO2、OR17、SR18、NR19R20或間雜有一或多個O之C1-C20烷基;或其各經一或多個C1-C20烷基取代,該C1-C20烷基未經取代或經一或多個以下基團取代:鹵素、COOR17、CONR19R20、苯基、C3-C8環烷基、C5-C20雜芳基、C6-C20芳氧基羰基、C5-C20雜芳氧基羰基、OR17、SR18或NR19R20;或R16係氫、C1-C20烷基,該C1-C20烷基未經取代或經一或多個以下基團取代:鹵素、苯基、OH、SH、C3-C6烯氧基、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)、O(CO)-苯基、(CO)OH或(CO)O(C1-C4烷基);或R16係C2-C12烷基,其間雜有一或多個O;或係(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C2-C12烯基或C3-C8環烷基,且n係1至20,例如1至12或1至8,尤其為1或2。 R 16 is, for example, a C 6 -C 20 aryl group (especially phenyl or naphthyl group, especially phenyl group) or a C 5 -C 20 heteroaryl group (especially thienyl group), each of which is unsubstituted or substituted by one or more Substituted by the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, CN, NO 2 , OR 17 , SR 18 , NR 19 R 20 or C 1 -C 20 alkyl interspersed with one or more O; Or each of them is substituted with one or more C 1 -C 20 alkyl groups, the C 1 -C 2 0 alkyl group is unsubstituted or substituted with one or more of the following groups: halogen, COOR 17 , CONR 19 R 20 , Phenyl, C 3 -C 8 cycloalkyl, C 5 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 5 -C 20 heteroaryloxycarbonyl, OR 17 , SR 18 or NR 19 R 20 ; or R 16 is hydrogen, C 1 -C 20 alkyl, the C 1 -C 20 alkyl is unsubstituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, C 3 -C 6 alkenyloxy, OCH 2 CH 2 (CO) O (C 1 -C 4 alkyl), O (CO)-(C 1 -C 4 alkyl), O (CO) -phenyl, (CO ) OH or (CO) O (C 1 -C 4 alkyl); or R 16 is C 2 -C 12 alkyl, with one or more O interposed therebetween; or (CH 2 CH 2 O) n + 1 H , (CH 2 CH 2 O) n (CO) - (C 1 -C 8 alkyl), C 2 -C 12 alkenyl or C 3 -C 8 cycloalkyl Group, and n lines 1 to 20, e.g. 1-12 or 1-8, in particular 1 or 2.
此外,R16係(例如)苯基或萘基,尤其為苯基、噻吩基或咔唑,其各未經取代或經一或多個以下基團取代: 苯基、鹵素、C1-C4鹵代烷基、OR17、SR18、NR19R20或C1-C20烷基;或R16係C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、苯基、OH、SH、C3-C6烯氧基、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)、O(CO)-苯基、(CO)OH或(CO)O(C1-C4烷基);或R16係C2-C12烷基,其間雜有一或多個O;或係(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C2-C12烯基或C3-C8環烷基,且n係1至20,例如1至12或1至8,尤其為1或2。 In addition, R 16 is, for example, phenyl or naphthyl, especially phenyl, thienyl, or carbazole, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4- haloalkyl, OR 17 , SR 18 , NR 19 R 20 or C 1 -C 20 alkyl; or R 16 is C 1 -C 20 alkyl, which is unsubstituted or substituted with one or more of the following groups: Halogen, phenyl, OH, SH, C 3 -C 6 alkenyloxy, OCH 2 CH 2 (CO) O (C 1 -C 4 alkyl), O (CO)-(C 1 -C 4 alkyl) , O (CO) -phenyl, (CO) OH or (CO) O (C 1 -C 4 alkyl); or R 16 is a C 2 -C 12 alkyl group with one or more O interposed therebetween; or (CH 2 CH 2 O) n + 1 H, (CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl), C 2 -C 12 alkenyl or C 3 -C 8 cycloalkyl And n is 1 to 20, such as 1 to 12 or 1 to 8, especially 1 or 2.
此外,R16係(例如)苯基或萘基,尤其為苯基,其各未經取代或經一或多個以下基團取代:苯基、鹵素、C1-C4鹵代烷基、OR17、SR18、NR19R20或C1-C20烷基;或R16係C3-C5雜芳基,尤其為噻吩基。 In addition, R 16 is, for example, phenyl or naphthyl, especially phenyl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, OR 17 , SR 18 , NR 19 R 20 or C 1 -C 20 alkyl; or R 16 is C 3 -C 5 heteroaryl, especially thienyl.
R16尤其為(例如)苯基,其未經取代或經一或多個以下基團取代:OR17、SR18、NR19R20或C1-C20烷基,或R16係噻吩基。 R 16 is, for example, phenyl, which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 or C 1 -C 20 alkyl, or R 16 is thienyl .
較佳地,R16係(例如)苯基或萘基,其各未經取代或經一或多個C1-C20烷基取代。 Preferably, R 16 is, for example, phenyl or naphthyl, each of which is unsubstituted or substituted with one or more C 1 -C 20 alkyl.
R16尤其為苯基,其經一或多個C1-C20烷基取代。 R 16 is especially phenyl, which is substituted with one or more C 1 -C 20 alkyl.
R17係(例如)氫、苯基-C1-C3烷基、C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、OH、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)、 O(CO)-(C2-C4)烯基、O(CO)-苯基、(CO)OH、(CO)O(C1-C4烷基)、C3-C20環烷基或間雜有一或多個O之C3-C20環烷基;或R17係C2-C20烷基,其間雜有一或多個O;係(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C1-C8烷醯基、C2-C12烯基、C3-C6烯醯基或C3-C20環烷基,其視情況間雜有一或多個O;或R17係苯甲醯基,其未經取代或經一或多個C1-C6烷基、鹵素、OH或C1-C3烷氧基取代;或R17係苯基、萘基或C5-C20雜芳基,其各未經取代或經一或多個以下基團取代:鹵素、OH、C1-C12烷基、C1-C12烷氧基、CN、NO2、苯基-C1-C3烷氧基、苯氧基、C1-C12烷基硫基、苯基硫基、N(C1-C12烷基)2、二苯基-胺基或 。 R 17 is, for example, hydrogen, phenyl-C 1 -C 3 alkyl, C 1 -C 20 alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, OH, OCH 2 CH 2 (CO) O (C 1 -C 4 alkyl), O (CO)-(C 1 -C 4 alkyl), O (CO)-(C 2 -C 4 ) alkenyl, O (CO) -benzene group, (CO) OH, (CO ) O (C 1 -C 4 alkyl), C 3 -C 20 cycloalkyl interrupted by one or more O or of C 3 -C 20 cycloalkyl; or R 17 lines C 2 -C 20 alkyl with one or more O interposed between it; (CH 2 CH 2 O) n + 1 H, (CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl) , C 1 -C 8 alkylfluorenyl, C 2 -C 12 alkenyl, C 3 -C 6 alkenyl, or C 3 -C 20 cycloalkyl, optionally mixed with one or more O; or R 17 series Benzamidine, which is unsubstituted or substituted with one or more C 1 -C 6 alkyl, halogen, OH or C 1 -C 3 alkoxy; or R 17 is phenyl, naphthyl or C 5- C 20 heteroaryl, each unsubstituted or substituted with one or more of the following groups: halogen, OH, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, CN, NO 2 , phenyl -C 1 -C 3 alkoxy, phenoxy, C 1 -C 12 alkylthio, phenylthio, N (C 1 -C 12 alkyl) 2 , diphenyl-amino or .
在另一實施例中,R17係(例如)氫、苯基-C1-C3烷基、C1-C20烷基,其未經取代或經一或多個以下基團取代:鹵素、O(CO)-(C1-C4烷基)、O(CO)-(C2-C4烯基)或間雜有一或多個O之C2-C20烷基;或係C1-C8烷醯基、C2-C12烯基、C3-C6烯醯基、間雜有一或多個O之C2-C20烷基、視情況間雜有一或多個O之C3-C20環烷基;或係苯甲醯基,其未經取代或經一或多個以下基團取代:C1-C6烷基、鹵素、OH或C1-C3烷氧基;或係苯基或萘基,其各未經取代或經一或多個以下基團取代:鹵素、C1-C12烷基或C1-C12烷氧基。 In another embodiment, R 17 is, for example, hydrogen, phenyl-C 1 -C 3 alkyl, C 1 -C 20 alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen , O (CO)-(C 1 -C 4 alkyl), O (CO)-(C 2 -C 4 alkenyl), or C 2 -C 20 alkyl interspersed with one or more O; or C 1 -C 8 alkyl, C 2 -C 12 alkenyl, C 3 -C 6 alkenyl, C 2 -C 20 alkyl interspersed with one or more O, optionally C 3 interspersed with one or more O -C 20 cycloalkyl; or a benzoyl group based, which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, OH or C 1 -C 3 alkoxy; Or is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C 1 -C 12 alkyl, or C 1 -C 12 alkoxy.
R17亦為(例如)氫、苯基-C1-C3烷基、C1-C8烷醯基、C1-C20烷基,其未經取代或經一或多個以下基團取 代:鹵素、C3-C20環烷基、O(CO)-(C1-C4烷基)、O(CO)-(C2-C4烯基)或間雜有一或多個O之C2-C20烷基,或R17係C2-C20烷基,其間雜有一或多個O。 R 17 is also, for example, hydrogen, phenyl-C 1 -C 3 alkyl, C 1 -C 8 alkyl, C 1 -C 20 alkyl, which is unsubstituted or via one or more of the following groups Substitution: halogen, C 3 -C 20 cycloalkyl, O (CO)-(C 1 -C 4 alkyl), O (CO)-(C 2 -C 4 alkenyl) or one or more O C 2 -C 20 alkyl, or R 17 is C 2 -C 20 alkyl, with one or more O interposed therebetween.
R17尤其為氫、C1-C8烷醯基、C1-C20烷基,其未經取代或經一或多個以下基團取代:O(CO)-(C1-C4烷基)、O(CO)-(C2-C4烯基)或間雜有一或多個O之C2-C20烷基,或R17係C2-C20烷基,其間雜有一或多個O。 R 17 is especially hydrogen, C 1 -C 8 alkyl, C 1 -C 20 alkyl, which are unsubstituted or substituted with one or more of the following groups: O (CO)-(C 1 -C 4 alkyl ), O (CO)-(C 2 -C 4 alkenyl), or C 2 -C 20 alkyl with one or more O interspersed, or R 17 C 2 -C 20 alkyl with one or more interspersed between A O.
R18係(例如)C3-C20環烷基,其未經間雜或間雜有一或多個O;或R18係C1-C20烷基,其未經取代或經一或多個以下基團取代:OH、O(CO)-(C2-C4)烯基、O(CO)-(C1-C4烷基)或(CO)OR17;或R18係C2-C20烷基,其間雜有一或多個O、S、CO、NR26或COOR17;或R18係C2-C8烷醯基或C3-C6烯醯基、苯甲醯基;或R18係苯基、萘基或C3-C20雜芳基,其各未經取代或經一或多個以下基團取代:鹵素、C1-C12烷基、C1-C4鹵代烷基、C1-C12烷氧基或NO2。 R 18 is, for example, a C 3 -C 20 cycloalkyl group, which is unsaturated or has one or more O; or R 18 is a C 1 -C 20 alkyl group, which is unsubstituted or after one or more Group substitution: OH, O (CO)-(C 2 -C 4 ) alkenyl, O (CO)-(C 1 -C 4 alkyl) or (CO) OR 17 ; or R 18 is C 2 -C 20 alkyl with one or more O, S, CO, NR 26 or COOR 17 interposed therebetween; or R 18 is a C 2 -C 8 alkylfluorenyl or C 3 -C 6 alkenyl, benzamidine; or R 18 is phenyl, naphthyl or C 3 -C 20 heteroaryl, each unsubstituted or substituted with one or more of the following groups: halogen, C 1 -C 12 alkyl, C 1 -C 4 haloalkane Radical, C 1 -C 12 alkoxy or NO 2 .
在另一實施例中,R18係(例如)C3-C20環烷基、C1-C20烷基,其未經取代或經一或多個以下基團取代:OH、O(CO)-(C2-C4烯基)、O(CO)-(C1-C4烷基)或(CO)OR17;或R18係苯基或萘基,其各未經取代或經一或多個鹵素或C1-C12烷基、尤其鹵素取代。 In another embodiment, R 18 is, for example, a C 3 -C 20 cycloalkyl group, a C 1 -C 20 alkyl group, which is unsubstituted or substituted with one or more of the following groups: OH, O (CO )-(C 2 -C 4 alkenyl), O (CO)-(C 1 -C 4 alkyl) or (CO) OR 17 ; or R 18 is phenyl or naphthyl, each of which is unsubstituted or One or more halogen or C 1 -C 12 alkyl, especially halogen substitution.
R18係(例如)C1-C20烷基、C2-C12烯基、C3-C20環烷基、苯基-C1-C3烷基、C2-C8烷醯基、苯甲醯基、苯基或萘基。 R 18- based (for example) C 1 -C 20 alkyl, C 2 -C 12 alkenyl, C 3 -C 20 cycloalkyl, phenyl-C 1 -C 3 alkyl, C 2 -C 8 alkyl , Benzamidine, phenyl or naphthyl.
舉例而言,R18係C1-C20烷基,其經一或多個以下基團取代:OH、O(CO)-(C2-C4烯基)、O(CO)-(C1-C4烷基)或(CO)OR17,或R18係苯基,其經一或多個鹵素取代。 For example, R 18 is a C 1 -C 20 alkyl group, which is substituted with one or more of the following groups: OH, O (CO)-(C 2 -C 4 alkenyl), O (CO)-(C 1- C 4 alkyl) or (CO) OR 17 , or R 18 is phenyl, which is substituted with one or more halogens.
較佳地,R18係C1-C8烷基,其如上文所定義經取代。 Preferably, R 18 is C 1 -C 8 alkyl, which is substituted as defined above.
舉例而言,R19及R20彼此獨立地為氫、C1-C20烷基、C2-C4羥基烷基、C3-C20環烷基、苯基-C1-C3烷基、苯基或萘基、C1-C8烷醯基、C1-C8烷醯基氧基、C3-C12烯醯基或苯甲醯基;或R19及R20與其所附接之N原子一起形成視情況間雜有O、S或NR17之5員或6員飽和或不飽和環;或R19及R20與其所附接之N原子一起形成雜芳香族環系統,該環系統未經取代或經一或多個以下基團取代:C1-C20烷基、C1-C4 鹵代烷基、或。 For example, R 19 and R 20 are independently of each other hydrogen, C 1 -C 20 alkyl, C 2 -C 4 hydroxyalkyl, C 3 -C 20 cycloalkyl, phenyl-C 1 -C 3 alkyl Phenyl, or naphthyl, C 1 -C 8 alkylfluorenyl, C 1 -C 8 alkylfluorenyloxy, C 3 -C 12 alkenyl or benzamyl; or R 19 and R 20 the attached N atom form together optionally interrupted with O, S or NR 5, or 6 of 17 membered saturated or unsaturated ring; or R 19 and R 20 appended thereto the N atom to form a heteroaromatic ring system together, The ring system is unsubstituted or substituted with one or more of the following: C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, or .
此外,舉例而言,R19及R20彼此獨立地為氫、C1-C20烷基、C2-C4羥基烷基、C3-C20環烷基、苯基-C1-C3烷基、C1-C8烷醯基、C1-C8烷醯基氧基、C3-C12烯醯基或苯甲醯基;或R19及R20與其所附接之N原子一起形成視情況間雜有O或NR17之5員或6員飽和環;或R19及R20與其所附接之N原子一起形成咔唑環。 In addition, for example, R 19 and R 20 are independently of each other hydrogen, C 1 -C 20 alkyl, C 2 -C 4 hydroxyalkyl, C 3 -C 20 cycloalkyl, phenyl-C 1 -C 3 alkyl, C 1 -C 8 alkylfluorenyl, C 1 -C 8 alkylfluorenyloxy, C 3 -C 12 alkenyl or benzamyl; or R 19 and R 20 with the N to which it is attached Atoms together form a 5- or 6-membered saturated ring optionally mixed with O or NR 17 ; or R 19 and R 20 together with the N atom to which they are attached form a carbazole ring.
舉例而言,R19及R20彼此獨立地為氫、C1-C20烷基、C2-C4羥基烷基、C3-C20環烷基、苯基-C1-C3烷基、 C1-C8烷醯基、C1-C8烷醯基氧基、C3-C12烯醯基或苯甲醯基;或R19及R20與其所附接之N原子一起形成視情況間雜有O或NR17之5員或6員飽和環。 For example, R 19 and R 20 are independently of each other hydrogen, C 1 -C 20 alkyl, C 2 -C 4 hydroxyalkyl, C 3 -C 20 cycloalkyl, phenyl-C 1 -C 3 alkyl , C 1 -C 8 alkylfluorenyl, C 1 -C 8 alkylfluorenyloxy, C 3 -C 12 alkenyl or benzamyl; or R 19 and R 20 together with the N atom to which they are attached A 5 or 6 member saturated ring with O or NR 17 interspersed as appropriate.
較佳地,R19及R20彼此獨立地為C1-C8烷醯基、C1-C8烷醯基氧基;或R19及R20與其所附接之N原子一起形成嗎啉環。 Preferably, R 19 and R 20 are independently of each other C 1 -C 8 alkylfluorenyl, C 1 -C 8 alkylfluorenyloxy; or R 19 and R 20 together with the N atom to which they are attached form a morpholine ring.
舉例而言,R21及R22彼此獨立地為氫、C1-C20烷基、C1-C4鹵代烷基、C3-C10環烷基或苯基;或R21及R22與其所附接之N原子一起形成嗎啉環。R21及R22尤其彼此獨立地為氫或C1-C20烷基。 For example, R 21 and R 22 are independently of each other hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 3 -C 10 cycloalkyl or phenyl; or R 21 and R 22 and The attached N atoms together form a morpholine ring. R 21 and R 22 are, independently of one another, hydrogen or C 1 -C 20 alkyl.
R23係(例如)氫、OH、苯基或C1-C20烷基。R23尤其為氫、OH或C1-C4烷基。 R 23 is, for example, hydrogen, OH, phenyl or C 1 -C 20 alkyl. R 23 is especially hydrogen, OH or C 1 -C 4 alkyl.
R24之較佳者係如針對R19及R20所給出。R25之較佳者係如針對R17所給出。 The better of R 24 is as given for R 19 and R 20 . The better of R 25 is as given for R 17 .
R26係(例如)氫、C1-C20烷基、C1-C4鹵代烷基、C2-C20烷基,其間雜有一或多個O或CO;或係苯基-C1-C4烷基、C3-C8環烷基,其視情況間雜有一或多個O或CO;或係(CO)R19或苯基,其未經取代或經一或多個以下基團取代:C1-C20烷基、鹵素、C1-C4鹵代烷基、OR17、SR18、NR19R20;或R26表示(例如)氫、C1-C20烷基、C1-C4鹵代烷基;係苯基-C1-C4烷基、C3-C8環烷基、(CO)R19或苯基,其未 經取代或經一或多個C1-C20烷基取代。此外,R26係(例如)氫或C1-C20烷基、尤其為C1-C4烷基。 R 26 is, for example, hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 2 -C 20 alkyl, interposed with one or more O or CO; or phenyl-C 1- C 4 alkyl, C 3 -C 8 cycloalkyl, optionally mixed with one or more O or CO; or (CO) R 19 or phenyl, unsubstituted or through one or more of the following groups Substitution: C 1 -C 20 alkyl, halogen, C 1 -C 4 haloalkyl, OR 17 , SR 18 , NR 19 R 20 ; or R 26 represents, for example, hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl; phenyl-C 1 -C 4 alkyl, C 3 -C 8 cycloalkyl, (CO) R 19 or phenyl, which is unsubstituted or substituted by one or more C 1 -C 20 alkyl substituted. Furthermore, R 26 is, for example, hydrogen or C 1 -C 20 alkyl, especially C 1 -C 4 alkyl.
本發明式(II)化合物之實例係
在一實施例中,前述式(II-1)所示之光起始劑的製備方法如下所述: In one embodiment, the method for preparing the photo-initiator represented by the aforementioned formula (II-1) is as follows:
(1)11-(2-乙基己基)-11H-苯并[a]咔唑之製備: (1) Preparation of 11- (2-ethylhexyl) -11H-benzo [a] carbazole:
首先,將氫化鈉加至溫度為0℃且溶有11H-苯并[a]咔唑之DMF溶液中。於0℃下攪拌1小時後,於0℃下添加1-溴-2-乙基己烷,並於室溫下攪拌過夜。接著,將反應產物傾倒至冰水中。經萃取後,即可製得如下式(II-1-1)所示之11-(2-乙基己基)-11H-苯并[a]咔唑:
(2)1-[11-(2-乙基己基)-5-(2,4,6-三甲基苯甲醯基)-11H-苯并[a]咔唑-8-基]-乙酮之製備: (2) 1- [11- (2-ethylhexyl) -5- (2,4,6-trimethylbenzyl) -11H-benzo [a] carbazole-8-yl] -ethyl Ketone preparation:
將前述所製得之11-(2-乙基己基)-11H-苯并[a]咔唑先溶於0℃之二氯甲烷中。然後,將2,4,6-三甲基苯甲醯氯及氯化鋁加至二氯甲烷溶液中。於室溫下攪拌2.5小時後,降至0℃,並添加乙醯氯及氯化鋁。升溫至室溫並反應攪拌
3小時。接著,將反應產物倒入冰水中,經萃取後,即可製得如下式(II-1-2)所示之1-[11-(2-乙基己基)-5-(2,4,6-三甲基苯甲醯基)-11H-苯并[a]咔唑-8-基]-乙酮:
(3)1-[11-(2-乙基己基)-5-(2,4,6-三甲基苯甲醯基)-11H-苯并[a]咔唑-8-基]-乙酮肟O-乙酸酯之製備: (3) 1- [11- (2-ethylhexyl) -5- (2,4,6-trimethylbenzyl) -11H-benzo [a] carbazole-8-yl] -ethyl Preparation of ketoxime O-acetate:
將前述之1-[11-(2-乙基己基)-5-(2,4,6-三甲基苯甲醯基)-11H-苯并[a]咔唑-8-基]-乙酮溶於甲苯及N-甲基吡咯啶酮中,並升溫至80℃。然後,將乙酸鈉及羥基氯化銨加至前述之溶液中,並升溫至100℃。反應攪拌過夜後,將反應溶液冷卻至0℃,並加入三乙胺及乙醯氯。 Add the aforementioned 1- [11- (2-ethylhexyl) -5- (2,4,6-trimethylbenzyl) -11H-benzo [a] carbazole-8-yl] -ethyl The ketone was dissolved in toluene and N-methylpyrrolidone and heated to 80 ° C. Then, sodium acetate and ammonium hydroxychloride were added to the aforementioned solution, and the temperature was raised to 100 ° C. After the reaction was stirred overnight, the reaction solution was cooled to 0 ° C, and triethylamine and acetamidine were added.
接著,於室溫下反應攪拌2小時後,經萃取濃縮,即可製得粗產物。利用第三丁基甲基醚洗滌此粗產物,即可製得如前述式(II-1)所示之光起始劑。 Next, the reaction was stirred at room temperature for 2 hours, and then extracted and concentrated to obtain a crude product. This crude product is washed with a third butyl methyl ether to obtain a photoinitiator represented by the aforementioned formula (II-1).
上述具有如式(II)所示之結構的光起始劑(E-1)可單獨一種使用或混合複數種使用。 The above-mentioned photoinitiators (E-1) having a structure represented by the formula (II) may be used alone or in combination.
基於前述鹼可溶性樹脂(C)之總使用量為100重量份,該具有如式(II)所示之結構的光起始劑(E-1)之使用量可為5重量份至65重量份,較佳可為10重量份至60重量份,且更佳可為15重量份至55重量份。 Based on the total used amount of the aforementioned alkali-soluble resin (C) being 100 parts by weight, the used amount of the photoinitiator (E-1) having a structure as shown in formula (II) may be 5 to 65 parts by weight It is preferably 10 to 60 parts by weight, and more preferably 15 to 55 parts by weight.
當本發明之光起始劑(E)未包含前述具有如式(II)所示之結構的光起始劑(E-1)時,所製得之彩色濾光片用感光性樹脂組成物具有圖案平滑性不佳之缺陷。 When the photoinitiator (E) of the present invention does not include the aforementioned photoinitiator (E-1) having a structure represented by the formula (II), the obtained photosensitive resin composition for a color filter With the defect of poor pattern smoothness.
其他自由基型光起始劑(E-2)Other radical photoinitiators (E-2)
該其他自由基型光起始劑(E-2)可選自於由苯乙酮系化合物(acetophenone)、二咪唑系化合物(biimidazole)、醯肟系化合物(acyl oxime)或上述光起始劑之任意組合。 The other free radical type photoinitiator (E-2) may be selected from the group consisting of acetophenone, biimidazole, acyl oxime, or the photoinitiator. Any combination.
該苯乙酮系化合物可包含但不限於對二甲胺苯乙酮(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-methylthiophenyl)-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-dimethylamino-1-(4-morpholinophenyl)-1-butanone]。 The acetophenone-based compound may include, but is not limited to, p-dimethylamino-acetophenone, α, α'-dimethoxyazoxy-acetophenone ), 2,2'-dimethyl-2-phenyl-acetophenone (2,2'-dimethyl-2-phenyl-acetophenone), p-methoxy-acetophenone, 2- Methyl-1- (4-methylthiophenyl) -2-morpholino-1-acetone [2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone], 2-benzyl 2--2-nitro, nitro-dimethylamine-1- (4-morpholinophenyl) -1-butanone [2-benzyl-2-N, N-dimethylamino-1- (4-morpholinophenyl) -1 -butanone].
該二咪唑系化合物可選自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’-tetra-phenyl-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]或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]等。 The diimidazole-based compound may be 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'-bis (o-methylphenyl) -4,4', 5,5'-tetraphenyl Diimidazole [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'-tetramethoxyphenyl) -4,4', 5,5'-tetraphenyldiimidazole [2,2'-bis (2,2 ', 4,4' -tetramethoxyphenyl) -4,4 ', 5,5'-tetra-phenyl-biimidazole], 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyldiimidazole [2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-biimidazole] or 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyldiimidazole [2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-biimidazole] and the like.
該醯肟系化合物可選自乙烷酮,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)}、1-[4-(苯基硫代)苯基]-辛烷-1,2-二酮2-(O-苯醯基肟){1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-benzoyloxime)、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-chloro-4-benzyl-thio-benzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime)}。 The oxime compound can be selected from acetone, 1- [9-ethyl-6- (2-methylbenzylidene) -9hydro-carbazole-3-substituent]-, 1- (oxy -Ethanedioxime) {Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyl oxime)}, 1- [4- (benzene Thio) phenyl] -octane-1,2-dione 2- (O-phenylfluorenyloxime) {1- [4- (phenylthio) phenyl] -octane-1,2-dione-2- ( O-benzoyloxime), acetone, 1- [9-ethyl-6- (2-chloro-4-benzyl-thio-benzylidene) -9hydro-carbazole-3-substituent] -, 1- (oxy-acetamoxime) {Ethanone, 1- [9-ethyl -6- (2-chloro-4-benzyl-thio-benzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyl oxime)}.
前述乙烷酮,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)之具體例可為Ciba Specialty Chemicals製造之商品,其型號為CGI-242,且其具有如下式(VI-1)所示之結構:
前述1-[4-(苯基硫代)苯基]-辛烷-1,2-二酮2-(O-苯醯基肟)之具體例可為Ciba Specialty Chemicals製造之商品,其型號為CGI-124,且其具有如下式(VI-2)所示之結構:
前述乙烷酮,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)之具體例可為旭電化公司製造之商品,且其具有如下式(VI-3)所示之結構:
較佳地,該其它自由基型光起始劑(E-2)可為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)或上述化合物之任意組合。 Preferably, the other free radical type photoinitiator (E-2) may be 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-acetone, 2- Benzyl-2-nitro, nitro-dimethylamine-1- (4-morpholinophenyl) -1-butanone, 2,2'-bis (o-chlorophenyl) -4,4 ', 5 , 5'-tetraphenyldiimidazole, acetone, 1- [9-ethyl-6- (2-methylbenzylidene) -9hydro-carbazole-3-substituent]-, 1- (Oxy-acetimoxime) or any combination of the above compounds.
該其他自由基型光起始劑(E-2)可進一步包含噻噸酮(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]或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)或乙醯基(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***(benzoin ethylether)或二苯乙醇酮異丙醚(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(acylphosphine oxide)類化合物;蒽醌(anthraquinone)或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)或三(三氯甲基)-s-三嗪[tris(trichloromethyl)-s-triazine]等之鹵化物;二-第三丁基過氧化物(di-tertbutylperoxide)等之過氧化物。 The other free radical type photoinitiator (E-2) may further include thioxanthone, 2,4-diethyl-thioxanthanone, and thioxanthone-4- Thioxanthone-4-sulfone, benzophenone, 4,4'-bis (dimethylamine) benzophenone [4,4'-bis (dimethylamino) benzophenone], or 4,4'- Bis (diethylamine) benzophenone [4,4'-bis (diethylamino) benzophenone] and other benzophenone compounds; benzil or acetyl and other alpha -Diketone (α-diketone) compounds; acyloin compounds such as benzoin; benzophenone methyl ether (benzoin methylether), benzoin ethylether or benzoin isopropyl ether (acyloin ether) compounds; 2,4,6-trimethylbenzene Diphenylphosphine oxide (2,4,6-trimethyl-benzoyl-diphenyl-phosphineoxide), bis- (2,6-dimethoxyphenylhydrazone) -2,4,4-trimethylphenylphosphine oxide [Bis- (2,6-dimethoxy-benzoyl) -2,4,4-trimethyl-benzyl-phosphineoxide] and other compounds such as acylphosphine oxide; anthraquinone or 1,4-naphthalene Quinones such as 1,4-naphthoquinone; phenacyl chloride, tribromomethyl-phenylsulfone, or tris (trichloromethyl) -s-tri Halides such as tris (trichloromethyl) -s-triazine; peroxides such as di-tertbutylperoxide.
前述之化合物較佳可為二苯甲酮(benzophenone)類化合物,且更佳可為4,4’-雙(二乙胺)二苯甲酮。 The aforementioned compound may preferably be a benzophenone compound, and more preferably may be 4,4'-bis (diethylamine) benzophenone.
上述其它自由基型光起始劑(E-2)可單獨一種使用或混合複數種使用。 The other radical-type photoinitiators (E-2) may be used alone or in combination.
基於前述鹼可溶性樹脂(C)之總使用量為100重量份,該其他自由基型光起始劑(E-2)之使用量可為0重量份至35重量份,較佳可為0重量份至30重量份,且更佳可為0重量份至25重量份。 Based on the total use amount of the aforementioned alkali-soluble resin (C) being 100 parts by weight, the use amount of the other radical-type photoinitiator (E-2) may be 0 parts by weight to 35 parts by weight, and preferably 0 parts by weight Parts to 30 parts by weight, and more preferably 0 to 25 parts by weight.
基於前述鹼可溶性樹脂(C)之總使用量為100重量份,光起始劑(E)之使用量可為5重量份至100重量份,較佳可為10重量份至90重量份,且更佳可為15重量份至80重量份。 Based on the total use amount of the aforementioned alkali-soluble resin (C) being 100 parts by weight, the use amount of the photoinitiator (E) may be 5 to 100 parts by weight, preferably 10 to 90 parts by weight, and More preferably, it may be 15 to 80 parts by weight.
本發明之有機溶劑(F)係指可將顏料(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)及光起始劑(E)溶解,但又不與上述之成分產生反應的有機溶劑。該有機溶劑較佳具有適當之揮發性。 The organic solvent (F) of the present invention means that the pigment (A), the dye (B), the alkali-soluble resin (C), the compound (D) having an ethylenically unsaturated group, and the photoinitiator (E) can be dissolved. An organic solvent that does not react with the above components. The organic solvent preferably has an appropriate volatility.
該有機溶劑(F)可包含但不限於乙二醇甲醚、乙二醇***、二甘醇甲醚、二甘醇***、二甘醇正丙醚、二甘醇正丁醚、三甘醇甲醚、三甘醇***、丙二醇甲醚、丙二醇***、一縮二丙二醇甲醚、一縮二丙二醇***、一縮二丙二醇正丙醚、一縮二丙二醇正丁醚、二縮三丙二醇甲醚(tripropylene glycol monomethyl ether)或二縮三丙二醇***(tripropylene glycol monoethyl ether)等之(聚)亞烷基二醇單烷醚類溶劑;乙二醇單甲醚醋酸酯、乙二醇單***醋酸酯、丙二醇單甲醚醋酸酯或丙二醇單***醋酸酯等之(聚)亞烷基二醇單烷醚醋酸酯類溶劑;二甘醇二甲醚、二甘醇甲***、二甘醇二***或四氫呋喃等之其他醚類溶劑;甲乙烷酮、環己酮、2-庚酮或3-庚酮等之酮類溶劑;2-羥基丙酸甲酯或2-羥基丙酸乙酯等之乳酸烷酯類溶劑;2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙 酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、乙酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯或2-氧基丁酸乙酯等之其他酯類溶劑;甲苯或二甲苯等之芳香族碳氫化合物溶劑;氮-甲基吡咯烷酮、氮,氮-二甲基甲醯胺或氮,氮-二甲基乙醯胺等之羧酸醯胺溶劑。該有機溶劑(F)可單獨一種使用或混合複數種使用。 The organic solvent (F) may include but is not limited to ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, and triethylene glycol methyl ether. , Triethylene glycol ether, propylene glycol methyl ether, propylene glycol ether, dipropylene glycol methyl ether, dipropylene glycol ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol dipropylene glycol (polyglycol monomethyl ether) or tripropylene glycol monoethyl ether, and other (poly) alkylene glycol monoalkyl ether solvents; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol (Poly) alkylene glycol monoalkyl ether acetate solvents such as monomethyl ether acetate or propylene glycol monoethyl ether acetate; diglyme, diethylene glycol diethyl ether, diethylene glycol diethyl ether, or tetrahydrofuran, etc. Other ether solvents; methyl ethyl ketone, cyclohexanone, 2-heptanone or 3-heptanone; ketone solvents; methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate Solvents; methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methoxy Methyl propionate, 3-methoxy propionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate Ethyl acetate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl- 3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate , Ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate Esters or other ester solvents such as ethyl 2-oxybutyrate; aromatic hydrocarbon solvents such as toluene or xylene; nitrogen-methylpyrrolidone, nitrogen, nitrogen-dimethylformamide or nitrogen, nitrogen -A carboxylic acid amine solvent such as dimethylacetamide. These organic solvents (F) can be used alone or in combination.
前述之有機溶劑(F)較佳可為丙二醇單甲醚醋酸酯、3-乙氧基丙酸乙酯或上述溶劑之任意組合。 The aforementioned organic solvent (F) may preferably be propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, or any combination thereof.
基於鹼可溶性樹脂(C)之總使用量為100重量份,該有機溶劑(F)之使用量可為500重量份至5000重量份,較佳可為800重量份至4500重量份,且更佳可為1000重量份至4000重量份。 Based on the total use amount of the alkali-soluble resin (C) being 100 parts by weight, the use amount of the organic solvent (F) may be 500 parts by weight to 5000 parts by weight, preferably 800 parts by weight to 4500 parts by weight, and more preferably It may be 1000 parts by weight to 4000 parts by weight.
在不影響本發明功效之前提下,本發明之彩色濾光片用感光性樹脂組成物可選擇性地包含添加劑(G)。該添加劑(G)可包含填充劑、前述鹼可溶性樹脂(C)以外之聚合物、密著促進劑、抗氧化劑、紫外線吸收劑、防凝集劑或陽離子型聚合性化合物。 Before the effects of the present invention are not affected, the photosensitive resin composition for a color filter of the present invention may optionally contain an additive (G). The additive (G) may contain a filler, a polymer other than the alkali-soluble resin (C), an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent, or a cationic polymerizable compound.
前述填充劑之具體例可包含但不限於玻璃或鋁等。 Specific examples of the filler may include, but are not limited to, glass, aluminum, and the like.
前述聚合物之具體例可包含但不限於聚乙烯醇、聚乙二醇單烷基醚、聚氟丙烯酸烷酯或上述聚合物之任意組合。 Specific examples of the aforementioned polymer may include, but are not limited to, polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, or any combination of the foregoing polymers.
前述密著促進劑之具體例可包含但不限於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或上述化合物之任意組合。 Specific examples of the adhesion promoter may include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, and nitrogen- (2-aminoethyl) ) -3-aminopropylmethyldimethoxysilane, nitrogen- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , 3-glycidyl propyl trimethoxysilane, 3-glycidyl propyl methyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3 -Chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, or a compound thereof Any combination.
前述抗氧化劑之具體例可包含但不限於2,2-硫代雙(4-甲基-6-第三丁基苯酚)、2,6-二-第三丁基苯酚或上述化合物之任意組合。 Specific examples of the foregoing antioxidant may include, but are not limited to, 2,2-thiobis (4-methyl-6-third butylphenol), 2,6-di-third butylphenol, or any combination thereof .
前述紫外線吸收劑之具體例可包含但不限於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(alkoxy phenone)或上述化合物之任意組合。 Specific examples of the aforementioned ultraviolet absorber may include, but are not limited to, 2- (3-thirdbutyl-5-methyl-2-hydroxyphenyl) -5-chlorophenyl azide, and alkoxy phenone ) Or any combination of the above.
前述防凝集劑之具體例可包含但不限於聚丙烯酸鈉(sodium polyacrylate)等。 Specific examples of the anti-aggregation agent may include, but are not limited to, sodium polyacrylate.
前述陽離子型聚合性化合物之具體例可包含但不限於汽巴精化有限公司製造之商品,且其型號可為Irgacure 250或Irgacure 261。 Specific examples of the aforementioned cationic polymerizable compound may include, but are not limited to, products made by Ciba Refining Co., Ltd., and the model may be Irgacure 250 or Irgacure 261.
基於鹼可溶性樹脂(C)之總使用量為100重量份,該添加劑(G)之使用量可為0.1重量份至10重量份,較佳為0.3重量份至7重量份,且更佳可為0.5重量份至4重量份。 Based on the total use amount of the alkali-soluble resin (C) being 100 parts by weight, the use amount of the additive (G) may be 0.1 to 10 parts by weight, preferably 0.3 to 7 parts by weight, and more preferably may be 0.5 to 4 parts by weight.
該彩色濾光片用感光性樹脂組成物的製備是將前述之顏料(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)及有機溶劑(F)放置於攪拌器中攪拌,使其均勻混合成溶液狀態,必要時可選擇性地添加添加劑(G)。 The photosensitive resin composition for a color filter is prepared by adding the aforementioned pigment (A), dye (B), alkali-soluble resin (C), compound (D) having an ethylenically unsaturated group, and a photoinitiator. (E) and organic solvent (F) are placed in a stirrer and stirred to uniformly mix them into a solution state, and additives (G) may be optionally added if necessary.
該彩色濾光片用之感光性樹脂組成物的製備方法沒有特別之限制,其可先將一部份的鹼可溶性樹脂(C)及具有乙烯性不飽和基之化合物(D)分散於一部份之有機溶劑(F)中,以形成分散溶液。然後,混合前述之混合溶液及顏料(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)與有機溶劑(F),即可製得本發明之彩色濾光片用感光性樹脂組成物。 The method for preparing the photosensitive resin composition for the color filter is not particularly limited. It may first disperse a part of the alkali-soluble resin (C) and the compound (D) having an ethylenically unsaturated group in one part. Parts of the organic solvent (F) to form a dispersion solution. Then, the aforementioned mixed solution and the pigment (A), the dye (B), the alkali-soluble resin (C), the compound (D) having an ethylenically unsaturated group, the photoinitiator (E), and the organic solvent (F) are mixed. That is, the photosensitive resin composition for a color filter of the present invention can be obtained.
此外,該彩色濾光片用感光性樹脂組成物可先將一部份之顏料(A)分散於一部份之有機溶劑(F)中,以形成顏料分散液。然後,混合前述之顏料分散液及顏料(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)與有機溶劑(F),即可製得本發明之彩色濾光片用感光性樹脂組成物。其中,前述之顏料(A)之分 散步驟可藉由珠磨機(beads mill)或輥磨機(roll mill)等混合器進行。 In addition, the photosensitive resin composition for a color filter may first disperse a part of the pigment (A) in a part of the organic solvent (F) to form a pigment dispersion liquid. Then, the aforementioned pigment dispersion liquid, pigment (A), dye (B), alkali-soluble resin (C), compound (D) having an ethylenically unsaturated group, a photoinitiator (E), and an organic solvent (F ) To obtain a photosensitive resin composition for a color filter of the present invention. Among them, the aforementioned pigment (A) The dispersing step may be performed by a mixer such as a beads mill or a roll mill.
本發明亦提供一種畫素層及彩色濾光片的形成方法,其係使用上述彩色濾光片用之感光性樹脂組成物來形成畫素層,以下亦將畫素層稱為畫素著色層。 The present invention also provides a pixel layer and a method for forming a color filter. The pixel layer is formed by using the photosensitive resin composition for the color filter. The pixel layer is also referred to as a pixel color layer hereinafter .
本發明亦提供一種彩色濾光片,其係藉由使用上述彩色濾光片的形成方法來製作。 The present invention also provides a color filter, which is manufactured by using the above-mentioned method for forming a color filter.
彩色濾光片的形成方法依序包含塗佈步驟、曝光步驟、顯影步驟、後烤步驟以及濺鍍氧化銦錫(Indium Tin Oxide;ITO)保護膜等步驟。 The method for forming a color filter includes steps including a coating step, an exposure step, a developing step, a post-baking step, and sputtering of an indium tin oxide (ITO) protective film.
前述塗佈步驟係藉由迴轉塗佈、流延塗佈或輥式塗佈等塗佈方式,將前述彩色濾光片用感光性樹脂組成物塗佈於基板上。 The coating step is a method in which the photosensitive resin composition for a color filter is coated on a substrate by a coating method such as spin coating, cast coating, or roll coating.
上述基板可為應用於液晶顯示裝置的無鹼玻璃、鈉鈣玻璃、硬質玻璃(派勒斯玻璃)、石英玻璃,以及附著有透明導電膜的此些玻璃,或者應用於光電變換裝置(如固體攝影裝置)的基板(如:矽基板)。 The above substrates may be alkali-free glass, soda-lime glass, hard glass (Pales glass), quartz glass applied to liquid crystal display devices, and these glasses with a transparent conductive film attached thereto, or they may be applied to photoelectric conversion devices such as solid Photographic device) substrate (such as a silicon substrate).
此外,在基板上塗佈彩色濾光片用感光性樹脂組成物前,基板上須先形成能隔離紅、綠、藍等畫素著色層上遮光用之黑色矩陣(black matrix)。 In addition, before coating a photosensitive resin composition for a color filter on a substrate, a black matrix for shielding light from a pixel colored layer such as red, green, and blue must be formed on the substrate.
進行塗佈步驟後,以減壓乾燥之方式去除彩色濾光片用感光性樹脂組成物中大部分的有機溶劑。然後,以 預烤(pre-bake)方式去除殘餘的有機溶劑,以形成預烤塗膜。 After the coating step is performed, most of the organic solvent in the photosensitive resin composition for a color filter is removed by drying under reduced pressure. And then The pre-bake method removes residual organic solvents to form a pre-bake coating film.
上述減壓乾燥及預烤的操作條件可依各成份的種類、配合比率而異。減壓乾燥一般在0毫米汞柱高至200毫米汞柱高的壓力下進行1秒鐘至60秒鐘,而預烤一般在70℃至110℃下進行1分鐘至15分鐘。 The operating conditions of the above-mentioned reduced-pressure drying and pre-baking may vary depending on the type of each component and the blending ratio. Drying under reduced pressure is generally performed at a pressure of 0 mm Hg to 200 mm Hg for 1 second to 60 seconds, and pre-baking is generally performed at 70 ° C to 110 ° C for 1 minute to 15 minutes.
前述之曝光步驟係藉由具有特定圖案的光罩對上述之預烤塗膜進行曝光。在曝光過程中所使用的光線較佳為g線、h線或i線等之紫外線,且用來提供紫外線的設備可為(超)高壓水銀燈及金屬鹵素燈。 The aforementioned exposure step is to expose the pre-baking coating film by using a photomask having a specific pattern. The light used in the exposure process is preferably ultraviolet rays such as g-line, h-line, or i-line, and the equipment used to provide ultraviolet light may be (ultra-high-pressure) mercury lamps and metal halide lamps.
前述之顯影步驟係將上述經曝光後的預烤塗膜浸漬於溫度為21℃至25℃的顯影液中,進行約15秒至5分鐘的顯影步驟,以去除上述經曝光後之預烤塗膜中不需要的部分,而可形成具有特定圖案的畫素著色層。 The aforementioned developing step is to dip the exposed pre-baking coating film in a developing solution at a temperature of 21 ° C to 25 ° C, and perform a developing step of about 15 seconds to 5 minutes to remove the above-mentioned pre-baking coating after exposure. Unwanted portions of the film can form a pixel-colored layer having a specific pattern.
上述之顯影液可包含由氫氧化鈉、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、呱啶或1,8-二氮雜二環-(5,4,0)-7-十一烯等鹼性化合物所組成之鹼性水溶液。 The developer may include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methyl silicate, ammonia, ethylamine, diethylamine, and dimethyl. Basic compounds such as methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, pyridine, or 1,8-diazabicyclo- (5,4,0) -7-undecene Composition of alkaline aqueous solution.
該顯影液之濃度一般可為0.001重量百分比至10重量百分比,較佳可為0.005重量百分比至5重量百分比,且更佳可為0.01重量百分比至1重量百分比。 The concentration of the developing solution may be generally from 0.001 to 10 weight percent, preferably from 0.005 to 5 weight percent, and more preferably from 0.01 to 1 weight percent.
前述之後烤步驟係利用壓縮空氣或壓縮氮氣乾燥前述具有特定圖案之畫素著色層。然後,利用加熱板或烘 箱等加熱裝置對上述具有特定圖案之畫素著色層進行後烤(post-bake)處理,以固化畫素著色層。該後烤步驟之溫度可為150℃至250℃。若使用加熱板時,其加熱時間為5分鐘至60分鐘。若使用烘箱時,其加熱時間則為15分鐘至150分鐘。 The post-baking step is performed by using compressed air or compressed nitrogen to dry the pixel-colored layer having a specific pattern. Then, use a hot plate or baking A heating device such as a box performs a post-bake process on the pixel-colored layer having the specific pattern to cure the pixel-colored layer. The temperature of the post-baking step may be 150 ° C to 250 ° C. When using a hot plate, the heating time is 5 minutes to 60 minutes. When using an oven, the heating time is 15 minutes to 150 minutes.
重覆上述步驟,依序在基板上形成紅、綠、藍等畫素著色層。 Repeat the above steps to sequentially form pixel, colored layers such as red, green, and blue on the substrate.
前述濺鍍ITO保護膜之步驟係在220℃至250℃之真空環境中,藉由濺鍍製程在前述畫素著色層的表面上形成ITO保護膜,以形成具有畫素層的彩色濾光片。必要時,對該ITO保護膜進行蝕刻與佈線處理,並在ITO保護膜之表面塗佈液晶配向膜。 The aforementioned step of sputtering an ITO protective film is to form an ITO protective film on the surface of the pixel coloring layer by a sputtering process in a vacuum environment of 220 ° C to 250 ° C to form a color filter with a pixel layer. . If necessary, the ITO protective film is subjected to etching and wiring treatment, and a liquid crystal alignment film is coated on the surface of the ITO protective film.
本發明亦提供一種液晶顯示器,且該液晶顯示器包含前述之彩色濾光片。 The present invention also provides a liquid crystal display, and the liquid crystal display includes the aforementioned color filter.
該液晶顯示器是藉由將上述之彩色濾光片及設置有薄膜電晶體(thin film transistor;TFT)的基板作對向配置,並且在上述兩者之間形成間隙(晶胞間隔;cell gap)。然後,以黏著劑貼合彩色濾光片與上述基板的周圍部分並且留下液晶注入孔。接著,藉由液晶注入孔注入液晶,並封住注入孔,以形成液晶層。之後,將偏光板設置在彩色濾光片中相對液晶層的另一側與基板中相對液晶層的另一側,而可製成液晶顯示器。 In the liquid crystal display, the above-mentioned color filter and a substrate provided with a thin film transistor (TFT) are oppositely arranged, and a gap (cell gap) is formed between the two. Then, the color filter and the peripheral portion of the substrate are bonded with an adhesive, and a liquid crystal injection hole is left. Then, liquid crystal is injected through the liquid crystal injection hole, and the injection hole is sealed to form a liquid crystal layer. Thereafter, the polarizing plate is disposed on the other side of the color filter opposite to the liquid crystal layer and the other side of the substrate opposite to the liquid crystal layer, so that a liquid crystal display can be manufactured.
上述之液晶可為液晶化合物或液晶組成物。該液晶沒有特別之限定,且可使用任何一種液晶化合物及液晶組成物。 The liquid crystal may be a liquid crystal compound or a liquid crystal composition. The liquid crystal is not particularly limited, and any liquid crystal compound and liquid crystal composition can be used.
此外,彩色濾光片中所使用的液晶配向膜是用來限制液晶分子的配向,且其沒有特別的限制。 In addition, the liquid crystal alignment film used in the color filter is used to restrict the alignment of liquid crystal molecules, and it is not particularly limited.
以下利用數個實施方式以說明本發明之應用,然其並非用以限定本發明,本發明技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾。 The following uses several embodiments to explain the application of the present invention, but it is not intended to limit the present invention. Those with ordinary knowledge in the technical field of the present invention can make various changes and modifications without departing from the spirit and scope of the present invention. Retouch.
100‧‧‧裝置 100‧‧‧ device
110‧‧‧感光性樹脂層 110‧‧‧ photosensitive resin layer
120‧‧‧偏光板 120‧‧‧polarizing plate
120a‧‧‧方向 120a‧‧‧direction
130‧‧‧偏光板 130‧‧‧polarizing plate
130a‧‧‧方向 130a‧‧‧ direction
140‧‧‧光源 140‧‧‧light source
150‧‧‧輝度計 150‧‧‧ Luminance Meter
200‧‧‧裝置 200‧‧‧ device
210‧‧‧感光性樹脂層 210‧‧‧ photosensitive resin layer
220‧‧‧偏光板 220‧‧‧polarizing plate
220a‧‧‧方向 220a‧‧‧ direction
230‧‧‧偏光板 230‧‧‧Polarizer
230a‧‧‧方向 230a‧‧‧direction
240‧‧‧光源 240‧‧‧ light source
250‧‧‧輝度計 250‧‧‧ Luminance Meter
〔圖1〕係繪示根據本發明之評價方式中之對比度的檢測裝置之立體圖。 [Fig. 1] A perspective view showing a contrast detection device in an evaluation method according to the present invention.
〔圖2〕係繪示根據本發明之評價方式中之對比度的另一檢測裝置之立體圖。 [Fig. 2] A perspective view showing another detection device for contrast in the evaluation method according to the present invention.
以下係根據第1表製備合成例C-1-1至合成例C-1-7之第一鹼可溶性樹脂(C-1)。 The first alkali-soluble resin (C-1) of Synthesis Example C-1-1 to Synthesis Example C-1-7 was prepared in accordance with Table 1.
合成例C-1-1Synthesis Example C-1-1
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(以下簡稱為PGMEA)至四頸錐瓶中,並將溫度升溫至100℃。接著,將3重量份之二甲基-2,2’-[氧雙(亞甲基)]雙-2-丙烯酸酯(以下簡稱為DMOA)、82重量份之苯乙烯(以下簡稱為SM)、10重量份之甲基丙烯酸3,4-環氧環己基甲酯(以下簡稱為ECMMA)及4重量份之2,2’-偶氮雙-2-甲基丁腈(以下簡稱為AMBN)溶於100重量份之PGMEA中,並將此混合溶液於2小時內逐滴滴入四頸錐瓶中。於100℃反應6.5小時後,將15重量份之丙烯酸(以下簡稱為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-1-1之鹼可溶性樹脂(C-1-1)。 A four-necked conical flask was provided with a stirrer, a thermometer, a condenser tube, and a nitrogen inlet, and nitrogen was introduced. Then, 100 parts by weight of propylene glycol was added Methyl ether acetate (hereinafter referred to as PGMEA) was put into a four-necked conical flask, and the temperature was raised to 100 ° C. Next, 3 parts by weight of dimethyl-2,2 '-[oxybis (methylene)] bis-2-acrylate (hereinafter referred to as DMOA) and 82 parts by weight of styrene (hereinafter referred to as SM) 10 parts by weight of 3,4-epoxycyclohexyl methyl methacrylate (hereinafter referred to as ECMMA) and 4 parts by weight of 2,2'-azobis-2-methylbutyronitrile (hereinafter referred to as AMBN) It was dissolved in 100 parts by weight of PGMEA, and the mixed solution was dropped into a four-necked conical flask dropwise within 2 hours. After reacting at 100 ° C for 6.5 hours, 15 parts by weight of acrylic acid (hereinafter referred to as AA) was added to a four-necked conical flask filled with nitrogen, and the temperature was raised to 110 ° C. After 6 hours of reaction, the alkali-soluble resin (C-1-1) of Synthesis Example C-1-1 was obtained.
合成例C-1-2至合成例C-1-7Synthesis Example C-1-2 to Synthesis Example C-1-7
合成例C-1-2至合成例C-1-7係使用與合成例C-1-1之第一鹼可溶性樹脂的製作方法相同之製備方法,不同之處在於合成例C-1-2至合成例C-1-7係改變第一鹼可溶性樹脂中原料的種類及使用量,其配方分別如第1表所示,此處不另贅述。 Synthesis Example C-1-2 to Synthesis Example C-1-7 use the same preparation method as that of the first alkali-soluble resin of Synthesis Example C-1-1, except for Synthesis Example C-1-2 To Synthesis Example C-1-7, the types and amounts of raw materials in the first alkali-soluble resin were changed, and their formulations are shown in Table 1, respectively, and will not be repeated here.
合成例C-2-1Synthesis Example C-2-1
將100重量份的芴環氧化合物(新日鐵化學製造,且型號為ESF-300;環氧當量為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的四頸燒瓶中,且入料速度控制為每分鐘25 重量份,並將溫度維持在100℃至110℃。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 a rhenium epoxy compound (manufactured by Nippon Steel Chemical Co., Ltd. and model ESF-300; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, Parts by weight of 2,6-di-tert-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 to 25 per minute Parts by weight, and the temperature is maintained at 100 ° C to 110 ° C. After 15 hours of reaction, a pale yellow transparent mixed solution having a solid content concentration of 50% by weight was obtained.
接著,將100重量份的上述混合液溶解於25重量份的乙二醇***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1623之合成例C-2-1的第二鹼可溶性樹脂(C-2-1)。 Next, 100 parts by weight of the above mixed solution was dissolved in 25 parts by weight of ethylene glycol ether acetate, and 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of benzophenone tetracarboxylic dianhydride were added at the same time. And heated to 110 ° C to 115 ° C. After the reaction for 2 hours, the second alkali-soluble resin (C-2-1) of Synthesis Example C-2-1 having an acid value of 98.0 mgKOH / g and a number average molecular weight of 1623 was obtained.
合成例C-2-2Synthesis Example C-2-2
將100重量份的芴環氧化合物(新日鐵化學製造,且型號為ESF-300;環氧當量為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的四頸燒瓶中,且入料速度控制為每分鐘25重量份,並將溫度維持在100℃至110℃。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 a rhenium epoxy compound (manufactured by Nippon Steel Chemical Co., Ltd. and model ESF-300; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 Parts by weight of 2,6-di-tert-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 to 25 parts by weight per minute, and the temperature was controlled. Maintained at 100 ° C to 110 ° C. After 15 hours of reaction, a pale yellow transparent mixed solution having a solid content concentration of 50% by weight was obtained.
接著,將100重量份的上述混合液溶解於25重量份的乙二醇***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小時後,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2162之合成例C-2-2的第二鹼可溶性樹脂(C-2-2)。 Next, 100 parts by weight of the above-mentioned mixed solution was dissolved in 25 parts by weight of ethylene glycol ether acetate, and 13 parts by weight of benzophenonetetracarboxylic dianhydride was added at the same time. After reacting at 90 ° C to 95 ° C for 2 hours, adding 6 parts by weight of tetrahydrophthalic anhydride and reacting at 90 ° C to 95 ° C for 4 hours, an acid value of 99.0 mgKOH / g and an average number can be obtained. The second alkali-soluble resin (C-2-2) of Synthesis Example C-2-2 having a molecular weight of 2162.
合成例C-2-3Synthesis Example C-2-3
將400重量份的環氧化合物(日本化藥(株)製造,且型號為NC-3000;環氧當量為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2589之合成例C-2-3的第二鹼可溶性樹脂(C-2-3)。 400 parts by weight of an epoxy compound (manufactured by Nippon Kayaku Co., Ltd. and model number NC-3000; epoxy equivalent weight is 288), 102 parts by weight of acrylic acid, 0.3 parts by weight of methoxyphenol, 5 Part 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 intermediate product having an acid value of 2.2 mgKOH / g was obtained. Next, 151 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain Synthesis Example C-2-3 with an acid value of 102 mgKOH / g and a number average molecular weight of 2589. The second alkali-soluble resin (C-2-3).
以下係根據第1表製備合成例C’-1-1及合成例C’-1-2之其他鹼可溶性樹脂(C’-1)。 In the following, other alkali-soluble resins (C'-1) of Synthesis Example C'-1-1 and Synthesis Example C'-1-2 were prepared according to Table 1.
合成例C’-1-1Synthesis Example C’-1-1
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(以下簡稱為PGMEA)至四頸錐瓶中,並將溫度升溫至100℃。接著,將70重量份之甲基丙烯酸-2-羥基乙酯(以下簡稱為HEMA)、5重量份之甲基丙烯酸2-甲基環氧丙酯(以下簡稱為MGMA)、及4.5重量份之AMBN溶於100重量份之PGMEA中,並將此混合溶液於2小時內逐滴滴入四頸錐瓶中。於105℃反應6小時後,將15重量份之2-甲基丙烯醯乙氧基丁二酸酯(以下簡稱為HOMS)及15重量份之 甲基丙烯酸(以下簡稱為MAA)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’-1-1之鹼可溶性樹脂(C’-1-1)。 A four-necked conical flask was provided with a stirrer, a thermometer, a condenser tube, and a nitrogen inlet, and nitrogen was introduced. Then, 100 parts by weight of propylene glycol methyl ether acetate (hereinafter referred to as PGMEA) was added to a four-necked conical flask, and the temperature was raised to 100 ° C. Next, 70 parts by weight of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA), 5 parts by weight of 2-methylepoxypropyl methacrylate (hereinafter referred to as MGMA), and 4.5 parts by weight AMBN was dissolved in 100 parts by weight of PGMEA, and the mixed solution was dropped into a four-necked conical flask dropwise within 2 hours. After reacting at 105 ° C for 6 hours, 15 parts by weight of 2-methacrylic acid ethoxysuccinate (hereinafter referred to as HOMS) and 15 parts by weight of Methacrylic acid (hereinafter referred to as MAA) was added to a four-necked conical flask filled with nitrogen, and the temperature was increased to 110 ° C. After 6 hours of reaction, the alkali-soluble resin (C'-1-1) of Synthesis Example C'-1-1 was obtained.
合成例C’-1-2Synthesis Example C’-1-2
合成例C’-1-2係使用與合成例C’-1-1之其他鹼可溶性樹脂的製作方法相同之製備方法,不同之處在於合成例C’-1-2係改變其他鹼可溶性樹脂中原料的種類及使用量,其配方如第1表所示,此處不另贅述。 Synthesis Example C'-1-2 uses the same preparation method as that of other alkali-soluble resins in Synthesis Example C'-1-1. The difference is that Synthesis Example C'-1-2 uses other alkali-soluble resins. The type and amount of raw materials used in the formula are shown in Table 1 and will not be repeated here.
以下係根據第2表製備實施例1至實施例12及比較例1至比較例5之彩色濾光片用感光性樹脂組成物。 The photosensitive resin compositions for color filters of Examples 1 to 12 and Comparative Examples 1 to 5 are prepared according to Table 2 below.
實施例1Example 1
將50重量份之C.I.顏料紅254(以下簡稱為A-1)、15重量份之C.I.酸性紅37(以下簡稱為B-2-1)、100重量份前述合成例C-1-1之鹼可溶性樹脂(C-1-1)、20重量份之EO改質之三丙烯酸三羥甲基丙酯(以下簡稱為D-1)及30重量份之具有如式(II-1)所示之結構的光起始劑(以下簡稱為E-1-1)加至1500重量份之3-乙氧基丙酸乙酯(以下簡稱為F-1)中,並以搖動式攪拌器(shaking type stirrer)攪拌均勻後,即可製得實施例1之彩色濾光片用感光性樹脂組成物。所得之彩色濾光片用感光性樹脂組成物以下列之評價方式進行評價,其結果如第2表所示,其中泡狀之顯示缺陷、圖案平滑性及對比度之評價方法容後再述。 50 parts by weight of CI Pigment Red 254 (hereinafter referred to as A-1), 15 parts by weight of CI Acid Red 37 (hereinafter referred to as B-2-1), and 100 parts by weight of the base of the aforementioned Synthesis Example C-1-1 Soluble resin (C-1-1), 20 parts by weight of EO modified trimethylolpropyl triacrylate (hereinafter abbreviated as D-1) and 30 parts by weight of the compound having the formula (II-1) A structured photoinitiator (hereinafter abbreviated as E-1-1) was added to 1500 parts by weight of ethyl 3-ethoxypropionate (hereinafter abbreviated as F-1), and a shaking type (shaking type After stirrer), the photosensitive resin composition for a color filter of Example 1 can be obtained. The obtained photosensitive resin composition for a color filter was evaluated by the following evaluation methods. The results are shown in Table 2. The evaluation methods of the bubble-like display defects, pattern smoothness, and contrast will be described later.
實施例2至12及比較例1至5Examples 2 to 12 and Comparative Examples 1 to 5
實施例2至實施例12及比較例1至比較例5係使用與實施例1之彩色濾光片用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至實施例12及比較例1至比較例5係改變彩色濾光片用感光性樹脂組成物中原料的種類及使用量,其配方及評價結果分別如第2表所示,此處不另贅述。 Examples 2 to 12 and Comparative Examples 1 to 5 use the same production method as the method for producing the photosensitive resin composition for a color filter of Example 1, except that Examples 2 to Examples are different. 12 and Comparative Examples 1 to 5 change the types and amounts of raw materials in the photosensitive resin composition for color filters, and their formulations and evaluation results are shown in Table 2, respectively, and are not repeated here.
將利用前述實施例1至實施例12及比較例1至比較例5所製成之液晶顯示元件放置於溫度為100℃且相對濕度為95%之環境中,以肉眼觀察泡狀之顯示缺陷出現之時間t,並依據以下基準進行評價:◎:500小時<t;○:400小時<t≦500小時;△:300小時<t≦400小時;×:t≦300小時。 The liquid crystal display elements prepared by using the foregoing Examples 1 to 12 and Comparative Examples 1 to 5 were placed in an environment having a temperature of 100 ° C and a relative humidity of 95%, and the appearance of bubble-like display defects was observed with the naked eye. The time t is evaluated based on the following criteria: ◎: 500 hours <t; ○: 400 hours <t ≦ 500 hours; △: 300 hours <t ≦ 400 hours; ×: t ≦ 300 hours.
將實施例1至實施例12及比較例1至比較例5之彩色濾光片用感光性樹脂組成物以旋轉塗佈的方式,塗佈在具有SiO2膜之鈉玻璃基板上,並於90℃預烤100秒,以形成一膜厚為2.5μm之預烤塗膜。接著,待基板冷卻至室溫後,再介入光罩並使用包含365nm、405nm及436nm之波 長的高壓水銀燈進行照射,該照射量為400J/m2。然後將基板浸漬於23℃的0.04wt%之氫氧化鉀水溶液1分鐘進行顯影。接著用純水洗淨基板並風乾,再於220℃的烘箱內烘烤30分鐘而得到畫素著色層。 The photosensitive resin compositions for color filters of Examples 1 to 12 and Comparative Examples 1 to 5 were spin-coated on a soda glass substrate having a SiO 2 film, and were applied at 90 ° C. Pre-bake at 100 ° C for 100 seconds to form a pre-bake coating film with a film thickness of 2.5 μm. Then, after the substrate is cooled to room temperature, the photomask is introduced and irradiated with a high-pressure mercury lamp including wavelengths of 365 nm, 405 nm, and 436 nm, and the irradiation amount is 400 J / m 2 . Then, the substrate was immersed in a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute for development. Then, the substrate was washed with pure water and air-dried, and then baked in an oven at 220 ° C. for 30 minutes to obtain a pixel-colored layer.
然後,以Digital Instruments公司製造之原子力顯微鏡量測該畫素著色層之表面的表面粗度,並依據以下基準進行評價:◎:表面粗度<40Å;○:40Å≦表面粗度<50Å;△:50Å≦表面粗度<60Å;×:60Å≦表面粗度。 Then, the surface roughness of the surface of the pixel colored layer was measured with an atomic force microscope manufactured by Digital Instruments, and evaluated according to the following criteria: ◎: Surface roughness <40Å; ○: 40Å ≦ Surface roughness <50Å; △ : 50Å ≦ surface roughness <60Å; ×: 60Å ≦ surface roughness.
將實施例1至實施例12及比較例1至比較例5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100mJ/cm2的紫外光(曝光機為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235℃進行後烤製程。經過30分鐘後,即可在玻璃基板上形成膜厚為2.0μm之感光性樹脂層。 The photosensitive resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 5 were spin-coated on a glass substrate having a size of 100 mm × 100 mm. Then, it was dried under reduced pressure at a pressure of 100 mmHg and a time of 30 seconds. Next, a pre-baking process is performed. The temperature is 80 ° C. and the time is 2 minutes, and a pre-baking coating film with a film thickness of 2.5 μm can be formed. After the pre-baking process, the pre-bake coating film is irradiated with ultraviolet light (exposure machine: Canon PLA-501F) with an energy of 100 mJ / cm 2 , and the pre-bake coating film after exposure is immersed in a developing solution at 23 ° C. After 1 minute, the coating film was washed with pure water, and a post-baking process was performed at 235 ° C. After 30 minutes, a photosensitive resin layer having a film thickness of 2.0 μm was formed on the glass substrate.
將前述膜厚約2.0μm的感光性樹脂層,以圖1及圖2所繪示之檢測裝置來量測感光性樹脂層之輝度值,並 計算輝度之比值。於圖1之檢測裝置100中,上述製得之感光性樹脂層110係設置於兩枚偏光板120及130之間,從光源140所發射出來的光依序穿透過偏光板120、感光性樹脂層110及偏光板130。然後,利用輝度計150(Topcon公司製,型號為BM-5A)量測穿透過偏光板130之光的輝度值(cd/cm2)。 The photosensitive resin layer with a thickness of about 2.0 μm was measured with the detection device shown in FIG. 1 and FIG. 2 to measure the brightness value of the photosensitive resin layer, and the brightness ratio was calculated. In the detection device 100 of FIG. 1, the above-mentioned photosensitive resin layer 110 is disposed between two polarizing plates 120 and 130, and the light emitted from the light source 140 sequentially passes through the polarizing plate 120 and the photosensitive resin. Layer 110 and polarizing plate 130. Then, the luminance value (cd / cm 2 ) of the light passing through the polarizing plate 130 was measured with a luminance meter 150 (manufactured by Topcon, model: BM-5A).
其中,偏光板120的偏光方向120a係平行於偏光板130的偏光方向130a,且利用圖1之裝置100所測得之輝度值為A。圖2所繪示之檢測裝置200大致上與第1圖所繪示之檢測裝置100相同,不同的是檢測裝置200中之偏光板220之偏光方向220a係垂直於偏光板230之偏光方向230a,且利用裝置200所測得之輝度值為B。 Wherein, the polarization direction 120 a of the polarizing plate 120 is parallel to the polarization direction 130 a of the polarizing plate 130, and the luminance value measured by the apparatus 100 of FIG. 1 is A. The detection device 200 shown in FIG. 2 is substantially the same as the detection device 100 shown in FIG. 1, except that the polarization direction 220 a of the polarizing plate 220 in the detection device 200 is perpendicular to the polarization direction 230 a of the polarizing plate 230. And the luminance value measured by the apparatus 200 is B.
接著,以下式(VII)計算感光性樹脂組成物之對比度,並依據以下基準進行評價:
◎:3500≦對比度;○:3300≦對比度<3500;△:3000≦對比度<3300;×:對比度<3000。 ◎: 3500 ≦ contrast; ○: 3300 ≦ contrast <3500; △: 3000 ≦ contrast <3300; ×: contrast <3000.
由第2表之結果可知,當本發明之鹼可溶性樹脂(C)的第一鹼可溶性樹脂(C-1)不包含具有如式(I-1)所示之結構的乙烯性不飽和單體(c-1-1)時,所製得之彩色濾光片用感光性樹脂組成物會具有泡狀之顯示缺陷。 As is clear from the results in Table 2, when the first alkali-soluble resin (C-1) of the alkali-soluble resin (C) of the present invention does not contain an ethylenically unsaturated monomer having a structure represented by the formula (I-1) In the case of (c-1-1), the obtained photosensitive resin composition for a color filter may have bubble-like display defects.
當光起始劑(E)不包含具有如式(II)所示之結構的光起始劑(E-1)時,所製得之彩色濾光片用感光性樹脂組成物具有圖案平滑性不佳之缺陷。 When the photoinitiator (E) does not include a photoinitiator (E-1) having a structure represented by the formula (II), the obtained photosensitive resin composition for a color filter has pattern smoothness. Poor flaws.
其次,當本發明之染料(B)包含具有如式(V)所示之結構的呫噸系染料(B-1)時,該彩色濾光片用感光性樹脂組成物具有較佳之對比度。 Next, when the dye (B) of the present invention contains a xanthene-based dye (B-1) having a structure represented by the formula (V), the photosensitive resin composition for a color filter has better contrast.
再者,當該具有如式(I-1)所示之結構的乙烯性不飽和單體(c-1-1)之使用量為前述之範圍時,該彩色濾光片用感光性樹脂組成物經微影製程後,所形成之畫素著色層則具有較佳之耐濺鍍性,且更不易具有泡狀之顯示缺陷。 When the amount of the ethylenically unsaturated monomer (c-1-1) having the structure represented by the formula (I-1) is within the foregoing range, the photosensitive resin for a color filter is composed of After the object is subjected to the lithography process, the formed pixel coloring layer has better sputtering resistance and is less likely to have bubble-like display defects.
此外,當彩色濾光片用感光性樹脂組成物之鹼可溶性樹脂(C)包含第二鹼可溶性樹脂(C-2)時,所製得之感光性樹脂組成物更不易具有泡狀之顯示缺陷。 In addition, when the alkali-soluble resin (C) of the photosensitive resin composition for a color filter contains the second alkali-soluble resin (C-2), the obtained photosensitive resin composition is less likely to have a bubble-like display defect. .
需補充的是,本發明雖以特定的化合物、組成、反應條件、製程、分析方法或特定儀器作為例示,說明本發明之彩色濾光片用感光性樹脂組成物及其應用,惟本發明所屬技術領域中任何具有通常知識者可知,本發明並不限於此,在不脫離本發明之精神和範圍內,本發明之彩色濾光片用感光性樹脂組成物及其應用亦可使用其他的化合物、組成、反應條件、製程、分析方法或儀器進行。 It should be added that although the present invention exemplifies specific compounds, compositions, reaction conditions, processes, analytical methods, or specific instruments, the photosensitive resin composition for color filters of the present invention and its applications are explained, but the present invention belongs to Anyone with ordinary knowledge in the technical field knows that the present invention is not limited to this, and without departing from the spirit and scope of the present invention, the photosensitive resin composition for a color filter of the present invention and its application may use other compounds. , Composition, reaction conditions, process, analytical method or instrument.
雖然本發明已以實施方式揭露如上,然其並非用以限定本發明,在本發明所屬技術領域中任何具有通常知識者,在不脫離本發明之精神和範圍內,當可作各種之更動 與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field to which the present invention pertains may make various changes without departing from the spirit and scope of the present invention. And retouching, so the scope of protection of the present invention shall be determined by the scope of the attached patent application.
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
B-1-1 式(V-1)所示之化合物(Rc與Rd為-SO3 -,t為0) B-1-1 Compound represented by formula (V-1) (R c and R d are -SO 3 - and t is 0)
B-1-2 式(V-22)所示之化合物 B-1-2 Compound represented by formula (V-22)
B-1-3 式(V-28)所示之化合物 B-1-3 Compound represented by formula (V-28)
B-2-1 C.I.酸性红37 B-2-1 C.I. Acid Red 37
B-2-2 C.I.分散紅60 B-2-2 C.I. Disperse Red 60
B-2-3 C.I.分散藍60 B-2-3 C.I. Disperse Blue 60
D-1 EO改質之三丙烯酸三經甲基丙酯 D-1 EO modified triacrylic acid trimethyl acrylate
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 Hexacrylate
E-1-1 具有如式(II-1)所示之結構的光起始劑 E-1-1 Photoinitiator having a structure represented by formula (II-1)
E-1-2 具有如式(II-11)所示之結構的光起始劑 E-1-2 Photoinitiator having a structure shown by formula (II-11)
E-1-3 具有如式(II-27)所示之結構的光起始劑 E-1-3 Photoinitiator having a structure shown by formula (II-27)
E-2-1 2-甲基-1-(4-甲基硫代苯基)-2-嗎啉代-1-丙酮 E-2-1 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-acetone
E-2-2 2,2’-雙(鄰-氯苯基)-4,4’,5,5’-四苯基二咪唑 E-2-2 2,2’-bis (o-chlorophenyl) -4,4 ’, 5,5’-tetraphenyldiimidazole
E-2-3 1-[4-(苯基硫代)苯基]-辛烷-1,2-二酮2-(O-苯醯基肟) E-2-3 1- [4- (phenylthio) phenyl] -octane-1,2-dione 2- (O-phenylhydrazine)
F-1 3-乙氧基丙酸乙酯 F-1 ethyl 3-ethoxypropionate
F-2 丙二醇甲醚醋酸酯 F-2 Propylene glycol methyl ether acetate
F-3 甲基異丁基酮 F-3 methyl isobutyl ketone
G-1 3-硫醇基丙基三甲氧基矽烷 G-1 3-Mercaptopropyltrimethoxysilane
G-2 2,2-硫代雙(4-甲基-6-第三丁基苯酚) G-2 2,2-thiobis (4-methyl-6-tert-butylphenol)
G-3 2-(3-第三丁基-5-甲基-2-經基苯基)-5-氯苯基疊氮 G-3 2- (3-Third-butyl-5-methyl-2-merylphenyl) -5-chlorophenyl azide
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TW201432323A (en) * | 2012-12-27 | 2014-08-16 | Fujifilm Corp | Composition for color filter, infrared ray transmitting filter and fabricating method thereof, and infrared ray sensor |
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