TWI604270B - Colored photosensitive resin composition - Google Patents

Colored photosensitive resin composition Download PDF

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TWI604270B
TWI604270B TW103103612A TW103103612A TWI604270B TW I604270 B TWI604270 B TW I604270B TW 103103612 A TW103103612 A TW 103103612A TW 103103612 A TW103103612 A TW 103103612A TW I604270 B TWI604270 B TW I604270B
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compound
photo
group
composition
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TW201432375A (en
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申泳璨
安大熙
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東友精細化工有限公司
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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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • 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
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)

Description

彩色光敏樹脂組合物Color photosensitive resin composition

本發明與彩色光敏樹脂組合物有關。
The present invention relates to a color photosensitive resin composition.

彩色濾光片是廣泛使用於成像裝置，也就是所謂的電荷耦合元件（CCD）、液晶顯示器（LCD）等，且許多利用彩色濾光片的應用已快速擴展。用於彩色LCD或CCD的彩色濾光片，一般是藉由重複製程而製造，該製程包括：均勻地將彩色光敏樹脂組合物（包括分別對應於紅、綠及藍色的色素）塗佈至其上具有圖樣化黑色基質的基板上；將基板加熱及乾燥（通常稱為「前-鍛燒」）以形成包覆膜；將該包覆膜曝光及顯像；以及視需要進一步針對每個顏色加熱及固化（通常稱為「鍛燒」），以便形成個別顏色的畫素。
用於彩色光敏樹脂組合物的著色劑一般是基於色素分散的著色劑。為了這個目的，可使用色素分散法。這樣的色素分散法可包括一種經由光蝕刻而製造彩色濾光片的方法，利用包括分散於各種光敏組合物中的色素之彩色照射敏感性的組合物。這個方法因為使用了該色素，因此可確保對光或熱足夠的可信度，因此，較佳及廣泛地用於製造彩色濾光片，以用於具有大尺寸螢幕及高解析度的彩色顯示器。
近幾年，雖然顯示器的大小快速地增加，以及高對比度的持續需求，但傳統的色素分散系統具有形成微細顆粒的限制，並且承擔因粗顆粒所造成顏色不均的問題。目前，一種同步利用色素及染料作為著色劑的方法正受到討論（參見韓國專利註冊第10-0881860號）。
然而，當彩色濾光片是利用包括染料作為著色劑的彩色光敏樹脂組合物而製造時，因為染料的相對低耐光性或耐熱性，導致頻繁地發生顏色的改變，這接著會降低顯像速率並缺少敏感性。因此，在利用鹼性顯像劑的顯像過程中會有剝離形成的圖樣的問題。
因此，解決上述問題的研究正進行中。例如，韓國專利公開第2011-0085005號揭露一種高的熱穩定基於酮肟（ketooxim）酯的光-起始劑及其製備方法，以改善既存基於OXE-1酮肟酯的光-起始劑之不佳的可應用性能及低的熱穩定性。
此外，韓國專利公開第2010-0088529號揭露用於彩色濾光片及黑色基質的光敏樹脂組合物，包括二季戊四醇的丙烯酸化產物，具有範圍在70 mg KOH/g至130 mg KOH/g的羥基，以克服傳統丙烯酸單體所未解決的問題，例如，對於基板不滿意的黏著性、解析度、顯像性質、敏感度等等。
然而，仍必須努力解決上述的傳統問題，例如，顯像速率及敏感度、利用鹼性顯像劑的顯像期間之圖樣剝離的問題等等。
Color filters are widely used in imaging devices, that is, so-called charge coupled devices (CCDs), liquid crystal displays (LCDs), etc., and many applications using color filters have rapidly expanded. A color filter for a color LCD or CCD is generally manufactured by a repetitive process comprising uniformly applying a color photosensitive resin composition (including pigments corresponding to red, green, and blue colors, respectively) to a substrate having a patterned black matrix thereon; heating and drying the substrate (generally referred to as "pre-calcining") to form a coating film; exposing and developing the coating film; and further Color heating and curing (commonly referred to as "calcining") to form individual color pixels.
The color former used in the color photosensitive resin composition is generally a pigment dispersion-based coloring agent. For this purpose, a pigment dispersion method can be used. Such a pigment dispersion method may include a method of producing a color filter by photo-etching, using a color-irradiation-sensitive composition including a pigment dispersed in various photosensitive compositions. This method, because of the use of the pigment, ensures sufficient confidence in light or heat, and is therefore preferably and widely used in the manufacture of color filters for color displays having large screens and high resolution. .
In recent years, although the size of displays has rapidly increased, and the continuous demand for high contrast, conventional pigment dispersion systems have limitations in forming fine particles and suffer from color unevenness due to coarse particles. At present, a method of simultaneously using a pigment and a dye as a coloring agent is being discussed (see Korean Patent Registration No. 10-0881860).
However, when the color filter is manufactured using a color photosensitive resin composition including a dye as a colorant, color change is frequently caused due to relatively low light resistance or heat resistance of the dye, which in turn lowers the development rate. And lack of sensitivity. Therefore, there is a problem of a pattern formed by peeling off during development using an alkaline developer.
Therefore, research to solve the above problems is underway. For example, Korean Patent Publication No. 2011-0085005 discloses a high heat stable ketooxim ester-based photo-initiator and a preparation method thereof for improving the existing photo-initiator based on OXE-1 ketoxime ester. Poor application performance and low thermal stability.
Further, Korean Patent Publication No. 2010-0088529 discloses a photosensitive resin composition for a color filter and a black matrix, comprising an acrylated product of dipentaerythritol having a hydroxyl group ranging from 70 mg KOH/g to 130 mg KOH/g. To overcome the problems unsolved by conventional acrylic monomers, such as adhesiveness, resolution, imaging properties, sensitivity, etc., which are unsatisfactory for the substrate.
However, efforts must still be made to solve the above conventional problems such as development speed and sensitivity, pattern peeling during development using an alkaline developer, and the like.

因此，本發明的一項目的係提供具有高顯像速率及優異敏感性及黏著性的彩色光敏樹脂組合物，在顯像期間不會產生圖樣的剝離。
本發明的另一目的係提供具有優異儲存安定性的彩色光敏樹脂組合物，即使在長儲存期間，也不會顯示敏感性的降低或黏度的增加。
本發明的另一目的係提供一彩色光敏樹脂組合物，其可形成具有高對比度的彩色濾光片。
本發明的上述目的將藉由以下特徵而達成：
(1) 一種彩色光敏樹脂組合物，包括一著色劑、一鹼性可溶性樹脂、一光-可聚合化合物、一光-聚合起始劑以及一溶劑，其中該著色劑包括一色素及染料；該鹼性可溶性樹脂具有30至170 mg KOH/g的酸值，並且是以組合物總重量的5至10 wt.%固含量的量而包含於其中；該鹼性可溶性樹脂及該光-可聚合化合物的羥基值的總和範圍為30至180 mg KOH/g；以及該光-聚合起始劑包括以下式1所示之化合物：
[式1]Accordingly, it is an object of the present invention to provide a color photosensitive resin composition having high development speed and excellent sensitivity and adhesion without peeling off of a pattern during development.
Another object of the present invention is to provide a color photosensitive resin composition having excellent storage stability which does not exhibit a decrease in sensitivity or an increase in viscosity even during long storage.
Another object of the present invention is to provide a color photosensitive resin composition which can form a color filter having high contrast.
The above object of the present invention is achieved by the following features:
(1) A color photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photo-polymerizable compound, a photo-polymerization initiator, and a solvent, wherein the colorant comprises a pigment and a dye; The alkali-soluble resin has an acid value of 30 to 170 mg KOH/g, and is contained therein in an amount of 5 to 10 wt.% solid content based on the total weight of the composition; the alkali-soluble resin and the photo-polymerizable The sum of the hydroxyl values of the compounds ranges from 30 to 180 mg KOH/g; and the photo-polymerization initiator comprises the compound of the following formula 1:
[Formula 1]



其中R1代表；R2及R3各自獨立地是具有1至8個碳原子的烷基、苯基、苄基或二苯硫醚基，其係以羥基或具有1至8個碳原子的烷基取代或不取代；R4是具有1至4個碳原子的伸烷基；以及R5是具有3至8個碳原子的環烷基。
(2) 根據上述(1)的組合物，其中該鹼性可溶性樹脂具有50至160 mg KOH/g的酸值。
(3) 根據上述(1)的組合物，其中該鹼性可溶性樹脂及該光-可聚合化合物的羥基值的總和範圍為40至140 mg KOH/g。
(4) 根據上述(1)的組合物，其中該著色劑是以5至60 wt.%的量而包含於其中；以及該光-可聚合化合物是以彩色光敏樹脂組合物的總重量的5至70 wt.%固含量的量而包含於其中；該光-聚合起始劑是以該鹼性可溶性樹脂及該光-可聚合化合物的含量總和的0.1至40 wt.%固含量的量而包含於其中；以及該溶劑是以彩色光敏樹脂組合物的總重量的60至90 wt.%的量而包含於其中。
(5) 根據上述(1)的組合物，其中式1所示之化合物是以該光-聚合起始劑的總重量的10至100 wt.% 的量而包含於其中。
(6) 根據上述(1)的組合物，更包括至少一光-聚合起始劑，其是選自由苯乙酮化合物、二苯基酮化合物、三嗪化合物、雙咪唑化合物以及硫雜蒽酮化合物所組成的群組。
(7) 根據上述(1)的組合物，更包括至少一光-聚合起始增強劑，其是選自由胺類化合物、羧酸化合物以及含硫醇基的有機硫化合物所組成的群組。
(8) 一種彩色濾光片，係利用上述(1)至(7)中任一個彩色光敏樹脂組合物所形成。
(9) 一種液晶顯示器裝置，包括上述(8)之彩色濾光片。
根據本發明，顯像速率是高的，並且敏感性及黏著性可以是優異的，藉此抑制在顯像過程間圖樣的剝離。
本發明的彩色光敏樹脂組合物具有優異的儲存安定性，藉此，即使在長儲存期間，也不會顯示敏感性的降低或黏度的增加。
利用本發明的彩色光敏樹脂組合物所形成之彩色濾光片，可具有高對比度。

Where R 1 represents And R 2 and R 3 are each independently an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group or a diphenyl sulfide group, which is substituted with a hydroxyl group or an alkyl group having 1 to 8 carbon atoms or Not substituted; R 4 is an alkylene group having 1 to 4 carbon atoms; and R 5 is a cycloalkyl group having 3 to 8 carbon atoms.
(2) The composition according to the above (1), wherein the alkali-soluble resin has an acid value of 50 to 160 mg KOH/g.
(3) The composition according to the above (1), wherein the sum of the hydroxyl values of the alkali-soluble resin and the photo-polymerizable compound ranges from 40 to 140 mg KOH/g.
(4) The composition according to the above (1), wherein the colorant is contained therein in an amount of 5 to 60 wt.%; and the photo-polymerizable compound is 5 in total weight of the color photosensitive resin composition And contained in an amount of 70 wt.% solid content; the photo-polymerization initiator is in an amount of 0.1 to 40 wt.% solid content of the total content of the alkali-soluble resin and the photo-polymerizable compound Included therein; and the solvent is contained in an amount of 60 to 90 wt.% based on the total weight of the color photosensitive resin composition.
(5) The composition according to the above (1), wherein the compound represented by Formula 1 is contained in an amount of 10 to 100 wt.% based on the total weight of the photo-polymerization initiator.
(6) The composition according to the above (1), further comprising at least one photo-polymerization initiator selected from the group consisting of an acetophenone compound, a diphenylketone compound, a triazine compound, a diimidazole compound, and a thioxanthone A group of compounds.
(7) The composition according to the above (1), further comprising at least one photo-polymerization initiation enhancer selected from the group consisting of an amine compound, a carboxylic acid compound, and a thiol group-containing organic sulfur compound.
(8) A color filter formed by using the color photosensitive resin composition of any one of the above (1) to (7).
(9) A liquid crystal display device comprising the color filter of the above (8).
According to the present invention, the development rate is high, and sensitivity and adhesion can be excellent, thereby suppressing peeling of the pattern between development processes.
The color photosensitive resin composition of the present invention has excellent storage stability, whereby the decrease in sensitivity or the increase in viscosity is not exhibited even during long storage.
The color filter formed by the color photosensitive resin composition of the present invention can have high contrast.

本發明揭露一種彩色光敏樹脂組合物，包括著色劑、鹼性可溶性樹脂、光-可聚合化合物、光-聚合起始劑以及一溶劑，其中該著色劑包括一色素及染料；該鹼性可溶性樹脂具有30至170 mg KOH/g的酸值，並且是以組合物總重量的5至10 wt.%固含量的量而包含於其中；該鹼性可溶性樹脂及該光-可聚合化合物的羥基值的總和範圍為30至180 mg KOH/g；以及該光-聚合起始劑包括式1所示之化合物，藉此該組合物可具有高顯像速率以及優異的敏感性及黏著性，以抑制在顯像過程間圖樣的剝離，並且具有優異的儲存安定性，即使在長儲存期間，也不會顯示敏感性的降低或黏度的增加，因此，利用相同組合物所製造的彩色濾光片可具有優異的高對比度。
本發明將更詳盡地說明如下。
本發明的彩色光敏樹脂組合物可包括著色劑、鹼性可溶性樹脂、光-可聚合化合物、光-聚合起始劑以及溶劑。
<著色劑>
著色劑包括色素及染料。
用於本發明的色素可包括在此技藝一般使用的任何有機色素、無機色素或其混合物。
有機色素並無特別地限制，但可包括用於印刷油墨、噴墨油墨等的任何一般色素，更特別是水溶性的偶氮色素、水不溶性的偶氮色素、酞花青色素、喹吖酮色素、異吲哚啉酮色素、異吲哚啉色素、苝色素、紫環酮色素、雙噁嗪色素、菎蔥色素、二菎蔥基色素、菎嘧啶色素、蒽缔蒽酮色素、藍蒽酮色素、黃士酮色素、皮蒽酮色素、二酮基吡咯並吡咯色素等等，其可單獨使用或結合兩種或多種而使用。
無機色素並無特別地限制，但可包括金屬化合物，例如，金屬氧化物或金屬錯合物，更特別是選自由鐵、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、鋅、銻以及碳黑所組成的群組中之至少一種金屬的氧化物，其可單獨使用或結合兩種或多種而使用。
有機色素及無機色素可包括根據色指數（由染色家學會出版）分類為色素的化合物。更特別是可使用C.I.色素黃色13、20、24、31、53、83、86、93、94、109、110、117、125、137、138、139、147、148、150、153、154、166、173、180及185；C.I.色素橙色13、31、36、38、40、42、43、51、55、59、61、64、65及71；C.I.色素紅色9、97、105、122、123、144、149、166、168、176、177、180、192、208、215、216、224、242、254、255及264；C.I.色素紫色14、19、23、29、32、33、36、37及38；C.I.色素藍色15（15:3、15:4、15:6等）、21、28、60、64及76；C.I.色素綠色7、10、15、25、36、47及58；C.I色素棕色28；C.I色素黑色1及7等。較佳可使用C.I.色素黃色138、C.I.色素黃色139、C.I.色素黃色150、C.I.色素黃色185、C.I.色素橙色38、C.I.色素紅色122、C.I.色素紅色166、C.I.色素紅色177、C.I.色素紅色208、C.I.色素紅色242、C.I.色素紅色254、C.I.色素紅色255、C.I.色素紫色23、C.I.色素藍色15:3、色素藍色15:6、C.I.色素綠色7、C.I.色素綠色36及C.I.色素綠色58等。這些可單獨使用或結合兩種或多種而使用。
色素的含量並無特別限制，但範圍可例如為著色劑總重量的5至95 wt.%的固含量，較佳是10至90 wt.%的固含量。如果色素的含量是在上述範圍內的話，則利用相同組合物所製造的彩色濾光片可具有充足的顏色區域及優異的穿透性，並可確保所要的敏感性，藉此可避免在顯像期間的挑色（圖樣）。
染料並無特別限制，只要它在有機溶劑中具有溶解度，並且確保可信度（例如，在鹼性顯像劑中的溶解度、耐熱性、耐溶劑性等）即可。染料可包括例如：具有酸性基團的酸性染料，例如，磺酸、羧酸等；含氮化合物以及酸性染料的鹽類；酸性染料的磺醯胺及其衍生物；基於偶氮-、氧雜蒽-及/或酞花青-的酸性染料及其衍生物等等。
染料較佳地包括在色指數（由染色家學會出版）中分類為染料的化合物，或在染料筆記（彩色染料公司）中列舉的紅色、藍色及紫色染料。
染料並無特別限制，但可包括例如C.I.溶劑染料：黃色染料，例如，C.I.溶劑黃色4、14、15、16、21、23、24、38、56、62、63、68、79、82、93、94、98、99、151、162、163等；紅色染料，例如，C.I.溶劑紅色8、45、49、89、111、122、125、130、132、146、179等；橙色染料，例如，C.I.溶劑橙色2、7、11、15、26、41、45、56、62等；藍色染料，例如，C.I.溶劑藍色5、35、36、37、44、59、67、70等；紫色染料，例如，C.I.溶劑紫色8、9、13、14、36、37、47、49等；綠色染料，例如，C.I.溶劑綠色1、3、4、5、7、28、29、32、33、34、35等，以及在有機溶劑中優異溶解度的方面較佳是C.I.溶劑黃色14、16、21、56、151、79、93；C.I.溶劑紅色8、49、89、111、122、132、146、179；C.I.溶劑橙色41、45、62；C.I.溶劑藍色35、36、44、45、70；C.I.溶劑紫色13等，以及更佳可使用C.I.溶劑黃色21、79；C.I.溶劑紅色8、122、132；C.I.溶劑橙色45、62。
此外，染料也可包括如C.I.酸性染料：黃色染料，例如，C.I.酸性黃色1、3、7、9、11、17、23、25、29、34、36、38、40、42、54、65、72、73、76、79、98、99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、212、214、220、221、228、230、232、235、238、240、242、243、251等；紅色染料，例如，C.I.酸性紅色1、4、8、14、17、18、26、27、29、31、34、35、37、42、44、50、51、52、57、66、73、80、87、88、91、92、94、97、103、111、114、129、133、134、138、143、145、150、151、158、176、182、183、198、206、211、215、216、217、227、228、249、252、257、258、260、261、266、268、270、274、277、280、281、195、308、312、315、316、339、341、345、346、349、382、383、394、401、412、417、418、422、426等；橙色染料，例如，C.I.酸性橙色6、7、8、10、12、26、50、51、52、56、62、63、64、74、75、94、95、107、108、169、173等；藍色染料，例如，C.I.酸性藍色1、7、9、15、18、23、25、27、29、40、42、45、51、62、70、74、80、83、86、87、90、92、96、103、112、113、120、129、138、147、150、158、171、182、192、210、242、243、256、259、267、278、280、285、290、296、315、324:1、335、340等；紫色染料，例如，C.I.酸性紫色6B、7、9、17、19、66等；綠色染料，例如，C.I.酸性綠色1、3、5、9、16、25、27、50、58、63、65、80、104、105、106、109等，以及在有機溶劑中優異溶解度的方面較佳是C.I.酸性黃色42；C.I.酸性紅色92；C.I.酸性藍色80、90；C.I.酸性紫色66；C.I.酸性綠色27等。
此外，染料也可包括如直接染料：黃色染料，例如，C.I.直接黃色2、33、34、35、38、39、43、47、50、54、58、68、69、70、71、86、93、94、95、98、102、108、109、129、136、138、141等；紅色染料，例如C.I.直接紅色79、82、83、84、91、92、96、97、98、99、105、106、107、172、173、176、177、179、181、182、184、204、207、211、213、218、220、221、222、232、233、234、241、243、246、250等；橙色染料，例如，C.I.直接橙色34、39、41、46、50、52、56、57、61、64、65、68、70、96、97、106、107等；藍色染料，例如，C.I.直接藍色38、44、57、70、77、80、81、84、85、86、90、93、94、95、97、98、99、100、101、106、107、108、109、113、114、115、117、119、137、149、150、153、155、156、158、159、160、161、162、163、164、166、167、170、171、172、173、188、189、190、192、193、194、196、198、199、200、207、209、210、212、213、214、222、228、229、237、238、242、243、244、245、247、248、250、251、252、256、257、259、260、268、274、275、293等；紫色染料，例如C.I.直接紫色47、52、54、59、60、65、66、79、80、81、82、84、89、90、93、95、96、103、104等；綠色染料，例如C.I.直接綠色25、27、31、32、34、37、63、65、66、67、68、69、72、77、79、82等。
此外，染料也可包括如C.I.媒染染料：黃色染料，例如C.I.媒染黃色5、8、10、16、20、26、30、31、33、42、43、45、56、61、62、65等；紅色染料，例如，C.I.媒染紅色1、2、3、4、9、11、12、14、17、18、19、22、23、24、25、26、30、32、33、36、37、38、39、41、43、45、46、48、53、56、63、71、74、85、86、88、90、94、95等；橙色染料，例如C.I.媒染橙色3、4、5、8、12、13、14、20、21、23、24、28、29、32、34、35、36、37、42、43、47、48等；藍色染料，例如C.I.媒染藍色1、2、3、7、8、9、12、13、15、16、19、20、21、22、23、24、26、30、31、32、39、40、41、43、44、48、49、53、61、74、77、83、84等；紫色染料，例如C.I.媒染紫色1、2、4、5、7、14、22、24、30、31、32、37、40、41、44、45、47、48、53、58等；綠色染料，例如C.I.媒染綠色1、3、4、5、10、15、19、26、29、33、34、35、41、43、53等。
這些可單獨使用或結合兩種或多種而使用。
染料的含量並無特別限制，但範圍可例如為著色劑總重量的5至95 wt.%固含量，較佳是10至90 wt.%固含量。如果染料的含量是在上述範圍內的話，則可避免可信度的惡化（例如在圖樣化之後因有機溶劑引起的染料沖提），同時達到優異的敏感性。
著色劑的含量並無特別限制，但範圍可例如為彩色光敏樹脂組合物總重量的 5至60 wt.%固含量，較佳是10至45 wt.%固含量。如果著色劑的含量是在上述範圍內的話，則畫素可具有充足的色密度，以及在顯像期間非畫素部分的缺漏不會減少。因此，可減少殘留的發生。
著色劑是以分散液的形式加到組合物中，以均勻地混合在組合物中。分散液可在納入通常用於組合物的分散劑及溶劑（而非著色劑）時而製備。
加入分散劑是為了去凝結及維持色素和染料的安定性。分散劑可包括在此技藝中一般使用的任何分散劑，而無限制。較佳可使用丙烯酸酯分散劑，例如，甲基丙烯酸丁酯（BMA）或甲基丙烯酸N,N-二甲基胺基乙基酯（DMAEMA）；聚羧酸酯；不飽和聚醯胺；聚羧酸；聚羧酸的（部分）胺鹽；聚羧酸的銨鹽；聚羧酸的烷基胺鹽；聚矽氧烷；長鏈聚胺基醯胺磷酸鹽；含羥基的聚羧酸酯及其修飾產物；由含游離羧基的聚酯及聚(低級伸烷基亞胺)反應所形成的醯胺或其鹽類；水溶性樹脂或水溶性聚合化合物，例如，(甲基)丙烯酸-苯乙烯共聚物、(甲基)丙烯酸-(甲基)丙烯酸酯共聚物、苯乙烯-買來酸共聚物、聚乙烯醇或聚乙烯吡咯啶酮等；聚酯；修飾的聚丙烯酸酯；環氧乙烷/環氧丙烷的加合產物；磷酸酯等等。這些化合物可單獨使用或結合兩種或多種而使用。
可用於本發明的市售分散劑可包括，例如：DISPER BYK-160、DISPER BYK-161、DISPER BYK-162、DISPER BYK-163、DISPER BYK-164、DISPER BYK-166、DISPER BYK-171、DISPER BYK-182、DISPER BYK-184、DISPER BYK-2000、DISPER BYK-2001、DISPER BYK-2070、DISPER BYK-2150（BYK化學公司）；EFKA-44、EFKA-46、EFKA-47、EFKA-48、EFKA-4010、EFKA-4050、EFKA-4055、EFKA-4020、EFKA-4015、EFKA-4060、EFKA-4300、EFKA-4330、EFKA-4400、EFKA-4406、EFKA-4510、EFKA-4800（BASF公司）；SOLSPERS-24000、SOLSPERS-32550、NBZ-4204/10（Lubirzol公司）；HINOACT T-6000、HINOACT T-7000、HINOACT T-8000（Kawaken精密化學公司）；AJISPUR PB-821、AJISPUR PB-822、AJISPUR PB-823（Ajinomoto公司）；FLORENE DOPA-17HF、FLORENE DOPA-15BHF、FLORENE DOPA-33、FLORENE DOPA-44（Kyoeisha化學公司）等，其可單獨使用或結合兩種或多種而使用。
分散劑的含量並無特別限制，但範圍可例如為色素的5至60重量份之固含量，較佳是色素的15至50重量份至100重量份之固含量。如果分散劑的含量是在上述範圍內的話，則色素可適當地形成細微顆粒，以及著色劑分散液可具有所要的黏度。
<鹼性可溶性樹脂>
鹼性可溶性樹脂是在納入具有羧基的乙烯系不飽和單體而聚合。具有羧基的乙烯系不飽和單體是賦予當形成圖樣時在顯像製程中所使用的鹼性顯像劑可溶性質的成分。
具有羧基的乙烯系不飽和單體並無特別限制，但可包括例如：單羧酸，例如，丙烯酸、甲基丙烯酸、巴豆酸等；二羧酸，例如，富馬酸、甲基阿康酸、伊康酸等及其酐類；在其兩端具有羧基及羥基的聚合物之單(甲基)丙烯酸酯，例如，ω-羧基聚己內酯單(甲基)丙烯酸酯等，以及較佳是丙烯酸及甲基丙烯酸，其可單獨使用或結合兩種或多種而使用。
鹼性可溶性樹脂的酸值並無特別限制，但範圍可例如為30至170 mg KOH/g，以及較佳為50至160 mg KOH/g。如果鹼性可溶性樹脂的酸值是在上述範圍內的話，樹脂可與染料更相容，以避免染料沈澱、彩色光敏樹脂組合物可具有優異的儲存安定性以維持想要的黏度，以及充分的顯像速率。
為了確保鹼性可溶性樹脂的進一步顯像性質，因此，樹脂可具有羥基。鹼性可溶性樹脂及光-可聚合化合物的羥基值的總和的範圍可為30至180 mg KOH/g，以及較佳是40至140 mg KOH/g。如果鹼性可溶性樹脂及光-可聚合化合物的羥基值的總和是在上述範圍內的話，則圖樣的平直度以及樹脂與染料的相溶性可以是優異的。
將羥基提供給鹼性可溶性樹脂的方法並無特別限制，但可包括例如：在進一步加入具有羥基的乙烯系不飽和單體時將樹脂進行聚合化作用；將樹脂與具有環氧丙基的化合物進行反應；將藉由進一步加入具有羥基的乙烯系不飽和單體而聚合的共聚物與具有環氧丙基的化合物進行反應等等。
具有羥基的乙烯系不飽和單體並無特別限制，但可包括例如：(甲基)丙烯酸2-羥基乙基酯、(甲基)丙烯酸2-羥基丙基酯、(甲基)丙烯酸4-羥基丁基酯、(甲基)丙烯酸2-羥基-3-苯氧基丙基酯、N-羥基乙基丙烯醯胺等，以及較佳是(甲基)丙烯酸2-羥基乙基酯。這些可單獨使用或結合兩種或多種而使用。
具有環氧丙基的化合物並無特別限制，但可包括例如：丁基縮水甘油醚、縮水甘油丙基醚、縮水甘油苯基醚、2-乙基己基縮水甘油醚、縮水甘油丁酸酯、縮水甘油甲基醚、乙基縮水甘油醚、縮水甘油異丙基醚、第三-丁基縮水甘油醚、苄基縮水甘油醚、縮水甘油-4-第三-丁基苯甲酸酯、縮水甘油硬脂酸酯、芳基縮水甘油醚、甲基丙烯酸縮水甘油酯等，以及較佳是丁基縮水甘油醚、芳基縮水甘油醚及甲基丙烯酸縮水甘油酯。這些可單獨使用或結合兩種或多種而使用。
本發明的鹼性可溶性樹脂可在進一步納入至少一種可與上述單體共聚合的其他單體的同時進行聚合化。例如，芳香族乙烯基化合物，例如，苯乙烯、乙烯基甲苯、甲基苯乙烯、對-氯苯乙烯、鄰-甲氧基苯乙烯、間-甲氧基苯乙烯、對-甲氧基苯乙烯、鄰-乙烯基苄基甲基醚、間-乙烯基苄基甲基醚、對-乙烯基苄基甲基醚、鄰-乙烯基苄基縮水甘油醚、間-乙烯基苄基縮水甘油醚、對-乙烯基苄基縮水甘油醚等；N-取代的馬來醯亞胺化合物，例如，N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、N-苯基馬來醯亞胺、N-鄰-羥基苯基馬來醯亞胺、N-間-羥基苯基馬來醯亞胺、N-對-羥基苯基馬來醯亞胺、N-鄰-甲基苯基馬來醯亞胺、N-間-甲基苯基馬來醯亞胺、N-對-甲基苯基馬來醯亞胺、N-鄰-甲氧基苯基馬來醯亞胺、N-間-甲氧基苯基馬來醯亞胺、N-對-甲氧基苯基馬來醯亞胺等；(甲基)丙烯酸烷基酯，例如，(甲基)丙烯酸甲基酯、(甲基)丙烯酸乙基酯、(甲基)丙烯酸正-丙基酯、(甲基)丙烯酸異-丙基酯、(甲基)丙烯酸正-丁基酯、(甲基)丙烯酸異-丁基酯、(甲基)丙烯酸第二-丁基酯、(甲基)丙烯酸第三-丁基酯等；(甲基)丙烯酸脂環族酯，例如，(甲基)丙烯酸環戊基酯、(甲基)丙烯酸環己基酯、(甲基)丙烯酸2-甲基環己基酯、(甲基)丙烯酸三環[5.2.1.0.2.6]癸-8-基酯、(甲基)丙烯酸2-二環戊二醇氧乙基酯、(甲基)丙烯酸異莰基酯等；(甲基)丙烯酸芳基酯，例如，(甲基)丙烯酸苯基酯、(甲基)丙烯酸苄基酯等；不飽和的環氧丙烷化合物，例如，3-(甲基丙烯醯基氧甲基)環氧丙烷、3-(甲基丙烯醯基氧甲基)-3-乙基環氧丙烷、3-(甲基丙烯醯基氧甲基)-2-三氟甲基環氧丙烷、3-(甲基丙烯醯基氧甲基)-2-苯基環氧丙烷、2-(甲基丙烯醯基氧甲基)環氧丙烷、2-(甲基丙烯醯基氧甲基)-4-四氟甲基環氧丙烷等，其可單獨使用或結合兩種或多種而使用。
鹼性可溶性樹脂的含量並無特別限制，但範圍可例如為彩色光敏樹脂組合物總重量的5至10 wt.%固含量。如果鹼性可溶性樹脂的含量是在上述範圍內的話，則它在顯像劑中可具有充分的溶解性質，使得圖樣化容易，並可避免在顯像期間曝光部分的畫素部分之薄膜(film)減少，導致非畫素部分的缺漏之減少。
製備鹼性可溶性樹脂的方法之具體實施例將說明如下。
將上述例示的單體、相對於單體含量的0.5至20倍溶劑以及單體莫耳數的0.1至10%之聚合起始劑，加到配備有攪拌器、溫度計、迴流冷卻管、滴定裝置以及氮氣導入管的錐形瓶中，然後以氮氣取代。之後，將其於40至140℃攪動1至10小時。
本文所使用的溶劑可以是任何一種習知用於自由基聚合反應的溶劑，並可包括例如任何一種選自由四氫呋喃、二氧雜環、乙二醇二甲醚、二乙二醇二甲醚、丙酮、甲基乙基酮、甲基異丁基酮、環己酮、乙酸乙酯、乙酸丁酯、乙酸丙二醇單甲基乙酯、乙酸3-甲氧基丁酯、甲醇、乙醇、丙醇、正-丁醇、乙二醇單甲基醚、丙二醇單甲基醚、甲苯、二甲苯、乙苯、氯仿以及二甲基亞碸所組成的群組中者，其可單獨使用或以混合物而使用。
聚合起始劑可以是任何習知用於相關技藝中之聚合起始劑，並無特別限制。更特別地可包括有機過氧化物，例如，二異丙苯過氧化氫、二-第三-丁基過氧化物、過氧化苯甲醯、異丙基碳酸第三-丁基過氧化酯、己酸第三-戊基過氧基-2-乙基酯、己酸第三-丁基過氧基-2-乙基酯等；以及氮化合物，例如，2,2'-偶氮雙(異丁腈)、2,2'-偶氮雙(2,4-二甲基丁腈)、二甲基-2,2'-偶氮雙(2-甲基丙酸)等；其可單獨使用或結合兩種或多種而使用。
為了控制上述製程期間的分子量，因此可使用α-甲基苯乙烯二聚體或巰化合物作為鏈移轉劑。這樣的α-甲基苯乙烯二聚體或巰化合物可以單體的0.005至5重量份至100重量份的量而使用。關於聚合作用的條件，進料方法及反應溫度可考量聚合作用或製造設備的放熱值而適當地控制。
<光-可聚合化合物>
光-可聚合化合物是一種強化圖樣強度的成分，並可包括單-官能、雙-官能或多-官能的單體等，較佳是雙-官能或更多的單體。例如，其特定的例子可包括：單-官能的單體，例如，丙烯酸壬基苯基卡必醇酯、丙烯酸2-羥基-3-苯氧基丙基酯、丙烯酸2-乙基己基卡必醇酯、丙烯酸2-羥基乙基酯、N-乙烯基吡咯啶酮等；雙-官能的單體，例如，二(甲基)丙烯酸1,6-己二醇酯、二(甲基)丙烯酸乙二醇酯、二(甲基)丙烯酸新戊二醇酯、二(甲基)丙烯酸三乙二醇酯、雙酚A的雙(丙烯醯基氧乙基)醚、二(甲基)丙烯酸3-甲基戊二醇酯、甲基丙烯酸3-(丙烯醯基氧基)-2-羥基丙基酯、2-羥基-1,3-二甲基丙烯醯基氧基丙烷、2-羥基-1-丙烯醯基-3-甲基丙烯基氧基丙烷等；三-官能的單體，例如，三(甲基)丙烯酸三羥甲基丙烷酯、三(甲基)丙烯酸季戊四醇酯等；四-官能的單體，例如，四(甲基)丙烯酸季戊四醇酯；五-官能的單體，例如，五(甲基)丙烯酸二季戊四醇酯；六-官能的單體，例如，六(甲基)丙烯酸二季戊四醇酯等，其可單獨使用或結合兩種或多種而使用。
在強化圖樣強度及改善平滑度的方面，光-可聚合化合物可包括雙-官能的或更高多-官能的單體，以及更佳是五-官能的或更高多-官能的單體。
市售的光-可聚合化合物產品可包括，例如，701（NK ESTER）、701A（NK ESTER）、ATMM-3L（NK ESTER）、KAYARAD DPHA（Nippon Chemicals）等。
光-可聚合化合物含量並無特別限制，只要鹼性可溶性樹脂及光-可聚合化合物的羥基值的總和滿足上述範圍即可，然而，例如範圍可為彩色光敏樹脂組合物總重量的5至70 wt.%固含量，較佳是15至65 wt.%固含量。如果光-可聚合化合物含量是在上述範圍內的話，則畫素部分可具有有利的強度或平滑度。
<光-聚合起使劑>
本發明的光-聚合起使劑可包括以下式1所示的化合物：
[式1]


其中R1代表；R2及R3各自獨立地是具有1至8個碳原子的烷基、苯基、苄基或二苯硫醚基，其係以羥基或具有1至8個碳原子的烷基而取代或不取代；R4是具有1至4個碳原子的伸烷基；以及R5是具有3至8個碳原子的環烷基。
式1所示的光-聚合起使劑可避免敏感性因染料的關係而降低，因此可提供包含染料的彩色光敏樹脂組合物之有效的光-聚合性質。
除了式2所示的光-聚合起使劑之外，本發明的彩色光敏樹脂組合物可更包括至少一種一般用於相關技藝中的光-聚合起使劑。例如，可包括苯乙酮化合物、二苯基酮化合物、三嗪化合物、雙咪唑化合物、硫雜蒽酮化合物等。這些化合物可單獨使用或結合兩種或多種而使用。
苯乙酮化合物並無特別限制，但可包括例如：二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙-1-酮、苄基二甲基縮酮、2-羥基-1-[4-(2-羥基乙氧基)苯基]-2-甲基丙-1-酮、1-羥基還己基苯基酮、2-甲基-1-(4-甲基硫苯基)-2-嗎啉基丙-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)丁-1-酮、2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙-1-酮、2-(4-甲基苄基)-2-(二甲基胺基)-1-(4-嗎啉基苯基)丁-1-酮等。
二苯基酮化合物並無特別限制，但可包括例如：二苯基酮、鄰-苯甲酸苄醯基甲基酯、4-苯基二苯基酮、4-苄醯基-4'-甲基二苯基硫化物、3,3',4,4'-四(第三-丁基過氧基羰基)二苯基酮、2,4,6-三甲基二苯基酮等。
三嗪化合物並無特別限制，但可包括例如：2,4-二(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-二(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三嗪、2,4-二(三氯甲基)-6-向日葵基-1,3,5-三嗪、2,4-二(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三嗪、2,4-二(三氯甲基)-6-[2-(5-甲基呋喃-2-基) 乙烯基]-1,3,5-三嗪、2,4-二(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-二(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三嗪、2,4-二(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三嗪等。
雙咪唑化合物並無特別限制，但可包括例如：2,2'-二(2-氯苯基)-4,4',5,5'-四苯基雙咪唑、2,2'-二(2,3-二氯苯基)-4,4',5,5'-四苯基雙咪唑、2,2'-二(2-氯苯基)-4,4',5,5'-四(烷氧基苯基)雙咪唑、2,2'-二(2-氯苯基)-4,4',5,5'-四(三烷氧基苯基)雙咪唑、2,2-二(2,6-二氯苯基)-4,4',5,5'-四苯基-1,2'-雙咪唑或在4,4’,5,5’位置具有經碳烷氧基取代的苯基之任何咪唑化合物，在上述化合物中較佳是二(2-氯苯基)-4,4',5,5'-四苯基雙咪唑、2,2'-二(2,3-二氯苯基)-4,4',5,5'-四苯基雙咪唑或2,2-二(2,6-二氯苯基)-4,4',5,5'-四苯基-1,2'-雙咪唑等。
硫雜蒽酮化合物並無特別限制，但可包括例如：2-異丙基硫雜蒽酮、2,4-二乙基硫雜蒽酮、2,4-二氯硫雜蒽酮、1-氯-4-丙氧基硫雜蒽酮等。
光-聚合起使劑的含量並無特別限制，但範圍可例如為鹼性可溶性樹脂及光-可聚合化合物的含量總和的0.1至40 wt.%固含量，較佳是1至30 wt.%固含量。如果光-聚合起使劑的含量是在上述範圍內的話，則彩色光敏樹脂組合物會變成高度敏感性的，以減少曝光時間，因此可改善產率同時保留高解析度。此外，所形成的畫素部分也可具有有利的強度，並可在畫素部分的表面達到優異的平滑度。
在上述光-聚合起使劑中，式1所示化合物的含量並無特別限制，但範圍可例如為光-聚合起使劑的總重量的10至100 wt.%，較佳是20至100 wt.%。如果式1所示化合物的含量是在上述範圍內的話，則改善敏感度的效果可達到最大。
<光-聚合起始增強劑>
本發明的彩色光敏樹脂組合物可更包括光-聚合起始增強劑，以改善敏感度。
光-聚合起始增強劑並無特別限制，但可包括例如：胺類化合物、羧酸化合物或含硫醇基的有機硫化合物等，其可單獨使用或結合兩種或多種而使用。
胺類化合物並無特別限制，但可包括例如：脂肪族胺類化合物，例如，三乙醇胺、甲基二乙醇胺、三異丙醇胺等；芳香族胺類化合物，例如，4-二甲基胺基苯甲酸甲基酯、4-二甲基胺基苯甲酸乙基酯、4-二甲基胺基苯甲酸異戊基酯、4-二甲基胺基苯甲酸2-乙基己基酯、苯甲酸2-二甲基胺基乙基酯、N,N-二甲基鄰甲苯胺、4,4'-雙(二甲基胺基)二苯基酮、4,4'-雙(二乙基胺基)二苯基酮等。
羧酸化合物並無特別限制，但可包括例如：芳香族雜醋酸，例如，苯基硫醋酸、甲基苯基硫醋酸、乙基苯基硫醋酸、甲基乙基苯基硫醋酸、二甲基苯基硫醋酸、甲氧基苯基硫醋酸、二甲氧基苯基硫醋酸、氯苯基硫醋酸、二氯苯基硫醋酸、N-苯基甘胺酸、苯氧基醋酸、萘基硫醋酸、N-萘基甘胺酸、萘氧基醋酸等。
具有硫醇基團的有機硫化合物並無特別限制，但可包括例如：2-巰基苯並噻唑、1,4-雙(3-巰基丁醯基氧基)丁烷、1,3,5-三(3-巰基丁基氧基乙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、三羥甲基丙烷三(3-巰基丙酸)、季戊四醇四(3-巰基丁酸)、季戊四醇四(3-巰基丙酸)、二季戊四醇六(3-巰基丙酸)、四乙二醇雙(3-巰基丙酸)等。
光-聚合起始增強劑的含量並無特別限制，但範圍可例如為彩色光敏樹脂組合物總重量的0.1至40 wt.%固含量，較佳是1至30 wt.%固含量。如果光-聚合起始增強劑的含量是在上述範圍內的話，則可進一步改善彩色光敏樹脂組合物的敏感度，藉此增強產率。
<溶劑>
本發明所使用的溶劑並無特別限制，只要它可溶解上述成份即可，但可包括例如：醚、芳香族烴、酮、醇、酯等，其可單獨使用或結合兩種或多種而使用。
特別的例子可包括：乙二醇單烷基醚，例如，乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚等; 醚例如，二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丙基醚、二乙二醇單丁基醚、甲基賽路醋酸酯、乙基賽路醋酸酯、丙二醇單乙基醚醋酸酯、丙二醇單丙基醚醋酸酯、甲氧基丁基醋酸酯、甲氧基戊基醋酸酯等；芳香族烴例如，苯、甲苯、二甲苯、均三甲苯等；酮例如，甲基乙基酮、丙酮、甲基戊基酮、甲基異丁基酮、環己酮等；醇例如，乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、甘油等；酯例如，3-乙氧基丙酸乙基酯、3-甲氧基丙酸甲基酯、γ-丁內酯等，以及較佳係使用丙二醇單甲基醚醋酸酯、丙二醇單乙基醚醋酸酯、環己酮乳酸乙基酯、乳酸丁基酯、3-乙氧基丙酸乙基酯、3-甲氧基丙酸甲基酯。
在應用性及乾燥的方面，溶劑較佳是具有沸點100至200℃的有機溶劑。
溶劑的含量並無特別限制，但溶劑可例如包括在著色劑分散液中的所含的溶劑，以及整體含量的範圍可為彩色光敏樹脂組合物總重量的60至90 wt.%，較佳是70至85 wt.%。如果溶劑的含量是在上述範圍內的話，則可達到有利的應用性。
<添加物>
本發明的彩色光敏樹脂組合物可更包括選自由替代性聚合化合物、固化劑、界面活性劑、附著增強劑、UV吸收劑及抗凝劑等所組成的群組中之任何一種添加物。
這樣的替代性聚合化合物並無特別限制，但可包括例如：可固化的樹脂，例如，環氧樹脂、馬來醯亞胺樹脂等；熱塑性樹脂，例如，聚乙烯醇、聚丙烯酸、聚乙二醇單烷基醚、聚氟烷基丙烯酸酯、聚酯、聚氨基甲酸乙酯等。
固化劑是用於深層固化並增加機械強度的成份，固化劑的種類並無特別限制，但可包括例如：環氧化合物、多-官能的異氰酸酯化合物、三聚氰胺化合物、環氧丙烷化合物等。
環氧化合物並無特別限制，但可包括例如：雙酚A環氧樹脂、氫化的雙酚A環氧樹脂、雙酚F環氧樹脂、氫化的雙酚F環氧樹脂、酚醛環氧樹脂、其他的芳香族環氧樹脂、脂肪族環氧樹脂、縮水甘油酯樹脂、縮水甘油胺樹脂、或環氧樹脂溴化的衍生物；除了環氧樹脂及其溴化的衍生物外的脂肪族、脂環族或芳香族化合物；丁二烯(共)聚合物環氧化物；異戊二烯(共)聚合物環氧化物；環氧丙基(甲基)丙烯酸(共)聚合物；異氰尿酸三縮水甘油酯等。
環氧丙烷化合物並無特別限制，但可包括例如：碳酸酯雙氧雜環丁烷、二甲苯雙氧雜環丁烷、己二酸雙氧雜環丁烷、對苯二甲酸雙氧雜環丁烷、環己烷二羧酸雙氧雜環丁烷等。
固化劑可與固化助化合物相容，固化助化合物可使環氧化合物的環氧基或環氧丙烷化合物的環氧丙烷骨架行開環聚合反應。
固化助化合物並無特別限制，但可包括例如：多價的羧酸、多價的羧酸酐、酸產生劑等。多價的羧酸酐可包括市售的任何環氧樹脂固化劑。
可用於本發明之該等市售的環氧樹脂固化劑並無特別限制，但可包括例如：Adekahadona EH-700（商品名，由Adeka工程有限公司所製造）、Likashitdo HH（商品名，由新日本化學有限公司所製造）、MH-700（商品名，由新日本化學有限公司所製造）等。
界面活性劑是用以改善光敏樹脂組合物的塗佈成形性，其種類並無特別限制，但可包括例如：氟界面活性劑、矽界面活性劑或其混合物。
矽界面活性劑並無特別限制，但可包括市售的產品，例如：由Dow-corning Doray Silicon公司所製造的DC3PA、DC7PA、SH11PA、SH21PA、SH8400等；由GE Toshiba Silicon公司所製造的TSF-4440、TSF-4300、TSF-4445、TSF-4446、TSF-4460、TSF-4452等等。
氟界面活性劑並無特別限制，但可包括市售的產品，例如：由大日本油墨化學工業所製造的大片段F-470、F-471、F-475、F-482、F-489等。
附著增強劑的種類並無特別限制，但可包括例如：乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(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-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基二甲氧基矽烷、2-(3,4-環氧基環己基)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-甲基丙烯醯基氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-異氰酸丙基三甲氧基矽烷、3-異氰酸丙基三乙氧基矽烷等，其可單獨使用或結合兩種或多種而使用。
附著增強劑的含量並無特別限制，但範圍可例如為彩色光敏樹脂組合物總重量的0.01至10 wt.%固含量，較佳是0.05至2 wt.%固含量。
抗氧化劑的種類並無特別限制，但可包括例如：2,2’-硫二(4-甲基-6-第三-丁基酚), 2,6-二-第三-丁基-4-甲基酚等。
UV吸收劑的種類並無特別限制，但可包括例如：2-(3-第三-丁基-2-羥基-5-甲基苯基)-5-氯苯並三唑、烷氧基二苯基酮等。
抗凝劑並無特別限制，但可包括例如聚丙烯酸鈉。
<彩色光敏樹脂組合物之製備>
製備本發明彩色光敏樹脂組合物的方法可包括，例如：將著色劑及分散劑加到溶劑中，並將其分散以製備具有均勻顆粒大小的著色劑分散液；將鹼性可溶性樹脂、光-可聚合化合物、光-聚合起始劑以及視需要的其他添加物溶解於溶劑中，並將其與上述著色劑分散液混合；以及視需要進一步加入新鮮溶劑。
<彩色濾光片>
此外，本發明也提供利用上述彩色光敏樹脂組合物所製造的彩色濾光片。
彩色濾光片包括一基板及形成於基板上方的一彩色層。
基板可以是用於彩色濾光片本身的原始基板，或在彩色濾光片被放置其上的顯示裝置的部分，因此，並無特別限制。
基板可以是玻璃、矽(Si)、氧化矽(SiOx)或聚合物基板，以及聚合物基板可由聚醚碸(PES)、聚碳酸酯(PC)等所形成。
彩色層是包含本發明彩色光敏樹脂組合物的層，並可藉由將彩色光敏樹脂組合物塗佈到該層而形成，並且將塗佈層曝光、顯像及熱固化，以形成所要的圖樣。
具有上述基板及彩色層的彩色濾光片可進一步包括在各別彩色圖樣及/或黑色基質之間所形成的障壁層。此外，彩色濾光片也可包括形成於彩色層上方的保護層。
<液晶顯示器裝置>
此外，本發明也提供包括上述彩色濾光片的液晶顯示器裝置。
本發明的液晶顯示器裝置可包括本發明所屬技藝中已知的技術配置，除了具有上述彩色濾光片之外，並無特別限制。
以下將說明較佳具體實施例以更具體地理解本發明。然而，對於熟悉於此技藝者明顯的是，該等具體實施例是以說明之目的而提供，而非對於所附申請專利範圍的特別限制，在不脫離本發明的範疇及精神之外，各種的修飾及改變都是可能的，以及該等的修飾及改變是適當地包含於其中如所附申請專利範圍定義之本發明中。
實施例
製備實施例-著色劑分散液的製備
著色劑分散液是藉由將14重量份的C.I.色素紅色254、6重量份的AJISPUR PB821（由AJINOMOTO Fine Techno有限公司所製造）作為分散劑，以及包括60重量份的丙二醇單甲基醚醋酸酯及20重量份的環己酮的溶劑，藉由玻珠-研磨的方式混合及分散12小時而製備。
合成實施例–鹼性可溶性樹脂的合成
(1) 合成實施例1
將120份的丙二醇單甲基醚醋酸酯、80份的丙二醇單甲基醚、2份的偶氮雙異丁腈(AIBN)、13.0份的丙烯酸、10份的甲基丙烯酸苄基酯、57.0 份的4-甲基苯乙烯、20份的甲基丙烯酸甲基酯及3份的正-十二烷基硫醇，導入到配備有攪拌器、溫度計、迴流冷卻管、滴定裝置以及氮氣導入管的錐形瓶中，並將錐形瓶中的空氣以氮氣交換。接著，執行反應6小時同時將溫度升高至110℃並且攪動。合成的鹼性可溶性樹脂具有100.2 mg KOH/g的酸值以及0 mg KOH/g（固含量）的羥基值，以及由GPC所測量的約15,110之重量平均分子量（Mw）。
(2) 合成實施例2
將120份的丙二醇單甲基醚醋酸酯、80份的丙二醇單甲基醚、2份的偶氮雙異丁腈、9.0份的丙烯酸、10份的甲基丙烯酸苄基酯、54.0份的4-甲基苯乙烯、20份的甲基丙烯酸甲基酯、7.0份的(甲基)丙烯酸2-羥基乙基酯及3份的正-十二烷基硫醇，導入到配備有攪拌器、溫度計、迴流冷卻管、滴定裝置以及氮氣導入管的錐形瓶中，並將錐形瓶中的空氣以氮氣交換。接著，執行反應6小時同時將溫度升高至110℃並且攪動。合成的鹼性可溶性樹脂具有69.4 mg KOH/g的酸值以及29.8 mg KOH/g（固含量）的羥基值，以及由GPC所測量的約13,180之重量平均分子量（Mw）。
(3) 合成實施例3
將120份的丙二醇單甲基醚醋酸酯、80份的丙二醇單甲基醚、2份的偶氮雙異丁腈、3.5份的丙烯酸、10份的甲基丙烯酸苄基酯、66.5份的4-甲基苯乙烯、20份的甲基丙烯酸甲基酯及3份的正-十二烷基硫醇，導入到配備有攪拌器、溫度計、迴流冷卻管、滴定裝置以及氮氣導入管的錐形瓶中，並將錐形瓶中的空氣以氮氣交換。接著，執行反應6小時同時將溫度升高至110℃並且攪動。合成的鹼性可溶性樹脂具有26.5 mg KOH/g的酸值以及0 mg KOH/g（固含量）的羥基值，以及由GPC所測量的約16,070之重量平均分子量（Mw）。
(4) 合成實施例4
將120份的丙二醇單甲基醚醋酸酯、80份的丙二醇單甲基醚、2份的偶氮雙異丁腈、22.5份的丙烯酸、10份的甲基丙烯酸苄基酯、47.5份的4-甲基苯乙烯、20份的甲基丙烯酸甲基酯及3份的正-十二烷基硫醇，導入到配備有攪拌器、溫度計、迴流冷卻管、滴定裝置以及氮氣導入管的錐形瓶中，並將錐形瓶中的空氣以氮氣交換。接著，執行反應6小時同時將溫度升高至110℃並且攪動。合成的鹼性可溶性樹脂具有172.3 mg KOH/g的酸值以及0 mg KOH/g（固含量）的羥基值，以及由GPC所測量的約14,850之重量平均分子量（Mw）。
實施例1
彩色光敏樹脂組合物是藉由混合33.8份的著色劑分散液、0.5份的C.I.酸性紅色52（由TCI America公司所製造）、4.1份在合成實施例1中所合成的樹脂、5.6份具有41 mg KOH/g的羥基值的二季戊四醇之丙烯酸化產物（0.37份的四丙烯酸二季戊四醇酯/1.31份的五丙烯酸二季戊四醇酯/3.92份的六丙烯酸二季戊四醇酯）、0.2份的Irgacure 369（由BASF公司所製造）、0.5份具有以下式2所示結構的TR-PBG-305（由TRONLY公司所製造）、29.8份的丙二醇單甲基醚醋酸酯及25.5份的二丙酮醇而製備。
[式2]


實施例2

彩色光敏樹脂組合物是藉由混合33.8份的著色劑分散液、0.5份的C.I.酸性紅色52（由TCI America公司所製造）、4.1份在合成實施例1中所合成的樹脂、5.6份具有80 mg KOH/g的羥基值的二季戊四醇之丙烯酸化產物（1.13份的四丙烯酸二季戊四醇酯/1.65份的五丙烯酸二季戊四醇酯/2.82份的六丙烯酸二季戊四醇酯）、0.2份的Irgacure 369（由BASF公司所製造）、0.5份具有式2所示結構的TR-PBG-305（由TRONLY公司所製造）、29.8份的丙二醇單甲基醚醋酸酯及25.5份的二丙酮醇而製備。
實施例3
彩色光敏樹脂組合物是藉由混合33.8份的著色劑分散液、0.5份的C.I.酸性紅色52（由TCI America公司所製造）、4.1份在合成實施例1中所合成的樹脂、5.6份具有104 mg KOH/g的羥基值的二季戊四醇之丙烯酸化產物（1.59份的四丙烯酸二季戊四醇酯/1.86份的五丙烯酸二季戊四醇酯/2.15份的六丙烯酸二季戊四醇酯）、0.2份的Irgacure 369（由BASF公司所製造）、0.5份具有式2所示結構的TR-PBG-305（由TRONLY公司所製造）、29.8份的丙二醇單甲基醚醋酸酯及25.5份的二丙酮醇而製備。
實施例4
彩色光敏樹脂組合物是藉由混合33.8份的著色劑分散液、0.5份的C.I.酸性紅色52（由TCI America公司所製造）、4.1份在合成實施例1中所合成的樹脂、5.6份具有162 mg KOH/g的羥基值的二季戊四醇之丙烯酸化產物（2.72份的四丙烯酸二季戊四醇酯/2.37份的五丙烯酸二季戊四醇酯/0.51份的六丙烯酸二季戊四醇酯）、0.2份的Irgacure 369（由BASF公司所製造）、0.5份具有式2所示結構的TR-PBG-305（由TRONLY公司所製造）、29.8份的丙二醇單甲基醚醋酸酯及25.5份的二丙酮醇而製備。
實施例5
彩色光敏樹脂組合物是藉由混合33.8份的著色劑分散液、0.5份的C.I.酸性紅色52（由TCI America公司所製造）、4.1份在合成實施例2中所合成的樹脂、5.6份具有41 mg KOH/g的羥基值的二季戊四醇之丙烯酸化產物（0.37份的四丙烯酸二季戊四醇酯/1.31份的五丙烯酸二季戊四醇酯/3.92份的六丙烯酸二季戊四醇酯）、0.2份的Irgacure 369（由BASF公司所製造）、0.5份具有式2所示結構的TR-PBG-305（由TRONLY公司所製造）、29.8份的丙二醇單甲基醚醋酸酯及25.5份的二丙酮醇而製備。
實施例6
彩色光敏樹脂組合物是藉由混合33.8份的著色劑分散液、0.5份的C.I.酸性紅色52（由TCI America公司所製造）、4.1份在合成實施例2中所合成的樹脂、5.6份具有80 mg KOH/g的羥基值的二季戊四醇之丙烯酸化產物（1.13份的四丙烯酸二季戊四醇酯/1.65份的五丙烯酸二季戊四醇酯/2.82份的六丙烯酸二季戊四醇酯）、0.2份的Irgacure 369（由BASF公司所製造）、0.5份具有式2所示結構的TR-PBG-305（由TRONLY公司所製造）、29.8份的丙二醇單甲基醚醋酸酯及25.5份的二丙酮醇而製備。
實施例7
彩色光敏樹脂組合物是藉由混合33.8份的著色劑分散液、0.5份的C.I.酸性紅色52（由TCI America公司所製造）、4.1份在合成實施例2中所合成的樹脂、5.6份具有104 mg KOH/g的羥基值的二季戊四醇之丙烯酸化產物（1.59份的四丙烯酸二季戊四醇酯/1.86份的五丙烯酸二季戊四醇酯/2.15份的六丙烯酸二季戊四醇酯）、0.2份的Irgacure 369（由BASF公司所製造）、0.5份具有式2所示結構的TR-PBG-305（由TRONLY公司所製造）、29.8份的丙二醇單甲基醚醋酸酯及25.5份的二丙酮醇而製備。
比較實施例1
彩色光敏樹脂組合物是藉由混合33.8份的著色劑分散液、0.5份的C.I.酸性紅色52（由TCI America公司所製造）、4.1份在合成實施例1中所合成的樹脂、5.6份具有22 mg KOH/g的羥基值的二季戊四醇之丙烯酸化產物（1.15份的五丙烯酸二季戊四醇酯/4.45份的六丙烯酸二季戊四醇酯）、0.2份的Irgacure 369（由BASF公司所製造）、0.5份具有以上式2所示結構的TR-PBG-305（由TRONLY公司所製造）、29.8份的丙二醇單甲基醚醋酸酯及25.5份的二丙酮醇而製備。
比較實施例2
彩色光敏樹脂組合物是藉由混合33.8份的著色劑分散液、0.5份的C.I.酸性紅色52（由TCI America公司所製造）、4.1份在合成實施例1中所合成的樹脂、5.6份具有162 mg KOH/g的羥基值的二季戊四醇之丙烯酸化產物（2.72份的四丙烯酸二季戊四醇酯/2.37份的五丙烯酸二季戊四醇酯/0.51份的六丙烯酸二季戊四醇酯）、0.2份的Irgacure 369（由BASF公司所製造）、0.5份具有以上式2所示結構的TR-PBG-305（由TRONLY公司所製造）、29.8份的丙二醇單甲基醚醋酸酯及25.5份的二丙酮醇而製備。
比較實施例3
彩色光敏樹脂組合物是藉由混合33.8份的著色劑分散液、0.5份的C.I.酸性紅色52（由TCI America公司所製造）、4.1份在合成實施例3中所合成的樹脂、5.6份具有80 mg KOH/g的羥基值的二季戊四醇之丙烯酸化產物（1.13份的四丙烯酸二季戊四醇酯/1.65份的五丙烯酸二季戊四醇酯/2.82份的六丙烯酸二季戊四醇酯）、0.2份的Irgacure 369（由BASF公司所製造）、0.5份具有以上式2所示結構的TR-PBG-305（由TRONLY公司所製造）、29.8份的丙二醇單甲基醚醋酸酯及25.5份的二丙酮醇而製備。
比較實施例4
彩色光敏樹脂組合物是藉由混合33.8份的著色劑分散液、0.5份的C.I.酸性紅色52（由TCI America公司所製造）、4.1份在合成實施例4中所合成的樹脂、5.6份具有80 mg KOH/g的羥基值的二季戊四醇之丙烯酸化產物（1.13份的四丙烯酸二季戊四醇酯/1.65份的五丙烯酸二季戊四醇酯/2.82份的六丙烯酸二季戊四醇酯）、0.2份的Irgacure 369（由BASF公司所製造）、0.5份具有以上式2所示結構的TR-PBG-305（由TRONLY公司所製造）、29.8份的丙二醇單甲基醚醋酸酯及25.5份的二丙酮醇而製備。
比較實施例5
彩色光敏樹脂組合物是藉由混合33.8份的著色劑分散液、0.5份的C.I.酸性紅色52（由TCI America公司所製造）、4.1份在合成實施例1中所合成的樹脂、5.6份具有80 mg KOH/g的羥基值的二季戊四醇之丙烯酸化產物（1.13份的四丙烯酸二季戊四醇酯/1.65份的五丙烯酸二季戊四醇酯/2.82份的六丙烯酸二季戊四醇酯）、0.2份的Irgacure 369（由BASF公司所製造）、0.5份具有以上式2所示結構的TR-PBG-305（由TRONLY公司所製造）、29.8份的丙二醇單甲基醚醋酸酯及25.5份的二丙酮醇而製備。
比較實施例6
彩色光敏樹脂組合物是藉由混合33.8份的著色劑分散液、0.5份的C.I.酸性紅色52（由TCI America公司所製造）、10.2份在合成實施例1中所合成的樹脂、3.5份具有80 mg KOH/g的羥基值的二季戊四醇之丙烯酸化產物（0.71份的四丙烯酸二季戊四醇酯/1.03份的五丙烯酸二季戊四醇酯/1.76份的六丙烯酸二季戊四醇酯）、0.2份的Irgacure 369（由BASF公司所製造）、0.5份具有以上式2所示結構的TR-PBG-305（由TRONLY公司所製造）、29.8份的丙二醇單甲基醚醋酸酯及25.5份的二丙酮醇而製備。
比較實施例7
彩色光敏樹脂組合物是藉由混合33.8份的著色劑分散液、0.5份的C.I.酸性紅色52（由TCI America公司所製造）、2.0份在合成實施例1中所合成的樹脂、6.3份具有80 mg KOH/g的羥基值的二季戊四醇之丙烯酸化產物（1.27份的四丙烯酸二季戊四醇酯/1.86份的五丙烯酸二季戊四醇酯/3.17份的六丙烯酸二季戊四醇酯）、0.2份的Irgacure 369（由BASF公司所製造）、0.5份具有以上式2所示結構的TR-PBG-305（由TRONLY公司所製造）、29.8份的丙二醇單甲基醚醋酸酯及25.5份的二丙酮醇而製備。
比較實施例8
彩色光敏樹脂組合物是藉由混合33.8份的著色劑分散液、4.1份在合成實施例1中所合成的樹脂、5.6份具有41 mg KOH/g的羥基值的二季戊四醇之丙烯酸化產物（0.37份的四丙烯酸二季戊四醇酯/1.31份的五丙烯酸二季戊四醇酯/3.92份的六丙烯酸二季戊四醇酯）、0.2份的Irgacure 369（由BASF公司所製造）、0.5份具有以上式2所示結構的TR-PBG-305（由TRONLY公司所製造）、29.8份的丙二醇單甲基醚醋酸酯及25.5份的二丙酮醇而製備。
實驗實施例1 – 儲存安定性的評估
將實施例及比較實施例中所製備的每個彩色光敏樹脂組合物的初始黏度予以測量，並且將其在5℃儲存1個月之後再次測量黏度，然後從這些所測量的數值中觀察黏度的改變。黏度的測量是在25℃利用Brookfield黏度計（DVI+，由Brookfield公司所製造）而執行。測量的結果顯示於以下表1。
○：5%或更少的黏度改變
△：高於5%至10%的黏度改變
X：高於10%的黏度改變
實驗實施例2
在將實施例及比較實施例中所製備的每個彩色光敏樹脂組合物，經由旋轉塗佈法以2英吋的角度（由Corning公司所製造的「EAGLE XG」）分別塗佈到玻璃基板後，將塗佈的基板置於加熱板上，並將其在100℃的溫度留置3分鐘，以形成一薄膜。接著，將具有範圍1至100%的步進式改變穿透性的圖樣及大小1至50μm的線條/空間圖樣之測試光罩置於該薄膜上，然後在100 μm的距離以UV照射該測試光罩。此處，用於UV照射的光源是1KW高壓汞（Hg）燈，其包含所有的g、h及i-方向，並且以100 mJ/cm2的照射強度發散光。將UV照射的薄膜在pH 10.5的KOH顯像劑溶液中浸泡2分鐘，藉以顯像。在塗佈薄膜的玻璃基板以蒸餾水清洗之後，藉由氮氣吹乾，並且在200℃的熱烘箱中加熱25分鐘。結果形成一彩色濾光片。上述所形成的彩色濾光片具有2.3 μm的膜厚度。
(1) 顯像速率的測量
測量在顯像期間直到非曝光部分完全溶解所需的時間，以及測量的結果是顯示於表1。
(2) 圖樣線條寬度的測量
觀察所形成的圖樣之線條寬度，並且利用掃瞄式電子顯微鏡測量線條寬度。當所測量的線條寬度不小於光罩的線條寬度時，可決定該彩色光敏樹脂組合物具有足夠延伸線條寬度的敏感度。相對於光罩之延伸的線條寬度是顯示於表1。
(3) 黏著性的評估
藉由通過光學顯微鏡觀察所形成的圖樣，圖樣挑選是根據以下圖樣挑選的標準而評估。評估的結果是顯示於表1。
○：沒有觀察到圖樣挑選
△：1至3個圖樣挑選
X：4或更多個圖樣挑選
實驗實施例3 – 穿透性的測量
彩色濾光片是根據如實驗實施例2所述之相同方法而形成，除了不使用測試用之光罩外。
利用色度計（由Olympus公司所製造的OSP-200）測量在可見光區域的穿透性。測量的結果是顯示於表1。

參考上述表1，實施例1至8所製備的組合物具有優異的儲存安定性，涉及小的黏度改變、高的顯像速率及優異的敏感性圖樣黏著性。此外，也可觀察到利用相同組合物所製造的彩色濾光片具有高的穿透性。
相反地，發現到在比較實施例1至8所製備的組合物具有惡化的儲存安定性，其造成黏度的改變或差的特性，例如，顯像速率、敏感性、黏著性等，以及利用相同組合物所製造的彩色濾光片顯示穿透性的降低。
The present invention discloses a color photosensitive resin composition comprising a colorant, an alkali soluble resin, a photo-polymerizable compound, a photo-polymerization initiator, and a solvent, wherein the colorant comprises a pigment and a dye; the alkaline soluble resin An acid value of 30 to 170 mg KOH/g, and is contained therein in an amount of 5 to 10 wt.% solid content based on the total weight of the composition; the basic soluble resin and the hydroxyl value of the photo-polymerizable compound The sum of the range is from 30 to 180 mg KOH/g; and the photo-polymerization initiator includes the compound of Formula 1, whereby the composition can have a high imaging rate and excellent sensitivity and adhesion to inhibit The peeling of the pattern during the development process, and excellent storage stability, does not show a decrease in sensitivity or an increase in viscosity even during long storage, and therefore, a color filter manufactured using the same composition can be used. Excellent high contrast.
The invention will be explained in more detail below.
The color photosensitive resin composition of the present invention may include a colorant, an alkali soluble resin, a photo-polymerizable compound, a photo-polymerization initiator, and a solvent.
<colorant>
Colorants include pigments and dyes.
The pigment used in the present invention may include any of the organic pigments, inorganic pigments or mixtures thereof generally used in the art.
The organic dye is not particularly limited, but may include any general pigment used for printing inks, inkjet inks, etc., more particularly water-soluble azo dyes, water-insoluble azo dyes, phthalocyanine pigments, quinophthalones. Pigment, isoindolinone pigment, isoporphyrin pigment, anthraquinone pigment, purple ketone pigment, bisoxazine pigment, lyche pigment, lycopene pigment, pyrimidine pigment, quinone ketone pigment, blue quinone A ketone pigment, a yellow ketone pigment, a dermatoside dye, a diketopyrrolopyrrole pigment, or the like, which may be used singly or in combination of two or more.
The inorganic pigment is not particularly limited, but may include a metal compound such as a metal oxide or a metal complex, more particularly selected from the group consisting of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, An oxide of at least one metal selected from the group consisting of ruthenium and carbon black, which may be used singly or in combination of two or more.
The organic pigments and inorganic pigments may include compounds classified as pigments according to a color index (published by the Society of Colorists). More particularly, CI pigment yellows 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154 can be used. 166, 173, 180 and 185; CI pigments orange 13, 13, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71; CI pigment red 9, 97, 105, 122, 123,144,149,166,168,176,177,180,192,208,215,216,224,242,254,255, and 264; CI pigment purple 14, 19, 23, 29, 32, 33, , 37 and 38; CI pigment blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64 and 76; CI pigment green 7, 10, 15, 25, 36, 47 and 58; CI pigment brown 28; CI pigment black 1 and 7, and the like. Preferably, CI pigment yellow 138, CI pigment yellow 139, CI pigment yellow 150, CI pigment yellow 185, CI pigment orange 38, CI pigment red 122, CI pigment red 166, CI pigment red 177, CI pigment red 208, CI can be used. Pigment red 242, CI pigment red 254, CI pigment red 255, CI pigment purple 23, CI pigment blue 15:3, pigment blue 15:6, CI pigment green 7, CI pigment green 36, and CI pigment green 58, and the like. These may be used singly or in combination of two or more.
The content of the pigment is not particularly limited, but may range, for example, from 5 to 95 wt.% of the total weight of the colorant, preferably from 10 to 90 wt.%. If the content of the pigment is within the above range, the color filter manufactured by using the same composition can have a sufficient color area and excellent penetrability, and can ensure the desired sensitivity, thereby avoiding the display. Like the color picking during the period (pattern).
The dye is not particularly limited as long as it has solubility in an organic solvent and ensures reliability (for example, solubility in an alkali developer, heat resistance, solvent resistance, etc.). The dye may include, for example, an acid dye having an acidic group, for example, a sulfonic acid, a carboxylic acid, or the like; a salt of a nitrogen-containing compound and an acid dye; a sulfonamide of an acid dye and a derivative thereof; based on azo-, oxa Acid dyes and their derivatives, etc. of 蒽- and/or phthalocyanine.
The dye preferably includes a compound classified as a dye in a color index (published by the Society of Dyes), or a red, blue, and violet dye listed in the dye note (color dye company).
The dye is not particularly limited, but may include, for example, a CI solvent dye: a yellow dye, for example, CI solvent yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163, etc.; red dye, for example, CI solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179, etc.; orange dye, for example , CI solvent orange 2, 7, 11, 15, 26, 41, 45, 56, 62, etc.; blue dye, for example, CI solvent blue 5, 35, 36, 37, 44, 59, 67, 70, etc.; Purple dye, for example, CI solvent purple 8, 9, 13, 14, 36, 37, 47, 49, etc.; green dye, for example, CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33 34, 35, etc., and in terms of excellent solubility in an organic solvent, preferably CI solvent yellow 14, 16, 21, 56, 151, 79, 93; CI solvent red 8, 49, 89, 111, 122, 132, 146, 179; CI solvent orange 41, 45, 62; CI solvent blue 35, 36, 44, 45, 70; CI solvent purple 13, etc., and more preferably CI solvent yellow 21, 79; CI solvent red 8, 122, 132; CI solvent orange 45, 62.
In addition, the dye may also include, for example, CI acid dyes: yellow dyes, for example, CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65 , 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161 , 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232 , 235, 238, 240, 242, 243, 251, etc.; red dye, for example, CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426, etc. Orange dyes, for example, CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, etc. Blue dye, for example, CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87 , 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290 , 296, 315, 324: 1, 335, 340, etc.; purple dyes, for example, CI acid purple 6B, 7, 9, 17, 19, 66, etc.; green dyes, for example, CI acid green 1, 3, 5, 9 , 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc., and in terms of excellent solubility in an organic solvent, preferably CI acid yellow 42; CI acid red 92; CI acidity Blue 80, 90; CI acid purple 66; CI acid green 27 and so on.
In addition, the dye may also include, for example, a direct dye: a yellow dye, for example, CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141, etc.; red dyes, such as CI direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250 or the like; orange dye, for example, CI direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, etc.; blue dye, For example, CI direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109,113,114,115,117,119,137,149,150,153,155,156,158,159,160,161,162,163,164,166,167,170,171,172,173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 22 2, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc.; purple dyes, such as CI Directly purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104, etc.; green dyes, such as CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, and the like.
In addition, the dye may also include, for example, CI mordant dye: yellow dye, such as CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, etc. Red dye, for example, CI mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37 , 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95, etc.; orange dyes, such as CI mordant orange 3, 4, 5 , 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc.; blue dye, such as CI mord blue 1 , 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48 , 49, 53, 61, 74, 77, 83, 84, etc.; purple dyes, such as CI mordant purple 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41 , 44, 45, 47, 48, 53, 58 etc.; green dyes, such as CI mord green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 Wait.
These may be used singly or in combination of two or more.
The content of the dye is not particularly limited, but may range, for example, from 5 to 95 wt.% solid content based on the total weight of the colorant, preferably from 10 to 90 wt.% solid content. If the content of the dye is within the above range, deterioration of credibility (for example, dye elution due to an organic solvent after patterning) can be avoided while achieving excellent sensitivity.
The content of the colorant is not particularly limited, but may range, for example, from 5 to 60 wt.% solid content, preferably from 10 to 45 wt.% solid content, based on the total weight of the color photosensitive resin composition. If the content of the colorant is within the above range, the pixels can have a sufficient color density, and the lack of a non-pixel portion during development does not decrease. Therefore, the occurrence of residue can be reduced.
The colorant is added to the composition in the form of a dispersion to be uniformly mixed in the composition. The dispersion can be prepared by incorporating a dispersant and a solvent (not a colorant) which are usually used in the composition.
The dispersant is added to deagglomerate and maintain the stability of the pigment and dye. The dispersing agent can include any dispersing agent generally used in the art without limitation. Preferably, an acrylate dispersant such as butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA); a polycarboxylate; an unsaturated polyamine; Polycarboxylic acid; (partial) amine salt of polycarboxylic acid; ammonium salt of polycarboxylic acid; alkylamine salt of polycarboxylic acid; polyoxyalkylene; long chain polyamine phthalamide phosphate; hydroxyl group-containing polycarboxylate An acid ester and a modified product thereof; a guanamine or a salt thereof formed by reacting a polyester having a free carboxyl group and a poly(lower alkylene imine); a water-soluble resin or a water-soluble polymeric compound, for example, (methyl) Acrylic-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene-buy acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; polyester; modified polyacrylate Addition products of ethylene oxide/propylene oxide; phosphate esters and the like. These compounds may be used singly or in combination of two or more.
Commercially available dispersants useful in the present invention may include, for example, DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184, DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150 (BYK Chemical Company); EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800 (BASF) ;SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 (Lubirzol); HINOACT T-6000, HINOACT T-7000, HINOACT T-8000 (Kawaken Precision Chemical Company); AJISPUR PB-821, AJISPUR PB-822 AJISPUR PB-823 (Ajinomoto Co., Ltd.); FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44 (Kyoeisha Chemical Co., Ltd.), etc., which may be used singly or in combination of two or more.
The content of the dispersant is not particularly limited, but may be, for example, a solid content of 5 to 60 parts by weight of the pigment, preferably 15 to 50 parts by weight to 100 parts by weight of the pigment. If the content of the dispersant is within the above range, the pigment may suitably form fine particles, and the colorant dispersion may have a desired viscosity.
<alkaline soluble resin>
The alkali-soluble resin is polymerized by incorporating an ethylenically unsaturated monomer having a carboxyl group. The ethylenically unsaturated monomer having a carboxyl group is a component which imparts a soluble substance to the alkaline developer used in the development process when forming a pattern.
The ethylenically unsaturated monomer having a carboxyl group is not particularly limited, but may include, for example, a monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid or the like; a dicarboxylic acid such as fumaric acid or methyl aconaconic acid. And itaconic acid and the like; and a mono(meth)acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends thereof, for example, ω-carboxypolycaprolactone mono(meth)acrylate, etc. Acrylic acid and methacrylic acid are preferably used alone or in combination of two or more.
The acid value of the alkali-soluble resin is not particularly limited, but may range, for example, from 30 to 170 mg KOH/g, and preferably from 50 to 160 mg KOH/g. If the acid value of the alkali-soluble resin is within the above range, the resin can be more compatible with the dye to avoid dye precipitation, the color photosensitive resin composition can have excellent storage stability to maintain the desired viscosity, and sufficient Development rate.
In order to ensure further development properties of the alkali-soluble resin, the resin may have a hydroxyl group. The sum of the hydroxyl values of the alkali-soluble resin and the photo-polymerizable compound may range from 30 to 180 mg KOH/g, and preferably from 40 to 140 mg KOH/g. If the sum of the hydroxyl values of the alkali-soluble resin and the photo-polymerizable compound is within the above range, the flatness of the pattern and the compatibility of the resin with the dye may be excellent.
The method of supplying a hydroxyl group to the alkali-soluble resin is not particularly limited, but may include, for example, polymerization of a resin when further adding an ethylenically unsaturated monomer having a hydroxyl group; and a resin and a compound having a glycidyl group; The reaction is carried out; a copolymer polymerized by further adding a vinyl group-unsaturated monomer having a hydroxyl group is allowed to react with a compound having a glycidyl group and the like.
The ethylenically unsaturated monomer having a hydroxyl group is not particularly limited, but may include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 4- Hydroxybutyl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, N-hydroxyethyl acrylamide, and the like, and preferably 2-hydroxyethyl (meth)acrylate. These may be used singly or in combination of two or more.
The compound having a glycidyl group is not particularly limited, but may include, for example, butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, Glycidyl methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, benzyl glycidyl ether, glycidyl-4-third-butyl benzoate, shrinkage Glyceryl stearate, aryl glycidyl ether, glycidyl methacrylate, and the like, and preferably butyl glycidyl ether, aryl glycidyl ether, and glycidyl methacrylate. These may be used singly or in combination of two or more.
The alkali-soluble resin of the present invention can be polymerized while further incorporating at least one other monomer copolymerizable with the above monomers. For example, aromatic vinyl compounds, for example, styrene, vinyl toluene, methyl styrene, p-chlorostyrene, o-methoxy styrene, m-methoxy styrene, p-methoxy benzene Ethylene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidol Ether, p-vinylbenzyl glycidyl ether, etc.; N-substituted maleimide compound, for example, N-cyclohexylmaleimine, N-benzyl maleimide, N-phenyl Maleate, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-A Phenyl-maleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenyl malayan Amine, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide, etc.; alkyl (meth)acrylate, for example, (meth)acrylic acid Base ester, ethyl (meth)acrylate, n-propyl (meth)acrylate, (methyl) Isopropyl acrylate, n-butyl (meth) acrylate, isobutyl butyl (meth) acrylate, second butyl (meth) acrylate, third (meth) acrylate Butyl ester or the like; (meth) acrylate cycloaliphatic ester, for example, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, ( Methyl)acrylic acid tricyclo[5.2.1.0.2.6]癸-8-yl ester, 2-dicyclopentanediol oxyethyl (meth)acrylate, isodecyl (meth)acrylate, etc.; An aryl acrylate, for example, phenyl (meth) acrylate, benzyl (meth) acrylate, etc.; an unsaturated propylene oxide compound, for example, 3-(methacryl fluorenyloxymethyl) Propylene oxide, 3-(methacryloyloxymethyl)-3-ethyl propylene oxide, 3-(methacryloyloxymethyl)-2-trifluoromethyl propylene oxide, 3- (Methacrylium decyloxymethyl)-2-phenyl propylene oxide, 2-(methacryl fluorenyloxymethyl) propylene oxide, 2-(methacryl fluorenyloxymethyl)-4- Tetrafluoromethyl propylene oxide or the like, which may be used singly or in combination of two or more.
The content of the alkali-soluble resin is not particularly limited, but may range, for example, from 5 to 10 wt.% solid content based on the total weight of the color photosensitive resin composition. If the content of the alkali-soluble resin is within the above range, it can have sufficient solubility properties in the developer, making patterning easy, and avoiding the film of the pixel portion of the exposed portion during development (film) ) reduction, resulting in a reduction in the lack of non-pixel parts.
Specific examples of a method of preparing an alkali-soluble resin will be explained below.
Adding the above-exemplified monomer, 0.5 to 20 times solvent relative to the monomer content, and 0.1 to 10% of the polymerization initiator of the monomer molar amount, to a device equipped with a stirrer, a thermometer, a reflux cooling tube, and a titration device And a nitrogen inlet tube in an Erlenmeyer flask, and then replaced with nitrogen. Thereafter, it was stirred at 40 to 140 ° C for 1 to 10 hours.
The solvent used herein may be any solvent conventionally used for radical polymerization, and may include, for example, any one selected from the group consisting of tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ethyl acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol , a group consisting of n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, toluene, xylene, ethylbenzene, chloroform and dimethyl azine, which may be used alone or in a mixture And use.
The polymerization initiator may be any polymerization initiator conventionally used in the related art, and is not particularly limited. More particularly, organic peroxides may be included, for example, dicumyl hydroperoxide, di-tert-butyl peroxide, benzammonium peroxide, third-butyl peroxyester isopropyl carbonate, Tris-pentylperoxy-2-ethyl hexanoate, third-butylperoxy-2-ethyl hexanoate, etc.; and nitrogen compounds, for example, 2,2'-azobis ( Isobutyronitrile), 2,2'-azobis(2,4-dimethylbutyronitrile), dimethyl-2,2'-azobis(2-methylpropionic acid), etc.; Use or combine two or more types.
In order to control the molecular weight during the above process, an α-methylstyrene dimer or an anthracene compound can be used as a chain transfer agent. Such an α-methylstyrene dimer or an anthracene compound may be used in an amount of from 0.005 to 5 parts by weight to 100 parts by weight of the monomer. With regard to the conditions of the polymerization, the feeding method and the reaction temperature can be appropriately controlled in consideration of the exothermic value of the polymerization or the manufacturing equipment.
<Light-polymerizable compound>
The photo-polymerizable compound is a component which enhances the strength of the pattern and may include a mono-functional, di- or poly-functional monomer or the like, preferably a di-functional or more monomer. For example, specific examples thereof may include: a mono-functional monomer such as nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl acrylate Alcohol ester, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, etc.; bis-functional monomer, for example, 1,6-hexanediol di(meth)acrylate, di(meth)acrylic acid Ethylene glycol ester, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, di(meth)acrylic acid 3-methylpentanediol ester, 3-(propylene decyloxy)-2-hydroxypropyl methacrylate, 2-hydroxy-1,3-dimethylpropenyloxypropane, 2-hydroxyl 1-propenylmercapto-3-methylpropenyloxypropane or the like; a tri-functional monomer, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and the like; a tetra-functional monomer, for example, pentaerythritol tetra(meth)acrylate; a penta-functional monomer, for example, dipentaerythritol penta(meth)acrylate; a hexa-functional monomer, for example, hexa-methyl Dipentaerythritol Acrylate And the like, which may be used alone or in combination of two or more is used.
The photo-polymerizable compound may include a bis-functional or higher poly-functional monomer, and more preferably a five-functional or higher poly-functional monomer, in terms of enhancing pattern strength and improving smoothness.
Commercially available photo-polymerizable compound products may include, for example, 701 (NK ESTER), 701A (NK ESTER), ATMM-3L (NK ESTER), KAYARAD DPHA (Nippon Chemicals), and the like.
The content of the photo-polymerizable compound is not particularly limited as long as the sum of the hydroxyl values of the alkali-soluble resin and the photo-polymerizable compound satisfies the above range, however, for example, the range may be from 5 to 70 based on the total weight of the color photosensitive resin composition. The wt.% solids content is preferably 15 to 65 wt.% solids. If the photo-polymerizable compound content is within the above range, the pixel portion may have favorable strength or smoothness.
<Light-polymerization initiator>
The photo-polymerization initiator of the present invention may include a compound represented by the following formula 1:
[Formula 1]


Where R 1 representative ;R 2 And R 3 Each independently is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group or a diphenyl sulfide group, which is substituted or unsubstituted with a hydroxyl group or an alkyl group having 1 to 8 carbon atoms; 4 Is an alkylene group having 1 to 4 carbon atoms; and R 5 It is a cycloalkyl group having 3 to 8 carbon atoms.
The photo-polymerization initiator shown in Formula 1 can prevent the sensitivity from being lowered by the relationship of the dye, and thus can provide an effective photo-polymerization property of the color photosensitive resin composition containing the dye.
In addition to the photo-polymerization initiator represented by Formula 2, the color photosensitive resin composition of the present invention may further comprise at least one photo-polymerization initiator generally used in the related art. For example, an acetophenone compound, a diphenylketone compound, a triazine compound, a biimidazole compound, a thioxanthone compound, or the like can be included. These compounds may be used singly or in combination of two or more.
The acetophenone compound is not particularly limited, but may include, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2 -hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxyhexyl phenyl ketone, 2-methyl-1-(4-methyl Thiophenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-hydroxyl -2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1 -(4-morpholinylphenyl)butan-1-one.
The diphenyl ketone compound is not particularly limited, but may include, for example, diphenyl ketone, benzhydryl methyl benzoate, 4-phenyl diphenyl ketone, 4-benzyl fluorenyl-4'-A Diphenyl sulfide, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)diphenyl ketone, 2,4,6-trimethyldiphenyl ketone, and the like.
The triazine compound is not particularly limited, but may include, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4- Di(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-di(trichloromethyl)-6-mallowyl-1,3, 5-triazine, 2,4-di(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-di(trichloromethyl) -6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-di(trichloromethyl)-6-[2-(furan- 2-yl)vinyl]-1,3,5-triazine, 2,4-di(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl) Vinyl]-1,3,5-triazine, 2,4-di(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3, 5-triazine and the like.
The biimidazole compound is not particularly limited, but may include, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-di ( 2,3-Dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'- Tetrakis(alkoxyphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)bisimidazole, 2,2 - bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole or having a carbene at the 4,4',5,5' position Any imidazole compound of an oxy-substituted phenyl group is preferably bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-di (in the above compound). 2,3-Dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole or 2,2-bis(2,6-dichlorophenyl)-4,4',5,5 '-Tetraphenyl-1,2'-bisimidazole and the like.
The thioxanthone compound is not particularly limited, but may include, for example, 2-isopropylthioxanthone, 2,4-diethylthiaxanone, 2,4-dichlorothiazepinone, 1- Chloro-4-propoxythiaxanthone and the like.
The content of the photo-polymerization initiator is not particularly limited, but may be, for example, 0.1 to 40 wt.% solid content, preferably 1 to 30 wt.%, based on the total content of the alkali-soluble resin and the photo-polymerizable compound. Solid content. If the content of the photo-polymerization initiator is within the above range, the color photosensitive resin composition becomes highly sensitive to reduce the exposure time, thereby improving the yield while retaining high resolution. Further, the formed pixel portion can also have advantageous strength and can achieve excellent smoothness on the surface of the pixel portion.
In the above photo-polymerization initiator, the content of the compound represented by Formula 1 is not particularly limited, but may be, for example, 10 to 100 wt.%, preferably 20 to 100, based on the total weight of the photo-polymerization initiator. Wt.%. If the content of the compound represented by Formula 1 is within the above range, the effect of improving the sensitivity can be maximized.
<Light-polymerization initiation enhancer>
The color photosensitive resin composition of the present invention may further include a photo-polymerization initiation enhancer to improve sensitivity.
The photo-polymerization initiation enhancer is not particularly limited, but may include, for example, an amine compound, a carboxylic acid compound or a thiol group-containing organic sulfur compound, etc., which may be used singly or in combination of two or more.
The amine compound is not particularly limited, but may include, for example, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, triisopropanolamine or the like; an aromatic amine compound such as 4-dimethylamine. Methyl benzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl o-toluidine, 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis (two Ethylamino)diphenyl ketone and the like.
The carboxylic acid compound is not particularly limited, but may include, for example, an aromatic heteroacetic acid such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylsulfuric acid, and dimethyl ester. Phenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthalene Sulfuric acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.
The organic sulfur compound having a thiol group is not particularly limited, but may include, for example, 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyloxy)butane, 1,3,5-tri ( 3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionic acid), Pentaerythritol tetrakis(3-mercaptobutyric acid), pentaerythritol tetrakis(3-mercaptopropionic acid), dipentaerythritol hexakis(3-mercaptopropionic acid), tetraethylene glycol bis(3-mercaptopropionic acid), and the like.
The content of the photo-polymerization initiation enhancer is not particularly limited, but may be, for example, 0.1 to 40 wt.% solid content, preferably 1 to 30 wt.% solid content, based on the total weight of the color photosensitive resin composition. If the content of the photo-polymerization initiation enhancer is within the above range, the sensitivity of the color photosensitive resin composition can be further improved, thereby enhancing the yield.
<solvent>
The solvent to be used in the present invention is not particularly limited as long as it can dissolve the above components, but may include, for example, an ether, an aromatic hydrocarbon, a ketone, an alcohol, an ester, etc., which may be used singly or in combination of two or more. .
Specific examples may include: ethylene glycol monoalkyl ethers, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, etc.; For example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, methyl racere acetate, ethyl racemic acid acetate Ester, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, a diol, glycerin or the like; an ester such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, γ-butyrolactone or the like, and preferably propylene glycol monomethyl ether acetate , propylene glycol monoethyl ether acetate, cyclohexanone ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate.
The solvent is preferably an organic solvent having a boiling point of 100 to 200 ° C in terms of applicability and drying.
The content of the solvent is not particularly limited, but the solvent may, for example, include the solvent contained in the colorant dispersion, and the overall content may range from 60 to 90 wt.%, based on the total weight of the color photosensitive resin composition, preferably 70 to 85 wt.%. If the content of the solvent is within the above range, advantageous applicability can be achieved.
<additive>
The color photosensitive resin composition of the present invention may further comprise any one selected from the group consisting of an alternative polymeric compound, a curing agent, a surfactant, an adhesion enhancer, a UV absorber, and an anticoagulant.
Such an alternative polymeric compound is not particularly limited, but may include, for example, a curable resin such as an epoxy resin, a maleimide resin, or the like; a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, or polyethylene. Alcohol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, and the like.
The curing agent is a component for deep curing and increasing mechanical strength, and the kind of the curing agent is not particularly limited, but may include, for example, an epoxy compound, a poly-functional isocyanate compound, a melamine compound, a propylene oxide compound, or the like.
The epoxy compound is not particularly limited, but may include, for example, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, Other aromatic epoxy resins, aliphatic epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of epoxy resins; aliphatics other than epoxy resins and their brominated derivatives, Cycloaliphatic or aromatic compound; butadiene (co)polymer epoxide; isoprene (co)polymer epoxide; glycidyl (meth)acrylic (co)polymer; isocyanide Triglycidyl urate and the like.
The propylene oxide compound is not particularly limited, but may include, for example, carbonate dioxetane, xylene dioxetane, adipic acid dioxetane, and dioxyethylene terephthalate. Butane, cyclohexanedicarboxylic acid dioxetane, and the like.
The curing agent may be compatible with the curing aid compound, and the curing assistant compound may cause ring-opening polymerization of the epoxy group of the epoxy compound or the propylene oxide skeleton of the propylene oxide compound.
The curing assistant compound is not particularly limited, but may include, for example, a polyvalent carboxylic acid, a polyvalent carboxylic anhydride, an acid generator, and the like. The polyvalent carboxylic anhydride may include any commercially available epoxy curing agent.
The commercially available epoxy resin curing agents which can be used in the present invention are not particularly limited, but may include, for example, Adekahadona EH-700 (trade name, manufactured by Adeka Engineering Co., Ltd.), Likashitdo HH (trade name, by new Manufactured by Nippon Chemical Co., Ltd., MH-700 (trade name, manufactured by Nippon Chemical Co., Ltd.), etc.
The surfactant is used to improve the coating formability of the photosensitive resin composition, and the kind thereof is not particularly limited, but may include, for example, a fluorine surfactant, a quinone surfactant, or a mixture thereof.
The 矽 surfactant is not particularly limited, but may include commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc. manufactured by Dow-corning Doray Silicon Co., Ltd.; TSF- manufactured by GE Toshiba Silicon Co., Ltd. 4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452, and the like.
The fluorosurfactant is not particularly limited, but may include commercially available products such as large fragments F-470, F-471, F-475, F-482, F-489, etc. manufactured by Dainippon Ink Chemical Industry. .
The kind of the adhesion enhancer is not particularly limited, but may include, for example, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2- Aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethyl Oxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Baseline, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxy Oxane, 3-isocyanatopropyltrimethoxydecane, 3-isocyanatopropyltriethoxydecane, etc., may be used singly or in combination of two or more.
The content of the adhesion enhancer is not particularly limited, but may range, for example, from 0.01 to 10 wt.% solid content, preferably from 0.05 to 2 wt.% solid content, based on the total weight of the color photosensitive resin composition.
The kind of the antioxidant is not particularly limited, but may include, for example, 2,2'-thiobis(4-methyl-6-tri-butylphenol), 2,6-di-third-butyl-4 -methylphenol and the like.
The kind of the UV absorber is not particularly limited, but may include, for example, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxy Phenyl ketone and the like.
The anticoagulant is not particularly limited, but may include, for example, sodium polyacrylate.
<Preparation of color photosensitive resin composition>
The method of preparing the color photosensitive resin composition of the present invention may include, for example, adding a coloring agent and a dispersing agent to a solvent and dispersing it to prepare a coloring agent dispersion having a uniform particle size; and an alkali soluble resin, light- The polymerizable compound, the photo-polymerization initiator, and optionally other additives are dissolved in a solvent and mixed with the above-described colorant dispersion; and a fresh solvent is further added as needed.
<Color Filter>
Further, the present invention also provides a color filter manufactured using the above-described color photosensitive resin composition.
The color filter includes a substrate and a color layer formed over the substrate.
The substrate may be an original substrate for the color filter itself or a portion of the display device on which the color filter is placed, and therefore, is not particularly limited.
The substrate may be glass, germanium (Si), or germanium oxide (SiO) x Or a polymer substrate, and the polymer substrate may be formed of polyether oxime (PES), polycarbonate (PC) or the like.
The color layer is a layer containing the color photosensitive resin composition of the present invention, and can be formed by applying a color photosensitive resin composition to the layer, and exposing, developing, and thermally curing the coating layer to form a desired pattern. .
The color filter having the above substrate and color layer may further include a barrier layer formed between the respective color patterns and/or black matrix. In addition, the color filter may also include a protective layer formed over the color layer.
<Liquid Crystal Display Device>
Further, the present invention also provides a liquid crystal display device including the above color filter.
The liquid crystal display device of the present invention may include a technical configuration known in the art to which the present invention pertains, and is not particularly limited except for having the above-described color filter.
The preferred embodiments are described below to more specifically understand the present invention. However, it is obvious to those skilled in the art that the specific embodiments are provided for the purpose of illustration, and are not intended to limit the scope of the appended claims. Modifications and variations are possible, and such modifications and changes are appropriately included in the invention as defined in the appended claims.
Example
Preparation Example - Preparation of Colorant Dispersion
The colorant dispersion was prepared by dispersing 14 parts by weight of CI Pigment Red 254, 6 parts by weight of AJISPUR PB821 (manufactured by AJINOMOTO Fine Techno Co., Ltd.) as a dispersing agent, and 60 parts by weight of propylene glycol monomethyl ether acetate. The solvent of 20 parts by weight of cyclohexanone was prepared by mixing and dispersing for 12 hours by a bead-grinding method.
Synthesis Example - Synthesis of Alkaline Soluble Resin
(1) Synthesis Example 1
120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of azobisisobutyronitrile (AIBN), 13.0 parts of acrylic acid, 10 parts of benzyl methacrylate, 57.0 Parts of 4-methylstyrene, 20 parts of methyl methacrylate and 3 parts of n-dodecyl mercaptan, introduced into a mixer, thermometer, reflux cooling tube, titration device and nitrogen inlet tube In the conical flask, the air in the conical flask was exchanged with nitrogen. Next, the reaction was carried out for 6 hours while raising the temperature to 110 ° C and stirring. The synthesized alkali-soluble resin had an acid value of 100.2 mg KOH/g and a hydroxyl value of 0 mg KOH/g (solid content), and a weight average molecular weight (Mw) of about 15,110 as measured by GPC.
(2) Synthesis Example 2
120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of azobisisobutyronitrile, 9.0 parts of acrylic acid, 10 parts of benzyl methacrylate, 54.0 parts of 4 -methylstyrene, 20 parts of methyl methacrylate, 7.0 parts of 2-hydroxyethyl (meth)acrylate and 3 parts of n-dodecyl mercaptan, introduced into a blender, The thermometer, the reflux cooling tube, the titration device, and the conical flask of the nitrogen introduction tube were used, and the air in the conical flask was exchanged with nitrogen. Next, the reaction was carried out for 6 hours while raising the temperature to 110 ° C and stirring. The synthesized alkali-soluble resin had an acid value of 69.4 mg KOH/g and a hydroxyl value of 29.8 mg KOH/g (solid content), and a weight average molecular weight (Mw) of about 13,180 as measured by GPC.
(3) Synthesis Example 3
120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of azobisisobutyronitrile, 3.5 parts of acrylic acid, 10 parts of benzyl methacrylate, 66.5 parts of 4 -methylstyrene, 20 parts of methyl methacrylate and 3 parts of n-dodecyl mercaptan, introduced into a cone equipped with a stirrer, thermometer, reflux cooling tube, titrator and nitrogen inlet tube In the bottle, the air in the conical flask is exchanged with nitrogen. Next, the reaction was carried out for 6 hours while raising the temperature to 110 ° C and stirring. The synthesized alkali-soluble resin had an acid value of 26.5 mg KOH/g and a hydroxyl value of 0 mg KOH/g (solid content), and a weight average molecular weight (Mw) of about 16,070 as measured by GPC.
(4) Synthesis Example 4
120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of azobisisobutyronitrile, 22.5 parts of acrylic acid, 10 parts of benzyl methacrylate, 47.5 parts of 4 -methylstyrene, 20 parts of methyl methacrylate and 3 parts of n-dodecyl mercaptan, introduced into a cone equipped with a stirrer, thermometer, reflux cooling tube, titrator and nitrogen inlet tube In the bottle, the air in the conical flask is exchanged with nitrogen. Next, the reaction was carried out for 6 hours while raising the temperature to 110 ° C and stirring. The synthesized alkali-soluble resin had an acid value of 172.3 mg KOH/g and a hydroxyl value of 0 mg KOH/g (solid content), and a weight average molecular weight (Mw) of about 14,850 as measured by GPC.
Example 1
The color photosensitive resin composition was prepared by mixing 33.8 parts of a colorant dispersion, 0.5 part of CI Acid Red 52 (manufactured by TCI America Co., Ltd.), 4.1 parts of the resin synthesized in Synthesis Example 1, and 5.6 parts. Mg KOH/g hydroxyl value of dipentaerythritol acrylated product (0.37 parts of dipentaerythritol tetraacrylate / 1.31 parts of dipentaerythritol pentaacrylate / 3.92 parts of dipentaerythritol hexaacrylate), 0.2 parts of Irgacure 369 (by (manufactured by BASF Corporation), 0.5 parts of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure shown in the following formula 2, 29.8 parts of propylene glycol monomethyl ether acetate, and 25.5 parts of diacetone alcohol were prepared.
[Formula 2]


Example 2

The color photosensitive resin composition was prepared by mixing 33.8 parts of a colorant dispersion, 0.5 part of CI Acid Red 52 (manufactured by TCI America Co., Ltd.), 4.1 parts of the resin synthesized in Synthesis Example 1, and 5.6 parts having 80 parts. Mg KOH/g hydroxyl value of dipentaerythritol acrylated product (1.13 parts of dipentaerythritol tetraacrylate / 1.65 parts of dipentaerythritol pentaacrylate / 2.82 parts of dipentaerythritol hexaacrylate), 0.2 parts of Irgacure 369 (by Prepared by BASF Corporation, 0.5 parts of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure shown in Formula 2, 29.8 parts of propylene glycol monomethyl ether acetate, and 25.5 parts of diacetone alcohol.
Example 3
The color photosensitive resin composition was prepared by mixing 33.8 parts of a colorant dispersion, 0.5 part of CI Acid Red 52 (manufactured by TCI America Co., Ltd.), 4.1 parts of the resin synthesized in Synthesis Example 1, and 5.6 parts. Mg KOH/g hydroxyl value of dipentaerythritol acrylated product (1.59 parts of dipentaerythritol tetraacrylate / 1.86 parts of dipentaerythritol pentaacrylate / 2.15 parts of dipentaerythritol hexaacrylate), 0.2 parts of Irgacure 369 (by Prepared by BASF Corporation, 0.5 parts of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure shown in Formula 2, 29.8 parts of propylene glycol monomethyl ether acetate, and 25.5 parts of diacetone alcohol.
Example 4
The color photosensitive resin composition was prepared by mixing 33.8 parts of a colorant dispersion, 0.5 part of CI Acid Red 52 (manufactured by TCI America Co., Ltd.), 4.1 parts of the resin synthesized in Synthesis Example 1, and 5.6 parts. Mg KOH / g hydroxyl value of dipentaerythritol acrylated product (2.72 parts of dipentaerythritol tetraacrylate / 2.37 parts of dipentaerythritol pentaacrylate / 0.51 parts of dipentaerythritol hexaacrylate), 0.2 parts of Irgacure 369 (by Prepared by BASF Corporation, 0.5 parts of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure shown in Formula 2, 29.8 parts of propylene glycol monomethyl ether acetate, and 25.5 parts of diacetone alcohol.
Example 5
The color photosensitive resin composition was prepared by mixing 33.8 parts of a colorant dispersion, 0.5 part of CI Acid Red 52 (manufactured by TCI America Co., Ltd.), 4.1 parts of the resin synthesized in Synthesis Example 2, and 5.6 parts. Mg KOH/g hydroxyl value of dipentaerythritol acrylated product (0.37 parts of dipentaerythritol tetraacrylate / 1.31 parts of dipentaerythritol pentaacrylate / 3.92 parts of dipentaerythritol hexaacrylate), 0.2 parts of Irgacure 369 (by Prepared by BASF Corporation, 0.5 parts of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure shown in Formula 2, 29.8 parts of propylene glycol monomethyl ether acetate, and 25.5 parts of diacetone alcohol.
Example 6
The color photosensitive resin composition was prepared by mixing 33.8 parts of a colorant dispersion, 0.5 part of CI Acid Red 52 (manufactured by TCI America Co., Ltd.), 4.1 parts of the resin synthesized in Synthesis Example 2, and 5.6 parts having 80 parts. Mg KOH/g hydroxyl value of dipentaerythritol acrylated product (1.13 parts of dipentaerythritol tetraacrylate / 1.65 parts of dipentaerythritol pentaacrylate / 2.82 parts of dipentaerythritol hexaacrylate), 0.2 parts of Irgacure 369 (by Prepared by BASF Corporation, 0.5 parts of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure shown in Formula 2, 29.8 parts of propylene glycol monomethyl ether acetate, and 25.5 parts of diacetone alcohol.
Example 7
The color photosensitive resin composition was prepared by mixing 33.8 parts of a colorant dispersion, 0.5 part of CI Acid Red 52 (manufactured by TCI America Co., Ltd.), 4.1 parts of the resin synthesized in Synthesis Example 2, and 5.6 parts. Mg KOH/g hydroxyl value of dipentaerythritol acrylated product (1.59 parts of dipentaerythritol tetraacrylate / 1.86 parts of dipentaerythritol pentaacrylate / 2.15 parts of dipentaerythritol hexaacrylate), 0.2 parts of Irgacure 369 (by Prepared by BASF Corporation, 0.5 parts of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure shown in Formula 2, 29.8 parts of propylene glycol monomethyl ether acetate, and 25.5 parts of diacetone alcohol.
Comparative Example 1
The color photosensitive resin composition was prepared by mixing 33.8 parts of a colorant dispersion, 0.5 part of CI Acid Red 52 (manufactured by TCI America Co., Ltd.), 4.1 parts of the resin synthesized in Synthesis Example 1, and 5.6 parts having 22 Mg KOH/g hydroxyl value of dipentaerythritol acrylated product (1.15 parts of dipentaerythritol pentaacrylate / 4.45 parts of dipentaerythritol hexaacrylate), 0.2 parts of Irgacure 369 (manufactured by BASF Corporation), 0.5 parts TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure shown in the above formula 2, 29.8 parts of propylene glycol monomethyl ether acetate, and 25.5 parts of diacetone alcohol were prepared.
Comparative Example 2
The color photosensitive resin composition was prepared by mixing 33.8 parts of a colorant dispersion, 0.5 part of CI Acid Red 52 (manufactured by TCI America Co., Ltd.), 4.1 parts of the resin synthesized in Synthesis Example 1, and 5.6 parts. Mg KOH / g hydroxyl value of dipentaerythritol acrylated product (2.72 parts of dipentaerythritol tetraacrylate / 2.37 parts of dipentaerythritol pentaacrylate / 0.51 parts of dipentaerythritol hexaacrylate), 0.2 parts of Irgacure 369 (by Prepared by BASF Corporation, 0.5 parts of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure shown in the above formula 2, 29.8 parts of propylene glycol monomethyl ether acetate, and 25.5 parts of diacetone alcohol.
Comparative Example 3
The color photosensitive resin composition was prepared by mixing 33.8 parts of a colorant dispersion, 0.5 part of CI Acid Red 52 (manufactured by TCI America Co., Ltd.), 4.1 parts of the resin synthesized in Synthesis Example 3, and 5.6 parts having 80 parts. Mg KOH/g hydroxyl value of dipentaerythritol acrylated product (1.13 parts of dipentaerythritol tetraacrylate / 1.65 parts of dipentaerythritol pentaacrylate / 2.82 parts of dipentaerythritol hexaacrylate), 0.2 parts of Irgacure 369 (by Prepared by BASF Corporation, 0.5 parts of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure shown in the above formula 2, 29.8 parts of propylene glycol monomethyl ether acetate, and 25.5 parts of diacetone alcohol.
Comparative Example 4
The color photosensitive resin composition was prepared by mixing 33.8 parts of a colorant dispersion, 0.5 part of CI Acid Red 52 (manufactured by TCI America Co., Ltd.), 4.1 parts of the resin synthesized in Synthesis Example 4, and 5.6 parts having 80 parts. Mg KOH/g hydroxyl value of dipentaerythritol acrylated product (1.13 parts of dipentaerythritol tetraacrylate / 1.65 parts of dipentaerythritol pentaacrylate / 2.82 parts of dipentaerythritol hexaacrylate), 0.2 parts of Irgacure 369 (by Prepared by BASF Corporation, 0.5 parts of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure shown in the above formula 2, 29.8 parts of propylene glycol monomethyl ether acetate, and 25.5 parts of diacetone alcohol.
Comparative Example 5
The color photosensitive resin composition was prepared by mixing 33.8 parts of a colorant dispersion, 0.5 part of CI Acid Red 52 (manufactured by TCI America Co., Ltd.), 4.1 parts of the resin synthesized in Synthesis Example 1, and 5.6 parts having 80 parts. Mg KOH/g hydroxyl value of dipentaerythritol acrylated product (1.13 parts of dipentaerythritol tetraacrylate / 1.65 parts of dipentaerythritol pentaacrylate / 2.82 parts of dipentaerythritol hexaacrylate), 0.2 parts of Irgacure 369 (by Prepared by BASF Corporation, 0.5 parts of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure shown in the above formula 2, 29.8 parts of propylene glycol monomethyl ether acetate, and 25.5 parts of diacetone alcohol.
Comparative Example 6
The color photosensitive resin composition was prepared by mixing 33.8 parts of a colorant dispersion, 0.5 part of CI Acid Red 52 (manufactured by TCI America Co., Ltd.), 10.2 parts of the resin synthesized in Synthesis Example 1, and 3.5 parts. Mg KOH / g hydroxyl value of dipentaerythritol acrylated product (0.71 parts of dipentaerythritol tetraacrylate / 1.03 parts of dipentaerythritol pentaacrylate / 1.76 parts of dipentaerythritol hexaacrylate), 0.2 parts of Irgacure 369 (by Prepared by BASF Corporation, 0.5 parts of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure shown in the above formula 2, 29.8 parts of propylene glycol monomethyl ether acetate, and 25.5 parts of diacetone alcohol.
Comparative Example 7
The color photosensitive resin composition was prepared by mixing 33.8 parts of a colorant dispersion, 0.5 part of CI Acid Red 52 (manufactured by TCI America Co., Ltd.), 2.0 parts of the resin synthesized in Synthesis Example 1, and 6.3 parts having 80 parts. Mg KOH/g hydroxyl value of dipentaerythritol acrylated product (1.27 parts of dipentaerythritol tetraacrylate / 1.86 parts of dipentaerythritol pentaacrylate / 3.17 parts of dipentaerythritol hexaacrylate), 0.2 parts of Irgacure 369 (by Prepared by BASF Corporation, 0.5 parts of TR-PBG-305 (manufactured by TRONLY Co., Ltd.) having the structure shown in the above formula 2, 29.8 parts of propylene glycol monomethyl ether acetate, and 25.5 parts of diacetone alcohol.
Comparative Example 8
The color photosensitive resin composition was obtained by mixing 33.8 parts of a colorant dispersion, 4.1 parts of the resin synthesized in Synthesis Example 1, and 5.6 parts of an acrylated product of dipentaerythritol having a hydroxyl value of 41 mg KOH/g (0.37). Parts of dipentaerythritol tetraacrylate / 1.31 parts of dipentaerythritol pentaacrylate / 3.92 parts of dipentaerythritol hexaacrylate), 0.2 parts of Irgacure 369 (manufactured by BASF Corporation), 0.5 parts of the structure of the above formula 2 TR-PBG-305 (manufactured by TRONLY Co., Ltd.), 29.8 parts of propylene glycol monomethyl ether acetate, and 25.5 parts of diacetone alcohol were prepared.
Experimental Example 1 - Evaluation of Storage Stability
The initial viscosity of each of the color photosensitive resin compositions prepared in the examples and the comparative examples was measured, and the viscosity was measured again after storage at 5 ° C for one month, and then the viscosity was observed from these measured values. change. Viscosity measurements were performed at 25 ° C using a Brookfield viscometer (DVI+, manufactured by Brookfield). The results of the measurements are shown in Table 1 below.
○: 5% or less viscosity change
△: viscosity change of more than 5% to 10%
X: viscosity change above 10%
Experimental Example 2
Each of the color photosensitive resin compositions prepared in the examples and the comparative examples was applied to a glass substrate by a spin coating method at an angle of 2 inches ("EAGLE XG" manufactured by Corning Co., Ltd.). The coated substrate was placed on a hot plate and allowed to stand at a temperature of 100 ° C for 3 minutes to form a film. Next, a test mask having a stepwise change permeability of 1 to 100% and a line/space pattern of 1 to 50 μm in size was placed on the film, and then the test was irradiated with UV at a distance of 100 μm. Photomask. Here, the source for UV irradiation is a 1 KW high pressure mercury (Hg) lamp containing all g, h and i-directions, and at 100 mJ/cm 2 The intensity of the radiation diverges light. The UV-irradiated film was immersed in a KOH developer solution at pH 10.5 for 2 minutes for visualization. After the film-coated glass substrate was washed with distilled water, it was dried by nitrogen gas and heated in a hot oven at 200 ° C for 25 minutes. As a result, a color filter is formed. The color filter formed as described above has a film thickness of 2.3 μm.
(1) Measurement of imaging rate
The time required until the non-exposed portion was completely dissolved during development was measured, and the results of the measurement are shown in Table 1.
(2) Measurement of line width of pattern
The line width of the formed pattern was observed, and the line width was measured using a scanning electron microscope. When the measured line width is not less than the line width of the mask, it is determined that the color photosensitive resin composition has a sensitivity sufficient to extend the line width. The line width relative to the extension of the reticle is shown in Table 1.
(3) Evaluation of adhesion
By observing the formed pattern by an optical microscope, the pattern selection was evaluated according to the criteria selected in the following pattern. The results of the evaluation are shown in Table 1.
○: No pattern selection was observed
△: 1 to 3 pattern selection
X: 4 or more pattern selection
Experimental Example 3 - Measurement of penetration
The color filter was formed in the same manner as described in Experimental Example 2 except that the photomask for testing was not used.
The permeability in the visible light region was measured using a colorimeter (OSP-200 manufactured by Olympus Corporation). The results of the measurements are shown in Table 1.

Referring to Table 1 above, the compositions prepared in Examples 1 to 8 have excellent storage stability, involve small viscosity changes, high imaging speed, and excellent sensitivity pattern adhesion. Further, it was also observed that the color filter manufactured using the same composition has high penetrability.
On the contrary, it was found that the compositions prepared in Comparative Examples 1 to 8 have deteriorated storage stability, which causes changes in viscosity or poor characteristics such as development speed, sensitivity, adhesion, etc., and utilization of the same The color filter produced by the composition showed a decrease in permeability.

Claims (9)

一種彩色光敏樹脂組合物，包括：一著色劑、一鹼性可溶性樹脂、一光-可聚合化合物、一光-聚合起始劑以及一溶劑，其中該著色劑包括一色素及染料；該鹼性可溶性樹脂具有30至170 mg KOH/g的一酸值，並且是以該組合物的一總重量的5至10 wt.%固含量的量而包含於其中；該鹼性可溶性樹脂及該光-可聚合化合物的羥基值的總和範圍為30至180 mg KOH/g；以及該光-聚合起始劑包括以下式1所示之一化合物：[式1] 其中R1代表；R2及R3各自獨立地是具有1至8個碳原子的烷基、苯基、苄基或二苯硫醚基，其係以一羥基或具有1至8個碳原子的烷基取代或不取代；R4是具有1至4個碳原子的一伸烷基；以及R5是具有3至8個碳原子的一環烷基。A color photosensitive resin composition comprising: a colorant, an alkali soluble resin, a photo-polymerizable compound, a photo-polymerization initiator, and a solvent, wherein the colorant comprises a pigment and a dye; The soluble resin has an acid value of 30 to 170 mg KOH/g, and is contained therein in an amount of 5 to 10 wt.% solid content based on a total weight of the composition; the alkali soluble resin and the light- The sum of the hydroxyl values of the polymerizable compound ranges from 30 to 180 mg KOH/g; and the photo-polymerization initiator includes one of the compounds represented by the following formula 1: [Formula 1] Where R 1 represents And R 2 and R 3 are each independently an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group or a diphenyl sulfide group, which is substituted with a monohydroxy group or an alkyl group having 1 to 8 carbon atoms; Or not substituted; R 4 is a monoalkyl group having 1 to 4 carbon atoms; and R 5 is a monoalkyl group having 3 to 8 carbon atoms. 如申請專利範圍第1項之組合物，其中該鹼性可溶性樹脂具有50至160 mg KOH/g的一酸值。The composition of claim 1, wherein the alkali-soluble resin has an acid value of 50 to 160 mg KOH/g. 如申請專利範圍第1項之組合物，其中該鹼性可溶性樹脂及該光-可聚合化合物的該羥基值的總和範圍為40至140 mg KOH/g。The composition of claim 1, wherein the alkali soluble resin and the photo-polymerizable compound have a total value of the hydroxyl value ranging from 40 to 140 mg KOH/g. 如申請專利範圍第1項之組合物，其中該著色劑是以5至60 wt.%的量而包含於其中；以及該光-可聚合化合物是以該彩色光敏樹脂組合物的一總重量的5至70 wt.%固含量的量而包含於其中；該光-聚合起始劑是以該鹼性可溶性樹脂及該光-可聚合化合物的含量總和的0.1至40 wt.%固含量的量而包含於其中；以及該溶劑是以該彩色光敏樹脂組合物的一總重量的60至90 wt.%的量而包含於其中。The composition of claim 1, wherein the colorant is contained in an amount of 5 to 60 wt.%; and the photo-polymerizable compound is a total weight of the color photosensitive resin composition. Included in an amount of 5 to 70 wt.% solid content; the photo-polymerization initiator is an amount of 0.1 to 40 wt.% solid content based on the total content of the alkali-soluble resin and the photo-polymerizable compound And contained therein; and the solvent is contained in an amount of 60 to 90 wt.% based on a total weight of the color photosensitive resin composition. 如申請專利範圍第1項之組合物，其中式1所示之化合物是以該光-聚合起始劑的一總重量的10至100 wt.% 的量而包含於其中。The composition of claim 1, wherein the compound of the formula 1 is contained in an amount of 10 to 100 wt.% based on the total weight of the photo-polymerization initiator. 如申請專利範圍第1項之組合物，更包括至少一光-聚合起始劑，其是選自由一苯乙酮化合物、二苯基酮化合物、三嗪化合物、雙咪唑化合物以及硫雜蒽酮化合物所組成的群組。The composition of claim 1, further comprising at least one photo-polymerization initiator selected from the group consisting of a acetophenone compound, a diphenyl ketone compound, a triazine compound, a diimidazole compound, and a thioxanthone A group of compounds. 如申請專利範圍第1項之組合物，更包括至少一光-聚合起始增強劑，其是選自由胺類化合物、羧酸化合物以及含硫醇基的有機硫化合物所組成的群組。The composition of claim 1, further comprising at least one photo-polymerization initiation enhancer selected from the group consisting of an amine compound, a carboxylic acid compound, and a thiol group-containing organic sulfur compound. 一種彩色濾光片，係利用申請專利範圍第1項至第7項中任一項之彩色光敏樹脂組合物所形成。A color filter formed by using the color photosensitive resin composition of any one of claims 1 to 7. 一種液晶顯示器裝置，包括申請專利範圍第8項之彩色濾光片。A liquid crystal display device comprising the color filter of claim 8 of the patent application.
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