TW201537292A - Colored photosensitive resin composition and color filter comprising the same - Google Patents

Colored photosensitive resin composition and color filter comprising the same Download PDF

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TW201537292A
TW201537292A TW104109048A TW104109048A TW201537292A TW 201537292 A TW201537292 A TW 201537292A TW 104109048 A TW104109048 A TW 104109048A TW 104109048 A TW104109048 A TW 104109048A TW 201537292 A TW201537292 A TW 201537292A
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photosensitive resin
resin composition
colored photosensitive
color filter
acrylate
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TW104109048A
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Chinese (zh)
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Hyun-Chul Shin
Hyun-Jin Yoon
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Dongwoo Fine Chem Co Ltd
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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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)

Abstract

The present invention provides a colored photosensitive resin composition, comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), the colorant (A) comprising C.I. Pigment Green 7, C.I. Pigment Yellow 185 and C.I. Pigment Yellow 129, a color filter formed by using the composition, and a liquid crystal display device having the color filter. The colored photosensitive resin composition according to the present invention has high contrast and luminance as well as good color strength and pattern-forming property.

Description

著色感光性樹脂組合物及包含其之彩色濾光片 Colored photosensitive resin composition and color filter containing the same

本發明係關於一種著色感光性樹脂組合物及包含其之彩色濾光片。特定言之，本發明提供一種著色感光性樹脂組合物，其具有高對比度及亮度以及優良色度及圖案形成特性；一種使用該組合物形成之彩色濾光片；及一種具有該彩色濾光片之液晶顯示裝置。 The present invention relates to a colored photosensitive resin composition and a color filter comprising the same. In particular, the present invention provides a colored photosensitive resin composition having high contrast and brightness and excellent color and pattern forming characteristics; a color filter formed using the composition; and a color filter having the color filter Liquid crystal display device.

彩色濾光片已廣泛用於成像裝置及液晶顯示器(LCD)中，且其應用正在擴大。習知彩色濾光片藉由以下來製備：在上面形成黑色圖案之黑色矩陣基板上均勻塗覆包含紅色、綠色或藍色之顏料的著色感光性樹脂組合物，接著加熱及乾燥，使所得塗層膜進行曝光及顯影，且必要時，進一步加熱及硬化，藉此形成各顏色之像素，且針對各顏色重複以上程序。 Color filters have been widely used in imaging devices and liquid crystal displays (LCDs), and their applications are expanding. A conventional color filter is prepared by uniformly coating a colored photosensitive resin composition containing a pigment of red, green or blue on a black matrix substrate on which a black pattern is formed, followed by heating and drying to obtain a coating. The film is exposed and developed, and if necessary, further heated and hardened, thereby forming pixels of respective colors, and the above procedure is repeated for each color.

在提供具有高品質之液晶顯示器所需要之彩色濾光片的特性中，實現彩色濾光片之高對比率為重要的。若彩色濾光片不能具有高對比率，則透射光漏出或減少，由此使得螢幕漸暗。因此，已經不斷地進行實現高對比率之研究。 Among the characteristics of providing a color filter required for a high quality liquid crystal display, it is important to achieve a high contrast ratio of the color filter. If the color filter cannot have a high contrast ratio, the transmitted light leaks or decreases, thereby causing the screen to darken. Therefore, research to achieve high contrast ratios has been continuously conducted.

韓國專利申請公開案第2010-0021360號揭示一種用於有機電致發光彩色濾光片之綠色組合物，其包含含有鋁酞菁與顏料綠7中之至少一者的綠色顏料及含有顏料黃185與顏料黃150中之至少一者的黃色顏 料，以便提供高度色彩再現性及高亮度。然而，該組合物難以提供高對比率，因此其無法有效地用於彩色濾光片。 Korean Patent Application Publication No. 2010-0021360 discloses a green composition for an organic electroluminescence color filter comprising a green pigment containing at least one of aluminum phthalocyanine and pigment green 7, and a pigment yellow 185. Yellow color with at least one of Pigment Yellow 150 Material to provide high color reproducibility and high brightness. However, this composition is difficult to provide a high contrast ratio, so it cannot be effectively used for a color filter.

本發明之一個目標為提供一種著色感光性樹脂組合物，其顯示高對比度及亮度以及寬色彩再現範圍且具有優良色度及圖案形成特性。 An object of the present invention is to provide a colored photosensitive resin composition which exhibits high contrast and brightness as well as a wide color reproduction range and has excellent chromaticity and pattern formation characteristics.

本發明之另一個目標為提供一種使用該著色感光性樹脂組合物形成之彩色濾光片。 Another object of the present invention is to provide a color filter formed using the colored photosensitive resin composition.

本發明之再一個目標為提供一種具有該彩色濾光片之液晶顯示裝置。 It is still another object of the present invention to provide a liquid crystal display device having the color filter.

根據本發明之一個態樣，提供一種著色感光性樹脂組合物，其包含著色劑(A)、黏合劑樹脂(B)、光可聚合化合物(C)、光聚合引發劑(D)及溶劑(E)，該著色劑(A)包含C.I.顏料綠7、C.I.顏料黃185及C.I.顏料黃129。 According to an aspect of the present invention, there is provided a colored photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent ( E), the colorant (A) comprises CI Pigment Green 7, CI Pigment Yellow 185, and CI Pigment Yellow 129.

在本發明之一個實施例中，C.I.顏料黃129以按C.I.顏料綠7、C.I.顏料黃185及C.I.顏料黃129之總固體含量計5至50wt%之量存在。 In one embodiment of the invention, C.I. Pigment Yellow 129 is present in an amount from 5 to 50% by weight based on the total solids content of C.I. Pigment Green 7, C.I. Pigment Yellow 185 and C.I. Pigment Yellow 129.

根據本發明之另一個態樣，提供一種使用該著色感光性樹脂組合物形成之彩色濾光片。 According to another aspect of the present invention, a color filter formed using the colored photosensitive resin composition is provided.

根據本發明之再一個態樣，提供一種具有該彩色濾光片之液晶顯示裝置。 According to still another aspect of the present invention, a liquid crystal display device having the color filter is provided.

本發明之著色感光性樹脂組合物包含C.I.顏料綠7及C.I.顏料黃185以及C.I.顏料黃129，以顯示高對比度及亮度且具有優良色度及圖案形成特性。 The colored photosensitive resin composition of the present invention comprises C.I. Pigment Green 7 and C.I. Pigment Yellow 185 and C.I. Pigment Yellow 129 to exhibit high contrast and brightness and to have excellent chromaticity and pattern formation characteristics.

本發明在下文中更詳細地描述。 The invention is described in more detail below.

本發明之一個實施例係關於一種著色感光性樹脂組合物，其包含著色劑(A)、黏合劑樹脂(B)、光可聚合化合物(C)、光聚合引發劑(D)及溶劑(E)，該著色劑(A)包含C.I.顏料綠7、C.I.顏料黃185及C.I.顏料黃129。 One embodiment of the present invention relates to a colored photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E) The colorant (A) comprises CI Pigment Green 7, CI Pigment Yellow 185, and CI Pigment Yellow 129.

著色劑(A)Colorant (A)

在本發明之一個實施例中，著色劑(A)之特徵在於包含C.I.顏料綠7、C.I.顏料黃185及C.I.顏料黃129。 In one embodiment of the invention, the colorant (A) is characterized by comprising C.I. Pigment Green 7, C.I. Pigment Yellow 185 and C.I. Pigment Yellow 129.

著色劑(A)包含C.I.顏料綠7作為提供能夠高度色彩再現之綠色層的綠色顏料，及C.I.顏料黃185及C.I.顏料黃129作為用於控制色調之黃色顏料。 The colorant (A) contains C.I. Pigment Green 7 as a green pigment which provides a green layer capable of high color reproduction, and C.I. Pigment Yellow 185 and C.I. Pigment Yellow 129 as a yellow pigment for controlling color tone.

在本發明之一個實施例中，C.I.顏料黃129以按C.I.顏料綠7、C.I.顏料黃185及C.I.顏料黃129之總固體含量計5至50wt%，較佳10至40wt%之量存在。若C.I.顏料黃129之量低於此類範圍，則難以獲得所希望之高對比度。若C.I.顏料黃129之量超過此類範圍，則難以獲得L/S模式之所希望之線寬度及楔度。 In one embodiment of the invention, C.I. Pigment Yellow 129 is present in an amount of from 5 to 50% by weight, preferably from 10 to 40% by weight, based on the total solids content of C.I. Pigment Green 7, C.I. Pigment Yellow 185 and C.I. Pigment Yellow 129. If the amount of C.I. Pigment Yellow 129 is lower than such a range, it is difficult to obtain a desired high contrast. If the amount of C.I. Pigment Yellow 129 exceeds such a range, it is difficult to obtain the desired line width and wedge of the L/S mode.

必要時，著色劑(A)可進一步包含一或多種顏料或染料以及C.I.顏料綠7、C.I.顏料黃185及C.I.顏料黃129。 If necessary, the colorant (A) may further comprise one or more pigments or dyes and C.I. Pigment Green 7, C.I. Pigment Yellow 185 and C.I. Pigment Yellow 129.

著色劑(A)以按本發明之著色感光性樹脂組合物之總固體含量計10至60wt%、較佳20至50wt%之量存在。當著色劑之量在10至60wt%範圍內時，像素之色彩濃度變充足，即使形成薄膜，且在顯影期間非像素化部分之滲漏未退化，由此難以產生殘餘物。 The colorant (A) is present in an amount of 10 to 60% by weight, preferably 20 to 50% by weight, based on the total solid content of the colored photosensitive resin composition of the present invention. When the amount of the colorant is in the range of 10 to 60% by weight, the color density of the pixel becomes sufficient even if a film is formed, and leakage of the non-pixelized portion is not deteriorated during development, whereby it is difficult to generate a residue.

當著色劑包含顏料時，使顏料與顏料分散劑一起開始分散，從而獲得顏料均勻分散之顏料分配溶液。 When the colorant contains a pigment, the pigment is dispersed together with the pigment dispersant, thereby obtaining a pigment distribution solution in which the pigment is uniformly dispersed.

顏料分散劑之特定實例可包括陽離子、陰離子、非離子、兩性、基於聚酯、基於多元胺及基於聚丙烯酸酯之界面活性劑，其可以單獨使用或兩者或兩者以上組合使用。較佳地，顏料分散劑以按1重量份著色劑計至多1重量份、更佳0.05至0.5重量份之量使用。當顏料分散劑之量滿足此類範圍時，可實現顏料之均勻分佈。 Specific examples of the pigment dispersant may include cationic, anionic, nonionic, amphoteric, polyester-based, polyamine-based, and polyacrylate-based surfactants, which may be used alone or in combination of two or more. Preferably, the pigment dispersant is used in an amount of up to 1 part by weight, more preferably 0.05 to 0.5 part by weight, based on 1 part by weight of the coloring agent. When the amount of the pigment dispersant satisfies such a range, uniform distribution of the pigment can be achieved.

如本文中所使用，術語著色感光性樹脂組合物之『總固體含量』是指著色感光性樹脂組合物中除溶劑外之其他組分的總重量。 As used herein, the term "total solid content" of the colored photosensitive resin composition means the total weight of the components other than the solvent in the colored photosensitive resin composition.

黏合劑樹脂(B)Adhesive resin (B)

在本發明之一個實施例中，黏合劑樹脂(B)習知在光或熱之作用下具有反應性及鹼溶解性，且充當著色劑之分散劑。本發明之著色感光性樹脂組合物中所含有的黏合劑樹脂(B)若充當著色劑(A)之黏合劑樹脂且其可溶於用於製備彩色濾光片之顯影步驟中使用的鹼性顯影溶液，則其不受限制。 In one embodiment of the present invention, the binder resin (B) is known to have reactivity and alkali solubility under the action of light or heat, and acts as a dispersing agent for the colorant. The binder resin (B) contained in the colored photosensitive resin composition of the present invention serves as a binder resin for the colorant (A) and is soluble in the alkalinity used in the development step for preparing a color filter. The developing solution is not limited.

舉例而言，本發明之黏合劑樹脂(B)可為含羧基單體與其他可與該單體共聚之單體的共聚物。 For example, the binder resin (B) of the present invention may be a copolymer of a carboxyl group-containing monomer and other monomers copolymerizable with the monomer.

含羧基單體可包括不飽和羧酸，例如不飽和單羧酸或不飽和聚羧酸，例如不飽和二甲酸及不飽和三羧酸。 The carboxyl group-containing monomer may include an unsaturated carboxylic acid such as an unsaturated monocarboxylic acid or an unsaturated polycarboxylic acid such as an unsaturated dicarboxylic acid and an unsaturated tricarboxylic acid.

不飽和單羧酸之實例可包括丙烯酸、甲基丙烯酸、丁烯酸、α-氯丙烯酸及肉桂酸。不飽和二甲酸之實例可包括順丁烯二酸、反丁烯二酸、伊康酸、甲基順丁烯二酸及甲基反丁烯二酸。不飽和聚羧酸可為酸酐，例如順丁烯二酸酐、伊康酸酐及甲基順丁烯二酸酐。此外，不飽和聚羧酸可為其單(2-甲基丙烯醯氧基烷基)酯，例如丁二酸單(2-丙烯醯氧基乙基)酯、丁二酸單(2-甲基丙烯醯氧基乙基)酯、鄰苯二甲酸單(2-丙烯醯氧基乙基)酯及鄰苯二甲酸單(2-甲基丙烯醯氧基乙基) 酯。不飽和聚羧酸可為二羧基聚合物在其兩個末端之單(甲基)丙烯酸酯，例如ω-羧基聚己內酯單丙烯酸酯及ω-羧基聚己內酯單甲基丙烯酸酯。此等單體可單獨使用或兩者或兩者以上組合使用。 Examples of the unsaturated monocarboxylic acid may include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid may include maleic acid, fumaric acid, itaconic acid, methyl maleic acid, and methyl fumaric acid. The unsaturated polycarboxylic acid may be an acid anhydride such as maleic anhydride, itaconic anhydride, and methyl maleic anhydride. Further, the unsaturated polycarboxylic acid may be a mono(2-methylpropenyloxyalkyl)ester thereof, such as succinic acid mono(2-propenyloxyethyl) ester, succinic acid mono (2-a) Acryloxyethyl)ester, mono(2-propenyloxyethyl) phthalate and mono(2-methylpropenyloxyethyl) phthalate ester. The unsaturated polycarboxylic acid may be a mono(meth)acrylate of a dicarboxy polymer at both ends thereof, such as ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. These monomers may be used singly or in combination of two or more.

其他可與含羧基之單體共聚的單體可包括例如芳族乙烯基化合物，諸如苯乙烯、α-甲基苯乙烯、鄰乙烯基甲苯、間乙烯基甲苯、對乙烯基甲苯、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、鄰乙烯基苯甲基甲基醚、間乙烯基苯甲基甲基醚、對乙烯基苯甲基甲基醚、鄰乙烯基苯甲基縮水甘油基醚、間乙烯基苯甲基縮水甘油基醚、對乙烯基苯甲基縮水甘油基醚、茚等；不飽和羧酸酯，諸如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸異丙酯、甲基丙烯酸異丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸異丁酯、甲基丙烯酸異丁酯、丙烯酸第二丁酯、甲基丙烯酸第二丁酯、丙烯酸第三丁酯、甲基丙烯酸第三丁酯、丙烯酸2-羥基乙酯、甲基丙烯酸2-羥基乙酯、丙烯酸2-羥基丙酯、甲基丙烯酸2-羥基丙酯、丙烯酸3-羥基丙酯、甲基丙烯酸3-羥基丙酯、丙烯酸2-羥基丁酯、甲基丙烯酸2-羥基丁酯、丙烯酸3-羥基丁酯、甲基丙烯酸3-羥基丁酯、丙烯酸4-羥基丁酯、甲基丙烯酸4-羥基丁酯、丙烯酸烯丙酯、甲基丙烯酸烯丙酯、丙烯酸苯甲酯、甲基丙烯酸苯甲酯、丙烯酸環己酯、甲基丙烯酸環己酯、丙烯酸苯酯、甲基丙烯酸苯酯、丙烯酸2-甲氧基乙酯、甲基丙烯酸2-甲氧基乙酯、丙烯酸2-苯氧基乙酯、甲基丙烯酸2-苯氧基乙酯、甲氧基二乙二醇丙烯酸酯、甲氧基二乙二醇甲基丙烯酸酯、甲氧基三乙二醇丙烯酸酯、甲氧基三乙二醇甲基丙烯酸酯、甲氧基丙二醇丙烯酸酯、甲氧基丙二醇甲基丙烯酸酯、甲氧基二丙二醇丙烯酸酯、甲氧基二丙二醇甲基丙烯酸酯、丙烯酸異冰片酯、甲基丙烯酸異冰片酯、丙烯酸二環戊二烯酯、甲基丙烯酸二環戊二烯酯、(甲基)丙烯酸金剛 烷酯、(甲基)丙烯酸降冰片烷酯、丙烯酸2-羥基-3-苯氧基丙酯、甲基丙烯酸2-羥基-3-苯氧基丙酯、單丙烯酸甘油酯、單甲基丙烯酸甘油酯等；不飽和羧酸之胺基烷基酯，諸如丙烯酸2-胺基乙酯、甲基丙烯酸2-胺基乙酯、丙烯酸2-二甲基胺基乙酯、甲基丙烯酸2-二甲基胺基乙酯、丙烯酸2-胺基丙酯、甲基丙烯酸2-胺基丙酯、丙烯酸2-二甲基胺基丙酯、甲基丙烯酸2-二甲基胺基丙酯、丙烯酸3-胺基丙酯、甲基丙烯酸3-胺基丙酯、丙烯酸3-二甲基胺基丙酯、甲基丙烯酸3-二甲基胺基丙酯等；不飽和羧酸之縮水甘油酯，諸如丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯等；羧酸之乙烯酯，諸如乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、苯甲酸乙烯酯等；不飽和醚，諸如乙烯基甲基醚、乙烯基乙基醚、烯丙基縮水甘油基醚等；氰化乙烯基化合物，諸如丙烯腈、甲基丙烯腈、α-氯丙烯腈、氰化亞乙烯等；不飽和醯胺，諸如丙烯醯胺、甲基丙烯醯胺、α-氯丙烯醯胺、N-2-羥乙基丙烯醯胺、N-2-羥乙基甲基丙烯醯胺等；不飽和醯亞胺，諸如順丁烯二醯亞胺、苯甲基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺等；脂族共軛二烯，諸如1,3-丁二烯、異戊二烯、氯丁二烯等；以及在聚苯乙烯、聚丙烯酸甲酯、聚甲基丙烯酸甲酯、聚丙烯酸正丁酯、聚甲基丙烯酸正丁酯或聚矽氧烷之聚合物鏈的末端具有單丙烯醯基或單甲基丙烯醯基的大分子單體。以上單體可單獨使用或兩者或兩者以上組合使用。 Other monomers copolymerizable with the carboxyl group-containing monomer may include, for example, an aromatic vinyl compound such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorobenzene. Ethylene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl Ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, hydrazine, etc.; unsaturated carboxylic acid esters, such as methyl acrylate, Methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate Ester, isobutyl acrylate, isobutyl methacrylate, second butyl acrylate, second butyl methacrylate, third butyl acrylate, third butyl methacrylate, 2-hydroxyethyl acrylate, A 2-hydroxyethyl acrylate, 2-hydroxy acrylate Ester, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, acrylic acid Cyclohexyl ester, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol Methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate , dicyclopentadienyl acrylate, dicyclopentane methacrylate Dienyl ester, gold (meth)acrylate Alkyl ester, norbornyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glyceryl monoacrylate, monomethacrylic acid Glycerides and the like; aminoalkyl esters of unsaturated carboxylic acids, such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-methacrylic acid 2- Dimethylaminoethyl ester, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate, etc.; glycidol of unsaturated carboxylic acid Esters such as glycidyl acrylate, glycidyl methacrylate, etc.; vinyl esters of carboxylic acids such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc.; unsaturated ethers such as vinyl Methyl ether, vinyl ethyl ether, allyl glycidyl ether, etc.; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, - chloroacrylonitrile, vinyl cyanide, etc.; unsaturated decylamines such as acrylamide, methacrylamide, alpha-chloropropenylamine, N-2-hydroxyethyl decylamine, N-2-hydroxyl Ethyl methacrylamide, etc.; unsaturated quinone imine, such as maleimide, benzyl maleimide, N-phenyl maleimide, N-ring Hexyl succinimide, etc.; aliphatic conjugated dienes, such as 1,3-butadiene, isoprene, chloroprene, etc.; and in polystyrene, polymethyl acrylate, polymethyl The polymer chain of methyl acrylate, n-butyl polyacrylate, n-butyl methacrylate or polyoxymethane has a macromolecular monomer having a monopropenyl fluorenyl group or a monomethacryl fluorenyl group at the end. The above monomers may be used singly or in combination of two or more.

較佳地，黏合劑樹脂(B)具有在20至200(KOH mg/g)範圍內之酸值。當酸值滿足此類範圍時，在顯影溶液中之溶解性得以提高，由此允許未曝光區域易於溶解且增加敏感性。因此，在顯影期間曝光區域之圖案保留，由此提高薄膜剩餘比。如本文中所使用，術語『酸值』是指量測為中和1g丙烯酸聚合物所需要的氫氧化鉀之量(mg)的值，且一般藉由使用氫氧化鉀水溶液滴定來獲得。 Preferably, the binder resin (B) has an acid value in the range of 20 to 200 (KOH mg/g). When the acid value satisfies such a range, the solubility in the developing solution is improved, thereby allowing the unexposed regions to be easily dissolved and increasing the sensitivity. Therefore, the pattern of the exposed area remains during development, thereby increasing the film remaining ratio. As used herein, the term "acid value" refers to a value measured by the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and is generally obtained by titration with an aqueous solution of potassium hydroxide.

此外，黏合劑樹脂(B)較佳具有3,000至200,000，更佳5,000至100,000之聚苯乙烯換算之重量平均分子量(Mw)，其藉由凝膠滲透層析法(GPC)使用四氫呋喃作為溶離溶劑來量測。當重量平均分子量(Mw)滿足此類範圍時，塗層膜具有提高之硬度，從而得到高薄膜剩餘比，增加未曝光區域之溶解性且提高解析度。 Further, the binder resin (B) preferably has a weight average molecular weight (M w ) in terms of polystyrene of 3,000 to 200,000, more preferably 5,000 to 100,000, which uses tetrahydrofuran as a dissolution by gel permeation chromatography (GPC). Solvent to measure. When the weight average molecular weight (M w ) satisfies such a range, the coating film has an increased hardness, thereby obtaining a high film remaining ratio, increasing the solubility of the unexposed region and improving the resolution.

黏合劑樹脂(B)可具有1.5至6.0、較佳1.8至4.0之分子量分佈[重量平均分子量(Mw)/數量平均分子量(Mn)]。當黏合劑樹脂之分子量分佈在1.5至6.0之範圍內時，可顯影性可得以提高。 The binder resin (B) may have a molecular weight distribution [weight average molecular weight (M w ) / number average molecular weight (M n )] of from 1.5 to 6.0, preferably from 1.8 to 4.0. When the molecular weight distribution of the binder resin is in the range of 1.5 to 6.0, the developability can be improved.

黏合劑樹脂(B)可以按著色感光性樹脂組合物之總固體含量計5至85wt%、更佳10至70wt%之量存在。當黏合劑樹脂(B)之量在5至85wt%之範圍內時，在顯影溶液中之溶解性可為足夠的，藉此難以在非像素化部分之基板上產生顯影殘餘物，且可防止在顯影期間曝光區域中像素化部分之膜減少，藉此允許非像素化部分良好滲漏。 The binder resin (B) may be present in an amount of 5 to 85 wt%, more preferably 10 to 70 wt%, based on the total solid content of the colored photosensitive resin composition. When the amount of the binder resin (B) is in the range of 5 to 85 wt%, the solubility in the developing solution may be sufficient, whereby it is difficult to produce development residue on the substrate of the non-pixelized portion, and it is possible to prevent The film of the pixelated portion in the exposed area is reduced during development, thereby allowing the non-pixelated portion to leak well.

光可聚合單體(C)Photopolymerizable monomer (C)

在本發明之一個實施例中，光可聚合化合物(C)為在光聚合引發劑(D)之作用下可聚合的化合物。可聚合化合物可為單官能單體、雙官能單體或多官能單體。 In one embodiment of the present invention, the photopolymerizable compound (C) is a compound polymerizable under the action of the photopolymerization initiator (D). The polymerizable compound may be a monofunctional monomer, a difunctional monomer or a polyfunctional monomer.

單官能單體之實例可包括壬基苯基卡必醇丙烯酸酯、丙烯酸2-羥基-3-苯氧基丙酯、2-乙基己基卡必醇丙烯酸酯、丙烯酸2-羥基乙酯及N-乙烯吡咯啶酮。 Examples of the monofunctional monomer may include mercaptophenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N - vinylpyrrolidone.

雙官能單體之實例可包括1,6-己二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、雙酚A之雙(丙烯醯氧基乙基)醚及3-甲基戊二醇二(甲基)丙烯酸酯。 Examples of the difunctional monomer may include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol. Di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A and 3-methylpentanediol di(meth)acrylate.

多官能單體之實例可包括三羥甲基丙烷三(甲基)丙烯酸酯、異戊四醇三(甲基)丙烯酸酯、異戊四醇四(甲基)丙烯酸酯、二異戊四醇五 (甲基)丙烯酸酯及二異戊四醇六(甲基)丙烯酸酯。其中，可較佳使用雙官能單體或多官能單體。 Examples of the polyfunctional monomer may include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, diisopentaerythritol. Fives (Meth) acrylate and diisopentaerythritol hexa (meth) acrylate. Among them, a difunctional monomer or a polyfunctional monomer can be preferably used.

光可聚合化合物(C)較佳以按著色感光性樹脂組合物之總固體含量計5至50wt%、更佳7至45wt%之量使用。當光可聚合化合物(C)之量在5至50wt%之範圍內時，可提高像素之強度及平滑度。 The photopolymerizable compound (C) is preferably used in an amount of 5 to 50% by weight, more preferably 7 to 45% by weight, based on the total solid content of the colored photosensitive resin composition. When the amount of the photopolymerizable compound (C) is in the range of 5 to 50% by weight, the strength and smoothness of the pixel can be improved.

光聚合引發劑(D)Photopolymerization initiator (D)

在本發明之一個實施例中，光聚合引發劑(D)較佳含有基於苯乙酮之化合物。基於苯乙酮之化合物的實例可包括二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙-1-酮、苯甲基二甲基縮酮、2-羥基-1-[4-(2-羥基乙氧基)苯基]-2-甲基丙-1-酮、1-羥基環己基苯基酮、2-甲基-1-(4-甲基噻吩基)-2-嗎啉基丙-1-酮、2-苯甲基-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-酮及2-(4-甲基苯甲基)-2-(二甲基胺基)-1-(4-嗎啉基苯基)丁-1-酮。其中，2-苯甲基-2-二甲基胺基-1-(4-嗎啉基苯基)丁-1-酮為較佳。 In one embodiment of the present invention, the photopolymerization initiator (D) preferably contains a compound based on acetophenone. Examples of the acetophenone-based compound may include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthienyl) -2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-hydroxy-2- Methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one and 2-(4-methylbenzyl)-2-(dimethylamino)-1-( 4-morpholinylphenyl)butan-1-one. Among them, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one is preferred.

此外，其他光聚合引發劑可與基於苯乙酮之化合物組合使用，且其他光聚合引發劑可為活性自由基產生劑，其藉由光照射、敏化劑或酸產生劑來產生活性自由基。 Further, other photopolymerization initiators may be used in combination with the acetophenone-based compound, and other photopolymerization initiators may be active radical generators which generate active radicals by light irradiation, sensitizers or acid generators. .

活性自由基產生劑可為基於安息香、二苯甲酮、噻噸酮、三嗪之化合物等。基於安息香之化合物的實例可包括安息香、安息香甲醚、安息香***、安息香異丙醚及安息香異丁醚。基於二苯甲酮之化合物的實例可包括二苯甲酮、鄰苯甲醯苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4'-甲基二苯基硫化物、3,3',4,4'-四(第三丁基過氧基羰基)二苯甲酮及2,4,6-三甲基二苯甲酮。基於噻噸酮之化合物的實例可包括2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮及1-氯-4-丙氧基噻噸酮。基於三嗪之化合物的實例可包括2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6- (4-甲氧基萘基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三嗪及2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三嗪。此外，作為活性自由基產生劑，可使用2,4,6-三甲基苯甲醯基二苯膦氧化物、2,2'-雙(鄰氯苯基)-4,4',5,5'-四苯基-1,2-聯咪唑、10-丁基-2-氯吖啶酮、2-乙基蒽醌、苯甲基、9,10-菲醌、樟腦醌、乙醛酸甲酯或二茂鈦化合物。 The living radical generating agent may be a compound based on benzoin, benzophenone, thioxanthone, triazine or the like. Examples of the benzoin-based compound may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the benzophenone-based compound may include benzophenone, methyl phthalate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide. , 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone. Examples of the thioxanthone-based compound may include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1 -Chloro-4-propoxythioxanthone. Examples of the triazine-based compound may include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloro) Methyl)-6- (4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5- Triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis ( Trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4 -diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-di Methoxyphenyl)vinyl]-1,3,5-triazine. Further, as the living radical generating agent, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4',5 may be used. 5'-Tetraphenyl-1,2-biimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzyl, 9,10-phenanthrenequinone, camphorquinone, glyoxylic acid Methyl or titanium titanate compound.

酸產生劑之實例可包括鎓鹽，諸如對甲苯磺酸4-羥基苯基二甲基鋶、六氟銻酸4-羥基苯基二甲基鋶、對甲苯磺酸4-乙醯氧基苯基二甲基鋶、六氟銻酸4-乙醯氧基苯基甲基苯甲基鋶、對甲苯磺酸三苯基鋶、六氟銻酸三苯基鋶、對甲苯磺酸二苯基碘及六氟銻酸二苯基碘、甲苯磺酸硝基苯甲酯及安息香甲苯磺酸酯。 Examples of the acid generator may include a phosphonium salt such as 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylhydrazine hexafluoroantimonate, and 4-acetoxybenzenebenzene p-toluenesulfonate. Dimethyl hydrazine, 4-ethenyloxyphenylmethyl benzyl hydrazine hexafluoroantimony, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium hexafluoroantimonate, diphenyl p-toluene sulfonate Iodine and diphenyliodonium hexafluoroantimonate, nitrobenzyl methyl tosylate and benzoin tosylate.

此外，一些以上活性自由基產生劑可產生酸以及活性自由基。舉例而言，基於三嗪之光聚合引發劑亦可用作酸產生劑。 In addition, some of the above active radical generators can produce acids as well as active free radicals. For example, a triazine-based photopolymerization initiator can also be used as the acid generator.

光聚合引發劑(D)可以按黏合劑樹脂(B)及光可聚合化合物(C)之總固體含量計0.1至40wt%、較佳1至30wt%之量存在。當光聚合引發劑(D)之量滿足此類範圍時，本發明之著色感光性樹脂組合物可具有高敏感性，從而提供足夠強度之像素及像素表面上優良平滑度。 The photopolymerization initiator (D) may be present in an amount of from 0.1 to 40% by weight, preferably from 1 to 30% by weight, based on the total solid content of the binder resin (B) and the photopolymerizable compound (C). When the amount of the photopolymerization initiator (D) satisfies such a range, the colored photosensitive resin composition of the present invention can have high sensitivity, thereby providing sufficient intensity of pixels and excellent smoothness on the surface of the pixel.

此外，在本發明中，光聚合引發劑可連同光引發助劑一起使用以便促進光聚合引發劑所引發之光聚合。光引發助劑可為基於胺、基於烷氧基蒽或基於噻噸酮之化合物。 Further, in the present invention, a photopolymerization initiator may be used together with a photoinitiator to promote photopolymerization initiated by a photopolymerization initiator. The photoinitiator may be an amine based, alkoxylated or thioxanthone based compound.

基於胺之化合物的實例可包括三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、苯甲酸2-二甲基胺基乙酯、4-二甲基胺基苯 甲酸2-乙基己酯、N,N-二甲基-對甲苯胺、4,4'-雙(二甲基胺基)二苯甲酮(米氏酮(Michler's ketone))、4,4'-雙(二乙基胺基)二苯甲酮及4,4'-雙(乙基甲基胺基)二苯甲酮。其中，4,4'-雙(二乙基胺基)二苯甲酮為較佳。 Examples of the amine-based compound may include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 4-dimethylaminobenzene 2-ethylhexyl formate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (Michler's ketone), 4,4 '-Bis(diethylamino)benzophenone and 4,4'-bis(ethylmethylamino)benzophenone. Among them, 4,4'-bis(diethylamino)benzophenone is preferred.

基於烷氧基蒽之化合物的實例可包括9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽及2-乙基-9,10-二乙氧基蒽。 Examples of the alkoxyquinone-based compound may include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl -9,10-diethoxyanthracene.

基於噻噸酮之化合物的實例可包括2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮及1-氯-4-丙氧基噻噸酮。 Examples of the thioxanthone-based compound may include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1 -Chloro-4-propoxythioxanthone.

此等光引發助劑可單獨使用或兩者或兩者以上組合使用。此外，光引發助劑可為市售產品，例如商標名「EAB-F」(Hodogaya Chemical Industries)。 These photoinitiating aids may be used singly or in combination of two or more. Further, the photoinitiator may be a commercially available product such as the trade name "EAB-F" (Hodogaya Chemical Industries).

光引發助劑較佳以按1mol光引發劑計10mol或10mol以下、更佳0.01至5mol之量使用。當光引發助劑之量滿足此類範圍時，本發明之著色感光性樹脂組合物可具有更加提高之敏感性且增強使用組合物形成之彩色濾光片的產率。 The photoinitiator is preferably used in an amount of 10 mol or less, more preferably 0.01 to 5 mol, based on 1 mol of the photoinitiator. When the amount of the photoinitiator aid satisfies such a range, the colored photosensitive resin composition of the present invention can have more improved sensitivity and enhance the yield of the color filter formed using the composition.

溶劑(E)Solvent (E)

在本發明之一個實施例中，溶劑(E)不特別限制，且可使用用於習知著色感光性樹脂組合物中之各種有機溶劑。 In one embodiment of the present invention, the solvent (E) is not particularly limited, and various organic solvents used in the conventional coloring photosensitive resin composition can be used.

舉例而言，溶劑(E)可包括乙二醇單烷醚，諸如乙二醇單甲醚、乙二醇單***、乙二醇單丙醚及乙二醇單丁醚；二乙二醇二烷醚，諸如二乙二醇二甲醚、二乙二醇二***、二乙二醇二丙醚及二乙二醇二丁醚；乙二醇烷基醚乙酸酯，諸如乙酸2-甲氧乙酯(methyl cellosolve acetate)及乙酸2-乙氧乙酯(ethyl cellosolve acetate)；烷二醇烷基醚乙酸酯，諸如丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、甲氧基丁基乙酸酯及甲氧基戊基乙酸酯；芳族烴，諸如苯、甲苯、二甲苯及均三甲苯；酮，諸如甲基乙基酮、丙酮、甲基戊 基酮、甲基異丁基酮及環己酮；醇，諸如乙醇、丙醇、丁醇、己醇、環己醇、乙二醇及丙三醇；酯，諸如3-乙氧基丙酸乙酯及3-甲氧基丙酸甲酯；及環狀酯，諸如γ-丁內酯。 For example, the solvent (E) may include ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; diethylene glycol II An alkyl ether such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetate, such as acetic acid 2-A Methyl cellosolve acetate and ethyl cellosolve acetate; alkylene glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Propyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; ketones such as methyl ethyl ketone, acetone Methyl pentane Ketone, methyl isobutyl ketone and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerol; esters such as 3-ethoxypropionic acid Ethyl ester and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone.

溶劑(E)較佳可為沸點100至200℃的有機溶劑(根據使用及乾燥角度)，更佳可為烷二醇烷基醚乙酸酯、酮、酯(諸如3-乙氧基丙酸乙酯及3-甲氧基丙酸甲酯)，甚至更佳可為丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、環己酮、3-乙氧基丙酸乙酯及3-甲氧基丙酸甲酯。以上溶劑可單獨使用或兩者或兩者以上組合使用。 The solvent (E) may preferably be an organic solvent having a boiling point of 100 to 200 ° C (depending on the use and drying angle), more preferably an alkylene glycol alkyl ether acetate, a ketone or an ester (such as 3-ethoxypropionic acid). Ethyl ester and methyl 3-methoxypropionate), even more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate and 3- Methyl methoxypropionate. The above solvents may be used singly or in combination of two or more.

溶劑(E)可較佳以按本發明之著色感光性樹脂組合物之總重量計60至90wt%、更佳70至85wt%之量存在。當溶劑(E)之量在60至90wt%之範圍內時，可使用塗覆機，諸如滾塗機、旋塗機、狹縫及旋轉塗佈機、縫塗機(亦稱為『模塗機』)及噴墨，獲得良好塗覆。 The solvent (E) is preferably present in an amount of from 60 to 90% by weight, more preferably from 70 to 85% by weight based on the total weight of the colored photosensitive resin composition of the present invention. When the amount of the solvent (E) is in the range of 60 to 90% by weight, a coating machine such as a roll coater, a spin coater, a slit and a spin coater, a slit coater (also referred to as "die coating" may be used. Machine") and inkjet, get good coating.

根據本發明之一個實施例的著色感光性樹脂組合物必要時可進一步包含添加劑(F)，例如填充劑、其他聚合物、顏料分散劑、黏著促進劑、抗氧化劑、UV吸收劑、防凝劑等。 The colored photosensitive resin composition according to an embodiment of the present invention may further contain an additive (F), such as a filler, other polymers, a pigment dispersant, an adhesion promoter, an antioxidant, a UV absorber, an anti-coagulant, if necessary. Wait.

填充劑之實例可包括玻璃、二氧化矽和氧化鋁。 Examples of the filler may include glass, cerium oxide, and aluminum oxide.

其他聚合物之實例可包括可固化樹脂，諸如環氧樹脂及順丁烯二醯亞胺樹脂；以及熱塑性樹脂，諸如聚乙烯醇、聚丙烯酸、聚乙二醇單烷醚、聚氟烷基丙烯酸酯、聚酯及聚胺基甲酸酯。 Examples of other polymers may include curable resins such as epoxy resins and maleimide resins; and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylic acid Esters, polyesters and polyurethanes.

顏料分散劑可包括市售界面活性劑，例如基於矽、基於氟、基於酯、陽離子、陰離子、非離子及兩性界面活性劑。此等界面活性劑可單獨使用或兩者或兩者以上組合使用。 Pigment dispersants can include commercially available surfactants such as ruthenium based, fluorine based, ester based, cationic, anionic, nonionic and amphoteric surfactants. These surfactants may be used singly or in combination of two or more.

界面活性劑之實例可包括聚氧化乙烯烷基醚、聚氧化乙烯烷基苯基醚、聚乙二醇二酯、脫水山梨糖醇脂肪酸酯、經脂肪酸改質之聚酯、經三級胺改質之聚胺基甲酸酯及聚乙烯亞胺。界面活性劑可包括以下商標名之產品：KP(Shin-Etsu Chemical Industry)、POLYFLOW (Kyoeisha Chemical)、EFTOP(Tochem Products)、MEGAFAC(Dainippon Ink and Chemical Industry)、Flourad(Sumitomo 3M)、Asahi Guard、Surflon(Asahi Glass)、SOLSPERSE(Lubrizol)、EFKA(EFKA Chemicals)、PB 821(Ajinomoto)及Disperbyk系列(BYK-Chemi)。 Examples of the surfactant may include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine Modified polyurethane and polyethyleneimine. Surfactants may include products under the trade names KP (Shin-Etsu Chemical Industry), POLYFLOW (Kyoeisha Chemical), EFTOP (Tochem Products), MEGAFAC (Dainippon Ink and Chemical Industry), Flourad (Sumitomo 3M), Asahi Guard, Surflon (Asahi Glass), SOLSPERSE (Lubrizol), EFKA (EFKA Chemicals), PB 821 (Ajinomoto) ) and the Disperbyk series (BYK-Chemi).

黏著促進劑之實例可包括乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基參(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-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、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-甲基丙烯醯氧基丙基三甲氧基矽烷及3-巰基丙基三甲氧基矽烷。 Examples of the adhesion promoter may include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, N-(2-aminoethyl)-3- Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidol Oxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropyl Methyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, and 3-mercaptopropyltrimethoxydecane.

抗氧化劑之實例可包括2,2'-硫基雙(4-甲基-6-第三丁基苯酚)及2,6-二-第三丁基-4-甲基苯酚。 Examples of the antioxidant may include 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol.

UV吸收劑之實例可包括2-(3-第三丁基-2-羥基-5-甲基苯基)-5-氯苯并***及烷氧基二苯甲酮。 Examples of the UV absorber may include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone.

防凝劑之實例可包括聚丙烯酸鈉。 Examples of the anti-coagulant may include sodium polyacrylate.

根據本發明之一個實施例的著色感光性樹脂組合物可藉由以下方法製備。 The colored photosensitive resin composition according to one embodiment of the present invention can be produced by the following method.

舉例而言，著色劑(A)與溶劑(E)混合，且使用珠磨機分散混合物，直至著色劑之平均直徑達約0.2μm或少於0.2μm。必要時，混合顏料分散劑或部分或所有黏合劑樹脂(B)。向混合分散液(亦稱為『漆漿』)添加其餘黏合劑樹脂(B)、光可聚合單體(C)、光聚合引發劑(D)及其他組分，且必要時，可進一步添加溶劑以便得到所需濃度，藉此製備著色感光性樹脂組合物。 For example, the colorant (A) is mixed with the solvent (E), and the mixture is dispersed using a bead mill until the average diameter of the colorant is about 0.2 μm or less. If necessary, mix the pigment dispersant or some or all of the binder resin (B). Adding the remaining binder resin (B), photopolymerizable monomer (C), photopolymerization initiator (D) and other components to the mixed dispersion (also referred to as "lacquer"), and if necessary, further adding The solvent is used to obtain a desired concentration, whereby a colored photosensitive resin composition is prepared.

本發明之一個實施例係關於一種彩色濾光片，其係使用以上提 及之著色感光性樹脂組合物形成。根據本發明之一個實施例的彩色濾光片包含著色層，其藉由在基板上塗覆著色感光性樹脂組合物，接著曝光及顯影形成圖案來形成。 One embodiment of the present invention relates to a color filter that uses the above And the colored photosensitive resin composition is formed. A color filter according to an embodiment of the present invention includes a colored layer formed by coating a colored photosensitive resin composition on a substrate, followed by exposure and development to form a pattern.

下文中，將詳細描述使用本發明之著色感光性樹脂組合物形成圖案之方法。 Hereinafter, a method of forming a pattern using the colored photosensitive resin composition of the present invention will be described in detail.

使用本發明之著色感光性樹脂組合物形成圖案的方法可藉由此項技術中已知之方法進行，且習知包含塗覆、曝光及移除之步驟。本發明之著色感光性樹脂組合物塗覆在基板上，接著光固化及顯影，形成待用作黑色矩陣或著色像素(著色圖像)之圖案。 The method of forming a pattern using the colored photosensitive resin composition of the present invention can be carried out by a method known in the art, and conventionally includes a step of coating, exposing and removing. The colored photosensitive resin composition of the present invention is coated on a substrate, followed by photocuring and developing to form a pattern to be used as a black matrix or a colored pixel (colored image).

在塗覆步驟中，本發明之著色感光性樹脂組合物塗覆在基板(此項技術中習用，例如但不限於玻璃或矽晶圓)上或在著色感光性樹脂組合物之預形成層上，接著預乾燥以移除揮發性組分，諸如溶劑，得到平滑塗層膜。塗層膜較佳具有1至3μm之厚度。 In the coating step, the colored photosensitive resin composition of the present invention is coated on a substrate (used in the art such as, but not limited to, a glass or tantalum wafer) or on a pre-formed layer of the colored photosensitive resin composition. Then, pre-drying to remove volatile components such as a solvent gives a smooth coating film. The coating film preferably has a thickness of from 1 to 3 μm.

在曝光步驟中，為獲得所需圖案，塗層膜在某些區域使用遮罩用UV照射。為用平行光線均勻照射整個區域且將遮罩與基板準確對準，較佳使用遮罩對準器或步進器。 In the exposure step, in order to obtain the desired pattern, the coating film is irradiated with UV in some areas using a mask. In order to uniformly illuminate the entire area with parallel rays and to accurately align the mask with the substrate, a mask aligner or stepper is preferably used.

在移除步驟中，藉由UV照射固化之塗層膜接觸鹼性水溶液，以溶解及顯影未曝光區，藉此獲得所需圖案。顯影後，必要時，乾燥可在150至230℃溫度下進行10至60分鐘。 In the removing step, the coating film cured by UV irradiation is contacted with an alkaline aqueous solution to dissolve and develop the unexposed regions, thereby obtaining a desired pattern. After development, if necessary, the drying may be carried out at a temperature of from 150 to 230 ° C for 10 to 60 minutes.

此項技術中已知之任何顯影溶液均可用於顯影。尤其可使用含有鹼性化合物及界面活性劑之水溶液。 Any developing solution known in the art can be used for development. In particular, an aqueous solution containing a basic compound and a surfactant can be used.

鹼性化合物可為無機或有機鹼性化合物。無機鹼性化合物之實例可包括氫氧化鈉、氫氧化鉀、磷酸氫二鈉、磷酸二氫鈉、磷酸氫二銨、磷酸二氫銨、磷酸二氫鉀、矽酸鈉、矽酸鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、硼酸鈉、硼酸鉀及氨。有機鹼性化合物之實例可包括氫氧化四甲基銨、氫氧化2-羥基乙基三甲基銨、單甲胺、二甲 胺、三甲胺、單乙胺、二乙胺、三乙胺、單異丙胺、二異丙胺及乙醇胺。此等無機及有機鹼性化合物可單獨使用或兩者或兩者以上之組合使用。鹼性化合物含量可為以顯影溶液之總重量計0.01至10重量份、較佳0.03至5重量份。 The basic compound may be an inorganic or organic basic compound. Examples of the inorganic basic compound may include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, potassium citrate, carbonic acid. Sodium, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate and ammonia. Examples of the organic basic compound may include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, and dimethyl Amine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine and ethanolamine. These inorganic and organic basic compounds may be used singly or in combination of two or more. The basic compound content may be from 0.01 to 10 parts by weight, preferably from 0.03 to 5 parts by weight, based on the total weight of the developing solution.

界面活性劑可選自由非離子、陰離子、陽離子界面活性劑及其混合物組成之群。非離子界面活性劑之實例可包括聚氧乙烯烷基醚、聚氧乙烯芳基醚、聚氧乙烯烷基芳基醚及其他聚氧乙烯衍生物、環氧乙烷-環氧丙烷嵌段共聚物、脫水山梨糖醇脂肪酸酯、聚氧乙烯脫水山梨糖醇脂肪酸酯、聚氧乙烯山梨糖醇脂肪酸酯、脂肪酸甘油酯、聚氧乙烯脂肪酸酯及聚氧乙烯烷基胺。陰離子界面活性劑之實例可包括高級醇硫酸鹽，諸如十二烷醇硫酸鈉及油醇硫酸鈉；烷基硫酸鹽，諸如十二烷基硫酸鈉及十二烷基硫酸銨；烷基芳基磺酸鹽，諸如十二烷基苯磺酸鈉及十二烷基萘磺酸鈉。陽離子界面活性劑之實例可包括胺及四級銨鹽，諸如十八胺鹽酸鹽及氯化月桂基三甲基銨。此等界面活性劑可單獨使用或兩者或兩者以上組合使用。界面活性劑較佳以按顯影溶液之總重量計0.01至10重量份、更佳0.05至8重量份、甚至更佳0.1至5重量份之量存在。 The surfactant can be selected from the group consisting of nonionic, anionic, cationic surfactants, and mixtures thereof. Examples of the nonionic surfactant may include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, and other polyoxyethylene derivatives, ethylene oxide-propylene oxide block copolymerization. , sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid ester and polyoxyethylene alkylamine. Examples of anionic surfactants may include higher alcohol sulfates such as sodium lauryl sulfate and sodium oleyl sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; alkyl aryl groups Sulfonic acid salts such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate. Examples of the cationic surfactant may include an amine and a quaternary ammonium salt such as octadecylamine hydrochloride and lauryl trimethylammonium chloride. These surfactants may be used singly or in combination of two or more. The surfactant is preferably present in an amount of from 0.01 to 10 parts by weight, more preferably from 0.05 to 8 parts by weight, even more preferably from 0.1 to 5 parts by weight, based on the total weight of the developing solution.

如上所提及，著色感光性樹脂組合物進行塗覆、乾燥、曝光以圖案化及顯影，得到對應於感光性樹脂組合物中著色材料之各顏色的像素或黑色矩陣，且根據彩色濾光片所需的顏色數目重複此類程序，藉此獲得彩色濾光片。此項技術中已知彩色濾光片之構造及製備，且因此本文中省略其詳細描述。 As described above, the colored photosensitive resin composition is coated, dried, exposed for patterning and development to obtain a pixel or a black matrix corresponding to each color of the coloring material in the photosensitive resin composition, and according to the color filter The number of colors required repeats such a procedure, thereby obtaining a color filter. The construction and preparation of color filters are known in the art, and thus detailed descriptions thereof are omitted herein.

本發明之一個實施例係關於一種具有以上提及之彩色濾光片的液晶顯示裝置。 One embodiment of the present invention relates to a liquid crystal display device having the above-mentioned color filter.

本發明之液晶顯示裝置具有以上提及之彩色濾光片且包含此項技術中已知之其他組件。亦即，可應用本發明彩色濾光片之任何液晶 顯示裝置均包括在本發明中。舉例而言，存在透射液晶顯示裝置，其中具有薄膜電晶體(TFT)之相反電極基板、像素電極及對準層彼此以預定間隔面對，且液晶材料引入間隔中以形成液晶層。此外，可提及在彩色濾光片基板與著色層之間具有反射層之反射液晶顯示裝置。另外，可提及一種液晶顯示裝置，其包含組合在彩色濾光片之透明電極上的薄膜電晶體(TFT)基板及固定在與彩色濾光片重疊之TFT基板位置上的背光。 The liquid crystal display device of the present invention has the above-mentioned color filter and includes other components known in the art. That is, any liquid crystal to which the color filter of the present invention can be applied Display devices are all included in the present invention. For example, there is a transmissive liquid crystal display device in which an opposite electrode substrate having a thin film transistor (TFT), a pixel electrode, and an alignment layer face each other at a predetermined interval, and a liquid crystal material is introduced into the space to form a liquid crystal layer. Further, a reflective liquid crystal display device having a reflective layer between the color filter substrate and the coloring layer may be mentioned. Further, a liquid crystal display device comprising a thin film transistor (TFT) substrate combined on a transparent electrode of a color filter and a backlight fixed at a position of the TFT substrate overlapping the color filter may be mentioned.

本發明進一步以以下實例、比較實例及實驗實例說明，該等實例不應解釋為限制本發明之範疇。 The invention is further illustrated by the following examples, comparative examples and experimental examples, which should not be construed as limiting the scope of the invention.

製備實例1：製備黏合劑樹脂Preparation Example 1: Preparation of Adhesive Resin

準備裝備有攪拌器、溫度計、回流冷凝器、滴加批料及用於引入氮氣之管的燒瓶。為製備單體滴加批料，將74.8g(0.20mol)苯甲基順丁烯二醯亞胺、43.2g(0.30mol)丙烯酸、118.0g(0.50mol)乙烯基甲苯、4g第三丁基過氧基-2-乙基己酸酯及40g丙二醇單甲醚乙酸酯(PGMEA)混合且攪拌。為製備鏈轉移劑滴加批料，將6g正十二硫醇及24g PGMEA混合且攪拌。隨後，將395g PGMEA添加至燒瓶且將燒瓶氛圍自空氣變成氮氣，且在攪拌下燒瓶溫度升高至90℃。單體及鏈轉移劑依序自滴加批料滴加。每次滴加進行2小時，同時溫度維持在90℃下。在1小時之後，溫度升高至110℃且維持3小時。隨後，氧氣/氮氣=5/95(v/v)之混合物鼓泡穿過用於引入氣體之管。隨後，28.4g(0.10mol，對應於按用於反應之丙烯酸之羧基計33mol%)甲基丙烯酸縮水甘油酯、0.4g 2,2'-亞甲基雙(4-甲基-6-第三丁基苯酚)及0.8g三乙胺置於燒瓶中且在110℃下繼續反應8小時，得到具有70mg KOH/g之酸值的黏合劑樹脂。 A flask equipped with a stirrer, a thermometer, a reflux condenser, a batch of the batch, and a tube for introducing nitrogen was prepared. For the preparation of the monomer dropwise addition, 74.8 g (0.20 mol) of benzyl maleimide, 43.2 g (0.30 mol) of acrylic acid, 118.0 g (0.50 mol) of vinyl toluene, 4 g of t-butyl group Peroxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were mixed and stirred. To prepare a chain transfer agent, a batch was added, and 6 g of n-dodecylmercaptan and 24 g of PGMEA were mixed and stirred. Subsequently, 395 g of PGMEA was added to the flask and the atmosphere of the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90 ° C with stirring. The monomer and the chain transfer agent are sequentially added dropwise from the dropwise addition batch. Each addition was carried out for 2 hours while maintaining the temperature at 90 °C. After 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours. Subsequently, a mixture of oxygen/nitrogen = 5/95 (v/v) was bubbled through the tube for introducing the gas. Subsequently, 28.4 g (0.10 mol, corresponding to 33 mol% based on the carboxyl group of the acrylic acid used for the reaction) glycidyl methacrylate, 0.4 g of 2,2'-methylenebis(4-methyl-6-third Butylphenol) and 0.8 g of triethylamine were placed in a flask and the reaction was continued at 110 ° C for 8 hours to obtain a binder resin having an acid value of 70 mg KOH / g.

黏合劑樹脂如藉由GPC量測所確定，具有16,000之聚苯乙烯換算之重量平均分子量(Mw)，及2.3之分子量分佈(Mw/Mn)。 The binder resin has a weight average molecular weight (M w ) of 16,000 in terms of polystyrene and a molecular weight distribution (M w /M n ) of 2.3 as determined by GPC measurement.

重量平均分子量(Mw)及數目平均分子量(Mn)使用GPC方法在以下條件下量測。所量測之重量平均分子量與所量測之數目平均分子量的比率係指分子量分佈(Mw/Mn)。 The weight average molecular weight (M w ) and the number average molecular weight (M n ) were measured by the GPC method under the following conditions. The ratio of the measured weight average molecular weight to the measured number average molecular weight refers to the molecular weight distribution (M w /M n ).

儀器：HLC-8120GPC(Tosoh Corporation) Instrument: HLC-8120GPC (Tosoh Corporation)

管柱：TSK-GELG400HXL+TSK-GELG2000HXL(串聯) Column: TSK-GELG400HXL+TSK-GELG2000HXL (series)

管柱溫度：40℃ Column temperature: 40 ° C

溶離溶劑：四氫呋喃 Dissolved solvent: tetrahydrofuran

通量：1.0ml/min Flux: 1.0ml/min

注射體積：50μl Injection volume: 50μl

偵測器：RI Detector: RI

樣品濃度：0.6wt%(溶劑：四氫呋喃) Sample concentration: 0.6 wt% (solvent: tetrahydrofuran)

用於校準之標準材料：TSK標準聚苯乙烯F-40、F-4、F-1、A-2500、A-500(Tosoh Corporation) Standard materials for calibration: TSK standard polystyrene F-40, F-4, F-1, A-2500, A-500 (Tosoh Corporation)

實例1至5及比較實例1至4：製備著色感光性樹脂組合物及彩色濾光片Examples 1 to 5 and Comparative Examples 1 to 4: Preparation of Colored Photosensitive Resin Composition and Color Filter

著色感光性樹脂組合物藉由將組分以下表1中所列之比率(單位：重量%)混合來製備。 The colored photosensitive resin composition was prepared by mixing the components (the unit: % by weight) listed in Table 1 below.

以上表1之每種組分如下。 Each of the components of Table 1 above is as follows.

G7：顏料綠7 G7: Pigment Green 7

Y185：顏料黃185 Y185: Pigment Yellow 185

Y129：顏料黃129 Y129: Pigment Yellow 129

Y138：顏料黃138 Y138: Pigment Yellow 138

Y139：顏料黃139 Y139: Pigment Yellow 139

B：製備實例1之黏合劑樹脂 B: Preparation of the binder resin of Example 1.

C：二異戊四醇六丙烯酸酯(KAYARAD DPHA，Nippon Kayaku) C: diisopentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku)

D：2-苯甲基-2-二甲基胺基-1-(4-嗎啉基苯基)丁-1-酮(Irgacure 369，Ciba Specialty Chemical) D: 2-Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one (Irgacure 369, Ciba Specialty Chemical)

E：丙二醇單甲醚乙酸酯 E: propylene glycol monomethyl ether acetate

F：基於丙烯酸酯之顏料分散劑(Disper byk-2001，BYK-Chemie) F: acrylate-based pigment dispersant (Disper byk-2001, BYK-Chemie)

實驗實例1：Experimental example 1: 實驗實例1-1：評估亮度、對比度及色度Experimental Example 1-1: Evaluation of Brightness, Contrast, and Chroma

實例1至5以及比較實例1至4中製備之著色感光性樹脂組合物用以製備著色層。特定言之，各著色感光性樹脂組合物藉助於旋塗塗覆在玻璃基板上，且玻璃基板置放於維持溫度100℃之加熱板上3分鐘，從而在玻璃基板上形成薄膜。隨後，各薄膜經受使用含有100mJ/cm2下g、h及i光線所有之1KW高壓汞燈的UV照射。未使用特殊光學濾光片。 The colored photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were used to prepare a colored layer. Specifically, each of the colored photosensitive resin compositions was coated on a glass substrate by spin coating, and the glass substrate was placed on a hot plate maintained at a temperature of 100 ° C for 3 minutes to form a film on the glass substrate. Subsequently, each film was subjected to UV irradiation using a 1 KW high pressure mercury lamp containing all of g, h and i rays at 100 mJ/cm 2 . No special optical filters were used.

各UV照射之薄膜浸在用作顯影溶液之KOH水溶液(pH 10.5)中2分鐘。顯影後，用蒸餾水洗滌經薄膜著色之玻璃且用氮氣乾燥，接著在設為200℃之烘箱中加熱30分鐘，得到具有1至5μm之厚度的著色層。 Each of the UV-irradiated films was immersed in an aqueous KOH solution (pH 10.5) used as a developing solution for 2 minutes. After development, the film-colored glass was washed with distilled water and dried with nitrogen, followed by heating in an oven set at 200 ° C for 30 minutes to obtain a coloring layer having a thickness of 1 to 5 μm.

藉由以下方法評估每個樣品之亮度、對比度及色度。結果展示在表2中。 The brightness, contrast, and chromaticity of each sample were evaluated by the following methods. The results are shown in Table 2.

(1)亮度 (1) Brightness

使用顯微光譜儀OSP-SP2000量測著色層之亮度(Y)。 The brightness (Y) of the colored layer was measured using a microspectrometer OSP-SP2000.

○：Y40 ○: Y 40

△：38Y<40 △: 38 Y<40

X：Y<38 X:Y<38

(2)對比度 (2) Contrast

著色層之對比率(CR)使用BM-5A(Topcon Corporation)基於玻璃基板(在形成著色層前)中1：30000之對比率來量測。 The contrast ratio (CR) of the colored layer was measured using a BM-5A (Topcon Corporation) based on a ratio of 1:30000 in the glass substrate (before forming the colored layer).

◎：CR15000 ◎: CR 15000

○：12000CR<15000 ○: 12000 CR<15000

△：10000CR<12000 △: 10000 CR<12000

X：CR<10000 X: CR<10000

(3)色度 (3) Chroma

在用於產生所希望之膜厚度的著色感光性樹脂組合物中，量測顏料之內含物比率。 The content ratio of the pigment is measured in the colored photosensitive resin composition for producing a desired film thickness.

○：色度<0.35 ○: Chroma <0.35

△：0.35色度<0.45 △: 0.35 Chroma <0.45

X：色度0.45 X: Chroma 0.45

實驗實例1-2：形成彩色濾光片圖案Experimental Example 1-2: Formation of a color filter pattern

藉助於旋轉塗佈，將實例1至5及比較實例1至4中製備之各著色感光性樹脂組合物塗覆在玻璃基板(#1737，Corning Inc.)上，且置放在100℃熱板上3分鐘以形成薄膜。隨後，測試光罩以1000μM之空間排列在薄膜上，該光罩具有將透射率在1至100%範圍內逐步改變之圖案，且在空氣氛圍下使用超高壓汞燈(USH-250D，Ushio Inc.)在40mJ/cm2曝光下進行紫外線(365nm)照射。使用噴霧顯影器，UV輻射膜在用作顯影溶液之KOH(pH 12.5)水溶液中顯影80秒。在顯影之後，將上面塗佈有薄膜之玻璃基板用蒸餾水洗滌且經氮氣乾燥，接著在設為220℃之烘箱中加熱20分鐘，以製備彩色濾光片。由此製備之彩色 濾光片經確定，具有2.5至2.9μm之圖案(薄膜)厚度。 Each of the colored photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 4 was coated on a glass substrate (#1737, Corning Inc.) by spin coating, and placed on a hot plate at 100 °C. It took 3 minutes to form a film. Subsequently, the test reticle was arranged on the film at a space of 1000 μM, which had a pattern in which the transmittance was gradually changed in the range of 1 to 100%, and an ultrahigh pressure mercury lamp (USH-250D, Ushio Inc.) was used in an air atmosphere. .) Irradiation (365 nm) was carried out under exposure of 40 mJ/cm 2 . Using a spray developer, the UV radiation film was developed in an aqueous solution of KOH (pH 12.5) used as a developing solution for 80 seconds. After the development, the glass substrate on which the film was coated was washed with distilled water and dried with nitrogen, followed by heating in an oven set at 220 ° C for 20 minutes to prepare a color filter. The color filter thus prepared was determined to have a pattern (film) thickness of 2.5 to 2.9 μm.

類似地，藉由相對於初始曝光，降低曝光程度，來重複圖案之形成程序。為評估圖案形成特性，計算圖案形成曝光相對於初始曝光之比率。 Similarly, the pattern forming process is repeated by reducing the degree of exposure with respect to the initial exposure. To evaluate the pattern formation characteristics, the ratio of the pattern forming exposure to the initial exposure was calculated.

<評估標準> <Evaluation criteria>

○：圖案形成特性<0.2 ○: Pattern formation characteristics <0.2

△：0.2圖案形成特性<0.6 △: 0.2 Pattern formation characteristics <0.6

X：圖案形成特性0.6 X: pattern formation characteristics 0.6

如表2中所示，根據本發明之實例1至5的著色感光性樹脂組合物顯示優於比較實例1至4之不具有C.I.顏料黃129之組合物的亮度、對比度、色度及圖案形成特性。因而，確定根據本發明之著色感光性樹脂組合物具有低概率的在液晶顯示裝置中產生顯示缺陷。 As shown in Table 2, the colored photosensitive resin compositions according to Examples 1 to 5 of the present invention showed brightness, contrast, chroma and pattern formation superior to those of Comparative Examples 1 to 4 without CI Pigment Yellow 129. characteristic. Thus, it was confirmed that the colored photosensitive resin composition according to the present invention has a low probability of causing display defects in the liquid crystal display device.

雖然已展示且描述本發明之特定實施例，但熟習此項技術者應瞭解不希望將本發明限制於較佳實施例，且熟習此項技術者顯而易見可在不偏離本發明之精神及範疇下作出各種改變及修改。 While a particular embodiment of the invention has been shown and described, it will be understood by those skilled in the art Make various changes and modifications.

因此，本發明之範疇由隨附申請專利範圍及其同等物界定。 Accordingly, the scope of the invention is defined by the scope of the appended claims and their equivalents.

Claims (5)

一種著色感光性樹脂組合物，其包含著色劑(A)、黏合劑樹脂(B)、光可聚合化合物(C)、光聚合引發劑(D)及溶劑(E)，該著色劑(A)包含C.I.顏料綠7、C.I.顏料黃185及C.I.顏料黃129。 A colored photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), the colorant (A) Contains CI Pigment Green 7, CI Pigment Yellow 185 and CI Pigment Yellow 129. 如請求項1之著色感光性樹脂組合物，其中該C.I.顏料黃129係以按該C.I.顏料綠7、C.I.顏料黃185及C.I.顏料黃129之總固體含量計5至50wt%之量存在。 The colored photosensitive resin composition of claim 1, wherein the C.I. Pigment Yellow 129 is present in an amount of from 5 to 50% by weight based on the total solid content of the C.I. Pigment Green 7, C.I. Pigment Yellow 185 and C.I. Pigment Yellow 129. 如請求項1之著色感光性樹脂組合物，其中該著色劑(A)係以按該著色感光性樹脂組合物之總固體含量計10至60wt%之量存在。 The colored photosensitive resin composition of claim 1, wherein the colorant (A) is present in an amount of 10 to 60% by weight based on the total solid content of the colored photosensitive resin composition. 一種彩色濾光片，其係使用如請求項1至3中任一項之著色感光性樹脂組合物形成。 A color filter formed using the colored photosensitive resin composition according to any one of claims 1 to 3. 一種液晶顯示裝置，其具有如請求項4之彩色濾光片。 A liquid crystal display device having the color filter of claim 4.
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