TWI287694B - Photosensitive black-colored composition, and black matrix substrate and color filter, using the same - Google Patents

Photosensitive black-colored composition, and black matrix substrate and color filter, using the same Download PDF

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TWI287694B
TWI287694B TW093117595A TW93117595A TWI287694B TW I287694 B TWI287694 B TW I287694B TW 093117595 A TW093117595 A TW 093117595A TW 93117595 A TW93117595 A TW 93117595A TW I287694 B TWI287694 B TW I287694B
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black
composition
photosensitive
black matrix
carbon black
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TW093117595A
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Chinese (zh)
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TW200506521A (en
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Hiroshi Sasaki
Kazunori Yamada
Koichi Minato
Takeshi Itoi
Mizuhiro Tani
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Toyo Ink Mfg Co
Toppan Printing Co Ltd
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007Filters, e.g. additive colour filters; Components for display devices
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/22Absorbing filters
    • G02B5/23Photochromic filters
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0045Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)

Abstract

There is provided a photosensitive black-colored composition, in which carbon black with specific surface area of 50 to 200 m<2>/g, pigment derivatives represented by the following formula (A) possessing alkali replacing groups with triazine rings, and ethylene unsaturated compounds are contained. Then there is provided a black matrix substrate with black matrix made from the black composition. And then there is provided a color filter made of filter segment including two colors at least but black. Formula (A): (In the formula, Q represents organic pigment residual group.)

Description

1287694 九、發明說明: (一) 發明所屬之技術領域: 本發明係關於可用於與液晶顯示裝置或固體攝影構件 等組合來使用之濾色器之黑色矩陣之製造上的感光性黑色 組成物、使用它之黑色矩陣基板及濾色器。 (二) 先前技術: 在濾色器之紅、綠、藍之濾色段間的間隙部分,係以 對比提升爲目的,一般形成稱爲具有遮光性之黑色矩陣的 格子狀黑色圖案。 以前,黑色矩陣雖以鉻、鎳等金屬薄膜所形成,但從 顯示品質及成本之觀點來看,嘗試使用已分散黑色著色劑 (碳黑等黑色顏料或混合數種顏料而形成黑色之著色劑) 之感光性黑色組成物來形成黑色矩陣。使用感光性黑色組 成物所形成之黑色矩陣係由於表面光反射率低、可進行製 造步驟之縮短化、可進行大型濾色器之生產,比使用鉻等 金屬材料所形成之黑色矩陣有較多之優點。 然而,在使用感光性黑色組成物而以光微影法來形成 黑色矩陣之情況下,雖然爲了得到高遮光性而有配合多量 碳黑等黑色著色劑於組成物中之必要,但黑色著色劑之含 有量變得愈高,均勻分散黑色著色劑變得愈困難,而有產 生所謂感光性黑色組成物之長時間黏度增加之分散安定性 降低的問題。又,遮光性變高連帶感度顯著條低,即使進 行活性能源射線之照射亦難以得到硬化塗膜,爲了得到充 分硬化之塗膜,則必須較多之曝光量,而有所謂招致生產 -7- 1287694 性降低或黑色矩陣形狀劣化的問題。 爲了解決如此之問題,提案在包含黑色矩陣之濾色器 形成用組成物中,配合以下述通式(B )所示之色素衍生物 (例如,參照日本國特開平3 - 1 5 3 7 8 0號公報。)。 通式(B ):1287694 IX. Description of the invention: (I) Technical field to which the invention pertains: The present invention relates to a photosensitive black composition for manufacturing a black matrix which can be used for a color filter used in combination with a liquid crystal display device or a solid-state imaging member, Use its black matrix substrate and color filter. (2) Prior art: In the gap portion between the color filter segments of red, green and blue of the color filter, for the purpose of contrast enhancement, a lattice-like black pattern called a black matrix having a light-shielding property is generally formed. In the past, although the black matrix was formed of a metal film such as chromium or nickel, it was attempted to use a black pigment such as a black pigment such as carbon black or a mixture of several pigments to form a black coloring agent from the viewpoint of display quality and cost. The photosensitive black composition forms a black matrix. The black matrix formed by using the photosensitive black composition has a low surface light reflectance, can shorten the manufacturing process, and can produce a large color filter, and has a larger number of black matrices than metal materials such as chrome. advantage. However, when a black matrix is formed by photolithography using a photosensitive black composition, it is necessary to blend a large amount of black colorant such as carbon black in the composition in order to obtain high light-shielding property, but black colorant. The higher the content of the black coloring agent becomes, the more difficult it is to uniformly disperse the black coloring agent, and the problem that the dispersion stability of the long-term viscosity increase of the so-called photosensitive black composition is lowered. In addition, the light-shielding property is high and the sensitivity is remarkably low, and it is difficult to obtain a hardened coating film even when irradiated with an active energy ray. In order to obtain a sufficiently hardened coating film, a large amount of exposure is required, and there is a so-called production -7- 1287694 Problem of reduced sex or black matrix shape degradation. In order to solve such a problem, it is proposed to blend a dye derivative represented by the following formula (B) in a color filter forming composition containing a black matrix (for example, refer to Japanese Patent Laid-Open 3 - 1 5 3 7 8 Bulletin No. 0.). General formula (B):

Q DQj (b) 其中,Q表示有機色素殘餘官能基,Q DQj (b) wherein Q represents the residual functional group of the organic pigment,

Xi係表示氫原子、羧基或磺酸基, X2表示以通式 一 A—Xi represents a hydrogen atom, a carboxyl group or a sulfonic acid group, and X2 represents a formula A-

所表示之取代基, i及j個別獨立地表示1〜4之整數, R:、1個別獨立地表示氫原子、或亦可具有取代基之 烷基、芳基或雜環殘餘官能基, Y表示氫原子、鹵素原子、—no2、一 nh2或一 so3h 1287694 k表示1〜4之整數, η表示1〜4之整數, Α表示以通式The substituents represented by i and j each independently represent an integer of 1 to 4, and R: and 1 each independently represent a hydrogen atom or an alkyl, aryl or heterocyclic residual functional group which may have a substituent, Y Representing a hydrogen atom, a halogen atom, -no2, a nh2 or a so3h 1287694 k represents an integer of 1 to 4, η represents an integer of 1 to 4, and Α represents a general formula

% 所表示之2價鍵結基, -S02NH — R3 —% indicates the 2-valent bond group, -S02NH — R3 —

、或一 CH2NHCOCH3 — R3—, (原文第3頁) Z2 表示—NH—或一 〇—, I表不趨基、院氧基、或以下述通式 /% 或Or a CH2NHCOCH3 — R3—, (original page 3) Z2 represents—NH—or a 〇—, I represents a non-radical, alkoxy, or the following formula /% or

所表示之取代基’但是’在i爲1之情況下,Ζ3亦可爲一 ΝΗ 一 Z i — Q 〇 雖然包含以通式(B)所表示之色素衍生物的感光性 黑色組成物在耐熱性、耐藥品性等顯示優異之特性,然而 ,關於分散安定性、感度、黑色矩陣形狀、對基板之密著 性、遮光性則未能滿足要求性能。 -9- 1287694 (三)發明內容: 發明之簡單槪要 其中,本發明係以在耐熱性、耐藥品性等顯示優異之 特性,再者對於分散安定性、感度、黑色矩陣形狀、對基 板之密著性、遮光性亦優異之感光性黑色組成物,用它之 黑色矩陣基板及濾色器之提供爲目的。 根據本發明之第1側面,提供了含有比表面槙爲 5 0〜2 00m2/g之碳黑、以下述通式(A)所表示之色素衍生 物、及乙烯性不飽和化合物之感光性黑色組成物。 通式(A):The substituent "but" in the case where i is 1, Ζ3 may also be a ΝΗ-Z i - Q 〇 although the photosensitive black composition containing the dye derivative represented by the general formula (B) is heat-resistant The properties, the chemical resistance, and the like are excellent, but the dispersion stability, the sensitivity, the black matrix shape, the adhesion to the substrate, and the light blocking property fail to satisfy the required performance. -9- 1287694 (III) SUMMARY OF THE INVENTION: In summary of the invention, the present invention exhibits excellent characteristics in heat resistance, chemical resistance, and the like, and further relates to dispersion stability, sensitivity, black matrix shape, and substrate. A photosensitive black composition excellent in adhesion and light-shielding property is provided for the purpose of providing the black matrix substrate and the color filter. According to the first aspect of the present invention, there is provided a photosensitive black containing carbon black having a specific surface enthalpy of 50 to 200 m 2 /g, a dye derivative represented by the following general formula (A), and an ethylenically unsaturated compound. Composition. General formula (A):

(A) 其中,Q表示有機色素殘餘官能基, X 表示直接鍵結、—CONH — Y2—、— S02NH — Y2 — 、或一 CH2NHCOCH2NH — Υ2—, Υ2表示亦可具有取代基之亞烴基或芳基, Υ!表示一 NH —或一 Ο—, Ζ表示羥基、烷氧基、或以通式(Ο : (如原文第4頁之通式(Ο ) 所示之取代基,但是’在η爲1之情況下,Ζ亦可爲-ΝΗ 一 X — Q, Υ3 表示一 ΝΗ- 或一 0—, -10- 1287694 ^及1個別獨立地表示取代或無取代之烷基 與r2亦可互相鍵結而形成至少包含氮原子之雜環, m表示1〜6之整數, η表示1〜4之整數。 在本發明之感光性黑色組成物中,碳黑之鄰苯 二丁酯的吸收量係以120cc/100g以下爲佳,碳黑之 次粒徑係以20〜50nm爲佳。 又,根據本發明之第2側面,提供具備由本發 光性黑色組成物所形成之黑色矩陣的黑色矩陣基板 色矩陣之平均l//m乾燥膜厚的光學濃度係以3.0以 〇 再者,根據本發明之第3側面,提供於本發明 矩陣基板上形成黑色以外至少2色之濾色段的濾色器 發明之詳細說明 首先,說明本發明之感光性黑色組成物。 本發明之感光性黑色組成物含有比表ί 50〜200m2/g之碳黑、以上述通式(Α)所示之色素 、及乙烯性不飽和化合物。 於本發明之感光性黑色組成物中所含有之碳黑 遮光性之黑色顏料,市售之碳黑方面,舉例有三菱 份有限公司製 #260、#25、#30、#32、#33、# 44、#45、#45L、#47、#50、#52、MA7、MA8 、MA100、MA100R、MA100S、MA230;迪嘉沙公 林特克斯L、普林特克斯P、普林特克斯30、普林特 ,或Ri 二甲酸 平均 1 明之感 。該黑 上爲佳 之黑色 哲積爲 衍生物 爲具有 化學股 40、# 、MAI 1 司製普 克斯35 -11- 1287694 、普林特克斯40、普林特克斯45、普林特克斯55、普林特 克斯60、普林特克斯300、普林特克斯35〇、特黑4、特黑 350、特黑550等。碳黑係可單獨地使用,亦可混合2種以 上來使用。 碳黑方面係使用比表面積爲50〜20 0m2/g者。在使用比 表面積未滿50m2/g之碳黑的情況下,引起黑色矩陣形狀之 劣化,在使用較200m2/g大之碳黑的情況下,過度吸附以 通式(A )所示之色素衍生物於碳黑中,爲了發現各物性而 產生配合多量之以通式(A)所示之色素衍生物的必要。 又,碳黑方面,由感度之觀點,以鄰苯二甲酸二丁酯 (以下,稱爲「DBP」。)之吸收量爲120cc/100g以下者 爲佳,該DBP吸收量必須變少而且愈少愈好。DBP吸收量 係可藉由使用吸收計來測定(參照日本工業規格JIS K62 17-4 )° 再者,碳黑之平均1次粒徑係以20〜50nm爲佳。平均 1次粒徑未滿20nm之碳黑係難以分散成高濃度,難以得到 長時間安定性良好之感光性黑色組成物’使用較5 Οηπι大之 碳黑時,則爲招致黑色矩陣形狀之劣化的原因。 感光性黑色組成物中之碳黑含有量係以組成物之固體 成分爲基準而以20〜7 0重量%爲佳,以30〜60重量%爲較佳 。在碳黑含有量未滿2 0重量%之情況下不能得到充分之遮 光性,在較7 〇重量%多之情況下則難以得到分散安定性’ 招致感度之降低,有黑色矩陣之形成變得困難之可能性。 於感光性黑色組成物中所含有之色素衍生物係以上述 1287694 S式(A)所示者,進行分散碳黑於乙烯性不飽和化合物中 之操作。 通式(A)中,Q表示有機色素之殘餘官能基。提供有 機色素殘餘官能基q之有機色素方面,舉例有具有酞青素 骨架之駄青素系色素、具有_鈉啉酮骨架之喹鈉啉酮系色 素' 具有喹鈉啉酮醌骨架之喹鈉啉酮醌系色素、具有異吲 @ '滿酮I骨架之異吲哚滿酮系色素、具有喹啉骨架之喹啉系 色素 '具有二酮吡咯基吡咯骨架之二酮吡咯基吡咯系色素 '具有菲骨架之茈系色素、具有茈酮骨架之茈酮系色素、 具有靛藍骨架之靛藍系色素、具有硫靛藍骨架之硫靛藍系 色素、具有二噚嗪骨架之二噚嗪系色素、具有蒽醌骨架之 葱醌系色素、具有吡蒽酮骨架之吡蒽酮系色素、具有嵌二 蒽酮骨架之嵌二蒽酮系色素、具有黃土酮骨架之黃土酮系 色素、具有陰丹士龍骨架之陰丹士龍系色素、金屬錯合物 系等縮合多環系有機顏料、具有苯并咪唑酮骨架之苯并咪 唑酮系色素、不溶性偶氮系色素、縮合偶氮系色素、溶解 性偶氮系色素等。該等色素之中,以酞青素系色素、蒽醌 系色素、苯并咪唑酮系色素爲佳。 通式(A)中,X表示直接鍵結、一 CONH—Y2—、— S02NH 一 Y2—、或—CH2NHCOCH2NH— Y2—,其中,Y2 表示亦可 具有取代基之烷基或芳基。舉出Υ2之較佳實例時,則有1〜6 碳數之烷基、苯基等。 通式(Α)中,Υι表示一 ΝΗ—或一 0—。 通式(A )中,Z表示羥基、烷氧基、或以通式(i ) -13- 1287694(A) wherein Q represents an organic functional residual functional group, X represents a direct bond, —CONH — Y 2 —, — S02NH — Y 2 — or —CH 2 NHCOCH 2 NH — Υ 2 —, Υ 2 represents an alkylene group or a aryl group which may also have a substituent. A group, Υ! represents an NH—or a Ο—, Ζ represents a hydroxy group, an alkoxy group, or a substituent of the formula (Ο: (as shown in the original formula (Ο) on page 4, but 'in η In the case of 1, Ζ may also be -ΝΗ -X - Q, Υ3 represents a ΝΗ- or a 0-, -10- 1287694 ^ and 1 independently represent a substituted or unsubstituted alkyl group and r2 may also be mutually Bonding to form a heterocyclic ring containing at least a nitrogen atom, m represents an integer of 1 to 6, and η represents an integer of 1 to 4. In the photosensitive black composition of the present invention, absorption of phthalic acid of carbon black Preferably, it is preferably 120 cc/100 g or less, and the secondary particle diameter of carbon black is preferably 20 to 50 nm. Further, according to the second aspect of the present invention, a black matrix substrate having a black matrix formed of the present luminescent black composition is provided. The average optical density of the color matrix is 1//m. The optical density of the dried film thickness is 3.0 or less. The third aspect of the invention provides a color filter for forming at least two color filter segments other than black on the matrix substrate of the present invention. DETAILED DESCRIPTION OF THE INVENTION First, the photosensitive black composition of the present invention will be described. The photosensitive black composition of the present invention a carbon black having a specific gravity of 50 to 200 m 2 /g, a dye represented by the above formula (Α), and an ethylenically unsaturated compound. The carbon black contained in the photosensitive black composition of the present invention is light-shielding. For black pigments and commercially available carbon blacks, examples are Mitsubishi Co., Ltd. #260, #25, #30, #32, #33, #44, #45, #45L, #47, #50, #52, MA7, MA8, MA100, MA100R, MA100S, MA230; Dijiasha Gonglintex L, Printex P, Plinx 30, Plint, or Ri dicarboxylic acid average 1 sense. Black is a good black philosophical derivative for the chemical stock 40, #, MAI 1 Division Pux 35 -11- 1287694, Plintex 40, Plintex 45, Printex 55, Plintex 60, Printex 300, Plettex 35 〇, Tehe 4, Tehei 350, Tehei 550, etc. Carbon black It may be used singly or in combination of two or more. In the case of carbon black, a specific surface area of 50 to 20 0 m 2 /g is used. When a carbon black having a specific surface area of less than 50 m 2 /g is used, a black matrix shape is caused. In the case of using carbon black which is larger than 200 m 2 /g, the dye derivative represented by the general formula (A) is excessively adsorbed in the carbon black, and in order to find each physical property, a large amount of the compound is obtained by the general formula (A). ) The necessity of the pigment derivative shown. In addition, in terms of sensitivity, it is preferable that the absorption amount of dibutyl phthalate (hereinafter referred to as "DBP") is 120 cc/100 g or less from the viewpoint of sensitivity, and the amount of DBP absorption must be reduced and Less is better. The DBP absorption amount can be measured by using an absorption meter (refer to Japanese Industrial Standard JIS K62 17-4). Further, the average primary particle diameter of carbon black is preferably 20 to 50 nm. It is difficult to obtain a high-concentration carbon black system having an average primary particle diameter of less than 20 nm, and it is difficult to obtain a photosensitive black composition having good long-term stability. When using a carbon black larger than 5 Οηπι, the black matrix shape is deteriorated. s reason. The content of the carbon black in the photosensitive black composition is preferably from 20 to 70% by weight, based on the solid content of the composition, and preferably from 30 to 60% by weight. When the content of the carbon black is less than 20% by weight, sufficient light-shielding property cannot be obtained, and when it is more than 7% by weight, it is difficult to obtain dispersion stability, and the sensitivity is lowered, and the formation of a black matrix becomes The possibility of difficulty. The dye derivative contained in the photosensitive black composition is subjected to the operation of dispersing carbon black in an ethylenically unsaturated compound as shown in the above formula (287). In the general formula (A), Q represents a residual functional group of the organic dye. Examples of the organic dye which provides the residual functional group q of the organic dye include an anthraquinone-based dye having an anthraquinone skeleton and a quinoxalinone-based dye having a quinolone skeleton. a ketone oxime dye, an isoindolinone dye having a heteroquinone @ 'full ketone I skeleton, a quinoline dye having a quinoline skeleton, and a diketopyrrolopyrrole dye having a diketopyrrolopyrrole skeleton An anthraquinone dye having a phenanthrene skeleton, an anthrone dye having an anthrone skeleton, an indigo dye having an indigo skeleton, a sulphur indigo dye having a sulphur indigo skeleton, a dioxazine dye having a dioxazine skeleton, and having a fluorene醌 之 之 醌 醌 醌 醌 、 、 、 、 、 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌 醌a condensed polycyclic organic pigment such as a dansone dye or a metal complex, a benzimidazolone dye having a benzimidazolone skeleton, an insoluble azo dye, a condensed azo dye, or a soluble couple nitrogen It is a pigment or the like. Among these pigments, an anthraquinone-based dye, an anthraquinone-based dye, and a benzimidazolone-based dye are preferred. In the formula (A), X represents a direct bond, a CONH-Y2-, -S02NH-Y2-, or -CH2NHCOCH2NH-Y2-, wherein Y2 represents an alkyl group or an aryl group which may have a substituent. When a preferred example of ruthenium 2 is given, there are an alkyl group having 1 to 6 carbon atoms, a phenyl group or the like. In the formula (Α), Υι denotes a ΝΗ—or a 0—. In the formula (A), Z represents a hydroxyl group, an alkoxy group, or a formula (i) -13-1287694

表示之取代基。但是,在η爲1之情況下,Z亦可爲- NH 一 X— Q。其中,γ3表示一 NH 一或一 〇 一。藉由2所表示之 院氧基方面,係以1〜6碳數之烷氧基爲佳。 於S式(A )中(於通式(i ·)中亦同),Ri及r2係個 別表示取代或無取代之烷基,或者心與r2亦可互相鍵結 而形成至少包含氮原子之雜環。藉由化1及r2所表示之烷 基方面’以1〜6碳素之烷基爲佳。又烷基之取代基方面, 以經基、1〜6碳素之烷氧基爲佳。Rl與R2亦可互相鍵結而 形成之雜環方面,以咪唑基、亞醯胺基、吡啶基、吡咯烷 基爲佳。 於通式(A)中(於通式(i)中亦同),m表示1〜6 之整數。 於通式(A)中(於通式(i)中亦同),n表示1〜4 之整數。 以通式(A)所示之色素衍生物方面,舉例有以下述通 式(1)〜(10)所表示之色素衍生物。 -14- 1287694Represents a substituent. However, in the case where η is 1, Z may also be -NH - X - Q. Where γ3 represents an NH or a 〇. The alkoxy group having 1 to 6 carbon atoms is preferred from the viewpoint of the hospitaloxy group represented by 2. In the formula (A) (also in the formula (i)), Ri and r2 each independently represent a substituted or unsubstituted alkyl group, or the core and r2 may be bonded to each other to form at least a nitrogen atom. Heterocyclic. The alkyl group represented by the formulas 1 and r2 is preferably an alkyl group of 1 to 6 carbon atoms. Further, in terms of the substituent of the alkyl group, alkoxy groups having a mercapto group and 1 to 6 carbon atoms are preferred. The heterocyclic ring in which R1 and R2 are bonded to each other to form a heterocyclic ring is preferably an imidazole group, an anthranylene group, a pyridyl group or a pyrrolidinyl group. In the formula (A) (also in the formula (i)), m represents an integer of 1 to 6. In the formula (A) (also in the formula (i)), n represents an integer of 1 to 4. In the case of the dye derivative represented by the formula (A), a dye derivative represented by the following general formulae (1) to (10) is exemplified. -14- 1287694

-15- 1287694-15- 1287694

-16- 1287694 酯、六(甲基)丙烯酸二異戊四醇酯等。又,寡聚物方面 ,舉出有環氧(甲基)丙烯酸酯、胺甲酸(甲基)丙烯酸 酯、酯(甲基)丙烯酸酯等,感光性樹脂方面,舉出有於 聚酯、聚胺甲酸酯、環氧樹脂、丙烯酸樹脂等中以公認之 方法導入乙烯性不飽和雙鍵者。乙烯性不飽和化合物係可 單獨使用1種,亦可混合2種以上來使用。該等乙烯性不 飽和化合物方面,以三(甲基)丙烯酸三羥甲基丙酯、三 (甲基)丙烯酸異戊四醇酯、六(甲基)丙烯酸二異戊四 醇酯爲佳。乙烯性不飽和化合物係以組成物之固體成分的 5%〜3 0%重量比例來使用爲佳。 於感光性黑色組成物中,在藉由紫外線照射硬化該組 成物來形成黑色矩陣的情況下,含有光聚合起始劑。光聚 合起始劑方面,舉例有4-苯氧基二氯苯乙酮、4-第三丁基 —氯本乙酿I、—乙氧基—氯本乙顚I、1 - ( 4 -異丙苯基)· 2 _ 經基-2-甲基丙-1-酮、1-經基環己基苯基酮、2 -卞基-2-二甲 胺基-1- (4-嗎林苯基)-丁 -1-酮等之苯乙酮系光聚合起始 劑;安息香、安息香甲基醚、安息香乙基醚、安息香異丙 基醚、苄基二甲基縮醛等安息香系光聚合起始劑;二苯基 酮、苯醯基安息香酸、苯醯基安息香酸甲酯、4-苯基二苯 基酮、羥基二苯基酮、丙烯酸化二苯基酮、4-苯醯基-4,-甲 苯二苯基硫化物等之二苯基酮系光聚合起始劑;噻噸酮、2_ 氯噻噸酮、2-甲基噻噸酮、異丙基噻噸酮、2,4_二異丙基噻 噸酮等噻噸酮系光聚合起始劑;2,4,6 -三氯·均三哄、2 -苯 基-4,6-雙(三氯甲基)-均三畊、2-(對甲氧基苯基)-4,6- -18- 1287694 雙(三氯甲基)·均三畊、2-(對甲苯基)-4,6-雙(三氯甲 基)-均三哄、2-胡椒基-4,6-雙(三氯甲基)-均三畊、2,4-雙(三氯甲基)-6-苯乙烯基-均三畊、2-(萘-1-醯基)-4,6-雙(三氯甲基)-均三畊、2- (4-甲氧基-萘-1-醯基)-4,6-雙(三氯甲基)-均三畊、2,4-三氯甲基-(胡椒基)-6-三哄 、2,4·三氯甲基(4,-甲氧基苯乙烯基)-6-均三畊等三畊系 光聚合起始劑;咔唑系光聚合起始劑、咪唑系光聚合起始 劑等。上述光聚合起始劑係可單獨地使用1種,或混合2 種以上來使用。光聚合起始劑係以組成物固體成分重量之5 %〜25%之比例來使用爲佳。 又,於感光性黑色組成物中,亦可含有增感劑。增感 劑方面,舉例有α -氧化醯基酯、醯基膦氧化物、二羥乙酸 甲基苯酯、苄酯、9,10-菲醌、莰醌、乙基蒽醌、4,4’-二乙 基異二苯酜、3,3’,4,4’-四(第三丁基過氧羧基)二苯基酮 、4,4’·二乙胺基二苯基酮等。上述增感劑係可單獨地使用 1種或混合2種以上來使用。增感劑係以光聚合起始劑重量 之3%〜60%比例來使用爲佳。 再者,在感光性黑色組成物中,由於該組成物爲鹼性 顯像型,可含有鹼性可溶性樹脂。又,在感光性黑色組成 物中,針對耐熱性或密著性之賦予等目的,與鹼性可溶性 樹脂一起,亦可含有不具有鹼性可溶性之樹脂。 鹼性可溶性樹脂方面,舉例有(甲基)丙烯酸共聚物 或苯乙烯-順丁烯二酸酐共聚物、具有羧基之聚酯樹脂等。 鹼性可溶性樹脂係針對塗膜之耐熱性或耐溶劑性、耐 -19· 1287694 ' 藥品性之賦予等種種目的而亦可組合2種以上樹脂來使用 0 鹼性可溶性樹脂含有量,以感光性黑色組成物爲基準 ,則以3〜70重量%爲佳,以5〜60重量%爲較佳。鹼性可溶 性樹脂含有量未滿3重量%則鹼性顯像性變低,超過70重 量%時則感光性黑色組成物之硬化性、或在使用於黑色矩 陣之形成的情況下遮光性變低。 在感光性黑色組成物中,爲了充分地分散碳黑、形成 所希望之膜厚的黑色矩陣而可含有溶劑。溶劑方面,舉例 有環己烷、乙基賽珞蘇乙醯酯、丁基賽洛蘇乙醯酯、乙酸- ^ 1-甲氧基-2-丙酯、二乙二醇二甲基醚、乙苯、乙二醇二乙 . 基醚、二甲苯、乙基賽洛蘇、甲基-正戊基酮、丙二醇單甲 基醚、甲苯、甲基乙基酮、乙酸乙酯、甲醇、乙醇、異丙 醇、丁醇、異丁基酮、石油系溶劑等。單獨或混合該等來 使用。溶劑係以感光性黑色組成物全量之60%〜95%之比例 來使用爲佳。 在感光性黑色組成物中,以塗佈性提昇、感度之提昇 、密著性之提昇等爲目的,亦可添加鏈轉移劑、界面活性 劑、矽烷偶合劑、其他添加劑等。 感光性黑色組成物係可藉由混合碳黑、以通式(A )所 示之色素衍生物、乙烯性不飽和化合物、及必要時之光聚 合起始劑、鹼性可溶性樹脂、溶劑、其他添加劑,使用三 輥硏磨機、雙輥硏磨機、砂磨機、捏合機、銼磨機等各種 分散裝置來分散所製造。 •20- 1287694 感光性黑色組成物係以離心分離、燒結過濾、薄膜過 濾等手段,進行5 // m以上之粗大粒子、以1 // m以上爲佳 之粗大粒子、以0 · 5 // m以上爲更加之粗大粒子及所混入之 灰麈的去除爲佳。 其次,說明黑色矩陣基板。 黑色矩陣基板係於玻璃板等透明基板上,藉由旋轉塗 布、狹縫塗布、輥塗等塗布方法塗布感光性黑色組成物之 後,經由光罩從組成物塗布面側照射活性能源射線,並浸 漬於溶劑或鹼性顯像液中或藉由噴霧器等噴灑顯像液來除 去未照射部分、即未硬化部分來進行顯像,藉由形成所希 望形狀之黑色矩陣來製成。 感光性黑色組成物膜厚係以在0.2〜5/zm (乾燥時)之 範圍爲佳,以容易取得塗布性與遮光性平衡之0.5〜2 // m之 範圍爲較佳。 又,平均l//m黑色矩陣之乾燥膜厚的光學濃度,從高 遮光性觀點來看,以3.0以上爲佳。雖然光學濃度愈高愈 佳,但由於在活性能源射線爲紫外線、可見光之情況下變 得難以得到硬化塗膜,則希望大約在4.5以下。 鹼性顯像液方面,可使用碳酸鈉、氫氧化鈉等水溶液 ’亦可使用二甲基苄胺、三乙醇胺等有機鹼。又,於顯像 液中,亦可添加消泡劑或界面活性劑。 還有,爲了提昇藉由活性能源射線之曝光感度,亦可 於塗布乾燥感光性黑色組成物後,塗布乾燥水溶性或鹼性 可溶性樹脂、例如聚乙烯醇或水溶性丙烯酸樹脂等來形成 -21- 1287694 防止因氧導致聚合妨害之薄膜後,從組成物塗布面側照射 活性能源射線。 活性能源射線方面,可使用電子射線、紫外線、 4 0 0〜5 0 Onm之可見光。在從組成物塗布面側所照射之電子 射線的射線源方面,可使用熱電子放射槍、電界放射槍等 ,又,紫外線及4〇〇〜\00nm之可見光之射線源(光源)方 面,可使用例如高壓水銀燈、超高壓水銀燈、金屬鹵化物 燈、鎵燈、氙氣燈、碳電弧燈等。具體而言,其爲點光源 時,由於亮度安定,多使用超高壓水銀燈、氙氣水銀燈。•馨 從組成物塗布面側所照射之活性能源射線雖可在5〜lOOOmJ * 之範圍中適時設定,但以工程上管理容易之20〜300mJ之範 - 圍爲佳。 最後,說明濾色器。 濾色器係於上述黑色矩陣基板上,形成有黑色以外至, 少2色之濾色段者。濾色段顏色係可從藍色、綠色、紅色 、氰色、黃色、洋紅色、橘色、紫色等選擇2〜6色左右。 亦可由同色系之顏色形成濃度不同之濾色段。 ·· 在黑色矩陣基板上之濾色段之形成方法方面,舉出有 凹版凸版印刷法、陰凸版印刷法、絹網印刷法、使用溶劑 顯像型或鹼性顯像型著色阻劑之光微影法、藉由膠粒之電 泳動電沉積形成著色材於透明導電膜上之電沉積法、於黑 色矩陣基板上轉印預先形成於轉印基板表面上之濾色段層 之轉印法等。 由於印刷法能僅以重複印刷與乾燥來進行圖案化,濾 -22- 1287694 色器之製造法方面則爲低成本且量產性優異。再者, 行由於印刷技術之發展而具有高尺寸精確度與平滑度 微圖案的印刷。在藉由印刷法製造爐色器之情況下, 的是於印刷機上之油墨流動性的控制,亦可進行藉由 劑或體質顏料之油墨黏度調整。 使用溶劑顯像型或鹼性顯像型著色阻劑之光微影 係於黑色矩陣基板上,藉由旋轉塗布、狹縫塗布、輥 塗布方法來塗布著色阻劑,其次經由光罩進行紫外線 ,以溶劑或鹼性顯像液沖洗未曝光部分並形成所希望 案後,針對其他顏色重複同樣之操作來製造濾色器之 。該製造'方法可製造比上述印刷法精度較高之濾色器。 著色阻劑係取代本發明中之感光性黑色組成物所 之碳黑,可使用所希望之顏色的著色劑來調制之阻劑 可不必含有以通式(A )所示之色素衍生物。著色劑方 雖可使用各種耐性優異之著色劑,但從耐光性、耐熱 耐溶劑性之觀點來看則以使用顏料爲佳,由光吸收能 小來看則以使用有機顏料爲特佳。以顏色指標(CI ) 來表示代表之顏色具體實例。 黃色著色劑方面,舉出有顏料黃12、13、14、20 、83、 86、 93、 94、 109、 110、 117、 125、 137、 138、 、147 、 148 、 153 、 154 、 166 、 173 等。 橘色著色劑方面,舉出顏料橘13、31、36、38、 42 、 43 、 51 、 55 、 59 、 61 、 64 、 65 等。 紅色及洋紅色著色劑方面,舉出有顏料紅9、97、 可進 之細 重要 分散 法, 塗等 曝光 之圖 方法 含有 ,亦 面, 性或 之大 數字 、24 139 40、 &gt; 122 -23- 1287694 、123、144、149、166、168、177、190、192、215、216 、224 、 254 、 255 等 ° 、 紫色著色劑方面,舉出有顏料紫19、23、29、32、33 、36 、 37 、 38 等。 藍色及氰色著色劑方面,舉出有顏料藍15(15、15: 1、15:2、15:3、15:4、15:6 等)、21、22、60、64 綠色著色劑方面,舉出有顏料綠7、10、36、47等。 該等著色劑係爲了得到所希望之顏色而可組合2種以♦ φ 上來使用。 - 以下,基於實例來具體地說明本發明。還有,實例中 . ’ 「份」及「%」係個別表示「重量份」.及「重量%」。 &lt;丙烯酸樹脂溶液之調製&gt; 於反應容器中置入800份環己烷,於容器中注入氮氣 並且加熱至100 °C,於同溫度下費時1小時滴入60.0份甲 基丙烯酸、65.0份甲基丙烯酸丁酯、65.〇份甲基丙烯酸甲 酯、及10.0份偶氮雙異丙烯腈之混合物,進一步於l〇(TC 反應3小時後,添加以5 〇份環己烷溶解2. ο份偶氮雙異丙 烯腈者’進一部於l〇(TC繼續反應1小時來合成樹脂溶液。 冷卻至室溫後,取樣約2g樹脂溶液並以180°C加熱乾燥20 分鐘來、測定非揮發份,在先前所合成之樹脂溶液中添加環 己烷成爲非揮發份爲20%來調製丙烯酸樹脂溶液。還有, 丙烯酸樹脂之重量平均分子量爲40000。 &lt;碳黑分散體之調製&gt; -24- 1287694 記載於下述實例及比較例之碳黑及色素衍生物與24份 上述丙烯酸樹脂溶液、40份環己烷均勻地混合,使用1mm 直徑之玻璃珠並以磨砂機藉由5小時之分散來調製碳黑分 散體。 於表1顯示使用於實例及比較例之碳黑物性値。 表1 碳黑 平均一次粒徑 DBP吸收量 (cc/lOOg) 比表面基 (m2/g ) #40 24nm 110 115 #260 40nm 74 79 MA77 23nm 68 130 黑珠800 17nm 68 210 MONARCH 120 75nm 71 25-16- 1287694 ester, diisopentyl hexa(meth)acrylate, and the like. Further, examples of the oligomer include epoxy (meth) acrylate, uric acid (meth) acrylate, and ester (meth) acrylate, and the photosensitive resin is exemplified by polyester or poly. A urethane, an epoxy resin, an acrylic resin, or the like is introduced into an ethylenically unsaturated double bond by an accepted method. The ethylenically unsaturated compound may be used singly or in combination of two or more. As the ethylenically unsaturated compound, trimethylolpropyl tris(meth)acrylate, isoamyl tris(meth)acrylate or diisopentyl hexa(meth)acrylate is preferred. The ethylenically unsaturated compound is preferably used in an amount of from 5% to 30% by weight based on the solid content of the composition. In the photosensitive black composition, when the composition is cured by ultraviolet irradiation to form a black matrix, a photopolymerization initiator is contained. As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-tert-butyl-chlorobenzyl I, ethoxylated-chlorobenzidine I, 1 - (4-iso) are exemplified. Propyl phenyl)· 2 _ benzyl-2-methylpropan-1-one, 1-cyclohexyl phenyl ketone, 2-mercapto-2-dimethylamino-1-(4-morphin Acetophenone photopolymerization initiators such as butyl ketone; benzoin photopolymerization of benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl acetal Starting agent; diphenyl ketone, benzoin benzoic acid, methyl benzoyl benzoate, 4-phenyl diphenyl ketone, hydroxy diphenyl ketone, acrylated diphenyl ketone, 4-phenyl fluorenyl a diphenyl ketone photopolymerization initiator such as -4,-toluenediphenyl sulfide; thioxanthone, 2- chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, a thioxanthone photopolymerization initiator such as 4_diisopropylthioxanthone; 2,4,6-trichloro·s-trimethylene, 2-phenyl-4,6-bis(trichloromethyl)- Three-plowed, 2-(p-methoxyphenyl)-4,6--18- 1287694 bis(trichloromethyl)·all three tillage, 2-(p-tolyl)-4,6-double (three Methyl)--tris-trimium, 2-piperidin-4,6-bis(trichloromethyl)-all three-plowed, 2,4-bis(trichloromethyl)-6-styryl-three-plowed , 2-(naphthalen-1-indenyl)-4,6-bis(trichloromethyl)-all three tillage, 2-(4-methoxy-naphthalen-1-indenyl)-4,6-double (trichloromethyl)-all three tillage, 2,4-trichloromethyl-(piperidyl)-6-triazine, 2,4·trichloromethyl (4,-methoxystyryl)- 6-average three-tillage three-grain photopolymerization initiator; oxazole photopolymerization initiator, imidazole photopolymerization initiator, and the like. The photopolymerization initiator may be used singly or in combination of two or more. The photopolymerization initiator is preferably used in a proportion of 5% to 25% by weight of the solid content of the composition. Further, a sensitizer may be contained in the photosensitive black composition. Examples of the sensitizer include α-decyl decyl ester, decyl phosphine oxide, methyl phenyl acetate, benzyl ester, 9,10-phenanthrenequinone, anthracene, ethyl hydrazine, 4, 4' -Diethylisodiphenyl hydrazine, 3,3',4,4'-tetrakis(t-butylperoxycarboxy)diphenyl ketone, 4,4'-diethylaminodiphenyl ketone, and the like. These sensitizers can be used singly or in combination of two or more. The sensitizer is preferably used in a proportion of 3% to 60% by weight based on the weight of the photopolymerization initiator. Further, in the photosensitive black composition, since the composition is of an alkaline development type, an alkali-soluble resin may be contained. Further, the photosensitive black composition may contain a resin which does not have an alkali solubility together with an alkali-soluble resin for the purpose of imparting heat resistance or adhesion. Examples of the alkali-soluble resin include a (meth)acrylic copolymer or a styrene-maleic anhydride copolymer, a polyester resin having a carboxyl group, and the like. The alkali-soluble resin may be used in combination with two or more kinds of resins for various purposes such as heat resistance and solvent resistance of the coating film, and resistance to -19·1287694'. The black composition is preferably from 3 to 70% by weight, preferably from 5 to 60% by weight, based on the black component. When the content of the alkali-soluble resin is less than 3% by weight, the basic developability is lowered, and when it exceeds 70% by weight, the curability of the photosensitive black composition is lowered, or when the black matrix is used, the light-shielding property is lowered. . In the photosensitive black composition, a solvent may be contained in order to sufficiently disperse carbon black and form a black matrix having a desired film thickness. Examples of the solvent include cyclohexane, ethyl cyproterone, butyl cyproxil, acetic acid-^ 1-methoxy-2-propyl ester, diethylene glycol dimethyl ether, Ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl celecoxib, methyl-n-pentyl ketone, propylene glycol monomethyl ether, toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol , isopropanol, butanol, isobutyl ketone, petroleum solvent, and the like. Use these alone or in combination. The solvent is preferably used in a proportion of 60% to 95% of the total amount of the photosensitive black composition. In the photosensitive black composition, a chain transfer agent, a surfactant, a decane coupling agent, and other additives may be added for the purpose of improving coating properties, improving sensitivity, and improving adhesion. The photosensitive black composition can be obtained by mixing carbon black, a dye derivative represented by the formula (A), an ethylenically unsaturated compound, and, if necessary, a photopolymerization initiator, an alkali soluble resin, a solvent, and the like. The additive is produced by dispersion using various dispersing devices such as a three-roll honing machine, a two-roll honing machine, a sand mill, a kneader, and a honing machine. • 20- 1287694 Photosensitive black composition is a coarse particle of 5 // m or more, and a coarse particle of 1 // m or more by centrifugation, sintering filtration, membrane filtration, etc., with 0 · 5 // m The above is better for the removal of the coarser particles and the mixed ash. Next, a black matrix substrate will be described. The black matrix substrate is coated on a transparent substrate such as a glass plate, and a photosensitive black composition is applied by a coating method such as spin coating, slit coating, or roll coating, and then irradiated with an active energy ray from the coated surface side of the composition via a photomask, and impregnated. The development is carried out by spraying a developing solution in a solvent or an alkaline developing solution or by a sprayer or the like to remove the unirradiated portion, that is, the unhardened portion, and forming it by forming a black matrix of a desired shape. The film thickness of the photosensitive black composition is preferably in the range of 0.2 to 5 / zm (during drying), and is preferably in the range of 0.5 to 2 // m which is easy to obtain a balance between coatability and light shielding property. Further, the optical density of the dry film thickness of the average l//m black matrix is preferably 3.0 or more from the viewpoint of high light-shielding property. Although the optical density is preferably higher, it is desirable to be about 4.5 or less because it is difficult to obtain a hardened coating film when the active energy ray is ultraviolet light or visible light. As the alkaline developing solution, an aqueous solution such as sodium carbonate or sodium hydroxide can be used. An organic base such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant may be added to the developing solution. Further, in order to enhance the exposure sensitivity by the active energy ray, after drying and drying the photosensitive black composition, a dry water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied to form - 21 - 1287694 After the film which is impaired by polymerization due to oxygen is prevented, the active energy ray is irradiated from the coated surface side of the composition. For active energy rays, electron beams, ultraviolet rays, and visible light of 400 to 50 Onm can be used. In terms of the radiation source of the electron beam irradiated from the coating surface side of the composition, a thermal electron ray gun, an electric radiation gun, or the like, and an ultraviolet ray and a visible light source (light source) of 4 Å to 00 nm may be used. For example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp or the like is used. Specifically, when it is a point light source, an ultrahigh pressure mercury lamp or a helium gas mercury lamp is often used because of the stable brightness. • Xin The active energy ray irradiated from the coated side of the composition can be set in a time range of 5 to 100 mJ*, but it is preferably 20 to 300 mJ which is easy to manage in engineering. Finally, the color filter will be explained. The color filter is attached to the black matrix substrate to form a color filter segment having a color other than black and having two colors. The color of the filter segment can be selected from blue, green, red, cyan, yellow, magenta, orange, purple, etc. 2~6 colors. It is also possible to form color filter segments having different concentrations from the colors of the same color system. · The method of forming the color filter segment on the black matrix substrate includes a gravure printing method, a negative letter printing method, a stencil printing method, and a light using a solvent developing type or an alkaline developing type coloring resist. A lithography method, an electrodeposition method of forming a color material on a transparent conductive film by electrophoretic electrophoretic deposition of a colloidal particle, and a transfer method of transferring a color filter layer layer previously formed on a surface of a transfer substrate on a black matrix substrate Wait. Since the printing method can be patterned only by repeated printing and drying, the manufacturing method of the filtration-22-1287694 colorator is low in cost and excellent in mass productivity. Furthermore, the printing of high-precision and smooth micro-patterns has been made due to the development of printing technology. In the case where the color former is manufactured by the printing method, the ink fluidity on the printing machine is controlled, and the ink viscosity of the agent or the body pigment can be adjusted. The light lithography using a solvent developing type or an alkaline developing type coloring resist is applied to a black matrix substrate, and the coloring resist is applied by spin coating, slit coating, and roll coating, and then ultraviolet light is passed through the mask. After rinsing the unexposed portion with a solvent or an alkaline developing solution and forming the desired case, the same operation is repeated for the other colors to manufacture the color filter. The manufacturing method can produce a color filter that is more precise than the above printing method. The coloring resist is a resin which is prepared by replacing the carbon black of the photosensitive black composition of the present invention with a coloring agent of a desired color, and does not necessarily contain the dye derivative represented by the formula (A). In the coloring agent, a coloring agent excellent in various resistances can be used. However, from the viewpoint of light resistance and heat resistance and solvent resistance, it is preferred to use a pigment, and it is particularly preferable to use an organic pigment from the viewpoint of light absorption energy. A specific example of the color represented by the color indicator (CI). Yellow pigments are exemplified by pigment yellows 12, 13, 14, 20, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, 173 Wait. For the orange coloring agent, pigment oranges 13, 31, 36, 38, 42, 43, 51, 55, 59, 61, 64, 65, etc. are mentioned. For the red and magenta coloring agents, there are pigment red 9,97, and the fine dispersion method that can be advanced, and the method of exposure, such as coating, is also included, the sex or the number is large, 24 139 40, &gt; 122 - 23- 1287694, 123, 144, 149, 166, 168, 177, 190, 192, 215, 216, 224, 254, 255, etc., purple coloring agent, given pigment purple 19, 23, 29, 32, 33, 36, 37, 38, etc. For blue and cyan colorants, there are pigment blue 15 (15, 15: 1, 15:2, 15:3, 15:4, 15:6, etc.), 21, 22, 60, 64 green colorants. In terms of pigment greens 7, 10, 36, 47, etc. These colorants can be used in combination of two types of ♦ φ in order to obtain a desired color. - Hereinafter, the present invention will be specifically described based on examples. Also, in the examples, ''" and "%" are used to mean "parts by weight" and "% by weight". &lt;Preparation of Acrylic Resin Solution&gt; 800 parts of cyclohexane was placed in a reaction vessel, nitrogen gas was injected into the vessel and heated to 100 ° C, and 60.0 parts of methacrylic acid and 65.0 parts were added dropwise at the same temperature for 1 hour. a mixture of butyl methacrylate, 65.5% methyl methacrylate, and 10.0 parts of azobisisoacrylonitrile, further dissolved in 5 Torr after 5 hours of TC reaction. ο Part of azobisisoacrylonitrile 'into one 〇 (TC continued to react for 1 hour to synthesize the resin solution. After cooling to room temperature, sample about 2g of resin solution and heat dry at 180 °C for 20 minutes, determine non The volatile matter was prepared by adding cyclohexane to a resin solution previously synthesized to have a nonvolatile content of 20% to prepare an acrylic resin solution. Further, the weight average molecular weight of the acrylic resin was 40,000. &lt;Modulation of carbon black dispersion&gt; -24- 1287694 The carbon black and pigment derivative described in the following examples and comparative examples were uniformly mixed with 24 parts of the above acrylic resin solution and 40 parts of cyclohexane, using 1 mm diameter glass beads and a sanding machine for 5 hours. Disperse to modulate carbon Black dispersion. Table 1 shows the carbon black enthalpy used in the examples and comparative examples. Table 1 Carbon black average primary particle size DBP absorption (cc/lOOg) Specific surface basis (m2/g) #40 24nm 110 115 # 260 40nm 74 79 MA77 23nm 68 130 Black beads 800 17nm 68 210 MONARCH 120 75nm 71 25

又,以下顯示下述實例及比較例中所使用之色素衍生 物0 色素衍生物①Further, the pigment derivative 0 pigment derivative 1 used in the following examples and comparative examples is shown below.

-25- 1287694 色素衍生物②-25- 1287694 Pigment Derivative 2

CuPfc (CuPc 色素衍生物③ 一 ΗCuPfc (CuPc pigment derivative 3 一

Μ_聊頻· 銅酞青素殘餘官能基) Η ΗΜ_聊频· Resveratrol Residual Functional Group) Η Η

【實例1】 I •碳黑(三菱化學公司製「# 40」) 1〇·〇份 •色素衍生物① 〇 . 5份 【實例2】 •碳黑(三菱化學公司製「# 260」) 8.0份 •色素衍生物② 〇 . 3份 【實例3】 •碳黑(三菱化學公司製「ΜΑ77」) 12.0份 •色素衍生物③ 1 . 〇份 【比較例1】 •碳黑(CABOT公司製「黑珠800」) 8.0份 •色素衍生物① 〇 · 2份 【比較例2】 •碳黑(CABOT 公司製「MONARCH 120」) 1〇·〇 份 •色素衍生物② 0.8份 -26- 1287694 &lt;碳黑分散體之長時間安定性評估&gt; 比較碳黑分散體分散後之黏度與於40°C下保存7日後 之黏度,來評估長時間安定性。結果示於表2。 &lt;感光性黑色組成物之調製&gt; 均勻攪拌混合60份碳黑分散體、4·3份三丙烯酸三甲 氧基丙酯(新中村化學公司製「ΝΚ酯ΑΤΜΡΤ」)、:1.4份 光聚合起始劑(汽巴蓋吉公司製「依耳嘉邱亞907」)、〇.2 份增感劑(保土谷化學公司舅「EAB-F」)、及21.6份環 己烷之混合物後,以1 // m之過濾器過濾來調製感光性黑色 組成物。針對所得之感光性黑色組成物,以下述方法評估 感度、黑色矩陣形狀、玻璃密著性、光學濃度。結果示於 表2 〇 [感度] 藉由旋轉塗布法塗布感光性黑色組成物於lOcmx l〇cm 之玻璃基板上之後,藉由於70°C下15分鐘之乾燥製成1 // m乾燥膜厚之塗膜。然後,使用超高壓水銀燈,經由光罩 曝光1 〇〇mJ/cm2紫外線。其次,使用碳酸鈉水溶液來噴霧 顯像未曝光部分之後,以離子交換水洗淨並除去未曝光部 分,測定曝光部分之顯像後的膜厚。結果合倂示於表2。 [黑色矩陣形狀] 以上述方法製成黑色矩陣基板。藉由光學顯微鏡觀察 形成於曝光部分之黑色矩陣形狀的直線性良否來進行評估 。結果合倂示於表2。 [玻璃密著性] -27- 1287694 藉由上述方法塗布感光性黑色組成物於玻璃基板上, 使用超高壓水銀燈,經由光罩曝光3 0 0 m J / c m2紫外線。.其 次,使用碳酸鈉水溶液來顯像未曝光部分之後,以離子交 換水洗淨並除去未曝光部分,於23 0°C下加熱1小時。其次 藉由依照:TIS K5400之棋盤網目附著性試驗方法來評估塗 膜之玻璃密著性,並計數1 〇 〇個棋盤網目中的剝離個數。 結果合倂示於表2。 [光學濃度] 藉由上述方法塗布感光性黑色組成物於玻璃基板之後 ,於230 °C加熱1小時。藉由馬克貝思濃度計(GRETAG D200-II )測定如此所得.之感光性黑色組成物塗布基板的光 學濃度(0D),求得在膜厚中之光學濃度。結果合 倂示於表2。 表2 : 碳黑 分散體 碳黑分散體之 長時間安定性 感度 黑色矩陣形狀 玻璃 密著性 光學濃度 實例1 〇 △ 〇 〇 3.6/ β m 實例2 Ο 〇 Δ 〇 3.6/ β m 實例3 〇 〇 Ο 〇 3.8/ β m 比較例1 X X X X 2.9/ β m 比較例2 △ X X X 3.5/ ^ m 表2中, 長時間安定性:〇;於40°C保存7曰後之黏度7製作之 後之黏度&lt; 1 · 3 △ ; 1.3$於40°C保存7日後之黏度/製 -28- 1287694 作之後之黏度&lt; 1. 8 X ;於40 °C保存7曰後之黏度/製作之 後之黏度^ 1 . 8 感度: 〇;膜厚g〇.95//m △ ; 0.90/zmS 膜厚 &lt;0.95ym x ;膜厚 &lt;0.90 &quot;m 黑色矩陣形狀:〇;直線性良好 △:部分直線性良好 X ;直線性不良 玻璃密著性: 〇;棋盤網目之剝離個數&lt; 3個 △ ; 3個S棋盤網目之剝離個數&lt;10個 X ;棋盤網目之剝離個數^ 10個 如表2所示,在未使用比表面積爲50〜200m2/g之碳黑 的情況下,不能得到碳黑分散體之長時間安定性、感度, 招致黑色矩陣之形狀不良,而變成不能得到剝離密著性。 相對於此,在使用比表面積爲50〜200m2/g之碳黑的情況下 ’碳黑分散體之長時間安定性良好,感度優異,黑色矩陣 $狀、剝離密著性良好。 如以上所述,藉由本發明,於高濃度下,可安定且分 敎碳黑。又,本發明之感光性黑色組成物係長時間安定性 傻異而達成高感度化,由於使用本發明之感光性黑色組成 物’黑色矩陣形狀、玻璃密著性、光學濃度均良好,得到 具備有構成黑色矩陣時所要求之性能的黑色矩陣基板。 (S )圖式簡單說明:無。 -29-[Example 1] I • Carbon black ("40" manufactured by Mitsubishi Chemical Corporation) 1〇·〇份•Pigment derivative 1 〇. 5 parts [Example 2] • Carbon black ("360" by Mitsubishi Chemical Corporation) 8.0 Parts • Pigment Derivatives 2 〇. 3 parts [Example 3] • Carbon black ("Mt 77" manufactured by Mitsubishi Chemical Corporation) 12.0 parts • Pigment derivatives 3 1 . 〇 [Comparative Example 1] • Carbon black (manufactured by CABOT Co., Ltd.) Black beads 800") 8.0 parts • Pigment derivatives 1 〇 · 2 parts [Comparative Example 2] • Carbon black ("MONARCH 120" manufactured by CABOT Co., Ltd.) 1 〇·〇份•Pigment derivatives 2 0.8 parts -26- 1287694 &lt;; Long-term stability evaluation of carbon black dispersion&gt; The long-term stability was evaluated by comparing the viscosity of the carbon black dispersion after dispersion to the viscosity after storage at 40 ° C for 7 days. The results are shown in Table 2. &lt;Preparation of photosensitive black composition&gt; 60 parts of carbon black dispersion and 4.3 parts of trimethoxypropyl triacrylate ("Nippon Chemical Co., Ltd.") were uniformly stirred and mixed, and 1.4 parts of photopolymerization was carried out. After the starter ("Erga Qiuya 907" made by Ciba Geji Co., Ltd.), 2 parts of sensitizer ("Eb-F" from Baotu Valley Chemical Co., Ltd.), and 21.6 parts of cyclohexane, The photosensitive black composition was prepared by filtering with a filter of 1 // m. With respect to the obtained photosensitive black composition, sensitivity, black matrix shape, glass adhesion, and optical density were evaluated by the following methods. The results are shown in Table 2. 感 [Sensitivity] After coating the photosensitive black composition on a glass substrate of 10 cm x 10 cm by spin coating, a dry film thickness of 1 // m was prepared by drying at 70 ° C for 15 minutes. Coating film. Then, an ultra-high pressure mercury lamp was used to expose 1 〇〇mJ/cm2 of ultraviolet light through a reticle. Next, after the unexposed portion was sprayed with an aqueous solution of sodium carbonate, the unexposed portion was washed with ion-exchanged water, and the film thickness after development of the exposed portion was measured. The results are shown in Table 2. [Black matrix shape] A black matrix substrate was produced in the above manner. The evaluation was made by observing the linearity of the shape of the black matrix formed in the exposed portion by an optical microscope. The results are shown in Table 2. [Glass Adhesion] -27- 1287694 A photosensitive black composition was applied onto a glass substrate by the above method, and an ultraviolet ray of 300 m J / c m 2 was exposed through a photomask using an ultrahigh pressure mercury lamp. Next, after the unexposed portion was developed using an aqueous sodium carbonate solution, it was washed with ion-exchanged water and the unexposed portion was removed, and heated at 23 ° C for 1 hour. Next, the glass adhesion of the coating film was evaluated by following the TIS K5400 checkerboard adhesion test method, and the number of peelings in the board of 1 〇 棋 was counted. The results are shown in Table 2. [Optical Concentration] After the photosensitive black composition was applied to the glass substrate by the above method, it was heated at 230 ° C for 1 hour. The optical density (0D) of the thus obtained photosensitive black composition-coated substrate was measured by a Markbes concentration meter (GRETAG D200-II) to determine the optical density in the film thickness. The results are shown in Table 2. Table 2: Long-term stability of carbon black dispersion carbon black dispersion. Black matrix shape glass adhesion optical density Example 1 〇 △ 〇〇 3.6 / β m Example 2 Ο 〇 Δ 〇 3.6 / β m Example 3 〇〇 Ο 〇 3.8 / β m Comparative Example 1 XXXX 2.9/ β m Comparative Example 2 △ XXX 3.5/ ^ m In Table 2, long-term stability: 〇; viscosity after storage at 7 ° C for 7 7 7 viscosity after production ; 1 · 3 △ ; 1.3$ at 70 ° C after 7 days of viscosity / -28 - 1287694 viscosity afterwards &lt; 1. 8 X; after 7 保存 storage at 40 ° C viscosity / viscosity after fabrication ^ 1.8 sensitivity: 〇; film thickness g〇.95//m △; 0.90/zmS film thickness &lt; 0.95ym x ; film thickness &lt;0.90 &quot;m black matrix shape: 〇; good linearity △: partial straight line Good sex X; poor linearity of glass: 〇; number of strips of checkerboard &lt; 3 △; number of strips of 3 S board nets &lt; 10 X; number of strips of checkerboard net ^ 10 As shown in Table 2, in the case where carbon black having a specific surface area of 50 to 200 m 2 /g was not used, long-term stability and feeling of the carbon black dispersion could not be obtained. , Leading to poor shape of the black matrix, peeling becomes adhesion can not be obtained. On the other hand, when carbon black having a specific surface area of 50 to 200 m 2 /g is used, the carbon black dispersion has good long-term stability and excellent sensitivity, and the black matrix has a good shape and good adhesion. As described above, with the present invention, carbon black can be stabilized and divided at a high concentration. Moreover, the photosensitive black composition of the present invention achieves high sensitivity by long-term stability and stupidity, and the photosensitive black composition of the present invention has good black matrix shape, glass adhesion, and optical density. A black matrix substrate that constitutes the performance required for a black matrix. (S) Schematic description: None. -29-

Claims (1)

1287694 牧年厂月内日修(¾正替換頁I 第93 1 1 7 5 95號「感光性黑色組成物,使用它之黑色矩陣基 板及濾色器」專利案 (2006年5月19日修正) 十、申請專利範圍: 1 · 一種感光性黑色組成物,其係含有: (a)比表面積爲50〜2〇〇m2/g之碳黑,該碳黑之平均一 次粒徑爲20〜50nm、 (b )以通式(A )所示之色素衍生物、1287694 The Year of the Pasture Factory is repaired in the month (3⁄4 is replacing the page I No. 93 1 1 7 5 95 "Photosensitive black composition, using its black matrix substrate and color filter" patent case (amended on May 19, 2006) X. Patent application scope: 1 · A photosensitive black composition containing: (a) carbon black having a specific surface area of 50 to 2 〇〇m 2 /g, and the average primary particle diameter of the carbon black is 20 to 50 nm (b) a pigment derivative represented by the formula (A), (其中,Q代表有機色素殘基, X 代表直接鍵、—CONH— Y2—、— S02NH — Y2 — 、或一 CH2NHCOCH2NH-Y2-, Y2代表具有取代基亦可之亞烴基或芳基, Υ!代表一 ΝΗ —或一 〇 —, Ζ代表羥基、烷氧基、或以通式(i )所示之取 代基,(wherein Q represents an organic pigment residue, X represents a direct bond, -CONH-Y2-, -S02NH-Y2-, or a CH2NHCOCH2NH-Y2-, and Y2 represents an alkylene or aryl group which may have a substituent, Υ! Representing a hydrazine, or a hydrazine, Ζ represents a hydroxy group, an alkoxy group, or a substituent represented by the formula (i), 但是,在η爲1之情況下,Z亦可爲一 NH - X — Q, Υ3 代表一 ΝΗ-或—〇-, 1287694 l及r2係個別獨立地代表取代或無取代之丨完基 ,或Ri與R2亦可互相鍵結而形成至少包含氮原子之雜 環, m代表1〜6之整數, η代表1〜4之整數);以及 (c )乙烯性不飽和化合物, 其中以組成物之全部固體成分的重量爲基準計,係含有 20〜70重量%之比例的碳黑。 2.如申請專利範圍第1項之感光性黑色組成物,其中該碳 黑之鄰苯二甲酸二丁酯的吸收量係在120cc/100g以下。 3 ·如申請專利範圍第1項之感光性黑色組成物,其中相對 於100重量份之碳黑計,係含有0.1〜30重量份之比例的 通式(A )所示之色素衍生物。 4.如申請專利範圍第3項之感光性黑色組成物,其係含有 組成物之固體成分重量的5 %〜3 0%之比例的乙烯性不飽 和化合物。 5 . —種黑色矩陣基板,其係具備如申請專利範圍第1至4 項中任一項之感光性黑色組成物所形成的黑色矩陣。 6 .如申請專利範圍第5項之黑色矩陣基板,其中平均1 // m 黑色矩陣之乾燥膜厚的光學濃度爲3 · 0以上。 7 . —種濾色器,其中如申請專利範圍第5項之黑色矩陣基 板上,形成有黑色以外之至少2色之濾色段。 • 2 -However, in the case where η is 1, Z may also be an NH - X - Q, Υ3 represents a ΝΗ- or -〇-, and 1287694 l and r2 each independently represent a substituted or unsubstituted oxime, or Ri and R2 may also be bonded to each other to form a heterocyclic ring containing at least a nitrogen atom, m represents an integer of 1 to 6, and η represents an integer of 1 to 4; and (c) an ethylenically unsaturated compound in which a composition is used The carbon black is contained in a ratio of 20 to 70% by weight based on the total weight of the solid component. 2. The photosensitive black composition of claim 1, wherein the carbon black dibutyl phthalate has an absorption of 120 cc/100 g or less. 3. The photosensitive black composition according to the first aspect of the invention, wherein the pigment derivative represented by the formula (A) is contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the carbon black. 4. The photosensitive black composition of claim 3, which is an ethylenically unsaturated compound containing a proportion of 5% to 30% by weight of the solid content of the composition. A black matrix substrate comprising a black matrix formed of the photosensitive black composition according to any one of claims 1 to 4. 6. The black matrix substrate of claim 5, wherein the optical density of the dry film thickness of the average 1 // m black matrix is 3.0 or more. A color filter in which a color filter segment of at least two colors other than black is formed as in the black matrix substrate of claim 5 of the patent application. • 2 -
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