TWI321146B - - Google Patents
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- TWI321146B TWI321146B TW095102776A TW95102776A TWI321146B TW I321146 B TWI321146 B TW I321146B TW 095102776 A TW095102776 A TW 095102776A TW 95102776 A TW95102776 A TW 95102776A TW I321146 B TWI321146 B TW I321146B
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
- E02D5/00—Bulkheads, piles, or other structural elements specially adapted to foundation engineering
- E02D5/74—Means for anchoring structural elements or bulkheads
- E02D5/76—Anchorings for bulkheads or sections thereof in as much as specially adapted therefor
- E02D5/765—Anchorings for bulkheads or sections thereof in as much as specially adapted therefor removable
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
- E02D5/00—Bulkheads, piles, or other structural elements specially adapted to foundation engineering
- E02D5/74—Means for anchoring structural elements or bulkheads
- E02D5/80—Ground anchors
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
- E02D2600/00—Miscellaneous
- E02D2600/30—Miscellaneous comprising anchoring details
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Description
1321146 _九、發明說明: /【發明所屬之技術領域】 本發明係有關在製造彩色液晶顯示裝置、彩色攝影管 元,等時之彩色濾光器中所使用的著色組成物,以及使用 該著色組成物之彩色濾光器以及其製造方法。 '【先前技術】 在構成液晶顯示器(LCD : liquid crystal display )、彩 色攝影管元件(CCD : charge coupled device)等彩色滅光5| 鲁之製造時,於透明基板上塗上塗佈液,必須形成乾燥日^ 膜厚約為1至3/zm之均勻塗膜,塗佈方式一般係使用旋 轉塗膜(spin costing)法。 旋轉塗膜A,係-面以一定之旋轉數旋轉透明基板 一面在透明基板上滴下塗佈液,藉由離心力使塗佈液薄薄 地延展’在透明基板之表面’藉由塗佈液黏度或旋轉數等 決定膜厚的-獅成㈣之㈣方式。旋轉㈣法中雖有 •大氣開放型及_式,但以任何之方式,透明基板之旋 令心部及外周部之塗膜厚度,均有厚於其中間部分之缺點。 為解決此缺點,在藉由旋轉塗佈法塗佈時,作為能妒 成中心部及外周部财間部分之财差距小之表面平= 優異之塗膜的組成物,已知有溶解或分解在特定之^ 劑中的顏料、黏合劑聚合物以及感光放射線化合物岭 參照曰本專利特開平6— 3521號公報)^ ' ’ 藉由使用前述組成物雖使塗膜之膜厚差距變巧 旋轉塗膜法中,於透明基板上所滴下㈣液中塗佈在= 317737 6 ^21146 .·基板之表面者不超過數%,而殘留之9〇數%塗佈液則排出 透明基板之外’因此有浪費過多之缺點,近年來隨著基板 的大型化,該項缺點便成為沈重之問題。 : 為了解決如此之旋轉塗膜法的缺點,近年來對擠壓式 .塗佈法正加以探討(例如,參照日本專利特開平7_168〇15 '號公報、特開2000— 193818號公報,以及特開2〇〇1 — • 195004號公報)。擠壓式塗佈法與旋轉塗膜法相比,除了 塗佈液之浪費少’同時具有㈣到末端為止,塗佈液之供 攀應導路為完全密閉系統等優點。 ’、 【發明内容】 (發明所欲解決之課題) 然而,在擠壓式塗佈法中,基板外周部之塗膜***、 其厚度較厚於基板中心部之塗膜,而有所謂的長角之缺 點,近年來隨著面板之大型化,而由於至基板邊端為止均 吏用面板因此在基板外周部即有膜厚之差距的產生因而 _不佳。此問題是在使用為了可形成中心部與外周部之膜厚 差距變小而得到表面平滑性優異之塗膜所開發之旋轉塗膜 用組成物,因所求之特性不同而難以解決。 在此,本發明之目的是提供:一種即使使用由擠壓式 塗佈法形成塗膜,在基板外周部亦難以產生塗膜膜厚不 句而可形成表面平滑性優異之塗膜的著色組成物。 =,本發明之目的是提供:一種具有中心部與外周部 之膜厚差距小,表面平滑性優異之濾、光器片段及/或黑色 矩陣的彩色濾光器。 317737 7 之膜厂明:目的是提供:一種具有中心部與外周部 、 表面平滑性優異之濾光器片段及/或里$ 矩陣的彩色據光器之製造方法。 &及从、、色 (解決課題之手段) ㈣ί發明之著色組成物,係含有由透明樹脂、其前驅體 ^ °物所成之色素载體、色素、有機溶劑、與塗 、、:之著色組成物,其特徵為該著色組成物在l00ms中之 ,匙表面張力⑴與在1〇〇〇ms中之動態表面張力(II), 能滿足下述關係式(1 )者。 [{( I )-( II )}/( I )] X 100^7.0 ........⑴ #又,本發明之彩色濾光器,其特徵係具備有由本發明 之著色組成物形成之據光器>!段及/或黑色矩陣。 又,本發明之彩色濾光器之製造方法,係具備有濾光 益片段及/或黑色矩陣的彩色遽光器之製造方法,其^徵 鲁為在基板上,以擠壓式塗佈方式塗佈本發明之著色組成 物以开)成;慮光器片段及/或黑色矩陣。 本申請案之揭示,係有關剔5年2月2日所提出之 日本專利中請案特願2⑻5—_3()號所記载之主題,係引 用此等之揭示内容來使用。 【實施方式】 發明實施之最佳形態: 首先,針對本發明中之著色組成物加以具體說明。 本發明之著色組成物,係含有由透明樹脂、其前驅體 317737 8 1321146 “中,m為14、n為77、X為10 )。又,其他之市售矽系塗 平劑,可列舉如BYK Chemie公司製造之「BYK_32〇」、 「BYK— 323」、「BYK—333」。塗平劑可單獨使用丄種, -或是混合2種以上使用。 塗平劑,於著色組成物中,相當於1〇〇重量份色素的 0.01至10重量份,較佳可使用〇 05至5重量份。 在本發明之著色組成物中,所含之色素載體,係由透 明樹脂、其前驅體或此等之混合物所構成。透明樹脂在400 鲁至700 nm的全波長可見光領域中,較佳之穿透率為8〇% 以上,最佳為95 %以上之樹脂。透明樹脂之例可列舉如: 熱塑性樹脂、熱硬化性樹脂,及感光性樹脂,其前驅體可 列舉如藉由放射線照射而硬化產生透明樹脂之單體,或寡 聚物。此等可以單獨使用,或是混合2種以上使用。 色素載體,於著色組成物中,相當於重量份色素 的30至700重量份,較佳者係可使用6〇至45〇重量份之 鲁量。又,使用透明樹脂與其前驅體之混合物做為色素載體 時,透明樹脂,於著色組成物中,可以使用相當於1〇〇重 里伤色素的20至400重量份,最好為5〇至25〇重量份之 量。又,透明樹脂之前驅體於著色組成物中,可使用相當 於100重^份色素之10至300重量份,較好為1〇至2⑼ 重量份之量。 熱塑性樹脂之例可列舉如:丁縮醛樹脂、苯乙烯一馬 來酸共聚物'氣化聚乙烯、氣化聚丙烯、聚氣乙烯、氣乙 稀-醋酸乙烯酯共聚物、聚醋酸乙婦醋、聚胺醋系樹脂、 317737 10 ^聚酯樹脂、丙烯酸系樹脂、醇酸樹脂、聚笨乙烯、聚醯胺 树脂、橡膠系樹脂、環化橡膠系樹脂、纖維素類、聚乙烯、 聚丁一稀、聚酿亞胺樹脂等。又熱硬化性樹脂之例可列舉 .如·裱氧樹脂、苯并鳥糞胺樹脂、松香改質馬來酸樹脂、 .松香改質昌馬酸樹脂、三聚氰胺樹脂、尿樹脂、酚樹脂等。 感光性樹脂在具有羥基、羧基、胺基等反應性取代基 .之線狀高分子中,可使用使具有異氰酸酯基、醛基、環氧 基等反應性取代基之(甲基)丙烯酸化合物或肉桂酸反應之 ♦(甲基)丙烯醯基、苯乙稀基等光交聯性基導入該線狀高分 子中之樹脂。又,亦可使用將含有苯乙烯—馬來酸酐共聚 物或α —烯烴一馬來酸酐共聚物等酸酐之線狀高分子,藉 由具有羥基烷基(曱基)丙烯酸酯等之羥基的(曱基)丙烯酸 化合物進行半酯化者。 做為透明樹脂之前驅物的單體及寡聚物者可列舉 如:(甲基)丙烯酸曱酯、(甲基)丙烯酸乙酯、(曱基)丙烯酸 籲一2 —羥基乙酯、(甲基)丙烯酸—2_羥基丙酯、(曱基)丙烯 酸環己酯、(曱基)丙烯酸石—羧基乙酯、聚乙二醇二(曱基) 丙稀酸酯、1,6 —己二醇二(曱基)丙烯酸酯、三乙二醇二(曱 基)丙烯酸醋、三丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷 二(曱基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、1,6 —己 二醇二縮水甘油醚二(曱基)丙烯酸酯、聯酚A二縮水甘油 醚二(曱基)丙烯酸酯、新戊二醇二縮水甘油醚二(甲基)丙烯 酸酯、二季戊四醇六(甲基)丙烯酸酯、(甲基)丙烯酸三環癸 醋、丙烯酸酯、羥甲基化三聚氰胺之(甲基)丙烯酸酯、環 11 317737 丄丄砰〇 .氧(甲基)丙烯酸醋、胺酉旨丙婦酸醋等之各種丙稀酸酉旨及曱 基丙締酸醋、(曱基)丙稀酸、苯乙稀、醋酸乙稀、經基乙 基乙婦喊、乙二醇二乙烯鍵、季戊四醇三乙稀喊、(甲基) 丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、N-乙烯曱醯 胺、丙烯腈等。 做為含在本發明之著色組成物的色素,可將有機或無 機的顏料以單獨使用或混合2種以上使用。顏料之中以 發色性高且耐熱性高之顏料,尤其以耐分解性高之顏料為 •宜,通常是使用有機顏料。 , 以下在本發明之著色組成物中,可以使用較佳之有機 顏料的具體例疋以顏色指數(C〇i〇r in(jex )號碼表示。 為了形成紅色濾光器片段之紅色著色組成物中,可以 使用例如 C. L Pigment Red 7、9、14、41、48 : 1、48 : 2、 48 · 3、48 : 4、81 :卜 81 : 2、81 : 3、97、122、123、146、 149 、 168 、 177 、 178 、 180 、 184 、 185 、 187 、 192 、 200 、 •202、208、210、215、216、217、220、223、224、226、 227、228、240、246 ' 254、255、264、272 等紅色顏料。 在紅色著色組成物中,可併用黃色顏料、橘色顏料。 為了形成黃色濾光器片段之黃色著色組成物中,可以 使用例如 C. I. Pigment Yellow 1、2、3、4、5、6、1〇、12、 13、14、15、16、17、18、20、24、31、32、34、35、35 : 1、36、36 :卜 37、37 : 1、40、42、43、53 ' 55、60、61、 62、63、65、73、74、77、81、83、86、93、94、95、97、 98、1〇〇、1〇1、1〇4、、1〇6、108、109、110、in、114、 12 317737 1321146 115 、 116 、 117 ' 118 、 119 、 120 、 123 ' 125 、 126 、 127 ' 128 、 129 、 137 、 138 、 139 、 147 、 148 、 150 、 151 、 152 、 153 ' 154 、 155 、 156 、 161 、 162 、 164 ' 166 、 167 、 168 、 169 ' 170 、 171 、 172 、 173 、 174 、 175 、 176 、 177 、 179 、 180、181、182、185、187、188、193、194、199 等之黃 色顏料。 ’ 為了形成橘色濾光器片段之橘色著色組成物中,可以 使用例如 c· I. Pigment Orange 36、43、51、55、59、61 _等之橘色顏料。 為了形成綠色濾光器片段之綠色著色組成物中,可以 使用例如C. I. Pigment Green 7、10、36、37等之綠色顏 料。綠色著色組成物中可併用黃色顏料。 為了形成藍色濾光器片段之藍色著色組成物中,可以 使用例如 C. I. Pigment Blue 15、15: 1、15: 2、15: 3、 15. 4、15: 6、16、22、60、64等之藍色顏料。藍色著色 籲組成物中可以併用 C· I. Pigment violet 1、19、23、27、29、 30、32、37、40、42、50等之紫色顏料。 為了形成青綠色濾光器片段之青綠色著色組成物 中’可以使用例如 C_ I. Pigment Biue 15 ·· j、15 : 2、15 4' 3、15: 6、16、81等之青綠色顏料。〇〇 17 為了形成洋紅色(magenta )濾光器片段之洋紅色著色1321146 _9, invention description: / [Technical field to which the invention pertains] The present invention relates to a coloring composition used in a color filter for manufacturing a color liquid crystal display device, a color photographic tube, and the like, and the use of the coloring A color filter of a composition and a method of manufacturing the same. '[Prior Art] When manufacturing a color light-emitting device such as a liquid crystal display (LCD) or a color photographic tube device (CCD: charge coupled device), it is necessary to apply a coating liquid on a transparent substrate. Drying day ^ A uniform coating film having a film thickness of about 1 to 3/zm, and the coating method is generally a spin costing method. Rotating the coating film A, the system-side is rotated on the transparent substrate with a certain number of rotations, and the coating liquid is dropped on the transparent substrate, and the coating liquid is thinly spread by the centrifugal force 'on the surface of the transparent substrate' by the viscosity of the coating liquid or The number of rotations determines the film thickness - the lion (4) (four) method. In the rotation (four) method, although the atmosphere is open type and _ type, in any case, the thickness of the coating of the transparent substrate and the outer peripheral portion of the transparent substrate are thicker than the intermediate portion. In order to solve this disadvantage, in the case of coating by the spin coating method, it is known that the composition of the coating film which is small in the center portion and the outer peripheral portion is small, and the coating film is excellent in dissolution and decomposition. In the specific agent, the pigment, the binder polymer, and the sensitizing radiation compound ridge are described in the above-mentioned composition, and the film thickness difference of the coating film is rotated by using the above composition. In the coating method, the liquid applied to the transparent substrate is coated at = 317737 6 ^ 21146. The surface of the substrate is not more than several %, and the remaining 9 % of the coating liquid is discharged outside the transparent substrate. Therefore, there is a disadvantage of excessive waste. In recent years, with the enlargement of the substrate, this shortcoming has become a serious problem. In order to solve the shortcomings of the spin coating method, the extrusion coating method is being discussed in recent years (for example, refer to Japanese Patent Laid-Open No. Hei 7-168〇15', No. 2000-193818, and Open 2〇〇1 — • Bulletin No. 195004). Compared with the spin coating method, the extrusion coating method has the advantages of less waste of the coating liquid and a (four) to the end, and the coating liquid is required to be a completely closed system. 'The Summary of the Invention' (Problems to be Solved by the Invention) However, in the extrusion coating method, the coating film on the outer peripheral portion of the substrate is thicker and thicker than the coating film at the center portion of the substrate, and has a so-called length. In the recent years, as the size of the panel has increased, the panel has been used up to the edge of the substrate, so that there is a difference in film thickness at the outer peripheral portion of the substrate. This problem is a composition for a spin coating film developed by using a coating film which is excellent in surface smoothness in order to form a film thickness difference between the center portion and the outer peripheral portion, and is difficult to solve due to the difference in properties. Here, an object of the present invention is to provide a coloring composition of a coating film which is excellent in surface smoothness and which is less likely to be formed on the outer peripheral portion of the substrate even when a coating film is formed by a squeeze coating method. Things. The object of the present invention is to provide a color filter having a filter, an optical segment and/or a black matrix having a small difference in film thickness between the center portion and the outer peripheral portion and having excellent surface smoothness. The film factory of 317737 7: The purpose is to provide a method for manufacturing a color light device having a central portion and a peripheral portion, a filter segment excellent in surface smoothness, and/or a matrix. &, and, color, (the means to solve the problem) (4) The color composition of the invention is a pigment carrier, a pigment, an organic solvent, a coating, and the like which are formed of a transparent resin and a precursor thereof. The coloring composition is characterized in that the coloring composition is in the range of 100 ms, and the surface tension (1) of the spoon and the dynamic surface tension (II) in 1 〇〇〇 ms satisfy the following relation (1). [{( I )-( II )}/( I )] X 100^7.0 . . . (1) # Further, the color filter of the present invention is characterized by having the colored composition of the present invention Formed by the lighter >! segment and / or black matrix. Moreover, the method for manufacturing a color filter of the present invention is a method for manufacturing a color chopper having a filter element and/or a black matrix, which is applied on a substrate by extrusion coating. The colored composition of the present invention is applied to form an optical component segment and/or a black matrix. The disclosure of this application is based on the subject matter described in Japanese Patent Application No. 2(8)5-_3(), filed on February 2, 2005, and is incorporated herein by reference. [Embodiment] The best mode for carrying out the invention: First, the coloring composition of the present invention will be specifically described. The colored composition of the present invention contains a transparent resin, and its precursor 317737 8 1321146 "where m is 14, n is 77, and X is 10". Further, other commercially available lanthanide coating agents may be mentioned, for example. "BYK_32〇", "BYK-323" and "BYK-333" manufactured by BYK Chemie. The leveling agent may be used alone or in combination of two or more. The coating agent is preferably used in an amount of 0.01 to 10 parts by weight based on 1 part by weight of the coloring matter, and preferably 5 to 5 parts by weight. In the coloring composition of the present invention, the pigment carrier contained is composed of a transparent resin, a precursor thereof or a mixture thereof. The transparent resin preferably has a transmittance of more than 8% by mass, preferably 95% or more, in a full-wavelength visible light range of 400 ul to 700 nm. Examples of the transparent resin include a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and examples of the precursor thereof include a monomer which is cured by radiation irradiation to produce a transparent resin, or an oligomer. These may be used alone or in combination of two or more. The pigment carrier is preferably 30 to 700 parts by weight based on parts by weight of the coloring matter, and preferably 6 to 45 parts by weight. Further, when a mixture of a transparent resin and a precursor thereof is used as a coloring matter carrier, a transparent resin may be used in the coloring composition in an amount of 20 to 400 parts by weight, preferably 5 to 25 inches, equivalent to 1 gram of the tartar dye. The amount by weight. Further, the transparent resin precursor may be used in an amount of from 10 to 300 parts by weight, preferably from 1 to 2 parts by weight, based on 100 parts by weight of the pigment. Examples of the thermoplastic resin include, for example, butyral resin, styrene-maleic acid copolymer, gasified polyethylene, vaporized polypropylene, polystyrene, ethylene-vinyl acetate copolymer, and polyacetate. Vinegar, polyurethane resin, 317737 10 ^ polyester resin, acrylic resin, alkyd resin, polystyrene, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene, poly Ding Yi, poly-imine resin and so on. Examples of the thermosetting resin include, for example, an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified maleic acid resin, a melamine resin, a urethane resin, and a phenol resin. The photosensitive resin may be a (meth)acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group, or a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amine group. A photocrosslinkable group such as ♦ (meth) acryloyl group or styrene group which is cinnamic acid is introduced into the resin of the linear polymer. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer may be used, and a hydroxyl group such as a hydroxyalkyl (mercapto) acrylate may be used ( The thiol) acrylate compound is semi-esterified. As the monomer and oligomer of the transparent resin precursor, for example, (meth)acrylic acid acrylate, ethyl (meth)acrylate, (mercapto)acrylic acid 2-hydroxyethyl ester, (A) Acrylic acid 2-hydroxypropyl ester, (cycloalkyl)cyclohexyl acrylate, (fluorenyl) acrylate-carboxyethyl ester, polyethylene glycol bis(indenyl) acrylate, 1,6-hexane Alcohol bis(mercapto) acrylate, triethylene glycol bis(indenyl) acrylate vinegar, tripropylene glycol di(meth) acrylate, trimethylolpropane bis(indenyl) acrylate, pentaerythritol tri(methyl) Acrylate, 1,6-hexanediol diglycidyl ether di(indenyl) acrylate, biphenol A diglycidyl ether di(indenyl) acrylate, neopentyl glycol diglycidyl ether di(methyl) Acrylate, dipentaerythritol hexa(meth) acrylate, (meth)acrylic acid tricyclic vinegar, acrylate, methylolated melamine (meth) acrylate, ring 11 317737 丄丄砰〇. oxygen (A Acrylic vinegar, alum, acetoacetate, etc.旨 曱 丙 丙 丙 缔 缔, 曱 ) 丙 丙 丙 、 、 、 、 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylamine, acrylonitrile, and the like. As the coloring matter contained in the coloring composition of the present invention, organic or inorganic pigments may be used singly or in combination of two or more kinds. Among the pigments, pigments having high color developability and high heat resistance are preferable, and pigments having high decomposition resistance are preferable, and organic pigments are usually used. Hereinafter, in the colored composition of the present invention, a specific example of a preferred organic pigment can be used, which is represented by a color index (C〇i〇r in (jex) number. In order to form a red coloring composition of a red filter segment For example, C. L Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48 · 3, 48: 4, 81: Bu 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, • 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246 ' 254, 255, 264, 272, etc. Red pigment. In the red coloring composition, a yellow pigment or an orange pigment may be used in combination. To form a yellow coloring composition of the yellow filter segment, for example, CI Pigment Yellow 1 may be used. 2,3,4,5,6,1〇,12,13,14,15,16,17,18,20,24,31,32,34,35,35: 1, 36, 36: Bu 37, 37 : 1, 40, 42, 43, 53 ' 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 1〇〇, 1〇1,1〇4 1, 、 6, 108, 109, 110, in, 114, 12 317737 1321146 115 , 116 , 117 ' 118 , 119 , 120 , 123 ' 125 , 126 , 127 ' 128 , 129 , 137 , 138 , 139 , 147 , 148, 150, 151, 152, 153 '154, 155, 156, 161, 162, 164' 166, 167, 168, 169 '170, 171, 172, 173, 174, 175, 176, 177, 179, 180, Yellow pigments such as 181, 182, 185, 187, 188, 193, 194, 199, etc. 'In order to form an orange coloring composition of an orange filter segment, for example, c·I. Pigment Orange 36, 43, An orange pigment of 51, 55, 59, 61, etc. In order to form a green coloring composition of a green filter segment, a green pigment such as CI Pigment Green 7, 10, 36, 37 or the like can be used. A yellow pigment can be used in combination with the green coloring composition. In order to form a blue coloring composition of the blue filter segment, for example, CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15. 4, 15: 6, 16, 22, 60 may be used. 64% blue pigment. Blue coloring The composition may be used in combination with C. I. Pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, etc. In order to form a cyan coloring composition of a cyan filter segment, a cyan pigment such as C_I. Pigment Biue 15 ·· j, 15: 2, 15 4' 3, 15: 6, 16, 81, etc. may be used. . 〇〇 17 To create magenta coloration of the magenta filter segment
、且成物中,可以使用例如c. I. Pigment Violet 1、19、c IAnd, for example, c. I. Pigment Violet 1, 19, c I can be used.
Pigment Red 144、146、177、169、81 等之紫色顏料及红 色顏料。在洋紅色著色組成物中,可併用黃色顏料。 317737 13 1321146 . 為了形成黑色矩陣之黑色著色組成物中,可以使用例 如碳黑、苯胺黑、蒽醌系黑色顏料、茈系黑色顏料,具體 上可使用 C. I. Pigment black 1、6、7、12、20、31 等。在 -黑色著色組成物中,亦可使用紅色顏料、藍色顏料、綠色 顏料之混合物。黑色顏料從價格、遮光性大小方面來看, 以使用碳黑為宜,碳黑可使用樹脂等加以表面處理。又, •為了調整色調,黑色著色組成物中可併用藍色顏料或紫色 顏料。 又,無機顏料之例可列舉如:硫酸鋇、氧化辞、硫g 鉛、黃色鉛、鋅黃、紅色氧化鐵(III) (red ir〇n⑷心)、鎖 2、、群青、普魯士藍、氧化鉻綠、#綠、琥珀色、鈦黑、 合成鐵黑、氧化鈦、四氧化鐵等金屬氧化物粉末,或金肩 硫化物粉末,或金屬粉末f。無機顏料為了獲得彩度斑清 ^平衡良好之塗佈性、感度、顯影性等,可與有機顏㈣ &使用。在本發明之著色組成物中,為了調色,可在不障 I低耐熱性之範圍内含有染料。 在本發明之著色組成物中,所含之有機 ::卜庚闕、4—庚w乙酸正丁醋、乙酸」; 乙曰、乙酸正戊酯、乙酸異戊酯、甲基異丁基酮、正丁基醇、 乙二醇單乙基醚、乙二醇-r其喊, 丞坪 二醇置乙基醚、乙二醇單甲基醚、乙 一%早丙基醚、乙二醇單異丙基 酯、〇—私早甲基驗乙酸 乙美二醋、丙二醇單甲基醚、丙二醇單 土- 丙一醇單丙基醚、丙二醇單甲美 醇單乙基醚乙酸酯、NN 一 "田 黾酯、丙二 夂軸一甲基甲醯胺、! 一 317737 14 1321146 丙烷、鄰氣甲苯、鄰二甲苯、間二曱苯、3_甲氧基_3 — 曱基一1—丁醇、1,3—丁二醇、3 一曱基—U—丁二醇、 甲基一1,3—丙二醇、二異丁基酮、乙二醇單丁基醚、 乙二醇單己基醚、乙二醇單丁基醚乙酸酯、乙二醇二丁基 醚、二乙二醇單曱基醚、二乙二醇單乙基醚、二乙二醇: 乙基醚、二乙二醇單異丙基醚、丙二醇單丁基醚、丙二醇 一乙酸酯、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙 二醇單丙基醚、二丙二醇二曱基醚、三丙二醇單甲基醚、3 乙氧基丙酸乙酯、3 —曱氧基丁基乙酸酯、3一甲氧基—3 —甲基丁基乙酸酯、T — 丁内酯、N, N_二曱基乙醯胺, 甲基吡咯烷酮、對氯曱苯、鄰二乙基苯、間二乙基苯、 對一乙基笨、鄰二氯苯、間二氯苯、正—丁基苯、第二丁 基苯、第三丁基苯、環己醇、曱基環己醇等。此等,可單 獨使用或混合2種以上使用。有機溶劑,於著色組成物中, 2對於100重量份之色素,可使用800至4〇〇〇重量份之 •里較佳為至2500重量份之量。 本發明之著色組成物中,在藉由紫外線等之光線照射 該組成物而硬化時,即添加光聚合起始劑。 〃作為光聚合起始劑可使用:4—苯氧基二氯乙酿苯、4 —第三丁基一二氣乙醯苯、二乙氧基乙醯苯、丨—異 基苯基)一2 —經基一2 — φ真系 1 甲基丙一1—綱、i —羥基環己基苯 土 _、2 $基—2-二甲胺基—卜(4—嗎琳苯基)丁 —卜 嗣等之乙醯苯系光聚合起始劑、苯偶因、苯偶因甲基驗、 苯偶因乙絲、苯偶因異丙基_、节基二甲_等苯偶因 317737 15 1321146 系光聚合起始劑、二苯甲酮、苯曱醯苯曱酸、苯甲醯苯甲 酸甲醋、4一苯基二苯曱酮、經基二苯甲酮、丙烯酸化二苯 曱酮、4—苯曱醯基一4’一甲基二苯基硫化物等之二苯曱酮 -系光聚合起始劑、嗟"煩酮(Thioxanthone )、2 —氣嘆嘴酿|、 2—曱基噻噸酮、異丙基噻噸酮、2, 4_二異丙基噻噸_等 嗟啼酮系光聚合起始劑、2, 4, 6 _三氯一第二一三p井、2 -苯基-4, 6 —雙(三氯曱基)—第二-三口井、2 —(對曱氧基 苯基)一4, 6 -雙(三氣曱基)-第二一三口井、2 -(對-曱苯 •基)一4,6 -雙(三氣甲基)—第二_三0井、2_胡椒基—4, 6 -雙(三氯甲基)一第二一三畊、2, 4 -雙(三氯甲基)—ό — 苯乙烯基一第二一三畊、2 —(萘—1_基)_4,6_雙(三氣 曱基)一第二一三畊、2-(4-甲氧基-萘」基)_4,6_雙(三氣甲 基)—第二—三啡、2, 4—三氯曱基一胡椒基_ό—三畊、 2,4—三氣曱基_(4,_甲氧基苯乙烯基)—6—三畊等三 畊系光聚合起始劑、硼酸酯系光聚合起始劑、9 _氮雜芴 籲(carbazole)系光聚合起始劑、咪唑系光聚合起始劑等。 光聚合起始劑,於著色組成物中,相對於100重量份色素, 可以使用5至200重量份,較佳為1〇至15〇重量份之量。 上述光聚合起始劑,雖可單獨使用亦可混合2種以上 使用,但亦可併用做為增感劑之醯氧基_cyloxy er) “I基q化氫氧化物、甲基苯基乙路酸醋、聯笨酿' ,*菲知樟驷醌、乙基蒽醌、4, 4’ 一二乙基間笨二曱 ,基,、3’ 3’’ 4’ 4’—四(第三丁基過氧化幾基)苯酿笨、4, -乙基胺基苯Si苯等化合物^增感劑,於著色組成物 317737 1321146 •中相對於100重量份色素,可以使用0.1至60重量份之量。 本發明之者色組成物係將1種或2種以上色素、塗平 .劑,及因應需求,加上上述光聚合起始劑,共同在色素載 -體及有機溶劑中,使用三輥研磨機、二輥研磨機、夾心研 磨機、捏合機(kneader)、微粉碎機等各種分散手段加以微 '細分散製造,塗平劑亦可在色素分散到色素載體及有機溶 劑中之後再添加。又,含有2種以上色素之著色組成物, 係可將各色素分別經微細分散在色素載體及有機溶劑中者 •加以混合而製得。色素分散在色素載體及有機溶劑中時, 可以適當地含有樹脂型顏料分散劑、界面活性劑、色素衍 生物等之分散助劑。分散助劑因使顏料良好地分散,而有 防止分散後顏料再度凝聚的優異效果,因此在使用分散助 劑使顏料分散到色素載體及有機溶劑中之著色組成物時, 可得到透明性優異之色彩濾光器。分散助劑,於著色組成 物中相對於100重量份色素,可以使用〇1至4〇重量份, 鲁較佳為0.1至3〇重量份之量。 樹脂型顏料分散劑,係具有含吸附顏料特質之顏料親 和性部位,及與色素載體有相溶部位之樹脂,吸附顏料後 對顏料之色素載體的分散有安定作用者。做為樹脂型顏料 为散劑者,具體上可列舉如:除了可使用做為上述透明樹 脂之外,經由將聚胺酯、聚丙烯酸酯等羧酸酯、不飽和聚 I胺♦幾k、聚幾酸酯(部分)胺鹽、聚缓酸錄鹽、聚緩 酸烷基胺鹽、聚矽氧烷、長鏈聚胺基胺基膦酸鹽、含羥基 之聚羧酸酯、或此等之改質物、聚(低級伸烷亞胺),與含 17 317737 1321146 •遊離羧基之聚酯反應所形成的醯胺或其鹽等的油性分散 劑;(曱基)丙烯酸一苯乙烯共聚物;(甲基)丙烯酸一(曱基) •丙烯酸酯共聚物;苯乙烯一馬來酸共聚物;聚乙烯醇;聚 -乙烯吡咯烷酮等之水溶性樹脂或水溶性高分子化合物;聚 醋系;改質聚丙烯酸酯系;環氧乙烷/環氧丙烷加成化合 物;磷酸酯系等’此等可單獨使用或混合2種以上使用。 界面活性劑可使用聚氧伸乙基烷基醚硫酸鹽、十二烧 基笨磺酸鈉、苯乙烯一丙烯酸共聚物之鹼鹽、烷基萘績酸 籲鈉、烧基二苯基ϋ二續酸鈉、月桂基硫酸單乙醇胺、月桂 基石;IL酉文二乙醇胺、月桂基硫酸錄、硬脂酸單乙醇胺、硬脂 酉欠納、月桂基硫酸納、苯乙烯一丙稀酸共聚合物之單乙醇 胺、聚氧伸乙基烷基醚磷酸酯等陰離子性界面活性劑;聚 氧伸乙基油基醚、聚氧伸乙基月桂基醚、聚氧伸乙基壬基 苯基醚、聚氧伸乙基烷基醚磷酸酯、聚氧伸乙基山梨糖醇 酐單硬脂酸酯、聚乙二醇單月桂酸酯等之非離子性界面活 鲁性劑;烷基4級銨鹽或該等之環氧乙烷加成物等之陽離子 性界面活性劑;炫基二甲基胺基醋酸甜菜驗等之院基甜菜 驗、院基咪唾琳等之兩性界面活性劑’此等可單獨使用亦 可混合2種以上使用。 色素衍生物係在有機色素中導入取代基之化合物。在 如此之有機色素中,通常亦包含並不稱為色素之萘系、葱 醌系等之淡黃色芳香族多環化合物。色素衍生物係可使用 曰本專利特開昭63- 305173號公報、特公昭57— 1562〇 號公報、特公昭59- 40172號公報、特公昭63— 171〇2號 317737 18 又=== ㈣性,亦可含有石夕燒偶合劑等之密著提高劑。 之 =存安㈣之例可料U基三甲 基羥基胺等之4級铉衰仆铷 , 柳一乙 刚'第:二:酸、草酸等之有機酸及其 播酿η 乙基膦、四苯基膦等之有 Η)〇重量ΓΓΙ等了存安定劑’於著色組成物中相對於 董里伤色素,可使用0.1至10重量份之量。 矽烷偶合劑之例可列舉如:乙烯參(卜甲氧基乙氧 石夕烧、乙稀乙氧基我、乙駐甲氧基我等乙烯錢類; r -甲基丙烯氧基丙基三甲氧基石夕烧等(甲基)丙稀石夕院 類|_万—(3,4—環氧環己基)乙基三甲氧基矽烷、万一(3 4 -環氧環己基)甲基三曱氧基石m_(3,4—環氧環己基) 丨乙基三乙氧基矽烷、沒—(3, 4—環氧環己基)甲基三乙氧基 夕烧γ環氧丙氧基丙基三甲氧基石夕烧、γ —環氧丙氧 基丙基三乙氧基矽烷等之環氧矽烷類;Ν—石—胺基乙基 —Τ —胺基丙基三曱氧基矽烷、Ν_卢一胺基乙基—γ: 胺基丙基三乙氧基矽烷、N—石—胺基乙基一胺基丙 基甲基二乙氧基矽烷、r_胺基丙基三乙氧基矽烷、丨― 胺基丙基三曱氧基矽烷、;^—笨基—r —胺基丙基三曱氧 基矽烷、N—笨基一r _胺基丙基三乙氧基矽烷等之胺基 矽烷類;r —氫硫基丙基三曱氧基矽烷、7 —氫硫基丙基 19 317737 丄以1146 ,、三乙氧基矽烷等之氫硫矽烷類等。矽烷偶合劑,於著色組 成物中相對於100重量份色素,可以使用0 01至1〇重量 *份’較佳為0.05至5重量份之量。 . 本發明之著色組成物,可以調製成照相凹版平版用印 刷油墨、無水平版印刷油墨、絲網版印刷用油墨、溶劑顯 影型或驗性顯影型|色光阻材料。;容劑顯影型紐性顯影 型著色光阻材料係在含有色素載體之熱塑性樹脂、熱硬化 性樹脂或感光性樹脂,單體、光聚合起始劑,與有機溶劑 _之組成物中分散色素者。 本發月之著色組成物,係以離心分離、锻燒滤過器、 膜滤器等方法,進行去除5//m以上之粗大粒子、較佳為玉 P以上之粗大粒子、最好是…m以上之粗大粒子及 混入之龙鹿。 个知月之者色組成物’為了不使發生塗佈不均而 得到均勾塗膜,便加以調整使E型黏度計以2 ,25°C中之黏度,以6mp — 疋锝歎 1 L a S以丁為宜,以調整至2 mPa · s以上’ 6 mPa · s以下者更佳。 造方^使用本發明著色組成物之彩色遽光器的製 本發明之彩色據光器係在基板上 /或黑色矩陣者,例如_ B 有應光态片奴及 干有例如,可具有黑色矩陣,與紅色、錄洛、 藍色慮光器片段。前述遽'光器片段及/或里色矩陣,係 ^播屡式塗佈方式塗佈本發明之著色組成物以在基板上、 317737 20 1321146 一 藉由擠壓式塗佈方式塗佈著色組成物,即可使用周知 之擠壓式塗佈機以進行,此時之塗佈條件,由著色組成物 '之組成、製造之彩色濾光器種類等而加以適當選擇即可。 -例如,噴嘴尖端之口宽以5〇至5〇〇以m,喷嘴尖端與基板 面之間隔以30至300以m較佳。要調整塗佈膜厚,只要調 整喷口移動速度及來自噴口之塗佈量即可。 衫色濾光器之基板,可使用穿透可見光之穿透率高的 鹼石灰玻璃、低鹼硼矽酸玻璃、無鹼鋁硼矽酸玻璃等之玻 •璃板、或聚碳酸酯、聚甲基丙烯酸甲酯、聚伸乙基對苯二 甲酸醋等樹脂板。X,在玻璃板或樹脂板之表面,為了平 板化後之液晶驅動,亦可形成由氧化銦、氧化錫等 透明電極。 藉由光微影法(Photo Lithography)形成各色濾光器片 段及黑色輯似下述之方法進行。亦即,在基板上°,將 做,溶劑顯影型或驗性顯影型著色樹脂材而調製之本發明 丨之著色組成物,使用擠壓式塗佈方式之塗佈裝置,塗^ 乾燥後之膜厚為0.2至i〇#m。因應需求,在乾燥之膜中, 通過設計成與此膜接觸或非接觸狀態之具有預定圖案之光 罩進行紫外線曝光。之後,浸潰在溶劑或鹼性顯影液中, 或經噴料讀㈣液,去除未硬化部即可㈣成所預期 之圖案’之後’將必要之顏色重覆同樣之操作即可形成各 ,之滤絲片段及黑色矩陣。再者,為促進著色級材之 聚合,可視需要而進行加熱。如依光微影法,即 密度高於印刷法之彩色濾光器。 、k 4Pigment Red 144, 146, 177, 169, 81 and other purple pigments and red pigments. In the magenta coloring composition, a yellow pigment may be used in combination. 317737 13 1321146 . In order to form a black colored composition of a black matrix, for example, carbon black, aniline black, lanthanum black pigment, lanthanide black pigment may be used, specifically CI Pigment black 1, 6, 7, 12 may be used. 20, 31, etc. A mixture of a red pigment, a blue pigment, and a green pigment may also be used in the -black coloring composition. The black pigment is preferably carbon black in terms of price and light-shielding property, and the carbon black may be surface-treated with a resin or the like. Also, • To adjust the color tone, a blue pigment or a purple pigment can be used in combination with the black coloring composition. Further, examples of the inorganic pigments include, for example, barium sulfate, oxidized words, sulfur g lead, yellow lead, zinc yellow, red iron oxide (III) (red ir〇n (4) heart), lock 2, ultramarine blue, Prussian blue, oxidation Metal oxide powder such as chrome green, #green, amber, titanium black, synthetic iron black, titanium oxide, iron oxide, or gold shoulder sulfide powder, or metal powder f. Inorganic pigments can be used with organic pigments in order to obtain chromatographically clear, well-balanced coating properties, sensitivity, developability, and the like. In the coloring composition of the present invention, for coloring, a dye may be contained in a range of low heat resistance. In the coloring composition of the present invention, the organic substance contained:: phloem, 4-g-w acetic acid n-butyl vinegar, acetic acid; acetamidine, n-amyl acetate, isoamyl acetate, methyl isobutyl ketone , n-butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol-r, shout, 丞 二醇 diol, ethyl ether, ethylene glycol monomethyl ether, ethyl methacrylate, ethylene glycol Isopropyl ester, 〇-private methyl acetate acetic acid ethyl acetonitrile, propylene glycol monomethyl ether, propylene glycol mono- propylene monopropyl ether, propylene glycol monomethylol monoethyl ether acetate, NN One " 黾 黾 ester, propylene dioxime axis monomethyl methamine,! A 317737 14 1321146 propane, o-toluene, o-xylene, m-nonylbenzene, 3-methoxy-3-indolyl-1-butanol, 1,3-butanediol, 3-mercapto-U- Butanediol, methyl-1,3-propanediol, diisobutyl ketone, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol dibutyl Ether, diethylene glycol monodecyl ether, diethylene glycol monoethyl ether, diethylene glycol: ethyl ether, diethylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetic acid Ester, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol didecyl ether, tripropylene glycol monomethyl ether, 3 ethoxy propionate ethyl ester, 3 - anthracene oxygen Butyl acetate, 3-methoxy-3-methylbutyl acetate, T-butyrolactone, N, N-dimercaptoacetamide, methylpyrrolidone, p-chlorophenyl, neighbor Diethylbenzene, m-diethylbenzene, p-ethylidene, o-dichlorobenzene, m-dichlorobenzene, n-butylbenzene, t-butylbenzene, t-butylbenzene, cyclohexanol, anthracene Cyclohexanol and the like. These can be used alone or in combination of two or more. The organic solvent, in the coloring composition, may be used in an amount of from 800 to 4 parts by weight, preferably from 2,500 parts by weight, per 100 parts by weight of the pigment. In the colored composition of the present invention, when the composition is cured by irradiation with light such as ultraviolet rays, a photopolymerization initiator is added. As a photopolymerization initiator, phthalocyanine can be used: 4-phenoxydichloroethane benzene, 4-tert-butyldioxabenzene, diethoxyethylbenzene, fluorenyl-isophenyl) 2 — 经基基-2 — φ真系1 methylpropan-1-yl, i-hydroxycyclohexylbenzene _, 2 $yl-2-ylamino-b (4-cylinylphenyl)- Dimethine photopolymerization initiator, benzoin, benzoin methylation, benzoin b, benzoin isopropyl, benzyl benzophenone 317737 15 1321146 is a photopolymerization initiator, benzophenone, benzoquinone, benzamidine benzoic acid, 4-phenyldibenzophenone, benzophenone, acrylated benzophenone a benzophenone-based photopolymerization initiator such as 4-benzoyl- 4'-methyldiphenyl sulfide, 嗟"Thioxanthone, 2-gas squeezing|, 2 - mercapto thioxanthone, isopropyl thioxanthone, 2, 4 - diisopropyl thioxanthone, etc. fluorenone photopolymerization initiator, 2, 4, 6 _ trichloro- 1-2 p Well, 2-phenyl-4,6-bis(trichloroindenyl)-second-three wells, 2-(p-oxyl Base) a 4, 6 - bis (three gas sulfhydryl) - second one three wells, 2 - (p-nonyl phenyl), a 4, 6 - bis (trimethyl) - second _ three Well, 2_Pepperyl-4,6-bis(trichloromethyl)-second 2-3, 2,4-bis(trichloromethyl)-hydrazine-styryl-second 1-3, 2 —(naphthalene-1_yl)_4,6_bis (trioxanyl)-second ternary tillage, 2-(4-methoxy-naphthalene)-based, 4,6-bis (tri-methyl) -Second-tri-morphine, 2,4-trichloroindenyl-piperonyl-ό-three-plowing, 2,4-trimethylsulfonyl-(4,_methoxystyryl)-6-three tillage, etc. A three-till photopolymerization initiator, a borate photopolymerization initiator, a 9-azacarb photopolymerization initiator, an imidazole photopolymerization initiator, and the like. The photopolymerization initiator may be used in an amount of 5 to 200 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the pigment in the coloring composition. The photopolymerization initiator may be used singly or in combination of two or more kinds, but may be used in combination as a sensitizer 醯oxy_cyloxy er) "I-based q-hydroxide, methylphenyl B Road sour vinegar, joint stupid ', * Philippine knows, ethyl hydrazine, 4, 4'-diethyl stigma, base, 3' 3'' 4' 4' - four (the first a compound such as tributyl peroxy)phenyl benzene, 4,-ethylaminobenzene benzene, etc., sensitizer, in the coloring composition 317737 1321146 • 0.1 to 60 weights relative to 100 parts by weight of the pigment The amount of the color composition of the present invention is one or two or more kinds of pigments, a coating agent, and a photopolymerization initiator according to the demand, together in a dye carrier and an organic solvent. It is micro-finely dispersed by various dispersing means such as a three-roll mill, a two-roll mill, a sandwich mill, a kneader, a micro-pulverizer, etc., and the coating agent can also be dispersed in the pigment carrier and the organic solvent. After that, the coloring composition containing two or more kinds of pigments can be finely dispersed in the respective colors. The carrier and the organic solvent are prepared by mixing them. When the pigment is dispersed in the dye carrier or the organic solvent, a dispersing aid such as a resin-based pigment dispersant, a surfactant, or a dye derivative may be appropriately contained. Since the pigment is well dispersed, it has an excellent effect of preventing re-agglomeration of the pigment after dispersion. Therefore, when the pigment is dispersed in the pigment carrier and the colored composition in the organic solvent using a dispersing aid, color filter excellent in transparency can be obtained. The dispersing aid may be used in the coloring composition in an amount of from 1 to 4 parts by weight, preferably from 0.1 to 3 parts by weight, based on 100 parts by weight of the pigment. Resin type pigment dispersant, The pigment affinity portion of the adsorbed pigment characteristic and the resin having a compatibility with the pigment carrier, and the pigment pigment is dispersed as a powder after adsorbing the pigment, and specific examples thereof include: In addition to being used as the above transparent resin, via a carboxylate such as polyurethane or polyacrylate, an unsaturated polyamine, a few k, a polyacid (partial) amine salt, poly-acid salt, poly-sulphate alkylamine salt, polyoxyalkylene oxide, long-chain polyamino amino phosphonate, hydroxyl-containing polycarboxylate, or the like , (polyalkyleneimine), an oily dispersant such as guanamine or a salt thereof formed by reacting a polyester containing 17 317737 1321146 • a free carboxyl group; (mercapto)acrylic-styrene copolymer; Acrylic acid (mercapto) acrylate copolymer; styrene-maleic acid copolymer; polyvinyl alcohol; water-soluble resin or water-soluble polymer compound such as poly-vinylpyrrolidone; polyacetate; modified polyacrylic acid Ethyl esters; ethylene oxide/propylene oxide addition compounds; phosphate esters, etc. These may be used alone or in combination of two or more. The surfactants may be polyoxyethylene ethyl ether sulfate, or twelve. Sodium sulfonate sodium sulfonate, alkali base of styrene-acrylic acid copolymer, sodium alkyl naphthoate, sodium diphenyl sulfonate, lauryl sulfate monoethanolamine, lauryl stone; IL bismuth diethanolamine , lauryl sulfate, stearic acid monoethanolamine, stearic acid owe Anionic surfactants such as monoethylamine, styrene-acrylic acid copolymer, polyoxyethylene ethyl ether phosphate, polyoxyethylene ethyl oleyl ether, polyoxyethyl ether Lauryl ether, polyoxyethylene ethyl phenyl ether, polyoxyethylene ethyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc. a nonionic interface active agent; a cationic surfactant such as an alkyl 4-grade ammonium salt or such an ethylene oxide adduct; a sylvestre-based sugar beet The amphoteric surfactants such as the test and the hospital's Kimi Sai Lin may be used alone or in combination of two or more. A pigment derivative is a compound in which a substituent is introduced into an organic dye. In such an organic dye, a pale yellow aromatic polycyclic compound such as a naphthalene or an onion system which is not called a pigment is usually included. For the pigment derivative, it is possible to use the Japanese Patent Laid-Open Publication No. SHO63-305173, the Japanese Patent Publication No. Sho 57- 1562, the Japanese Patent Publication No. 59- 40172, and the special public. No. 63-171-2, 317737 18 and === (4) The substance may also contain a adhesion enhancer such as a Shi Xi siu coupler. In the case of Cun'an (4), it is possible to use U-based trimethylhydroxylamine and other grade 4 铉 铷 铷, 柳一乙刚 '第:二: acid, oxalic acid and other organic acids and its broadcast η ethyl phosphine, The tetraphenylphosphine or the like may be used in an amount of from 0.1 to 10 parts by weight based on the weight of the stabilizer. Examples of the decane coupling agent include, for example, ethylene thiophene (b-methoxy ethoxylate, ethylene ethoxylate, ethylene, methoxy, etc.; r-methacryloxypropyltrimethyl) Oxygen stone kiln and other (meth) propyl sylvestre class | _ million - (3, 4-epoxycyclohexyl) ethyl trimethoxy decane, in case (3 4 - epoxy cyclohexyl) methyl three曱 石 m m_(3,4-epoxycyclohexyl) decyl triethoxy decane, bis-(3,4-epoxycyclohexyl)methyltriethoxy gamma epoxide propoxy propyl Epoxy decanes such as trimethoxy zeoxime, γ-glycidoxypropyltriethoxy decane; Ν-stone-aminoethyl-hydrazine-aminopropyltrimethoxy decane, hydrazine _ Lu-Aminoethyl-γ: Aminopropyltriethoxydecane, N-stone-aminoethyl-aminopropylmethyldiethoxydecane, r-aminopropyltriethoxy Base decane, hydrazine-aminopropyltrimethoxy decane, ?-styl-r-aminopropyltrimethoxy decane, N-styl-r-aminopropyltriethoxydecane, etc. Amino decanes; r-hydrothiopropyltrimethoxy decane, 7 —Hexylthiopropyl 19 317737 Hydrazine sulfonate such as 1146 or triethoxy decane. A decane coupling agent can be used in the coloring composition in an amount of from 0.01 to 1 relative to 100 parts by weight of the pigment. The weight *part' is preferably 0.05 to 5 parts by weight. The colored composition of the present invention can be prepared into a printing ink for gravure lithography, a horizontal printing ink, a screen printing ink, a solvent developing type or An invisible developing type|color resistive material; a toner developing type developing type colored resisting material is a thermoplastic resin containing a pigment carrier, a thermosetting resin or a photosensitive resin, a monomer, a photopolymerization initiator, and In the organic solvent, the pigment is dispersed in the composition. The coloring composition of the present month is obtained by removing a coarse particle of 5/m or more, preferably jade, by a method such as centrifugation, calcination filter or membrane filter. The coarse particles above P, preferably the coarse particles of ...m or more and the dragon deer mixed in. The color composition of the moon knows that the coating composition is adjusted so that it does not cause uneven coating. Type viscometer at 2,25 ° C The viscosity in the middle is 6mp - sigh 1 L a S is preferably butyl, and it is better to adjust to 2 mPa · s or more '6 mPa · s or less. 造方^Use the color ray of the coloring composition of the present invention The color light illuminator of the present invention is on a substrate or a black matrix, for example, _B has a light state of the slave and has, for example, can have a black matrix, and a red, recorded, blue optical filter segment Applying the coloring composition of the present invention to the substrate, 317737 20 1321146, by extrusion coating, coloring the coloring composition and/or the color matrix. The composition can be carried out by using a known extrusion coater, and the coating conditions at this time can be appropriately selected by the composition of the coloring composition, the type of color filter to be produced, and the like. For example, the nozzle tip has a mouth width of 5 Torr to 5 Torr, and the nozzle tip and the substrate face are preferably 30 to 300 Å apart. To adjust the coating film thickness, it is only necessary to adjust the nozzle moving speed and the coating amount from the nozzle. The substrate of the shirt color filter can be used for glass-glass plates, such as soda-lime glass, low-alkali borosilicate glass, alkali-free aluminoborosilicate glass, or polycarbonate, which can penetrate the visible light. A resin plate such as methyl methacrylate or polyethyl phthalate. X, on the surface of the glass plate or the resin plate, a transparent electrode such as indium oxide or tin oxide may be formed for driving the liquid crystal after the flattening. The color filter segments and the black color are formed by photolithography (Photo Lithography) in the following manner. In other words, the colored composition of the present invention prepared by using a solvent-developing type or an in-process development type colored resin material on a substrate is coated by a coating apparatus using a squeeze coating method. The film thickness is 0.2 to i 〇 #m. In the dry film, ultraviolet light exposure is carried out in a dried film by a mask having a predetermined pattern in contact with or in contact with the film. After that, it can be formed by dipping in a solvent or an alkaline developing solution, or by reading the (four) liquid by spraying, and removing the uncured portion (4) into the desired pattern 'after' and repeating the necessary colors to form the same. Filter wire segments and black matrix. Further, in order to promote polymerization of the coloring grade, heating may be performed as needed. For example, the lithography method is a color filter with a higher density than the printing method. , k 4
317737 21 1321146 —遽光H片段及黑色輯之乾龍厚度以02至1〇鋒 為且以0·2至〇·5//ιη為更佳。使塗佈膜乾燥之際,亦可 &用減壓㈣機 '烘烤爐 ' 紅外線烘烤爐。 板等。 … 顯影時,鹼性顯影液可使用碳酸鈉、氫氧化鈉等之水 溶液亦可使用二甲基节胺、三乙醇胺等之有機驗。又, 在顯影液中,亦可添加消泡劑或界面活性劑。顯影處理方 法’可適料淋顯影法、噴霧顯影法、浸潰(dip)顯影法、 镰浸置(puddle)顯影法等。 ,同日ττ,為了提尚紫外線曝光感度,於上述著色光阻材 料塗佈乾燥之後,塗佈水溶性或鹼性可溶性樹脂,例如塗 佈聚乙烯醇或水溶性丙烯酸樹脂等經乾燥,並藉由氧氣形 成防止妨礙聚合之膜後’亦可進行紫外線曝光。 本發明之著色組成物’由於在100 ms中之動態表面張 力和在1000 ms中之動態表面張力的變化率在7 〇%以 鲁下,所以經由使用此等,在基板外周部並無長角,使基板 外周部與基板中心部之膜厚差距小,而無塗佈不均現象, 即可形成均勻之塗膜。 因此’藉由使用本發明之著色組成物而形成濾光器片 段及黑色矩陣,即可製造出良好收率之彩色遽光器。 實施例 以下雖藉由實施例更具體說明本發明,但本發明並不 侷限於無超過主旨以下之實施例。 另外,於實施例及比較例中’ Γ份」及「%」係分別為「 22 317737 1321146 」重量份」以及「重量%」之意。 首先’說明有關在實施例及比較例中使用之丙烯酸系 ‘紺脂溶液之調製。樹脂之分子量係經凝膠滲透色譜 -(GPC ; Gel permeation chromatography)測定聚苯乙烯換算 之重量平均分子量。 ’(丙烯酸樹脂溶液之調製) 在反應器中放入370份之環己酮,在容器中一面注入 氮氣,一面在80°C中加熱,於同溫度下,以i小時之時 Φ間滴下述單體及熱聚合起始劑之混合物以進行聚合反 應。 甲基丙烯酸 20.0份 甲基丙烯酸曱酯 10.0份 甲基丙稀酸丁酯 55.0份 甲基丙烯酸2—羥基乙酯 15.0份 偶氮二異丁腈 4.0份317737 21 1321146 — The thickness of the dry H-segment and the black dry dragon is preferably from 02 to 1 且 and from 0·2 to 〇·5//ιη. When the coating film is dried, it is also possible to use a decompression (four) machine 'baking oven' infrared baking oven. Board and so on. When developing, the alkaline developer may be an organic solution such as sodium carbonate or sodium hydroxide, or an organic test such as dimethylamine or triethanolamine. Further, an antifoaming agent or a surfactant may be added to the developer. The development treatment method 'is a suitable development method, a spray development method, a dip development method, a puddle development method, and the like. On the same day, ττ, in order to improve the sensitivity of ultraviolet exposure, after coating and drying the above colored photoresist material, coating a water-soluble or alkaline-soluble resin, for example, coating polyvinyl alcohol or water-soluble acrylic resin, etc., by using After oxygen is formed to prevent the film from interfering with polymerization, it is also possible to perform ultraviolet exposure. Since the coloring composition of the present invention has a dynamic surface tension of 100 ms and a rate of change of dynamic surface tension in 1000 ms at 7 〇%, there is no long angle at the outer periphery of the substrate by using this. The film thickness difference between the outer peripheral portion of the substrate and the central portion of the substrate is small, and without coating unevenness, a uniform coating film can be formed. Therefore, a color chopper of a good yield can be produced by forming a filter segment and a black matrix by using the coloring composition of the present invention. EXAMPLES Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to the examples below. In addition, in the examples and comparative examples, 'parts' and '%' are "22 317737 1321146" parts by weight" and "% by weight". First, the modulation of the acrylic "resin solution" used in the examples and comparative examples will be described. The molecular weight of the resin was measured by gel permeation chromatography (GPC; Gel permeation chromatography) to determine the weight average molecular weight in terms of polystyrene. '(Preparation of acrylic resin solution) 370 parts of cyclohexanone was placed in a reactor, and nitrogen gas was injected into the vessel while being heated at 80 ° C, and at the same temperature, at the same time, Φ between Φ A mixture of a monomer and a thermal polymerization initiator is used to carry out the polymerization. Methacrylic acid 20.0 parts Ethyl methacrylate 10.0 parts Butyl methacrylate 55.0 parts 2-Hydroxyethyl methacrylate 15.0 parts Azobisisobutyronitrile 4.0 parts
滴入後再於10(TC下反應3小時之後,添加溶有W 偶氮一異丁腈之5〇份環己酮液,再持續於}⑻。[下反靡1 小時,可得丙烯酸樹脂之溶液。丙烯酸樹脂之重量平均^分 子量約為40,000。 刀 。冷却至室溫後,將約2 g之樹脂溶液做為試樣,在18( f中加熱乾燥2G分鐘後測定其不揮發分,添加環己㈣关 前所合成之樹脂溶液中使不揮發分成為2〇 %之方塑 丙烯酸樹脂溶液。 5 、 317737 23 1321146 [實施例i] 下述組成之混合物經均勻攪拌混合後,使用直徑丨mm 之玻璃珠,以砂磨機經5小時分散後,以5 // m之淚器過 濾,製成銅酞菁分散體。 ε 型銅酞菁顏料(C.I. Pigment Blue 15 : 6) 12 〇 份 (BASF 製「Heliogen. Blue L 6700F」) 分散劑(Zeneca公司製「蘇斯巴斯(音譯)20000」) 2.4份 丙烯酸樹脂溶液 28.1 份 環己酮 57.5 份 接著,將下述組成之混合物經均勻攪拌混合後,以 // m之濾過器過濾,得到調整成藍色光阻材之著色、组成 物。著色組成物之組成(著色組成物全量當作1〇〇之重量 比,括號内係相當於顏料100重量份之重量)在表1中表示 銅酞菁顏分散體 45.0 份 丙稀酸樹脂溶液 1 12.5 份 三羥曱基丙烷三丙烯酸酯 (新中村化學公司製「NH酯ATMPT」) 4.8份 光聚合起始劑(汽巴特化公司製「IRGACURE907」2.5份 增感劑(Hodogaya Chemical 公司製「EAB — F」)0.2 份 矽系塗平劑(BYK Chemie公司製「BYK— 330」之2%乙二 醇單乙基醚乙酸酯稀釋溶液) 1.0份 環己_ 34.0 份 24 317737 1321146 [實施例2至7以及比較例1] 除了將顏料、分散劑、丙烯酸樹脂、單體、光聚合起 始劑、增感劑、溶劑、塗平劑之組成,變更為如表1所示 之比率(著色組成物全量當作100之重量比,括號内係相當 於顏料100重量份之重量)以外’其餘與實施例1進行相同 操作,得到作為各色光阻材之經調整的著色組成物。 同時’實施例及比較例中所使用之色素載體的可見光 區域(400至700 nm )之穿透率,係在95 %以上。 表1 雜例1 實施例2 實施例3 實施例4 實施例5 實施例6 秋例7 ttmn 顏色 藍 紅 綠 黑 藍 藍 藍 藍 顏料 5.40(100) 6.10(100) 5.60(100) 5.50(100) 5.40(100) 5.40(100) 5.40(100) 5.40(100) ^t#J 1.08(20) 1.24(20) 1.12(20) 1.10(20) 1.08(20) 1.08(20) 1.08(20) 1.08(20) 5.02(93) 4.66(76) 4.78(85) 4.90(89) 5.02(93) 5.02(93) 5.02(93) 5.02(93) 單艘 4.80(89) 4.60(76) 4.80(86) 4.80(87) 4.80(89) 4.80(89) 4.80(89) 4.80(89) 聚 2.50(46) 2.20(36) 2.50(45) 2.50(45) 2.50(46) 2.50(46) 2.50(46) 2.50(46) 增感刻 0.20(3.7) 0.20(3.3) &20(3.6) 0.20(3.6) 0.20(3.7) 0.20(3.7) 0.20(3.7) 0.20(3.7) 有齡制 80.99(1500) 8059(1500) 80.99(1500) 80.99(1500) 80.99(1500) 80.99(1500) 8099(1500) 8059(1500) 塗· 0.01(0.19) 0.01(0.16) 0.01(0.18) 0.01(0.18) — — — — 塗補B — — 一 — 0.01(0.19) — — — 塗™。 — 一 一 — — 0.01(0.19) — — 塗科JD — 一 — — — — 0.01(0.19) 一 塗·E 一 — 一 — — — — 0.01(0.19) 藍色用顏料:ε型銅酞菁顏料(c.I. Pigment Blue 15 : 6) 5.40份 (BASF 製「Heliogen. Blue-L-6700F」) 紅色用顏料:二酮吡咯并吡咯系顏料(C.I. Pigment Red 254) (汽巴特化公司製「IRGAforRedB—CF」5.08份 蒽醌系顏料(C.I. Pigment Red 177 ) 0.82 份 (汽巴特化公司製「CROMOPHTAL Red A2B」 25 317737 1321146 蒽酉昆系顏料(C.I· Pigment Yellow 199) 0_20 份 (汽巴特化公司製「CROMOPHTAL Yellow GT-AD」 綠色用顏料:鹵化銅醜菁系顏料(C.I. Pigment Green 36) 3.25份 * (東洋油墨製造公司製「Ryonol Green6YK」) 單偶氮系顏料(C.I. Pigment Yellow 150) 2.35 份 (BAYER 公司製「Fanchon fast Yellow 5688」) ' 計5.60份 黑色用顏料:碳黑(Degussa公司製「Printex 75」)5.50份 鲁分散劑:Zeneca公司製「蘇斯巴斯20000」After the dropwise addition, the reaction was carried out for 10 hours at 10 °C, and 5 parts of cyclohexanone solution in which W azo-isobutyronitrile was dissolved was added thereto, and then continued at (8). [Under the reverse reaction for 1 hour, an acrylic resin was obtained. The solution has a weight average molecular weight of about 40,000. After cooling to room temperature, about 2 g of the resin solution is used as a sample, and the non-volatile matter is measured after heating in 18 (f for 2 G minutes, Adding a square acrylic resin solution in which the non-volatile content is 2% by weight in the resin solution synthesized before the cyclohexane (4). 5, 317737 23 1321146 [Example i] The mixture of the following composition is uniformly stirred and mixed, and the diameter is used. The glass beads of 丨mm were dispersed in a sand mill for 5 hours and then filtered through a 5 // m tear to form a copper phthalocyanine dispersion. ε type copper phthalocyanine pigment (CI Pigment Blue 15 : 6) 12 〇 (Participation of "Heliogen. Blue L 6700F" by BASF) Dispersant ("Susbas (200)" by Zeneca) 2.4 parts of acrylic resin solution 28.1 parts of cyclohexanone 57.5 parts Next, the mixture of the following composition was After uniformly stirring and mixing, filter with a filter of // m to obtain The coloring and composition of the blue photoresist material. The composition of the coloring composition (the total amount of the coloring composition is taken as the weight ratio of 1 ,, and the weight in parentheses corresponds to 100 parts by weight of the pigment). 45.0 parts of acrylic acid resin solution 1 12.5 parts of trishydroxypropyl propane triacrylate ("NH ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.8 parts of photopolymerization initiator (IRGACURE 907, manufactured by Vabat Chemical Co., Ltd.) 2.5 parts of sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts of bismuth-based leveling agent (2% ethylene glycol monoethyl ether acetate diluted solution of BYK Chemie "BYK-330") 1.0 Cyclohexane - 34.0 parts 24 317737 1321146 [Examples 2 to 7 and Comparative Example 1] In addition to the composition of pigments, dispersants, acrylic resins, monomers, photopolymerization initiators, sensitizers, solvents, and leveling agents And changed to the ratio shown in Table 1 (the total amount of the coloring composition was taken as a weight ratio of 100, and the weight in parentheses was equivalent to 100 parts by weight of the pigment), and the same operation as in Example 1 was carried out to obtain a photoresist as each color. Adjusted Composition: At the same time, the transmittance of the visible light region (400 to 700 nm) of the pigment carrier used in the examples and the comparative examples was 95% or more. Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Autumn Example 7 ttmn color blue red green black bluish pigment 5.40 (100) 6.10 (100) 5.60 (100) 5.50 (100) 5.40 (100) 5.40 (100) 5.40 (100) 5.40 ( 100) ^t#J 1.08(20) 1.24(20) 1.12(20) 1.10(20) 1.08(20) 1.08(20) 1.08(20) 1.08(20) 5.02(93) 4.66(76) 4.78(85) 4.90(89) 5.02(93) 5.02(93) 5.02(93) 5.02(93) Single 4.80(89) 4.60(76) 4.80(86) 4.80(87) 4.80(89) 4.80(89) 4.80(89) 4.80(89) Poly 2.50(46) 2.20(36) 2.50(45) 2.50(45) 2.50(46) 2.50(46) 2.50(46) 2.50(46) Sensitization 0.20(3.7) 0.20(3.3) & 20(3.6) 0.20(3.6) 0.20(3.7) 0.20(3.7) 0.20(3.7) 0.20(3.7) Ageing 80.99(1500) 8059(1500) 80.99(1500) 80.99(1500) 80.99(1500) 80.99(1500 8099(1500) 8059(1500) 涂·0.01(0.19) 0.01(0.16) 0.01(0.18) 0.01(0.18) — — — — 涂补 B — — 一 — 0.01(0.19) — — — 涂 涂. — 一一 — 0.01(0.19) — — 涂科JD — 一 — — — — 0.01(0.19) One coating·E 一—一— — — — 0.01(0.19) Blue pigment: ε type copper phthalocyanine pigment (cI Pigment Blue 15 : 6) 5.40 parts ("Heliogen. Blue-L-6700F" by BASF) Red pigment: Diketopyrrolopyrrole pigment (CI Pigment Red 254) (IRGAforRedB-CF manufactured by Vabat Company) 5.08 parts of CI Pigment Red 177 0.82 pieces (CROMOPHTAL Red A2B, manufactured by Diebat Chemical Co., Ltd.) 25 317737 1321146 · ment 颜料 颜料 (CI· Pigment Yellow 199) 0_20 copies (" CROMOPHTAL Yellow GT-AD" Green pigment: copper halide phthalocyanine pigment (CI Pigment Green 36) 3.25 parts* ("Ryonol Green 6YK" manufactured by Toyo Ink Co., Ltd.) Single azo pigment (CI Pigment Yellow 150) 2.35 parts ( "Fanchon fast Yellow 5688" manufactured by BAYER Corporation" 5.60 parts of black pigment: carbon black ("Printex 75" manufactured by Degussa Co., Ltd.) 5.50 parts of dispersant: "Sussbas 20000" manufactured by Zeneca
單 體:三羥曱基丙烷三丙烯酸酯(新中村化學公司製「NK 酉旨ATMPT」) 光聚合起始劑:汽巴特化公司製「IRGACURE907」 增 感 劑:Hodogaya Chemical 公司製「EAB — F」 矽系塗平劑A: (BYK化學公司製「BYK—330」之2 %乙二醇單 乙基醚乙酸酯稀釋溶液)Monomer: Trihydroxydecylpropane triacrylate ("NK 酉 A ATMPT", manufactured by Shin-Nakamura Chemical Co., Ltd.) Photopolymerization initiator: "IRGACURE 907" manufactured by Vabat Chemical Co., Ltd. Sensitizer: "EAB - F", manufactured by Hodogaya Chemical Co., Ltd. Tanning coating agent A: (2% ethylene glycol monoethyl ether acetate dilute solution of "BYK-330" manufactured by BYK Chemical Co., Ltd.)
矽系塗平劑B : (BYK化學公司製「BYK—323」之1 %環己酮稀 釋溶液) 矽系塗平劑C : (BYK化學公司製「BYK—333」之1%環己酮稀Tanning coating agent B: (1% cyclohexanone dilute solution of "BYK-323" manufactured by BYK Chemical Co., Ltd.) Tanning coating agent C: (1% cyclohexanone diluted by BYK Chemical Co., Ltd. "BYK-333"
I 釋溶液) 矽系塗平劑D : (BYK化學公司製「BYK—320」之1%環己酮稀 釋溶液) 矽系塗平劑E :(大日本油墨化學工業公司製「BL—20」之5% 乙二醇單乙基醚乙酸酯稀釋溶液) 26 317737 1321146 將實施例1至7以及比較例1所得之各色光阻材料, 在100 ms中之動態表面張力(1)和在1〇〇〇ms動態表面張 •力(II )以動態表面張力計(克魯斯(音譯)公司製)測定,求出 -[{(1)-(11)} /(I)]xl〇〇之值。又,所得之各色光阻材 料在25°C中之黏度,使用旋轉數為2〇rpmiEs黏度計 (Tokimec公司製)測定。又,所得之各色光阻材料使用&第工 '圖所示之擠壓式塗佈方式之塗佈裝置,在如第2圖所示之 360 mmx 465 mm大小之玻璃基板上,塗佈成平均膜厚為 _2.〇/zm,將所得之塗佈基板在7代中預烘2〇分鐘後,得 到乾燥塗膜。並將此乾燥塗膜由短邊中央至塗佈方向ι〇 cm為止,每5 mm測定其膜厚。此時之最大膜厚以 最小臈厚以Tmin、平均膜厚以、表示。由下式⑴估 膜厚之均-性U (Unif0rmity )’ *滿! %者為A、! %以上 且2〇/〇以下者為b、2%以上且5%以下者為c、5〇/。以上 者為13。 u [ /〇 ] - (T max- T min )/avg χ 2) --..(3) 均之二估關!^述塗佈基板,在白色透過光中進行塗佈不 女η *由目視’將無塗佈不均者記為Α、觀察到稍 塗佈不均者記為B,觀察到有明顯塗為 膜厚均-性及塗佈不均評估之結果係如表2=為。 後二二 1或52广,1係塗佈喷頭,2係前口,3係 吏:係歧s,5係縫隙,6係排管、7係閥、8係定量 泵9係濾過器、1〇係塗#'、 板,13係搬運台。佈液槽11係塗膜,⑴系塗佈基 317737 27 1321146 表 2I release solution) bismuth coating agent D: (1% cyclohexanone diluted solution of "BYK-320" manufactured by BYK Chemical Co., Ltd.) 矽-based coating agent E: ("BL-20" manufactured by Dainippon Ink Chemical Industry Co., Ltd. 5% ethylene glycol monoethyl ether acetate dilute solution) 26 317737 1321146 The dynamic surface tension (1) of each color resist material obtained in Examples 1 to 7 and Comparative Example 1 in 100 ms and at 1 〇〇〇ms dynamic surface tension and force (II) are measured by a dynamic surface tension meter (manufactured by Cruz), and -[{(1)-(11)} /(I)]xl〇〇 is obtained. The value. Further, the obtained viscosity of each color resist material at 25 ° C was measured using a 2 rpmiEs viscosity meter (manufactured by Tokimec Co., Ltd.). Further, the obtained photoresist materials of the respective colors were coated on a glass substrate of a size of 360 mm x 465 mm as shown in Fig. 2 by using a coating apparatus of a squeeze coating method as shown in Fig. 2 The average film thickness was _2.〇/zm, and the obtained coated substrate was prebaked in 7 passes for 2 minutes to obtain a dried coating film. The film thickness was measured every 5 mm from the center of the short side to the coating direction ι 〇 cm. The maximum film thickness at this time is expressed by the minimum thickness of Tmin and the average film thickness. Estimate the uniformity of the film thickness (Unif0rmity )' by the following formula (1) * Full! % is A,! % or more and 2〇/〇 or less are b, 2% or more, and 5% or less is c, 5〇/. The above is 13. u [ /〇] - (T max- T min ) / avg χ 2) --.. (3) The second evaluation of the two! The coated substrate, coated in white transmitted light is not female η * by Visually, 'No unevenness in coating was recorded as Α, and a slight uneven coating was observed as B. The results of evaluation of film thickness uniformity and coating unevenness were observed as shown in Table 2 = . After the second two 1 or 52 wide, 1 series coating nozzle, 2 series front mouth, 3 series 吏: system s, 5 series gap, 6 series tube, 7 series valve, 8 series quantitative pump 9 series filter, 1 〇 涂 coating #', board, 13 series transport platform. The cloth tank 11 is a coating film, (1) is a coating base 317737 27 1321146 Table 2
獅 魏 抛 雄 例1 例2 例3 例4 例5 例6 例7 例1 顏色 藍 紅 綠 里 η 转 耪 藍 [{(Ι)-<Π)}/(Ι)]χ1〇〇 5.1 63 6.7 65 6.7 6.9 7.0 11.1 · s) 3.8 4.6 4.3 47 3.7 3.8 3.8 55 膜厚均勻性 A A R R C C C D 塗佈^啊古 A A A A A B 使用實施例1至7之光阻材料所形成之塗膜,尤其是 _使用含有上述式(2 )所示石夕系塗平劑之實施例j至4之光 阻材料所形成之塗膜,其基板邊端面部與基板中心部之膜 厚差距小,為均勻之塗膜。另一方面,使用比較例i之光 阻材料所形成之塗膜,其基板邊端面部與基板中心部之膜 厚差距大。 又,在使用實施例1至7之光阻材料所形成之塗膜 上,看不到塗佈不均之現象,但使用比較例丨之光阻材料 •所形成之塗膜,則觀察到塗佈不均之情形。 將實施例1至7所得之光阻材料以擠壓式塗佈法在 360 mmx 465 mm大小之玻璃基板上塗佈,進行上述所示 之以光微影法製造彩色濾光過器。可得到基板外周部無長 角’且無塗佈不均之彩色過濾器。 【圖式簡單說明】 第1圖係實施例中所使用擠壓式塗佈方式之塗佈機的 概略圖。 第2圖係表示第1圖中經塗佈機(擠壓式塗佈)之塗佈 317737 28 1321146 狀態的透視圖。 【主要元件符號說明】 .1 塗佈喷頭 .2 前口 3 後口 ' 4 歧管 5 縫隙 6 排管 #7 閥 8 定量泵 9 慮過器 10 塗佈液 11 塗膜 12 塗裝基板 13 搬運台 29 317737狮魏雄雄1 Case 2 Case 3 Case 4 Case 5 Case 6 Case 7 Case 1 Color blue red green η turn indigo [{(Ι)-<Π)}/(Ι)]χ1〇〇5.1 63 6.7 65 6.7 6.9 7.0 11.1 · s) 3.8 4.6 4.3 47 3.7 3.8 3.8 55 Film thickness uniformity AARRCCCD coating ^ Augu AAAAAB The coating film formed by using the photoresist materials of Examples 1 to 7, especially _ use contains the above The coating film formed by the photoresist materials of Examples j to 4 of the Shi et al. coating agent represented by the formula (2) has a small film thickness difference between the substrate edge surface portion and the substrate center portion, and is a uniform coating film. On the other hand, the coating film formed using the photoresist material of Comparative Example i had a large difference in film thickness between the substrate edge portion and the substrate center portion. Further, in the coating film formed using the photoresist materials of Examples 1 to 7, the uneven coating was not observed, but the coating film formed by the comparative example of the photoresist material was observed, and the coating was observed. The situation of uneven cloth. The photoresist materials obtained in Examples 1 to 7 were applied by extrusion coating on a glass substrate of a size of 360 mm x 465 mm, and the color filter was produced by the photolithography method as described above. A color filter having no long angle on the outer peripheral portion of the substrate and having no coating unevenness can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a coating machine of an extrusion coating method used in the examples. Fig. 2 is a perspective view showing the state of coating 317737 28 1321146 by a coater (extrusion coating) in Fig. 1. [Main component symbol description] .1 Coating nozzle. 2 Front port 3 Rear port '4 Manifold 5 Gap 6 Row pipe #7 Valve 8 Dosing pump 9 Isolator 10 Coating liquid 11 Coating film 12 Coating substrate 13 Transfer platform 29 317737
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