TWI380058B

TWI380058B - Black matrix high sensitive photoresist composition for liquid crystal display and black matrix prepared by using the same

Info

Publication number: TWI380058B
Application number: TW96150009A
Authority: TW
Inventors: Dong-Chang Choi; Ho-Chan Ji; Geun-Young Cha; Dae-Hyun Kim; Kyung-Soo Choi; Han-Soo Kim; Sung-Hyun Kim
Original assignee: Lg Chemical Ltd
Priority date: 2006-12-26
Filing date: 2007-12-25
Publication date: 2012-12-21
Also published as: JP2010515098A; WO2008078953A1; JP5329430B2; CN101573663B; TW200835944A; CN101573663A; KR20080059815A; KR100996591B1

Description

1380058 九、發明說明：【發明所屬之技術領域】本發明係關於一種液晶顯示.器用之黑色矩陣光阻組成物及一種使用其製備之黑色矩陣。本發明尤其關於一種液 5晶顯不器用之黑色矩陣，其在確保具有較廣之製程限度下，能具有高光敏感度且僅以輕微的曝光量即可穩定形成圖案，因而能減少製程時間並提升產量，且能確保其具有極佳遮光特性，進而較容易應用在使用較亮背光之大尺寸電視上。〕本發明之優先權為韓國專利申請第1〇·2〇〇6_ΐ33555 號，於2006年12月26日向韓國智慧財產局_請，而其所有的内容皆可併入本發明以供參考。【先前技術】 15 20 一般而言，使用含有顏料之光阻组成物形成圖案，容易因顯影或水洗而產生缺陷，且若提升圖案附著力，非％像部分的溶解㈣在曝光時會劣化並易產生污染。而發^ ==密度以及光敏感度低，亦即在透過顯影形成圖案時其顯影限度較狹小。為了要提升對比度，-般是將一種稱為色晶格㈣置料线光片之彩色畫素&卜在本技術㈣中，於黑色矩陣中使用鉻。其製作過程其杌的八却主I Ύ 絡 >儿積於玻璃基表面，且透過钮刻製成形成圖案，而這程成本尚且會導致—些問題，如鉻之高反射率以及含鉻廢 5 水所產生的環境污染。因此，各方已利用可執行精密製程之顏料分散方法積極研究樹脂黑色矩陣。黑色矩唪光阻組成物的製備，是利用不同顏色的顏料或各種顏料昆合以具有黑色。由於光阻組成物是用來遮住 5光線’故其包含大量之不會受顯影溶液溶解之顏料。因此，黑色矩陣光阻組成物具有下列的問題：顯影性不佳、需長時間顯影、或不能取得所需之解析度。因此，在製備彩色濾光片巾’包含黑色矩陣之每一顏色都必須提升其顯影性。雖然以研究出-種方法其使用非碳黑之著色顏料來製 10備黑色組成物’然而非碳黑之著色顏料其遮光性不佳。因此’黑色矩陣光阻組成物必須包含具有高混合比例之著色顏料如此會造成組成物的黏度增加，使得組成物難以處理，或造成所形成薄膜的強度或薄膜與基板的黏著性減弱。因此，需要許多研究發展出一種液晶顯示器用之黑色 15矩陣光阻組成物，其具有極佳之著色強度、遮蓋力、以及絕緣性與顯影性。在此，已研究出此類的黑色矩陣光阻組成物。因此，已有許多光阻組成物的研究，而研究結果如下列所揭露。例如，日本專利申請公開第2〇〇5_15693〇揭露一 20種彩色遽光片組成物，其為了提升感光度而使用一種新發產出的黏著劑；而曰本專利申請公開第2〇〇5_338328號揭露 -種黑色樹脂組成物，其藉由使用高感光聚合起始劑來提升感光度。再者，曰本專利申請公開第2〇〇4 347916號揭露一種黑色矩陣組成物，其透過使用光聚合起始劑與有機磷 6 1380058 化合物來提升感光度。其他的例子，如曰本專利公開申請第 2005-215378號、第 2005-227797號、第 2005-275218號、第 2000-227654號、第 1999-326606號、以及第 1999-143056 號，美國專利第5,866,298號，以及韓國專利申請公開第 5 2006_0〇76413號及第2002-0031093號皆揭露黑色矩陣之顯影製程。近年來’液晶顯示器（LCD)在平面顯示器的領域中扮演重大的角色。著重於小型及中型行動設備用顯示器或螢幕之LCD領域，已朝大尺寸顯示器或電視發展。隨著玻璃的 10 尺寸加大，必須確保高感光度以減少反應時間。既然因為螢幕尺寸的增加而必須提升亮度，則已經採用能提升亮度之背光光源。隨著背光光源的亮度提升，已經需要有黑色矩陣以提供相較於本技術領域中更佳優異的遮光特性。由於為了提升遮光特性，從而提高組成物中碳黑之含量，常 15 ^造成黑色組成物之製程限度劣化。由於碳黑能有效吸收 1外光以及可見光’因而難以於照射紫外光形成圖案時，傳送光線至阻臈的底端。因此，底端難以硬化，附著力劣化\且在顯影時會產生一部分光阻移除或下端凹陷而形成Τ 頂型圖案（T-t〇p-typed pattern)。此外，照射的能量會持續的減;>'以節省製程時間，因此難以形成穩固的圖案。因此，必須進行許多研究，以能改善黑色矩陣光阻組成物與基板之附著力、較廣泛的顯影製程限度、並改善光感度。 7 1380058 【發明内容】為了解決上述相關技術領域中之問題，本案發明人發現在製備液顯示器用之黑色矩陣光阻組成物期間藉由控制各成刀中具特定結構之黏著劑的酸值與不飽和雙鍵的 5比例，可於製備黑色矩陣的同時確保高感光度及廣泛之製程限度，且所得到的圖案具有極佳特性。本發明提供一種液晶顯示器用之黑色矩陣光阻組成物，其使用一具有特定結構之黏著劑，並控制黏著劑酸值與不飽和雙鍵比例；且本發明提供一種液晶顯示器用之黑 10色矩陣’其採用液晶顯示器用之黑色矩陣光阻組成物所製備而成。再者本發明提供一種液晶顯示器，其包含液晶顯示器用之黑色矩陣。為達成上述目的，本發明提供一種液晶顯示器用之黑1380058 IX. Description of the Invention: [Technical Field] The present invention relates to a black matrix photoresist composition for a liquid crystal display device and a black matrix prepared using the same. The invention relates in particular to a black matrix for a liquid crystal display, which can have high light sensitivity and can form a pattern stably with only a slight exposure amount while ensuring a wide process limit, thereby reducing process time and improving The output is guaranteed to have excellent light-shielding properties, making it easier to apply to large-size TVs that use brighter backlights. The priority of the present invention is Korean Patent Application No. 1〇2〇〇6_ΐ33555, filed on December 26, 2006, to the Korean Intellectual Property Office, and all of its contents are incorporated herein by reference. [Prior Art] 15 20 In general, a pattern is formed using a photoresist composition containing a pigment, which is liable to cause defects due to development or water washing, and if the pattern adhesion is promoted, dissolution of a non-% image portion (4) is deteriorated upon exposure and Easy to produce pollution. The density of the film is low and the light sensitivity is low, that is, the development limit is narrow when the pattern is formed by development. In order to increase the contrast, a color pixel called a color lattice (four) ray line is used. In the technique (4), chrome is used in the black matrix. In the production process, the 八却主主主 & & 积积积积积积积积积积积积积积积积积积积积积积积积积积积积积积积积积积积积积积积积积积积Environmental pollution caused by waste 5 water. Therefore, various parties have actively studied resin black matrices using pigment dispersion methods that can perform precision processes. The black matrix photoresist composition is prepared by using pigments of different colors or various pigments to have a black color. Since the photoresist composition is used to cover 5 rays, it contains a large amount of pigment which is not dissolved by the developing solution. Therefore, the black matrix resist composition has the following problems: poor developability, development for a long time, or failure to obtain the desired resolution. Therefore, in the preparation of the color filter cloth, each color including the black matrix must be improved in developability. Although a non-carbon black coloring pigment is used to prepare a black composition by a research method, the non-carbon black coloring pigment has poor light-shielding properties. Therefore, the 'black matrix photoresist composition must contain a coloring pigment having a high mixing ratio, which causes an increase in the viscosity of the composition, making the composition difficult to handle, or causing the strength of the formed film or the adhesion of the film to the substrate to be weakened. Therefore, many studies are required to develop a black 15 matrix photoresist composition for liquid crystal displays which has excellent color strength, hiding power, and insulation and developability. Here, such a black matrix photoresist composition has been studied. Therefore, there have been many studies on photoresist compositions, and the results of the research are disclosed below. For example, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. discloses a black resin composition which enhances sensitivity by using a highly photosensitive polymerization initiator. Further, a black matrix composition which enhances sensitivity by using a photopolymerization initiator and an organophosphorus 6 1380058 compound is disclosed in Japanese Laid-Open Patent Publication No. 2,347,916. Other examples are, for example, Japanese Patent Application No. 2005-215378, No. 2005-227797, No. 2005-275218, No. 2000-227654, No. 1999-326606, and No. 1999-143056, U.S. Patent No. A development process of a black matrix is disclosed in Japanese Patent Application Laid-Open No. Hei. No. Hei. No. 5, No. 5, No. In recent years, liquid crystal displays (LCDs) have played a major role in the field of flat panel displays. The LCD field, which focuses on displays or screens for small and medium-sized mobile devices, has evolved toward large-size displays or televisions. As the size of the glass 10 increases, high sensitivity must be ensured to reduce reaction time. Since the brightness must be increased because of the increase in screen size, a backlight source that can increase the brightness has been used. As the brightness of the backlight source increases, a black matrix has been required to provide better shading characteristics than in the art. In order to improve the light-shielding property and thereby increase the content of carbon black in the composition, the process limit of the black composition is often deteriorated. Since carbon black can effectively absorb 1 external light as well as visible light, it is difficult to transmit light to the bottom end of the barrier when it is difficult to form a pattern by irradiating ultraviolet light. Therefore, the bottom end is hard to be hardened, the adhesion is deteriorated, and a part of the photoresist is removed or the lower end is recessed to develop a T-t〇p-typed pattern. In addition, the energy of the illumination is continuously reduced; > to save process time, so it is difficult to form a stable pattern. Therefore, many studies must be conducted to improve the adhesion of the black matrix resist composition to the substrate, the wider development process limit, and the improvement of the light sensitivity. 7 1380058 SUMMARY OF THE INVENTION In order to solve the above problems in the related art, the inventors of the present invention have found that the acid value of an adhesive having a specific structure in each of the knives is controlled during the preparation of the black matrix photoresist composition for the liquid display. The 5 ratio of the unsaturated double bonds ensures high sensitivity and wide process limits while preparing the black matrix, and the resulting pattern has excellent characteristics. The present invention provides a black matrix photoresist composition for a liquid crystal display, which uses an adhesive having a specific structure and controls the ratio of the acid value of the adhesive to the unsaturated double bond; and the present invention provides a black color for a liquid crystal display. The matrix 'is prepared using a black matrix photoresist composition for liquid crystal displays. Still further, the present invention provides a liquid crystal display comprising a black matrix for a liquid crystal display. In order to achieve the above object, the present invention provides a black for a liquid crystal display.

色矩陣光阻組成物，在100重量份之黑色矩陣光阻組成物中，包括：1) .1至40重量份之一含黑色顏料之著色劑；2) i 至2〇重置份之一如下式i所示之鹼溶性樹脂黏著劑；i至〇重量份之一具有乙烯性不飽和雙鍵之多官能基單體；4) 1至20重量份之一光聚合起始劑；以及5) 30至90重量份之一溶劑； [式1] 1380058The color matrix photoresist composition comprises, in 100 parts by weight of the black matrix photoresist composition, 1: 1 to 40 parts by weight of a coloring agent containing a black pigment; 2) one of i to 2 〇 a replacement portion An alkali-soluble resin adhesive represented by the following formula i; i to a polyfunctional monomer having one ethylidene unsaturated double bond; 4) 1 to 20 parts by weight of one photopolymerization initiator; 30 to 90 parts by weight of one solvent; [Formula 1] 1380058

A B c DA B c D

(其中’ R1為氫、或一形成醯亞胺結構或與X—同形成五元環羧酸酐之自由基，如丁二醯亞胺（succinimide)或丁二酸酐（succinic anhydride)， 5 R2係選自由氫、甲基、以及經f基所組成之群組， R3及R4可彼此相同或不同且獨立為氫或甲基， X係選自由（：1至012之烷基酯、C2至C6之經1或2個羥基取代之烷基酯、C2至Ce之經（:丨至匕之烷氧基取代之烷基酯、（^至（：6之經鹵素取代之烷基酯、（^至（：3之烷氧聚（n=2 10 至30)亞烷、C2及C3之二醇酯、（^至（：6之經苯基取代之烷基酯、經(^至仏之烷基取代之苯基、經(^至(：6之烷氧基取代之苯基、經鹵素取代之苯基、（:丨至匕之烷氧基甲基基團、縮水甘油醚氡（glycidoxy)曱基基團、以及一形成醯亞胺結構或與R1—同形成五元環羧酸酐之自由基所組成之群組，如 15 順丁婦二醯亞胺（maleimide)或順丁稀二酸酐（maieic anhydride)， Y係選自由c〇至c12之亞烧基、及c3至C6〇之包含1至10 酯類基團亞烷基酯所組成之群組， 9 i 1380058 Z係選自由亞乙基、亞丙基、亞丁基、ι，2-亞苯基、^(wherein 'R1 is hydrogen, or a radical forming a quinone imine structure or forming a five-membered cyclic carboxylic anhydride with X-, such as succinimide or succinic anhydride, 5 R2 Selective hydrogen, methyl, and a group consisting of f groups, R3 and R4 may be the same or different from each other and independently hydrogen or methyl, and X is selected from (1 to 012 alkyl esters, C2 to C6) The alkyl ester substituted by 1 or 2 hydroxy groups, the alkyl ester substituted by C2 to Ce (: 丨 to alkoxy substituted alkyl), (^ to (: 6 halogen-substituted alkyl ester, (^ To (: 3 alkoxy poly(n = 2 10 to 30) alkylene, C2 and C3 glycol esters, (^ to (: 6 phenyl substituted alkyl ester, by (^ to decane a phenyl group substituted with a phenyl group, a phenyl group substituted with an alkoxy group, a phenyl group substituted with a halogen, an alkoxymethyl group substituted with fluorene, a glycidoxy group. a thiol group, and a group of free radicals forming a quinone imine structure or forming a five-membered cyclic carboxylic anhydride with R1, such as 15 cis-butaneimide or cis-succinic anhydride (maieic anhydride) Y is selected from the group consisting of a alkylene group of c〇 to c12, and an alkylene ester containing 1 to 10 ester groups of c3 to C6〇, and the 9 i 1380058 Z series is selected from the group consisting of ethylene and arylene. Propyl, butylene, ι, 2-phenylene, ^

〇〇

10 15 環亞己基、組成之群組（其中*表示連接部分），以及汪、1>、（^以及(1分別表示八、]3、（：、以及1)之莫耳數比，且巳的範圍為1〇至90、b的範圍為0至60、c的範圍為〇至4〇、而d的範圍為〇至4〇)。再者’本發明提供一種液晶顯示器用之黑色矩陣，其製備方法之步驟包含： 1) 於一面板上，塗覆本發明之液晶顯示器用之黑色矩陣光阻組成物；以及 2) 曝光及顯影此塗覆之黑色矩陣光組成物。另外，本發明提供一種液晶顯示器，其包含液晶顯示器用之黑色矩陣。本發明之液晶顯示器用之黑色矩陣之優點，在於有極佳的顯影性、遮光性、以及絕緣性，而無殘基生成且免因熱處理而有顯示缺陷產生。且避亦即在本發明中，當藉由控制具有特定結構的酸值與不飽和雙鍵比例製備黑色 θ Β „ ^ 平時則可能利用少里曝光達到高光密度進行圖案化步驟， /娜固而能形成且. 佳強度及膜特性之圖案》项-、有極以及所 10 20 1380058 接下來，透過本發明光阻組成物之示例來加以說明本發明。然而，應了解的是本發明所述之實施例並不用來限制本發明，而僅用來說明實施態樣。本發明之含黑色顏料之著色劑可為一碳黑及至少一著 5 色顏料之混合物。碳黑的例子包括：SEAST 5HIISAF-HS、SEAST KH、 SEAST 3HHAF-HS、SEAST NH、SEAST 3M、SEAST 300HAF-LS、SEAST 116HMMAF-HS、SEAST 116MAF、 SEAST FMFEF-HS、SEAST SOFEF、SEAST VGPF、SEAST l〇 SVHSRF-HS、以及 SEAST SSRF (由 Tokai Carbon Co.，Ltd. 賭得）；DIAGRAM BLACK II、DIAGRAM BLACK N339、 DIAGRAM BLACK SH、DIAGRAM BLACK H、DIAGRAM LH、DIAGRAM HA、DIAGRAM SF、DIAGRAM N550M、 DIAGRAM M、DIAGRAM E、DIAGRAM G、DIAGRAM R、 15 DIAGRAM N760M、DIAGRAM LR、#2700、#2600、#2400、 #2350、#2300、#2200、#1000、#980、#900、MCF88、#52、10 15 cyclohexylene group, group of constituents (where * represents the linking portion), and Wang, 1 >, (^ and (1 respectively represent eight, ] 3, (:, and 1) molar ratio, and 巳The range is from 1 〇 to 90, the range of b is from 0 to 60, the range of c is from 〇 to 4 〇, and the range of d is from 〇 to 4 〇. Further, the present invention provides a black matrix for a liquid crystal display. The steps of the preparation method include: 1) coating a black matrix photoresist composition for a liquid crystal display of the present invention on one side plate; and 2) exposing and developing the coated black matrix light composition. Further, the present invention provides a liquid crystal display comprising a black matrix for a liquid crystal display. The black matrix for a liquid crystal display of the present invention is advantageous in that it has excellent developability, light-shielding property, and insulating property without residue generation and display defects due to heat treatment. And avoiding that in the present invention, when the black θ Β ^ ^ is prepared by controlling the ratio of the acid value to the unsaturated double bond having a specific structure, it is possible to use the low-intensity exposure to achieve a high optical density for the patterning step, Patterns that can be formed and have good strength and film properties. Item-, Polar and 10 20 1380058 Next, the present invention will be described by way of an example of the photoresist composition of the present invention. However, it should be understood that the present invention The examples are not intended to limit the invention, but are merely illustrative of the embodiment. The black pigment-containing coloring agent of the present invention may be a mixture of carbon black and at least one color pigment. Examples of carbon black include: SEAST 5HIISAF-HS, SEAST KH, SEAST 3HHAF-HS, SEAST NH, SEAST 3M, SEAST 300HAF-LS, SEAST 116HMMAF-HS, SEAST 116MAF, SEAST FMFEF-HS, SEAST SOFEF, SEAST VGPF, SEAST l〇SVHSRF-HS, and SEAST SSRF (taken by Tokai Carbon Co., Ltd.); DIAGRAM BLACK II, DIAGRAM BLACK N339, DIAGRAM BLACK SH, DIAGRAM BLACK H, DIAGRAM LH, DIAGRAM HA, DIAGRAM SF, DIAGRAM N550M, DIA GRAM M, DIAGRAM E, DIAGRAM G, DIAGRAM R, 15 DIAGRAM N760M, DIAGRAM LR, #2700, #2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52 ,

#50 ' #47 ' #45 ' #45L ' #25 ' #CF9 ' #95 ' #3030 ' #3050 ' MA7、MA77、MA8、MA11、OIL7B、OIL9B、OIL11B、 OIL30B、以及 OIL31B (由 Mitsubishi Chemical Corporation 20 購得）；PRINTEX-U、PRINTEX-V、PRINTEX-140U、 PRINTEX-140V 、 PRINTEX-95 、 PRINTEX-85 、 PRINTEX-75、PRINTEX-55、PRINTEX-45、PRINTEX-300、 PRINTEX-35、PRINTEX-25、PRINTEX-200、PRINTEX-40、#50 ' #47 ' #45 ' #45L ' #25 ' #CF9 ' #95 ' #3030 ' #3050 ' MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B (by Mitsubishi Chemical Corporation 20 purchased); PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX -25, PRINTEX-200, PRINTEX-40,

PRINTEX-30 、 PRINTEX-3 、 PRINTEX-A 、 SPECIAL π 1380058 5PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL π 1380058 5

BLACK-550 、 SPECIAL BLACK-350 、 SPECIAL BLACK-250、SPECIAL BLACK-100 、以及 LAMP BLACK-101 (由 Degussa Japan Company 購得）；以及 RAVEN-1100ULTRA 、 RAVEN-1080ULTRA 、 RAVEN-1O60ULTRA、RAVEN-1040、RAVEN-1035、 RAVEN-1020、RAVEN-1000、RAVEN- 890H、RAVEN-890、 RAVEN-880ULTRA、RAVEN-860ULTRA、RAVEN-850、 RAVEN-820、RAVEN_790ULTRA、RAVEN-780ULTRA、 RAVEN-760ULTRA 、 RAVEN-520 、 RAVEN-500 、 l〇 RAVEN-460 、 RAVEN-450 、 RAVEN-430ULTRA 、 RAVEN-420 、 RAVEN-410 、 RAVEN-2500ULTRA 、 RAVEN-2000、RAVEN-1500、RAVEN-1255、RAVEN-1250、 15BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101 (available from Degussa Japan Company); and RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1O60ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820, RAVEN_790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, l〇RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, 15

2020

RAVEN-1200、RAVEN-1190ULTRA、以及RAVEN-1170 (由 Columbia Carbon Co.購得）。可與碳黑混合之著色顏料包含：寶紅（Carmine 6B，C.I. 12490) ' 敗菁綠（Phthalo cyanine Green, C.I. 74260)、敌菁藍 (Phthalocyanine Blue, C.I. 74160) 三菱碳黑 MA100(Mitsubishi Carbon Black MA100)、花黑（Perylene Black，BASF K0084及 K0086)、青藍黑（Cyanine Black)、雷奥諾爾黃（Lionol Yellow, C.I. 21090)、雷奥諾爾黃 GRO(Lionol Yellow GRO, C.I.21090)、聯苯胺黃 4T-564D(Benzidine Yellow 4T-564D)、三菱碳黑 MA-40(Mitsubishi Carbon Black MA-40)、維多利亞魅藍 (Victoria Pure Blue, C.I. 42595)、C.I.顏料紅（PIGMENT 12 1380058 RED)97, 122，149，168，177，180，192，215 ; C.I.顏料綠 (Pigment Green)7, 36 ; C.I.顏料（PIGMENT)15:1，15:4, 15:6, 22，60，64;(：.1.顏料（？1〇]^^^)83，139;以及(：.1.顏料紫 (PIGMENT VIOLET)23。此外，可使用白色顏料以及螢光顏 5 料。再者，著色顏料可由一種或以上之著色顏料混合而得到黑色。RAVEN-1200, RAVEN-1190 ULTRA, and RAVEN-1170 (available from Columbia Carbon Co.). The color pigments that can be mixed with carbon black include: Carmine 6B (CI 12490) 'Phthalo cyanine Green (CI 74260), Phthalocyanine Blue (CI 74160) Mitsubishi Carbon Black MA100 (Mitsubishi Carbon Black) MA100), Perylene Black (BASF K0084 and K0086), Cyanine Black, Lionol Yellow (CI 21090), Leonol Yellow GRO (CI21090), Lian Benzidine Yellow 4T-564D, Mitsubishi Carbon Black MA-40, Victoria Pure Blue (CI 42595), CI Pigment Red (PIGMENT 12 1380058 RED) 97 , 122, 149, 168, 177, 180, 192, 215; CI Pigment Green 7, 36; CI Pigment (PIGMENT) 15: 1, 15: 4, 15: 6, 22, 60, 64; :.1. Pigment (?1〇]^^^) 83,139; and (:.1. PIGMENT VIOLET 23. In addition, white pigments and fluorescent pigments can be used. Further, coloring pigments Black can be obtained by mixing one or more coloring pigments.

1010

本發明之如式1所示之鹼溶性樹脂黏著劑可包含下列之單體。用以形成A部分之單體例子可包含選自由下列其中至少一者：不飽和碳酸自旨類（unsaturated carboxylic acid esters)，如曱基丙稀酸苯醋（benzyl (meth)acrylate)、曱基丙稀酸曱酉旨（methyl(meth)acrylate)、曱基丙烯酸乙醋 (ethyl(meth)acrylate) ' 曱基丙烯酸丁醋(butyl (meth)acrylate)、曱基丙稀酸二甲基胺基乙醋 (dimethyl amino ethyl(meth)acry late) ' 曱基丙稀酸異丁 S 旨 (isobutyl(meth)acrylate)、曱基丙稀酸第三丁醋 (t-butyl(meth) aery late)、甲基丙烯酸環己西旨 (cyclohexyl(meth)acrylate)、曱基丙烯酸異冰片酯 (is obornyl(meth) aery late)、曱基丙稀酸乙基己 S旨 (ethylhexyl(meth)acrylate)、曱基丙烯酸（2-苯氧乙基）酯 (2-phenoxyethyl(meth)acrylate)、甲基丙稀酸四氫0夫喃基酯 (tetrahydrofurfuryl (meth)acrylate)、甲基丙稀酸經乙 δ旨 (hydroxyethyl(meth)acrylate)、甲基丙稀酸（2-經丙基）醋 (2-hydroxypropyl(meth)acrylate)、甲基丙婦酸（2-經基-3-氯丙基）酉旨（2-hydroxy-3-chloropropyl(meth)acrylate)、曱基丙 13 1380058 5The alkali-soluble resin adhesive of the present invention as shown in Formula 1 may contain the following monomers. Examples of the monomer used to form the A moiety may comprise at least one selected from the group consisting of unsaturated unsaturated carboxylic acid esters, such as benzyl (meth)acrylate, sulfhydryl Methyl (meth)acrylate, ethyl(meth)acrylate 'butyl (meth)acrylate, mercapto dimethyl amide Dimethyl amino ethyl (meth) acry late) 'isobutyl (meth) acrylate, t-butyl (meth) aery late, Cyclohexyl (meth) acrylate, is obornyl (meth) aery late, ethylhexyl (meth) acrylate, hydrazine 2-phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, methyl acrylate (hydroxyethyl(meth)acrylate), 2-hydroxypropyl(meth)acrylate, methyl acetoacetate (2- -3-chloro-propyl) unitary purpose (2-hydroxy-3-chloropropyl (meth) acrylate), Yue propionic 1313800585

稀酸（4·經丁基）S旨（4-hydroxybutyl(meth)acrylate)、甲基丙烤酸（酿基辛氧基-2-經基丙基）g旨（acyloctyloxy-2-hydroxypropyl(meth)acrylate) ' 甲基丙稀駿甘油謎酯 (glycerol(meth)acrylate) '甲基丙稀酸（2-甲氧基乙基）酯 (2-methoxyethyl(meth)acrylate)、甲基丙烯酸（3-甲氧基丁基）醋（3-methoxybutyl(meth)acrylate)、甲基丙稀酸乙氧基二乙二醇醋（ethoxydiethylene glycol(meth)acrylate)、甲基丙稀酸甲氧基三乙二醇醋（methoxytriethyleneglycol(meth)-acrylate)、申基丙浠酸甲氧基三丙二醇醋 10 15Diacid (4. butyl) S (4-hydroxybutyl (meth) acrylate), methyl propyl benzoic acid (branched octyloxy-2- propyl propyl) g (acyloctyloxy-2-hydroxypropyl (meth) Acrylate) 'glycerol(meth)acrylate' 2-methoxyethyl(meth)acrylate, methacrylic acid (3) 3-methoxybutyl(meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methacrylic acid methoxy triethyl Methoxytriethyleneglycol (meth)-acrylate, methicillin methoxy tripropylene glycol vinegar 10 15

20 (methoxy-tripropyleneglycol(meth)acrylate)、甲基丙烯酸聚 (乙二醇）甲謎醋（poly(ethyleneglycol)methylether (meth)acrylate)、甲基丙烯酸苯氧基二乙二醇酯 (phenoxydiethyleneglycol(meth)acrylate)、甲基丙稀酸（對-壬基苯氧基聚乙二醇）酯 (p-nonylphenoxypolyethyleneglycol(meth)acrylate)、曱基丙烯酸（對-壬基苯氧基聚丙二醇）酯 (p-nonylphenoxypolypropylene glycol(meth)acrylate) ' 甲基丙婦酸縮水甘油S旨（glycidyl(meth)acrylate)、曱基丙婦酸四氟丙醋（tetrafluoropropyl (meth)acrylate)、甲基丙稀酸 (1,1,1,3,3,3- 六氟異丙基）酯 (l，l，l，3,3,3-hexafluoroisopropyl(meth)acrylate)、曱基丙豨酸八氟戊醋（octafluoropentyl(meth)acrylate)、曱基丙稀酸十七氟葵醋（heptadecafluorodecyl(meth)acrylate)、曱基丙稀酸三漠苯醋（tribromophenyl(meth)acrylate)、甲基丙烤酸二環 14 1380058 戊酿（dicyclopentanylmethacrylate)、曱基丙稀酸二環戍稀醋 (dicyclopentenyl methacrylate)、丙稀酸二環戊稀氧基乙醋 (dicyclopentenyloxy ethyl aery late) ' 甲基丙婦酸異冰片醋 (isobornylmethacrylate)、甲基乙烯酸金剛烧醋 (adamantylmethacrylate)、丙稀酸（曱基-α_經基曱基）醋 (methyl α-hydroxymethylacrylate)、丙稀酸（乙基-α-經基甲基）酯（ethyl α-hydroxymethylacrylate)、丙稀酸（丙基-α•經基甲20 (methoxy-tripropyleneglycol (meth)acrylate), poly(ethyleneglycol)methylether (meth)acrylate, phenoxydiethyleneglycol (meth) Acrylate), p-nonylphenoxypolyethylene glycol (meth)acrylate, methacrylic acid (p-nonylphenoxypolypropylene glycol) ester (p) -nonylphenoxypolypropylene glycol(meth)acrylate) 'glycidyl(meth)acrylate, tetrafluoropropyl (meth)acrylate, methyl acrylate (1) 1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, octafluoropentyl (octafluoropentyl) Meth)acrylate, heptadecafluorodecyl(meth)acrylate, tribromophenyl(meth)acrylate, methyl propyl acetonate 14 1380058 pent Dicyclopentanylmethacrylate, thioglycolic acid dicyclopenten Yl methacrylate), dicyclopentenyloxy ethyl aery late 'isobornylmethacrylate', methacrylate adamantylmethacrylate, acrylic acid Methyl-α-hydroxymethylacrylate, ethyl α-hydroxymethylacrylate, acrylic acid (propyl-α•transcarbyl) A

基）自旨（propyl α-hydroxymethylacrylate)、以及丙歸酸（丁基 -α-經基甲基）S旨（butyl α-hydroxymethylacrylate);芳香族乙 ίο 稀類（aromatic vinyls)，如苯乙烯（styrene)、α-甲基笨乙稀 (α-methylstyrene)、（鄰，間，對）-乙稀基曱苯 ((o，m，p)-vinyltoluene)、（鄰，間，對）-甲氧基笨乙烯 ((o，m，p)-methoxystyrene)、以及（鄰，間，對）-氣笨乙烯 15Propyl α-hydroxymethylacrylate, and butyl α-hydroxymethylacrylate; aromatic vinyls, such as styrene ( Styrene), α-methylstyrene, (o, m, p), ethenyl ((o, m, p)-vinyltoluene), (o, m, p) Oxystyrene ((o, m, p)-methoxystyrene), and (o, m, p) - gas stupid ethylene 15

((o，m，p)-chlorostyrene);不飽和謎類（unsaturated ethers)，如乙烯基甲趟（vinyl methy lether)、乙稀基乙趟（vinyl ethyl ether)、以及丙稀基縮水甘油醚（allyl glycidyl ether);不飽和酿亞胺類（unsaturated imides) ’如N-苯基順丁稀二醢亞胺 (N-phenylmaleimide)、N-(4-氣苯基）順丁稀二酿亞胺 (N-(4-chlorophenyl)maleimide)、N-(4-經苯基）順丁稀二醯亞 20 胺（N-(4-hydroxyphenyl)maleimide)、以及 N-環己基順丁稀二醯亞胺（N-cyclohexylmaleimide);以及順丁烯二酐類（maleic anhydrides)，如順丁稀二酐（maleic anhydride)以及曱基順丁. 稀二酐（methyl maleic anhydride)。然而，本發明並不只限於此。 15 1380058 用以形成如式1所示之B部分之單體可包含選自由甲基丙稀酸（(meth)acrylic acid)、丁稀酸（crotonic acid)、亞甲基丁二酸（itaconic acid)、順丁稀二酸（maleic acid)、反丁稀二酸（fumaric acid)、單甲基順丁稀二酸（monomethyl maleic 5 acid)、5-降冰片烤-2-碳酸（5-norbornene-2-carboxylic acid)、單-2-(甲基丙烯醯氧基）乙基鄰苯二甲酸酯 (mono-2-((meth)acryloyloxy)ethyl phthalate)、單-2-(曱基丙稀醯氧棊）乙基丁二酸 δ 旨（mono-2-((meth)acryloyloxy)ethyl succinate)、以及ω-叛基聚己内醋單甲基丙稀酸醋 10 (ω-carboxy polycaprolactone mono(meth)acrylate)戶斤組成之群組之其中一者。然而，本發明並不只限於此。式1之C部分的製程如下所述。將一形成A部分之單體與一形成B部分之單體進行聚合，以製備由A部分與B部分所組成之聚合物，而C部分則由聚合物之B部分衍伸而成。 15 至於將C部分導入於由A部分與B部分所組成之聚合物的方法，可採用將一聚合物B部分之酸性自由基、以及一曱基丙烯酸縮水甘油酯之環氧自由基，進行一開環縮合反應。進行此縮合反應的方法可採用熟知本技術領域者已知之方法。 20 再者，於式1中，D部分是從由A、B、以及C部分所組成之聚合物之C部分衍伸而成。至於將D部分導入於由A、 B、以及C所组成之聚合物之方法，可採用將C部分之羥基與碳酸if (carboxylic anhydride)，進行一開環縮合反應。具' 體而言，可使用在導入D部分之酸酐的例子包括：丁二酸酐 16 1380058 (succinic anhydride)、戊二酸針（glutaric anhydride)、己二酸酐（adipic anhydride)、鄰苯二甲針（phthalic anhydride)、六氫苯 gf(hexahydrophthalic anhydride)、順式-1，2,3,6-四氫苯 Sf (cis-l，2,3,6-tetrahydrophthalic anhydride)、3,4,5,6-四氫苯 5 奸（3,4,5,6-tetrahydrophthalic anhydride)、伊康酸針（itaconic anhydride)、三聚酐（trimellic anhydride)、以及順式-5-降冰片稀-2,3-二碳酸 Sf (cis-5-norbornene-endo-2,3-dicarboxylic anhydride) 〇然而，本發明並不只限於此。於本發明之如式1所示之鹼溶性樹脂黏著劑中，當d的 10 範圍為0至小於5時，b的範圍為5至60，且當d的範圍為5至 40時，b的範圍為0至10。再者，如式1所示之驗溶性樹脂黏著劑之酸值與不飽和雙鍵當量如下所述。於4的範圍為0至小於5時，較佳為鹼溶性樹脂黏著劑之酸值範圍大約50至150 KOH mg/g，而不飽 15 和雙鍵當量範圍為1000至2500，且（酸值xlO)與不飽和雙鍵當量之總和範圍為1500至4000。於d的範圍為5至40時，較佳為鹼溶性樹脂黏著劑之酸值範圍大約20至80 KOH mg/g，而不飽和雙鍵當量範圍為400至1000，且（酸值xlO) 與不飽和雙鍵當量之總和範圍為5 00至15 00 »在此，不飽和 20 雙鍵當量可如下面方程式1所示。 [方程式1] 雙鍵當量=(重複單元之分子量）/(重複單元之雙鍵數）假設驗溶性樹脂黏著劑之酸值為P(KOH mg/g)，而雙鍵當量為Q，當d的範圍為0至小於5時則符合50<P<150、 17 1380058 1〇〇〇<Q<2500、以及 1500<(10xP)+Q<4000之條件，而於d的範圍為5至40時則符合20<P<80、400<Q<l〇〇〇、以及500<(10 xP)+Q<15〇〇之條件，如此便可達到高感光度及高光密度。當驗溶性樹脂黏著劑之酸值為150或以上，且（酸值χ10) 5與不飽和雙鍵當量之總和小於1500(其中d的範圍為〇至小於5) ’則酸值太高而因此顯影限度範圍較窄。再者，所得到的圖案會具有過多的雙鍵而真直度（straightness)較差，會導致所得到的圖案不能用來作為黑色矩陣。當（酸值χ1〇)與不飽矛又鍵S里之總和為4〇〇〇或以上，由於較差的感光 ίο度，故需要較大量照射已形成圖案。此外，當酸值為5〇或以下，無法確實的進行顯影，而難以取得圖案。而且，會造成顯影時間的加長與製程特性的劣化。當d的範圍為5至40，可用鹼性顯影溶液顯影之羧酸基團不在主鍵上，反而突出在支鏈。因此，即使酸值很小，顯影性仍然良好。當酸值為8〇或以上，容易有過度顯影的情形發生，圖案可能會輕易刪除，而難以達到高感光度之目的》鹼溶性樹脂黏著劑之重量平均分子量之較佳範圍為 1000至200000，且更佳範圍為5〇〇〇至1〇〇〇〇〇。 20 鹼溶性樹脂黏著劑可獨立的使用。然而，較佳為兩種或以上之鹼溶性樹脂黏著劑混合使用。鹼溶性樹脂黏著劑的含量範圍較佳係佔光阻組成物總重量之i至25重量份。當鹼溶性樹脂組成物的含量少於丨重量份，形成的薄膜黏著: 1380058 5((o,m,p)-chlorostyrene); unsaturated ethers, such as vinyl methy lether, vinyl ethyl ether, and propylene glycidyl ether (allyl glycidyl ether); unsaturated iamidates such as N-phenylmaleimide, N-(4-phenylphenyl) cis-butadiene N-(4-chlorophenyl)maleimide, N-(4-phenylphenyl)-N-(4-hydroxyphenyl)maleimide, and N-cyclohexyl-cis-butane dioxime N-cyclohexylmaleimide; and maleic anhydrides such as maleic anhydride and methyl maleic anhydride. However, the invention is not limited to this. 15 1380058 The monomer used to form Part B as shown in Formula 1 may comprise a solvent selected from the group consisting of (meth)acrylic acid, crotonic acid, and itaconic acid. ), maleic acid, fumaric acid, monomethyl maleic 5 acid, 5-norbornne-2-carbonate -2-carboxylic acid), mono-2-((meth)acryloyloxy)ethyl phthalate, mono-2-(mercaptopropyl propylate)醯-醯丁乙基乙基 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( (meth)acrylate) One of the groups consisting of households. However, the invention is not limited to this. The process of Part C of Formula 1 is as follows. A monomer forming Part A is polymerized with a monomer forming Part B to prepare a polymer composed of Part A and Part B, and Part C is derived from Part B of the polymer. 15 As a method of introducing the C moiety into the polymer composed of the A portion and the B portion, an acidic radical of a polymer B portion and an epoxy radical of glycidyl methacrylate may be used. Ring-opening condensation reaction. The method of carrying out this condensation reaction can be carried out by a method known to those skilled in the art. Further, in the formula 1, the D portion is derived from the C portion of the polymer composed of the A, B, and C portions. As a method of introducing the D moiety into a polymer composed of A, B, and C, a ring-opening condensation reaction can be carried out by using a hydroxyl group of the C moiety and a carboxylic anhydride. Examples of the anhydride which can be used in the introduction of Part D include: succinic anhydride 16 succinic anhydride, glutaric anhydride, adipic anhydride, phthalate needle (phthalic anhydride), hexahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 3,4,5, 3,4,5,6-tetrahydrophthalic anhydride, itaconic anhydride, trimelic anhydride, and cis-5-norbornazole-2,3 - cis-5-norbornene-endo-2,3-dicarboxylic anhydride However, the present invention is not limited thereto. In the alkali-soluble resin adhesive of the present invention as shown in Formula 1, when the range of d of 10 is from 0 to less than 5, b ranges from 5 to 60, and when d ranges from 5 to 40, b The range is from 0 to 10. Further, the acid value and the unsaturated double bond equivalent of the test resin adhesive as shown in Formula 1 are as follows. When the range of 4 is from 0 to less than 5, it is preferred that the alkali-soluble resin adhesive has an acid value ranging from about 50 to 150 KOH mg/g, the unsaturated 15 and the double bond equivalent are in the range of from 1,000 to 2,500, and (acid value) The sum of the xlO) and unsaturated double bond equivalents ranges from 1500 to 4,000. When the range of d is from 5 to 40, it is preferred that the alkali-soluble resin adhesive has an acid value ranging from about 20 to 80 KOH mg/g, and the unsaturated double bond equivalent is in the range of from 400 to 1,000, and (acid value xlO) and The sum of the unsaturated double bond equivalents ranges from 500 to 15 00 » Here, the unsaturated 20 double bond equivalent can be as shown in Equation 1 below. [Equation 1] Double bond equivalent = (molecular weight of repeating unit) / (number of double bonds of repeating unit) Assuming that the acid value of the solvent-soluble resin adhesive is P (KOH mg/g), and the double bond equivalent is Q, when d The range of 0 to less than 5 is in accordance with the conditions of 50 < P < 150, 17 1380058 1 〇〇〇 < Q < 2500, and 1500 < (10xP) + Q < 4000, and the range of d is 5 to 40 The condition is 20 < P < 80, 400 < Q < l 〇〇〇 , and 500 < (10 x P) + Q < 15 ,, so that high sensitivity and high optical density can be achieved. When the acid value of the test-soluble resin adhesive is 150 or more, and the sum of the (acid value χ10) 5 and the unsaturated double bond equivalent is less than 1500 (wherein the range of d is 〇 to less than 5), the acid value is too high The development limit range is narrow. Furthermore, the resulting pattern will have too many double bonds and poor straightness, which will result in the resulting pattern not being used as a black matrix. When the sum of (acid value χ1〇) and the insufficient spear and key S is 4 〇〇〇 or more, a relatively large amount of illuminating pattern is required due to poor sensitivities. Further, when the acid value is 5 Å or less, development cannot be performed surely, and it is difficult to obtain a pattern. Moreover, the development time is lengthened and the process characteristics are deteriorated. When d is in the range of 5 to 40, the carboxylic acid group developed by the alkaline developing solution is not on the primary bond but instead protrudes in the branch. Therefore, even if the acid value is small, the developability is still good. When the acid value is 8 Å or more, it is easy to have excessive development, the pattern may be easily deleted, and it is difficult to achieve high sensitivity. The weight average molecular weight of the alkali-soluble resin adhesive is preferably in the range of 1,000 to 200,000. A better range is 5 to 1 inch. 20 Alkali-soluble resin adhesives can be used independently. However, it is preferred to use two or more alkali-soluble resin adhesives in combination. The content of the alkali-soluble resin adhesive is preferably in the range of from i to 25 parts by weight based on the total weight of the photoresist composition. When the content of the alkali-soluble resin composition is less than 丨 by weight, the formed film adheres: 1380058 5

10 1510 15

20 較低，且當其含量超過25重量份，形成圖像之強度與感光度較低。本發明之具有乙烯性不飽和雙鍵之多官能基單體可使用具有至少一不飽和自由基之化合物，其中此不飽和自由基能額外與沸點1〇〇°C或以上之單體、或為一導入有己内酯之官能基單體進行聚合。此具有至少一不飽和自由基之化合物，其中此不飽和自由基能額外與沸點100°C或以上之單體進行聚合，且該化合物可為：單一宫能基單體，如聚6二醇單官能基甲基丙稀酸醋（polyethylene glycolmono(meth)acrylate)、聚丙二醇單官能基甲基丙稀酸甲酯（polypropylene glycol mono(meth)acrylate)、或曱基丙稀酸苯氧乙醋 (phenoxyethyl(meth)acrylate);以及一多官能基單體，如聚乙二醇曱基丙稀酸 g 旨（polyethylene glycol(meth)acrylate)、聚丙二醇甲基丙烯酸酯（polypropylene glycol(meth)acryatle)、三經甲基乙烧三丙稀酸醋 (trimethylol ethane triacrylate)、三經甲基丙烧三丙稀酸醋 (trimethylol propane triacrylate)、新戊基乙二醇甲基丙稀酸醋（neopentyl glycol (meth)acrylate)、新戊四醇四丙烯酸醋 (pentaerythritol tetraacrylate)、新戍四醇三丙稀酸醋 (pentaerythritol triacrylate)、二新戊四醇五丙烯酸酉旨 (dipentaerythritol pentaacrylate)、或二新戊四醇六丙稀酸醋 (dipentaerythritol hexaacrylate) ° 19 1380058 再者，導入有己内酯之多官能基單體可為導入有二新戊四醇之KAYARAD DPCA-20, 30, 60, 120、導入有新戊四醇丙烯酸酯之KAYARAD TC-110S、或導入有羥基特戊酸新戊二醇醋（neopentylglycol hydroxypivalate)之 KAYARAD 5 HX-220及KAYARADHK-620。除上述之例子外，多官能基單體還可為雙酚A (bisphenol A)衍伸物之環氧丙烯酸 (epoxyacrylate)、驗搭環氧丙烤酸（novolac-epoxyacrylate)、及以胺甲酸乙酯（urethane)為主之多官能基丙烯酸酯之 U-324A ' U15HA、與U-4HA » 10 具乙烯性不飽和雙鍵之多官能基單體可為一單體或至少兩種單體之混合物。具乙烯性不飽和雙鍵之多官能基單體之含量較佳範圍為佔光阻組成物總重量之1至20重量份（佔固態樹脂組成物之5至50重量份）。當多官能基單體之含量少於1重量份，塗 15 膜之光感度或強度會降低。當其含量超過20重量份，光感樹脂層之附著力會過強，而導致在顯影的過程中塗膜強度不足且圖案消失等問題。本發明之光聚合起始劑是一種能透過光產生自由基且開始交聯反應之材料，且較佳是由一種或以上之下列化合 20 物混合而得，而這些化合物是選自由苯乙嗣（acetophenone ) 化合物、二咪峻（biimidazole)化合物、三c^(triazine)化合物、以及將類（oxime)化合物所組成之群組。可使用作為光聚合起始劑之苯乙酮化合物之例子包括 . 2 - 經基 -2 - 甲基 -1 - 本丙 -1 - 鋼 20 138005820 is lower, and when it exceeds 25 parts by weight, the intensity and sensitivity of image formation are low. The polyfunctional monomer having an ethylenically unsaturated double bond of the present invention may use a compound having at least one unsaturated radical, wherein the unsaturated radical can additionally be a monomer having a boiling point of 1 ° C or more, or The polymerization is carried out for a functional group monomer having a caprolactone introduced therein. The compound having at least one unsaturated radical, wherein the unsaturated radical can additionally be polymerized with a monomer having a boiling point of 100 ° C or higher, and the compound can be: a single uterine monomer, such as poly 6 diol Polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, or mercaptopropionic acid phenoxyacetate (phenoxyethyl(meth)acrylate); and a polyfunctional monomer such as polyethylene glycol (meth)acrylate, polypropylene glycol (meth) acryatle ), trimethylol ethane triacrylate, trimethylol propane triacrylate, neopentyl glycol methyl acrylate vinegar (neopentyl) Glycol (meth)acrylate), pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol pentidine (dipentaerythritol pe) Ntaacrylate), or dipentaerythritol hexaacrylate ° 19 1380058 Furthermore, the polyfunctional monomer introduced with caprolactone may be KAYARAD DPCA-20, 30 with dipentaerythritol introduced. , 60, 120, KAYARAD TC-110S introduced with pentaerythritol acrylate, or KAYARAD 5 HX-220 and KAYARADHK-620 introduced with neopentyllglycol hydroxypivalate. In addition to the above examples, the polyfunctional monomer may also be an epoxy acrylate of a bisphenol A derivative, a novolac-epoxyacrylate, and a urethane formic acid. U-324A ' U15HA, which is a urethane-based polyfunctional acrylate, and a polyfunctional monomer having an ethylenically unsaturated double bond with U-4HA » 10 may be a monomer or at least two monomers. mixture. The content of the polyfunctional monomer having an ethylenically unsaturated double bond is preferably in the range of 1 to 20 parts by weight based on the total weight of the photoresist composition (from 5 to 50 parts by weight based on the solid resin composition). When the content of the polyfunctional monomer is less than 1 part by weight, the light sensitivity or strength of the coating film may be lowered. When the content exceeds 20 parts by weight, the adhesion of the photosensitive resin layer may be too strong, resulting in problems such as insufficient coating strength and disappearance of the pattern during development. The photopolymerization initiator of the present invention is a material which is capable of generating a radical by light and starts a crosslinking reaction, and is preferably obtained by mixing one or more of the following compounds 20 selected from phenethyl hydrazine. (acetophenone) A compound, a biimidazole compound, a triazine compound, and a group of oxime compounds. Examples of acetophenone compounds which can be used as photopolymerization initiators include: 2 - mercapto -2 - methyl -1 - propenyl -1 - steel 20 1380058

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20 (2-hydroxy-2-methyl-l-phenylpropan-l-on) ' 1-(4-異丙基苯基）_2_ 羥基 -2- 曱基丙 -1- 酮 (l-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-l-on) 、 4-(2-羥基乙氧基）-苯基-(2-羥基-2-丙基）酮 (4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)ketone) 、1-經基環己基苯基_ (1-hydroxycyclohexylphenyl ketone)、苯甲酸曱基趟（benzoin methyl ether)、苯甲酸乙基 S|(benzoin ethyl ether)、苯甲酸異丁基醚（benzoin isobuthyl ether)、苯甲酸丁基醚（benzoin butyl ether)、2,2-二甲氧基-2-苯基苯乙鋼（2,2-dimethoxy-2-phenylacetophenone)、2-甲基 -(4-甲硫基）苯基-2-嗎啉基-1-丙-1-酮 (2-methyl-(4-methylthio)phenyl-2-morpholino-l-propan-1-〇 η)、2-苯基-2-二甲基胺基-1-(4-嗎啉基苯基）-丁：1-酮 (2-benzyl-2-dimethylamino-l-(4-morpholinophenyl)-butan-l-on)、2-(4-溴-苯基-2-二曱基胺基，1-(4-嗎啉基苯基）-丁-1-酮 (2-(4-bro mo-benzyl-2-dimethyl amino-l-(4-morpholinopheny l)-butan-l-on)、以及2-甲基-l-[4-(甲硫基）苯基]-2-嗎啉基丙 -1- 酮（2-methyl-l-[4-(methylthio)phenyl]-2- morpholinopropane-1-on)0 二口米0坐化合物的例子包括：2,2-雙（2- 氣苯基）-4,4',5,5'-四苯基二咪唑 (2,2-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl biimidazole)、2,2’-雙（鄰-氯苯基）-4,4|，5,5'·四（3,4,5-三曱氧基苯基）-1，2'- :^^(2,2'-bis(o-chlorophenyl)-4,4’，5,5'-tetrakis(3,4,5-trimethoxyphenyl)-l，2'-biimidazole)、2,2’-雙 (2,3- 二氯苯基）-4,4’，5,5·-四苯基二咪唆 21 25 1380058 520 (2-hydroxy-2-methyl-l-phenylpropan-l-on) ' 1-(4-isopropylphenyl)_2_hydroxy-2-indolyl-1-one (1-(4-isopropylphenyl) -2-hydroxy-2-methylpropan-l-on), 4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)one (4-(2-hydroxyethoxy)-phenyl- (2-hydroxy-2-propyl)ketone), 1-hydroxycyclohexylphenyl ketone, benzoin methyl ether, benzoin ethyl ether , benzoin isobuthyl ether, benzoin butyl ether, 2,2-dimethoxy-2-phenylacetophenone , 2-methyl-(4-methylthio)phenyl-2-morpholinyl-1-propan-1-one (2-methyl-(4-methylthio)phenyl-2-morpholino-l-propan- 1-〇η), 2-phenyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one (2-benzyl-2-dimethylamino-l-(4- Morpholinophenyl)-butan-l-on), 2-(4-bromo-phenyl-2-didecylamino, 1-(4-morpholinylphenyl)-butan-1-one (2-(4) -bro mo-benzyl-2-dimethyl amino-l-(4-morpholinopheny l)-butan-l-on), and 2- Methyl-l-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one (2-methyl-l-[4-(methylthio)phenyl]-2- morpholinopropane-1-on ) 0 Examples of two-seat rice-based compounds include: 2,2-bis(2-phenylphenyl)-4,4',5,5'-tetraphenyldiimidazole (2,2-bis(2-chlorophenyl) )-4,4',5,5'-tetraphenyl biimidazole), 2,2'-bis(o-chlorophenyl)-4,4|,5,5'·tetra (3,4,5-triterpene) Oxyphenyl)-1,2'- :^^(2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(3,4,5-trimethoxyphenyl)-l, 2'-biimidazole), 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5-tetraphenyldiimene 21 25 1380058 5

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20 (2,2'-bis(2,3-dichlorophenyl)-4,4,,5,5,-tetraphenyl biimidazole)、以及2,2·-雙（對-氯苯基）-4,4，,5,5'·四苯基-1,2，-二味吐（2,2'-bis(o-chlorophenyl)-4,4'，5,5'-tetraphenyl-l，2·-biimidazole)。三#化合物之例子包括：3-{4-[2,4-雙（三氯甲基）-s-三口井 -6-基]苯硫基}丙酸（3-{4-[2,4· bis (trichloromethyl)-s-triazin-6-yl]phenylthio} prop ionic acid)、1，1，1，3,3,3-六氟異丙基-3-{4-[2,4-雙（三氯曱基）-s-三口井-6-基]苯硫基}丙酸酯（1，1，1，3,3,3-1^\3£111〇1：〇13〇?11〇卩;^1-3- {4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio} 卩1：〇卩丨〇11纹{6)、乙基-2-{4-[2,4-雙（三氣曱基）-8-三讲-6-基]苯硫基}乙酸酯（61;11丫1-2-{4-[2,4-1^(1：14。111〇1>〇1116化)^1)-8-1；1^2111-6-yl]phenylthio}acetate)、2-環氧乙基-2-{4-[2,4-雙（三氯甲基）-s-三 -6-基]苯硫基}乙酸 S旨（2-epoxyethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate)、環己基-2-{4-[2,4-雙（三氣甲基）-s-三# -6-基]苯硫基}乙酸酯 (cyclohexyl-2- {4-[2,4-bis(trichloromethyl)-s-triazin-6-yl] phenylthio}acetate)、苯基-2-{4-[2,4-雙（三氣甲基）-s-三碑 -6-基]苯硫基}乙酸酯（benzyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio} acetate) 、 3-{氣-4-[2,4-雙（三氯甲基）-s-三c浒-6-基]苯硫基}丙酸（3-{chloro-4-[2,4-bis(trichloromethyl)-s-triazin-6-yl] phenylthio}propionic acid)、3-{4-[2,4·雙（三氣曱基）-s-三讲 •6- 基]苯硫基 } 丙醯胺（3-{4-[2,4-bis-(trichloromethyl)-s-triazin-6-yl]phenylthio}propionamide)、 2,4-雙（三氣甲基）-6-p-甲氧基苯乙烯基-s-三口井（2,4- 22 25 1380058 520 (2,2'-bis(2,3-dichlorophenyl)-4,4,5,5,-tetraphenyl biimidazole), and 2,2·-bis(p-chlorophenyl)-4,4,, 5,5'·Tetraphenyl-1,2,-disaccharide (2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-l,2·-biimidazole). Examples of the three compounds include: 3-{4-[2,4-bis(trichloromethyl)-s-three-well-6-yl]phenylthio}propionic acid (3-{4-[2,4 · bis (trichloromethyl)-s-triazin-6-yl]phenylthio} prop ionic acid), 1,1,1,3,3,3-hexafluoroisopropyl-3-{4-[2,4-double (Trichloromethane)-s-three well-6-yl]phenylthio}propionate (1,1,1,3,3,3-1^\3£111〇1:〇13〇?11 〇卩;^1-3- {4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio} 卩1: 〇卩丨〇11 pattern {6), ethyl-2-{ 4-[2,4-bis(trimethylsulfonyl)-8-tris-6-yl]phenylthio}acetate (61;11丫1-2-{4-[2,4-1^ (1:14.111〇1>〇1116))^1)-8-1;1^2111-6-yl]phenylthio}acetate), 2-epoxyethyl-2-{4-[2,4 -Bis(trichloromethyl)-s-tris-6-yl]phenylthio}acetic acid S (2-epoxyethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6- Yl]phenylthio}acetate), cyclohexyl-2-{4-[2,4-bis(trimethyl)-s-tris-6-yl]phenylthio}acetate (cyclohexyl-2-{ 4-[2,4-bis(trichloromethyl)-s-triazin-6-yl] phenylthio}acetate), phenyl-2-{4-[2,4-bis(trimethyl)-s-three monuments -6-yl]phenylthio} Benzyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio} acetate), 3-{ gas-4-[2,4-bis(trichloromethyl) 3-(chloro-4-[2,4-bis(trichloromethyl)-s-triazin-6-yl] phenylthio}propionic acid) , 3-{4-[2,4·bis(triseodecyl)-s-tricycle•6-yl]phenylthio}propanamine (3-{4-[2,4-bis-(trichloromethyl) )-s-triazin-6-yl]phenylthio}propionamide), 2,4-bis(trimethyl)-6-p-methoxystyryl-s-three wells (2,4- 22 25 1380058 5

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20 bis(trichloromethyl)-6-p-methoxystyryl-s-triazin)、2,4-雙（三氣甲基）-6-(1-?-二甲基胺基苯基）-1,3，-丁二烯基-3-三口井 (2,4-bis(trichloromethy 1)-6-( 1-p-dimethylaminophenyl)-1，3，-. butadienyl-s-triazin)、以及2-三氣曱基-4-胺基-6-p-甲氧基苯乙稀基-s-三口井（2-trichloromethyl-4-amino-6-p-methoxy-styryl-s-triazin)。肪類化合物的例子包括：1,2-辛二酮，-1-(4-苯硫基）苯基，-2-(o- 苯氧基肟基)(l,2-octadione,-l-(4-phenylthio)phenyl,-2-(o-benzoyloxi me))(CGI-124由 Ciba-Geigy Corp.製造）、以及乙嗣，-1-(9-乙基）-6-(2-甲基苯曱醯 -3- 基）-，1-(〇-乙醯 )(ethanon}- l-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-, l-(o-ace tyloxime))(CGI242)。在光阻組成物中，於100重量份之3)具有乙烯化不飽和雙鍵之.多官能基單體與包含在黏著劑之不飽和雙鍵中，聚合起始劑較佳的使用範圍為1至300重量份》特別是，光聚合起始劑較佳為1至30重量份之苯乙酮化合物、1至30重量份之二咪唑化合物、1至30重量份之三讲化合物、以及1至 30重量份之肟類化合物。光聚合起始劑可更包含0.01至10重量份之光交聯促進劑（作為辅助成分來加速自由基的生成）、或〇.〇1至1〇重量份之硬化劑（加速硬化反應）。光交聯起始劑包含：二苯基酮（benzophenone)化合物’ 如二苯基酮（benzophenone)、4,4-雙（二甲基胺基）二苯基_ (4,4-bis(dimethylamino)benzophenone)、4,4-雙（二乙基胺基）二苯基酮（4,4-bis(diethylamino)benzophenone)、2,4,6-三曱 23 25 1380058 520 bis(trichloromethyl)-6-p-methoxystyryl-s-triazin), 2,4-bis(trimethylmethyl)-6-(1-?-dimethylaminophenyl)-1,3,- Butadienyl-3-three wells (2,4-bis(trichloromethy 1)-6-( 1-p-dimethylaminophenyl)-1,3,-. butadienyl-s-triazin), and 2-trimethyl sulfhydryl 4-aminochloro-6-p-methoxy-styryl-s-triazin. Examples of the fatty compound include: 1,2-octanedione,-1-(4-phenylthio)phenyl,-2-(o-phenoxyfluorenyl) (l,2-octadione, -l- (4-phenylthio)phenyl,-2-(o-benzoyloxi me)) (CGI-124 manufactured by Ciba-Geigy Corp.), and acetamidine,-1-(9-ethyl)-6-(2-A Ethylene-3-yl)-,1-(〇-acetamidine)(ethanon}- l-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-, l-(o-ace Tyloxime)) (CGI242). In the photoresist composition, in 100 parts by weight of 3) polyfunctional monomer having an ethylenically unsaturated double bond and an unsaturated double bond contained in the adhesive, the preferred range of use of the polymerization initiator is 1 to 300 parts by weight" In particular, the photopolymerization initiator is preferably 1 to 30 parts by weight of an acetophenone compound, 1 to 30 parts by weight of a diimidazole compound, 1 to 30 parts by weight of a compound of 3 parts by weight, and 1 Up to 30 parts by weight of an anthraquinone compound. The photopolymerization initiator may further contain 0.01 to 10 parts by weight of a photocrosslinking accelerator (as an auxiliary component to accelerate the formation of radicals), or 硬化1 to 1 part by weight of a hardener (accelerated hardening reaction). The photocrosslinking initiator comprises: a benzophenone compound such as benzophenone, 4,4-bis(dimethylamino)diphenyl- (4,4-bis(dimethylamino) )benzophenone), 4,4-bis(diethylamino)benzophenone, 2,4,6-trisole 23 25 1380058 5

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20 基胺基二苯基嗣（2,4,6-trimethylaminobenzophenone)、甲基-鄰-苯基苯甲酸醋（methyl-o-benzoylbenzoate)、3,3-二甲基 -4- 甲氧基二苯基酮 (3,3-dimethyl-4-methoxybenzophenone)、以及3,3,4,4-四（第三丁基過氧羰基）二苯基綱 (3,3,4,4-tetra(t-butylperoxycarbonyl)benzophenone);葬 _ (fluorenone)化合物，如 9-苐鲷（9-fluorenone)、2-氯-9-苐_ (2-chloro-9-fluorenone)、以及 2-甲基-9-苐 _ (2-methyl-9-fluorenone);嘆嘴酮（thioxanthone)化合物，如嗔嘲鲷（thioxanthone)、2,4-二乙基嘆嘲酮（2,4-diethyl thioxanthone) ' 2-^ ^ (2-chloro thioxanthone) ' 丙氧基嗟嘲 (l-chloro-4-propyloxy thioxanthone)、異丙基. 嘆°镇酮（isopropylthioxanthone)、以及二異丙基嚷嘴_ (diisopropylthioxanthone);氧葱晒（xanthone)化合物，如氧葱酮（xanthone)及 2-甲基氧葱 _ (2-methylxanthone);蒽酿 (anthraquinone)化合物，如蒽酉昆（anthraquinone)、2_ 甲基蒽· 酉昆（2-methyl anthraquinone)、2-乙基蒽 S昆（2-ethyl anthraquinone)、第三丁基蒽酿（t-butyl anthraquinone)、以及2,6-二氣-9，10-尊酿（2,6-以。111〇1>〇-9，10-&1111^91^11〇116);〇丫淀（acridine)化合物，如 9-苯基。丫咬（9-phenylacridine)、1,7-. 雙（9-β丫咬基）庚炫（l，7-bis(9-acridinyl)heptane)、1，5-雙（9-°丫咬庚烧）（l，5-bis(9-acridinylpentane)、以及 1，3-雙（9-β丫咬）丙炫（l，3-bis(9-acridinyl)propane);二幾基（dicarbonyl)化合物，如苄基（benzyl)、1,7,7-三曱基-二環[2,2，1]庚烷-2,3-二 24 1380058 520,2,6-trimethylaminobenzophenone, methyl-o-benzoylbenzoate, 3,3-dimethyl-4-methoxydiphenyl 3,3-dimethyl-4-methoxybenzophenone, and 3,3,4,4-tetra(t-butylperoxycarbonyl)diphenyl (3,3,4,4-tetra(t-) Butylperoxycarbonyl)benzophenone); fluorenone compounds such as 9-fluorenone, 2-chloro-9-fluorenone, and 2-methyl-9-oxime _ (2-methyl-9-fluorenone); thioxanthone compound, such as thioxanthone, 2,4-diethyl thioxanthone ' 2-^ ^ (2-chloro thioxanthone) '1-chloro-4-propyloxy thioxanthone, isopropyl. isopropylthioxanthone, and diisopropylthioxanthone _ (oxyisopropyl onion) (xanthone) compounds such as xanthone and 2-methylxanthone; anthraquinone compounds such as anthraquinone, 2_methyl蒽·酉昆 (2 -methyl anthraquinone), 2-ethyl 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-digas-9,10-dign (2,6-to.111〇1>〇-9 , 10-&1111^91^11〇116); acridine compound, such as 9-phenyl. 9-phenylacridine, 1,7-. bis (9-β 丫基), l,7-bis (9-acridinyl) heptane, 1,5-double (9-° 丫庚(1,5-bis(9-acridinylpentane), and 1,3-bis(9-βridone) propane); dicarbonyl compounds , such as benzyl, 1,7,7-trimethyl-bicyclo[2,2,1]heptane-2,3-di 24 1380058 5

10 1510 15

20 _ (l，7,7-trimethyl-bicycIo[2,2，l]heptane-2,3-dione)、以及 9,10-菲酉昆（9,10-phenanthrenequinone);氧化鱗（phosphine oxide)化合物，如2,4,6-三曱基苯氧基二苯基氧化膦 (2,4,6-trimethybenzoyl diphenyl phosphine oxide)、以及雙 (2,6-二曱氧基苯氧基）-2,4,4·三甲基戊烯氧化膦 (bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentene phosphine oxide);二苯基酿I(benzophenone)化合物，如甲基 -4-( 二曱基胺基）-苯甲酸酯 (methyl-4-(dimethylamino)-benzoate)、乙基-4-(二甲基胺基）-苯曱酸酯（ethyl-4-(dimethylamino)-benzoate)、以及2-n-丁氧基乙基-4(二甲基胺基）-苯甲酸酯 (2-n-butoxyethyl-4(dimethylamino)-benzoate);胺基增效劑 (amino synergists)，如2,5-雙（4-二甲基胺基苯甲基）環戊酮 (2,5-bis(4-dimethylaminobenzal)cyclopentanone)、2,6-雙（4-二乙基胺基苯曱基）環己酮 (2,6-bis(4-diethylaminobenzal)cyclohexanon)、以及2,6-雙（4-二乙基胺基苯甲基）4-曱基-環戊酮 (2,6-bis(4-diethylaminobenzal)-4-methyl-cyclopentanone)；香豆素（coumarin)化合物，如3,3-幾基乙稀基-7-(二乙基'胺基）香豆素（3,3-carbonylvinyl-7-(diethylamino)coumarin)、3-(2-苯並噻唑）-7-(二乙基胺基）香豆素 (3-(2-benzothiazolyl)-7-(diethylamino)coumarin)、3-苯曱基 -7-( 二乙基胺基）香豆素 (3-benzoyl-7_(diethylamino)coumarin)、3-苯曱基-7-曱氧基· 香豆素（3-benz〇yl-7-methoxy-coumarin)、以及 10,10-幾基雙 25 25 1380058 [1，1，7,7-四甲基-2,3,6,7-四氫-1H，5H，11H-C1]-苯甲基吡喃基 [6,7,8-ij]- 喹嗪 -11- 酮 (10,10-carborny Ibis [1,1,7,7-tetramethy 1-2,3,6,7-tetrahydro-l H，5H，llH-Cl]-benzopyrano[6,7,8-ij]-quinolizin-ll-on);查綱 (chalcone)化合物，如4-二乙基胺基查網（4-diethylamino chalcone) ' 以及4-疊氛苯基苯乙婦基闺 (4-azidebenzalacetophenone);以及 2-苯曱基亞曱基 (2-benzoylmethylene) ' 或 3-甲基-b-萘基。惡嗤20 _ (l,7,7-trimethyl-bicycIo[2,2,l]heptane-2,3-dione), and 9,10-phenanthrenequinone; phosphine oxide a compound such as 2,4,6-trimethybenzoyl diphenyl phosphine oxide, and bis(2,6-dimethoxyphenoxy)-2 , 4,4·3,6-dimethoxybenzoyl-2,4,4-trimethylpentene phosphine oxide; diphenyl phenylphenone compound, such as methyl-4-( Methyl-4-(dimethylamino)-benzoate, ethyl-4-(dimethylamino)-benzoate And 2-n-butoxyethyl-4(dimethylamino)-benzoate; amino synergists Such as 2,5-bis(4-dimethylaminobenzal)cyclopentanone, 2,6-bis(4-diethylaminobenzene) 2,6-bis(4-diethylaminobenzal)cyclohexanon, and 2,6-bis(4-diethylaminobenzyl) 4-indolyl-cyclopentanone (2) , 6-bis(4-diethylaminobenzal)-4-methyl-cyclopentanone); coumarin compound, such as 3,3-methylethylene-7-(diethyl 'amino) coumarin ( 3,3-carbonylvinyl-7-(diethylamino)coumarin), 3-(2-benzothiazolyl)-7-(diethylamino)coumarin (3-(2-benzothiazolyl)-7-(diethylamino) Coumarin), 3-benzoyl-7-(diethylamino)coumarin, 3-phenylhydrazin-7-methoxy-coumarin (3 -benz〇yl-7-methoxy-coumarin), and 10,10-kilo double 25 25 1380058 [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H ,11H-C1]-benzylpyranyl[6,7,8-ij]-quinolizin-11-one (10,10-carborny Ibis [1,1,7,7-tetramethy 1-2,3 ,6,7-tetrahydro-l H,5H,llH-Cl]-benzopyrano[6,7,8-ij]-quinolizin-ll-on); chalcone compounds, such as 4-diethylamino 4-diethylamino chalcone ' and 4-azidebenzalacetophenone; and 2-benzoylmethylene ' or 3-methyl-b- Naphthyl. Evil

(3-methyl-b-naphthothiazoline)。 10 再者，硬化劑可為2-硫醇基苯並咪唑 (2-mercaptobenzoimidazole)、2-硫醇基苯並嚷唾硫 _ (2-mercaptobenzothiazole) 、2-硫醇基苯並"惡口坐 (2-mercaptobenzoxazole)、2,5-二硫醇基-1,3,4-售二〇坐 (2,5-dimercapto-l，3,4-thiadiazole)、2-硫醇基-4,6-二甲基胺 15 基础咬（2-mercapto-4,6-dimethylaminopyridine)、新戊四醇· 四 (3- 硫’ 醇基丙酸 g旨）(pentaerythritol-tetrakis(3-mercapt0propionate))、新戊四醇-三（3- 硫醇基丙酸醋）（pentaerythritol-tris(3-mercaptopropionate))、新戊四醇-20 四（2- 硫醇基丙酸醋）(pentaerythritol-tetrakis(2-mercaptoacetate))、新戊四醇-三（2- 硫醇基丙酸醋）(pentaerythritol-tris(2-mercaptoacetate))、三經甲基-三 (2- 硫醇基丙酸 25 SI )(trimethylolpropane-tris(2-mercaptoacetate))、或三經甲 26 1380058 5(3-methyl-b-naphthothiazoline). Further, the hardener may be 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-thiol benzo " 2-mercaptobenzoxazole, 2,5-dithiol-1,3,4-bis 2,5-dimercapto-l,3,4-thiadiazole, 2-thiol-4 6-dimethylcaprol-4, 6-dimethylaminopyridine, pentaerythritol-tetrakis (3-mercapt0propionate), Pentaerythritol-tris (3-mercaptopropionate), pentaerythritol-20 tetrakis(2-thiol propionate) (pentaerythritol-tetrakis) -mercaptoacetate)), pentaerythritol-tris (2-mercaptoacetate), tri-methyl-tris(2-thiol propionic acid 25 SI ) Trimethylolpropane-tris(2-mercaptoacetate)), or three-way A 26 1380058 5

10 1510 15

20 基-三（3- 硫醇基丙酸 S旨）（trimethylolpropane-tris(3-mercaptopropionate)) 〇考慮到溶解度、顏料分散度、及塗覆程度的話，本發明所使用的溶劑可為：丙二醇〒謎（propyleneglycol monomethyl ether)、乙二醇甲醚酷酸醋（ethyleneglycol monomethyl ether acetate)、丙二醇甲驗醋酸酯（propylene glycol monomethyl ether acetate)、丙二醇曱趟醋酸 S 旨 (propyleneglycol monoethyl ether acetate)、二乙二醇二曱醚 (diethyleneglycol dimethyl ether)、環己 _ (cyclohexanon)、 2-庚酿I (2-heptanon)、庚酮（3-heptanon)、丙酸-2-經基乙酷 (2-hydroxyethylpropionate)、丙酸-3-甲基-3 曱氧基丁醋 (3-methyl-3-methoxybutylpropionate)、3-甲氧基丙酸乙 δ旨 (ethyl-3-methoxypropionate) 、 3-乙氧基丙酸甲 8旨 (methyl-3-ethoxypropionate) 、3-乙氧基丙酸乙醋 (ethyl-3-ethoxypropionate)、醋酸丁酯（butylacetate)、戊酸戊醋（amylpermate)、醋酸異戊醋（isoamylacetate)、醋酸異丁醋（isobutylacetate)、丙酸丁醋（butylpropionate)、丁酸異丙酯（isopropylbutyrate)、丁酸乙酯（ethylbutyrate)、丁酸丁 S旨（butylbutyrate)、丙酮酸乙醋（ethylpyruvate)、或醋酸-γ-丁龜醋（γ-butyrolacetate)。本發明之溶劑可單獨使用，或可使用將兩種或以上之溶劑混合而成之混合物。本發明所使用之光阻組成物更可採用6) —第一添加劑，其選自由分散劑、附著促進劑、抗氧化劑、紫外光吸 27 收劑、熱聚合防止劑、以及均化劑所組成之群組之至少一者。分散劑之使用方法，可採用對顏料進行事先表面處理之形式將分散劑添加在顏料内，或可採用外在添加的方式將分散劑添加至顏料中。分散既可為聚合式分散劑、非離子分散劑、陰離子分散劑或陽離子分散劑。分散劑的例子可包括：聚亞坑基乙二醇（polyalkyleneglycol)及其醋類、聚氧化稀多元醇（polyoxyalkylene polyhydric alcohol)、醋稀氧化物添加劑（esteralkylene oxide additive)、醇稀氧化物添劑 (alcohol alkylene oxide additive)、確酸醋（sulfonate ester)、續酸鹽（sulphonate)、碳酸 S旨（carboxylic ester)、破酸鹽 (carboxylate)、.燒基醯胺基亞烧基氧化物添加劑 (alkylamidalkyleneoxide additive) 以及炫基胺 (alkylamin.e)。這些物質可以單獨添加，或是在混合兩種或以上之物質後添加。附著促進劑可包含乙烯基甲氧基矽烷 •y (vinyltrimethoxysilane)、乙稀基三乙氧基石夕烧 (vinyltriethoxysilarie)、乙稀基三（2-甲氧基乙氧基）-碎院 (vinyl tris(2-methoxyethoxy)-silane)、N-(2-胺基乙基）-3-胺基丙基甲基二甲氧基矽烷 (N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane)、 N-(2-胺基乙基）-3-胺基丙基乙基三甲氧基矽烷 (N-(2-aminoethyl)-3-aminopropylmethyltrimethoxysilane)、 3-胺基丙基三乙氧基石夕烧（3-aminopropyltriethoxysilane)、 1380058 3-縮水甘油醚基丙基三乙氧基矽烷 (3-glycidoxypropyltriethoxysilane)、3-縮水甘油醚丙基甲基二甲氧基石夕燒（3-glycidoxypropylmethyldimethoxysilane) ' 2-(3,4-乙氧基環己基）乙基三甲氧基矽烷 5 (2-(3,4-ethoxycyclohexyl)ethyltrimethoxysilane)、3-氯本基甲基二曱氧基矽烷 (3-chloropropylmethyldimethoxysilane)、3-氣丙基三甲氧基石夕烧（3-chloropropyltrimethoxysilane)、3-曱基丙稀酿氧基丙基三甲氧基石夕烧（3-methacryloxypropyltrimethoxysilane)、或 10 3- 硫醇基丙基三甲氧基矽烷 (3-mercaptopropyltrimethoxysilane) 〇至於抗氧化劑，可使用2,2-硫代雙（4-甲基-6-t-丁基苯紛（2,2-thiobis(4-methyl-6-t-butylphenol))、或 2,6-g，t-丁基苯盼（2,6-g，t-butylphenol);而至於子外光吸收劑，可使用 15 2-(3-t_ 丁基·5-曱基-2-羥基苯基）-5-氯-苯并三唑 (2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chloro-benzotria zol)、或烧氧基二苯基酮（alkoxy benzophencme)。光阻組成物可更包括7) —第二添加劑，其選自由碳黑分散劑、具官能基之樹脂黏著劑、單體、輻射敏感化合物、 20 及其他添加物所組成之群組之至少一者。本發明提供一種液晶顯示器用之黑色矩陣，其製備方法之步驟包含：1)於一面板上，塗覆本發明之液晶顯示器用之黑色矩陣光阻組成物；以及2)曝光及顯影此塗覆之黑色矩陣光組成物。 29 侵點，在於其具有極佳之且不會有殘基生成，同時液晶顯示器用之黑色矩陣的優點，顯影性、遮光性、以及絕緣性，且可避免因熱處理而導致之顯示缺陷產生。Trimethylolpropane-tris (3-mercaptopropionate) 〇 In consideration of solubility, pigment dispersion, and degree of coating, the solvent used in the present invention may be: propylene glycol Propyleneglycol monomethyl ether, ethyleneglycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Diethyleneglycol dimethyl ether, cyclohexanon, 2-heptanon, heptanone (3-heptanon), propionic acid-2-thioglycol (2- Hydroxyethylpropionate), 3-methyl-3-methoxybutylpropionate, 3-methoxypropionate, 3-ethoxypropionate (methyl-3-ethoxypropionate), ethyl-3-ethoxypropionate, butylacetate, amylpermate, isovalerate Isoamylacetate), isobutyl acetate Isobutylacetate, butylpropionate, isopropylbutyrate, ethylbutyrate, butybutyrate, ethylpyruvate, or acetic acid- Γ-butyrolacetate (γ-butyrolacetate). The solvent of the present invention may be used singly or as a mixture of two or more solvents. The photoresist composition used in the present invention may further comprise 6) a first additive selected from the group consisting of a dispersant, an adhesion promoter, an antioxidant, an ultraviolet light absorber, a thermal polymerization inhibitor, and a leveling agent. At least one of the groups. The dispersing agent may be used by adding a dispersing agent to the pigment in the form of a prior surface treatment of the pigment, or adding the dispersing agent to the pigment by external addition. The dispersion may be either a polymeric dispersant, a nonionic dispersant, an anionic dispersant or a cationic dispersant. Examples of the dispersing agent may include: polyalkyleneglycol and vinegar thereof, polyoxyalkylene polyhydric alcohol, esteralkylene oxide additive, and alcoholic oxide additive. (alcohol alkylene oxide additive), sulfonate ester, sulphonate, carboxylic acid, carboxylate, pyridyl amide-based sulphur-based oxide additive Alkylamidalkyleneoxide additive) and sulfoamine (alkylamin.e). These materials may be added singly or after mixing two or more substances. The adhesion promoter may comprise vinylmethoxymethoxysilane, vinyltriethoxysilarie, ethylenetris(2-methoxyethoxy)-vinyl tris (2-methoxyethoxy)-silane), N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-( N-(2-aminoethyl)-3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane ), 1380058 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane '2-(3,4- 2-(3,4-ethoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-cyclopropyltrimethylsilane 3-chloropropyltrimethoxysilane, 3-mercaptopropyl propylene oxide 3-methacryloxypropyltrimethoxysilane, or 3-mercaptopropyltrimethoxysilane, as an antioxidant, 2,2-thiobis(4-methyl-) 2,2-thiobis(4-methyl-6-t-butylphenol), or 2,6-g,t-butylbenzene (2,6-g, t-butylphenol) As for the external light absorber, 15 2-(3-t-butyl-5-mercapto-2-hydroxyphenyl)-5-chloro-benzotriazole (2-(3-t-) can be used. Butyl-5-methyl-2-hydroxyphenyl)-5-chloro-benzotria zol), or alkoxy benzophencme. The photoresist composition may further comprise 7) a second additive selected from at least one of the group consisting of a carbon black dispersant, a functional resin binder, a monomer, a radiation sensitive compound, 20 and other additives. By. The invention provides a black matrix for a liquid crystal display, the steps of the preparation method comprising: 1) coating a black matrix photoresist composition for a liquid crystal display of the invention on one side plate; and 2) exposing and developing the coating The black matrix light composition. 29 The point of intrusion is that it has excellent residue and no residue generation. At the same time, it has the advantages of black matrix for liquid crystal display, developability, opacity, and insulation, and can avoid display defects caused by heat treatment.

之液晶顯示器用之黑色矩陣。【實施方式】接下來，為說明本發明之目的，將揭露本發明之較佳實她例。然而，這些實施例僅為說明用，本發明不應侷限於這裡所述之實施例中β <實施例> 實施例1 混合750重量份之作為著色劑之碳黑分散劑（mikuni CORPORATION ’碳黑含量為20%)、60重量份之作為鹼溶性樹脂黏著劑之化合物[莫耳數比42(甲基丙烯酸苯酯）/8(苯乙烯）/6(N-苯基順丁稀二醯亞胺）/2〇(縮水甘.油基添加物）/24(丁二酸酐）、Mw = 12,000、酸值：62 KOH mg/g、以及雙鍵當量：494](此化合物是透過一開環反應所生成，在一部分之醇類自由基上使用丁二酸酐，其中醇類自由基是透過添加甲基丙烯酸縮水甘油酯至一甲基丙烯酸苯酯/苯乙烯/ N-苯基順丁稀二醯亞胺/曱基丙烯酸共聚物所形成）、70重量份之作為官能基單體之二新戊四醇六丙烯酸 1380058 酯、ίο重量份之作為光聚合起始劑之乙鲷，·1-(9乙基）6 (2_ 甲基苯甲酿-3-基）-，1-(〇-乙醢肪）、1〇重量份之2,2,雙（對氣笨基 Μ，4,5,5'-四苯基_12’·二咪唑 (2J2,-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyM,2I-biimidazo 5】e)、10重量份之4,4·雙（二乙基胺基）二苯基酮、5重量份之硫醇基苯並噻唑硫酮、5重量份之作為附著促進劑之3·甲基丙烯醯氧基丙基三曱氧基矽烷、丨重量份之均化劑、51〇重量份之丙二醇甲醚醋酸酯、以及51〇重量份之作為溶劑之乙 -3-甲氧基丁基醋（3-methoxybutyl acetate)。接著，將所得 10的混合物攪拌5小時，而製備得一黑色矩陣光阻組成物。將上述方法製備之光阻組成物溶液利用旋轉式塗佈於玻璃上，在大約1〇〇。(：的溫度下預烘2分鐘，然後形成一厚度約為1.29 μιη之塗膜。接著，於室溫下冷卻基板，在高壓汞燈能1為60 mj/cm2下使用光罩曝光。於25下，將曝光 15 基板使用喷塗法，在〇·〇4 %之KOH水溶液中進行顯影後，使用乾淨的清水清洗之，經乾燥後，在22〇<t之對流恆溫烤箱後焙30分鐘。利用上述方法製得之塗膜圖案，其厚度為丨1 μηι，且圖案並無遺漏，真直度極佳，且可得到不具有曝光部分污 20 柒物之乾淨的圖案特徵。光密度為4.0或以上，且可得到極佳之遮光性。 <敏感度測試> 使用實施例1所得之光阻組成物測量曝光之厚度變化’而曝光的變化量為20、30、40、50、60、70、80、90、 31 1380058 或100 mJ/cm，在曝光量為3〇 mj/cm2或以上，寸得到殘留比例為90%或以上（參閱圖1)。 <顯影性（製程限度）測試> 實鉍例1所製得之光阻組成物，利用旋轉式塗佈於玻璃 5上，在約1〇〇t之溫度下預烘2分鐘，便能形成厚度為ΐ.29μπι 之塗膜。接著，於室溫下冷卻基板，在高壓汞燈能量為6〇 mJ/cm2下使用光罩曝光。於25它下，將曝光基板使用噴塗法，在0_04 %之KOH水溶液中進行顯影。此時，當顯影的時間控制在60至90秒的範圍内時，進行製程限度測試。如 10 實驗結果所示，在顯影時間範圍為50至90秒時，線寬幾乎沒有改變，且維持圖案之穩定度（參閱圖2)。實施例2 混合750重量份之作為著色劑之碳黑分散劑（mikuni CORPORATION ’碳黑含量為20%)、30重量份之作為鹼溶性樹脂黏著劑之化合物[莫耳數比42(甲基丙烯酸苯酯）/8(苯乙烯）/6(N-苯基順丁稀二醯亞胺）/34(縮水甘油基添加物）/10(丁二酸酐）、Mw = 10,000、酸值：27 KOH mg/g、以及雙鍵當量：462](此化合物是透過一開環反應所生成，在一部分之醇類自由基上使用丁二酸酐，其中醇類自由基是 20 透過添加f基丙烯酸縮水甘油酯至一甲基丙烯酸苯酯/苯乙烯/ N-苯基順丁稀二醯亞胺/甲基丙烯酸共聚物所形成）、30重量份之曱基丙烯酸苯酯/苯乙烯/N-苯基順丁稀二醯亞胺/甲基丙烯酸/丙烯酸-甲基丙烯酸縮水甘油酯聚合物 [莫耳數比52(曱基丙烯酸苯酯）/8(苯乙烯）/6(N-苯基順丁稀 32 1380058 二酿亞胺）/28(曱基丙烯酸）/6(縮水甘油基添加物）、Mw = 18,000、酸值：106 KOH mg/g、以及雙鍵當量：2,466]、70 重量份之作為官能基單體之二新戊四醇六丙烯酸酯、10重量份之作為光聚合起始劑之乙酮-1-(9-乙基）-6-(2-曱基苯曱 5 醯_3_基）4-(0-乙醯肟）、10重量份之2,2，-雙（對-氯苯基）_4,4,5,5，·四苯基4,2，·二咪唑、10重量份之4,4_雙（二乙基胺基）二苯基酮、5重量份之硫醇基苯並噻唑硫酮、5重量份之作為附著促進劑之3_甲基丙烯醯氧基丙基三甲氧基矽烧、1重量份之均化劑、510重量份之丙二醇甲醚醋酸酯、 10 以及510重量份之作為溶劑之乙酸-3-甲氧基丁基酯。接著，將所得的混合物攪拌5小時’而製備得一黑色矩陣光阻組成物0 將上述所製備之光阻組成物利用與實施例1相同之方法進行各種製程。最後’所得之塗膜圖案之厚度為Μ μιη, 15 且圖案並無遺漏’真直度極佳，且可得到不具有曝光部分污染物之乾淨的圖案特徵。光密度為4〇或以上，且可得到極佳之遮光性。實施例3 製備一具有與實施例1相同的組成比例之光阻組成 20 物，除了實施例3是使用60重量份之作為鹼溶性樹脂黏著劑之化合物[莫耳數比5〇(甲基丙烯酸苯酯）/8(苯乙烯）/6(Ν苯基順丁稀二醯亞胺）/24(甲基丙烯酸）/12(縮水甘油基添加物）、Mw = 16,000、酸值：87 K0H mg/g、以及雙鍵當量： 1，289](此化合物是透過添加甲基丙烯酸縮水甘油酯至一甲 33 1380058 基丙烯酸苯酯/苯乙烯/ N_苯基順丁稀二醯亞胺/甲基丙烯酸共聚物所生成）。將上述所製備.之光阻組成物利用與實施例i相同之方法進行各種製程。最後，所得之塗膜圖案之厚度為Μ μιη， 5 且圖案並無遺漏，真直度極佳，且可得到不具有曝光部分 /亏染物之乾淨的圖案特徵。光密度為4.〇或以上，且可得到極佳之遮光性。實施例4 製備一具有與實施例1相同的組成比例之光阻組成 10 物，除了實施例4是使用10重量份之1>2_辛二酮•苯硫基）苯基，_2-(0-苯氧基肟基）、10重量份之2 2，_雙（對氯苯基）_4,4,5,5'-四苯基-1，2’-二咪。坐'1〇重量份之4,4-雙（二乙基胺基）二苯基_、以及5重量份之硫醇基苯並噻唑硫酮，作為光聚合起始劑。 15 將上述方法製備之光阻組成物溶液利用旋轉式塗佈於無驗玻璃上’在大約loot：的溫度下預烘2分鐘，然後形成一厚度約為1.3 μιη之塗膜。接著，於室溫下冷卻基板，在高壓汞燈能量為80 mJ/cm2下使用光罩曝光。於25。(：下，將曝光基板使用噴塗法，在〇.〇4 〇/。之KOH水溶液中進行顯影 2〇後’使用乾淨的清水清洗之，經乾燥後，在220°C之對流恆溫烤箱後焙30分鐘。將上述所製備之光阻組成物利用與實施例1相同之方法進行各種製程。最後，所得之塗膜圖案之厚度為Μ μηι，且圖案並無遺漏，真直度極佳，且可得到不具有曝光部分 34 1380058 5染物之乾淨的圖案特徵β光密度為4.0或以上，且可得到極佳之遮光性》實施例5 製備一具有與實施例1相同的組成比例之光阻組成 5物，除了實施例5是使用30重量份之2-苯基-2-(二曱基胺基）-1-(4-嗎啉基苯基）_丁_丨·酮、1〇重量份之2,2，雙（對氯苯基）4,4,5,5 _四本基·ι，2’_二喷唾、丨〇重量份之4 4雙（二乙基胺基）二苯基酮、以及5重量份之硫醇基苯並噻唑硫酮作為光聚合起始劑。 10 將上述方法製備之光阻組成物溶液利用旋轉式塗佈於無鹼玻璃上，.在大約1〇〇〇c的溫度下預烘2分鐘，然後形成一厚度約為1·37 μπι之塗膜。接著，於室溫下冷卻基板，在间壓汞燈能量為8〇 mj/em2下使用光罩曝光。於25。〇下將曝光基板使用喷塗法，在0.04 %之尺〇11水溶液中進行顯影 15後，使用乾淨的清水清洗之，經乾燥後，在220°C之對流恆溫烤箱後培3〇分鐘。將上述所製備之光阻組成物利用與實施例1相同之方法進行各種製程。最後，所得之塗膜圖案之厚度為1.1 μιη，且圖案並無遺漏，真直度極佳，且可得到不具有曝光部分 20污染物之乾淨的圖案特徵。光密度為4.0或以上，且可得到極佳之遮光性。實施例6 製備一具有與實施例1相同的組成比例之光阻組成物，除了實施例6是使用60重量份之作為黏著劑之化合物 35 1380058 [莫耳數比35(甲基丙烯酸苯酯）/10(苯乙烯）/10(甲基丙烯酸二環戊酯）/20(縮水甘油基添加物）/25( 丁二酸酐添加物）、 Mw = 10,000、酸值：63 KOH mg/g、以及雙鍵當量：492](此化合物是透過一開環反應所生成，在一部分之醇類自由基 5 上使用丁二酸酐，其中醇類自由基是透過添加甲基丙烯酸縮水甘油酯至一甲基丙烯酸苯酯/苯乙烯/曱基丙烯酸二環戊酯/甲基丙烯酸共聚物所形成）。將上述所製備之光阻組成物利用與實施例1相同之方法進行各種製程。最後’所得之塗膜圖案之厚度為 10 且圖案並無遺漏’真直度極佳，且可得到不具有曝光部分 /亏染物之乾淨的圖案特徵。光密度為4〇或以上，且可得到極佳之遮光性。比較例1 製備一具有與實施例1相同的組成比例之光阻組成 15 物’除了比較例1是使用60重量份之化合物[莫耳數比35(甲基丙稀酸笨醋）/25(縮水甘油基添加物）/4〇( 丁二酸酐添加物）、Mw = 12,〇〇〇、酸值：89 K〇H mg/g、以及雙鍵當量： 386](此化合物是透過一開環反應所生成，在一部分之醇類自由基上使用丁二酸酐，其中醇類自由基是透過添加甲基 20丙烯酸縮水甘油酯至一曱基丙烯酸苯酯/甲基丙烯酸共聚物所形成作為實施例1中之鹼溶性樹脂黏著劑。將上述所製備之光阻組成物利用與實施例1相同之方法進行各種製程。最後，所得之塗膜圖案因顯影而造成圖案遺漏，且無法得到極佳的圖案特徵。 36 1380058 比較例2 製備一具有與實施例1相同的組成比例之光阻组成物’除了比較例2疋使用60重量份之化合物[莫耳數比55(甲基丙烯酸苯酯）/20(甲基丙烯酸）/25(縮水甘油基添加物）、 5 Mw = 12,000、酸值：65 KOH mg/g、以及雙鍵當量：686](此化合物是透過添加甲基丙烯酸縮水甘油酯至一甲基丙烯酸笨酯/曱基丙烯酸共聚物所形成），作為實施例〗中之驗溶性樹脂黏著劑。 1 將上述所製備之光阻組成物利用與實施例1相同之方 10 法進行各種製程，然後進行顯影。最後，由於顯影時間過長，而難以得到圖案。再者，顯影圖案之真直度與薄膜特性皆不良。比較例3 製備一具有與實施例1相同的組成比例之光阻組成 15 物，除了比較例3是使用60重量份之化合物[莫耳數比55(曱基丙烯酸苯酯）/40(曱基丙烯酸）/5(縮水甘油基添加物）、Mw =12,000、酸值：157 KOH mg/g、以及雙鍵當量：2858](此 •化合物是透過添加曱基丙烯酸縮水甘油酯至一曱基丙烤酸笨酯/甲基丙烯酸共聚物所形成），作為實施例丨中之鹼溶性 20 樹脂黏著劑。將上述所製備之光阻組成物利用與實施例1相同之方法進行各種製程，然後進行顯影。最後，因顯影過快使得圖案有所遺漏。 37 1380058 【圖式簡單說明】圖1係本發明一較佳實施例之光阻組成物隨著曝光其厚度變化圖。圖2係本發明一較佳實施例之光阻組成物隨著顯影時間其 5 圖案變化圖。【主要元件符號說明】無0The black matrix used for liquid crystal displays. [Embodiment] Next, in order to explain the object of the present invention, a preferred embodiment of the present invention will be disclosed. However, these examples are for illustrative purposes only, and the present invention should not be limited to the examples described herein. [Examples] Example 1 Mixing 750 parts by weight of a carbon black dispersant (mikuni CORPORATION ' as a colorant a carbon black content of 20% by weight, 60 parts by weight of a compound as an alkali-soluble resin adhesive [molar ratio 42 (phenyl methacrylate) / 8 (styrene) / 6 (N-phenyl cis-butyl 2醯imino)/2〇(shrinkage.oil-based additive)/24 (succinic anhydride), Mw = 12,000, acid value: 62 KOH mg/g, and double bond equivalent: 494] (this compound is transmitted through a The ring-opening reaction is carried out by using succinic anhydride on a part of the alcohol radicals, wherein the alcohol radicals are added by adding glycidyl methacrylate to phenyl monomethacrylate/styrene/N-phenyl cis-butane. 70 parts by weight of dipentaerythritol hexaacrylic acid 1380058 ester as a functional monomer, and 重量 parts by weight of a photopolymerization initiator. 1-(9-ethyl)6 (2-methylbenzylidene-3-yl)-, 1-(anthracene-ethene), 2 parts by weight of 2,2, Double (4,5,5'-tetraphenyl- 12'-diimidazole (2J2,-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyM,2I-biimidazo 5 e), 10 parts by weight of 4,4·bis(diethylamino)diphenyl ketone, 5 parts by weight of thiol benzothiazole thione, and 5 parts by weight of the adhesion promoter a propylene methoxy propyl trimethoxy decane, a hydrazine part by weight homogenizing agent, 51 parts by weight of propylene glycol methyl ether acetate, and 51 parts by weight of ethyl-3-methoxybutyl group as a solvent 3-methoxybutyl acetate. Then, the obtained mixture of 10 was stirred for 5 hours to prepare a black matrix resist composition. The photoresist composition solution prepared by the above method was spin-coated on the glass. Pre-bake for about 2 minutes at a temperature of about 2 minutes, and then form a coating film having a thickness of about 1.29 μm. Then, the substrate is cooled at room temperature, and the light is used at a high-pressure mercury lamp of 1 m 60 m/cm 2 . The cover is exposed. Under the exposure of 25, the substrate is sprayed, and after developing in a 4% KOH aqueous solution, it is cleaned with clean water and dried. The film was baked for 30 minutes in a convection oven of 22 〇<t. The film pattern obtained by the above method has a thickness of 丨1 μηι, and the pattern is not missing, the straightness is excellent, and the exposed portion is obtained. A clean pattern characteristic of the stain 20. The optical density is 4.0 or more, and excellent light-shielding property can be obtained. <Sensitivity Test> The thickness variation of the exposure is measured using the photoresist composition obtained in Example 1 The amount of change in exposure is 20, 30, 40, 50, 60, 70, 80, 90, 31 1380058 or 100 mJ/cm, and the exposure amount is 3〇mj/cm2 or more, and the residual ratio is 90% or more. (See Figure 1). <Developability (Process Limit) Test> The photoresist composition obtained in Example 1 was spin-coated on the glass 5 and prebaked at a temperature of about 1 Torr for 2 minutes. A coating film having a thickness of ΐ.29 μm was formed. Next, the substrate was cooled at room temperature, and exposed to a reticle at a high pressure mercury lamp energy of 6 〇 mJ/cm 2 . Under the same conditions, the exposed substrate was developed by a spray coating method in a 0 - 04% aqueous KOH solution. At this time, the process limit test was performed when the development time was controlled within the range of 60 to 90 seconds. As shown in the results of the experiment, the line width is hardly changed during the development time range of 50 to 90 seconds, and the stability of the pattern is maintained (see Fig. 2). Example 2 750 parts by weight of a carbon black dispersant (mikuni CORPORATION 'carbon black content: 20%) as a coloring agent, and 30 parts by weight of a compound as an alkali-soluble resin adhesive [Mole ratio 42 (methacrylic acid) Phenyl ester) / 8 (styrene) / 6 (N-phenyl cis-butyl diimide imide) / 34 (glycidyl additive) / 10 (succinic anhydride), Mw = 10,000, acid value: 27 KOH Mg/g, and double bond equivalent: 462] (This compound is formed by a ring opening reaction, using succinic anhydride on a part of the alcohol radical, wherein the alcohol radical is 20 by adding f-based glycidol Ester to phenyl methacrylate / styrene / N-phenyl cis-butyl diimide / methacrylic acid copolymer), 30 parts by weight of phenyl methacrylate / styrene / N-phenyl Cis-butyl diimide imine/methacrylic acid/acrylic acid-glycidyl methacrylate polymer [molar ratio 52 (phenyl methacrylate) / 8 (styrene) / 6 (N-phenyl cis-butyl) Dilute 32 1380058 di-imino) / 28 (methacrylic acid) / 6 (glycidyl additive), Mw = 18,000, acid value: 106 KOH mg / g, And double bond equivalent: 2,466], 70 parts by weight of dipentaerythritol hexaacrylate as a functional monomer, and 10 parts by weight of ethyl ketone-1-(9-ethyl) as a photopolymerization initiator 6-(2-mercaptophenylhydrazine 5 醯_3_yl) 4-(0-acetamidine), 10 parts by weight of 2,2,-bis(p-chlorophenyl)_4,4,5,5 , tetraphenyl 4,2, diimidazole, 10 parts by weight of 4,4-bis(diethylamino)diphenyl ketone, 5 parts by weight of thiol benzothiazole thione, 5 parts by weight 3-methacryloxypropyltrimethoxysulfonate as an adhesion promoter, 1 part by weight of a leveling agent, 510 parts by weight of propylene glycol methyl ether acetate, 10 and 510 parts by weight of acetic acid as a solvent 3-methoxybutyl ester. Next, the obtained mixture was stirred for 5 hours to prepare a black matrix resist composition. The photoresist composition prepared above was subjected to various processes in the same manner as in Example 1. Finally, the resulting coating film pattern has a thickness of Μ μηη, 15 and the pattern is not missing. The true straightness is excellent, and a clean pattern feature having no exposed portion of the contaminant can be obtained. The optical density is 4 Å or more, and excellent light blocking properties are obtained. Example 3 A photoresist composition 20 having the same composition ratio as that of Example 1 was prepared, except that Example 3 was a compound using 60 parts by weight of an alkali-soluble resin adhesive [Mole Ratio 5 〇 (methacrylic acid) Phenyl ester) / 8 (styrene) / 6 (nonylphenyl cis-butyl diimide imine) / 24 (methacrylic acid) / 12 (glycidyl additive), Mw = 16,000, acid value: 87 K0H mg /g, and double bond equivalent: 1,289] (This compound is added by adding glycidyl methacrylate to a 33 3380058 phenyl acrylate / styrene / N_phenyl cis-butyl bis imimine / A Based on the acrylic acid copolymer). The photoresist composition prepared as described above was subjected to various processes in the same manner as in Example i. Finally, the resulting coating film has a thickness of Μ μηη, 5 and the pattern is not missing, the straightness is excellent, and a clean pattern feature without the exposed portion/loss is obtained. The optical density is 4. 〇 or more, and excellent light blocking properties are obtained. Example 4 A photoresist composition 10 having the same compositional ratio as in Example 1 was prepared except that in Example 4, 10 parts by weight of 1 > 2 -octanedione phenylthio)phenyl group, _2-(0) was used. - phenoxy fluorenyl), 10 parts by weight of 2 2, bis(p-chlorophenyl)-4,4,5,5'-tetraphenyl-1,2'-diime. A 1 part by weight of 4,4-bis(diethylamino)diphenyl-, and 5 parts by weight of a thiolbenzothiazolethione were used as a photopolymerization initiator. 15 The photoresist composition solution prepared by the above method was spin-coated on the non-inspected glass, and prebaked at a temperature of about loot: for 2 minutes, and then a coating film having a thickness of about 1.3 μm was formed. Next, the substrate was cooled at room temperature, and exposed to a reticle at a high pressure mercury lamp energy of 80 mJ/cm2. At 25. (: Next, the exposed substrate is sprayed, and developed in a KOH aqueous solution of 〇.〇4 〇/. 2 〇, 'cleaned with clean water, dried, then baked at 220 ° C in a convection oven 30 minutes. The photoresist composition prepared above was subjected to various processes in the same manner as in Example 1. Finally, the thickness of the obtained coating film pattern was Μ μηι, and the pattern was not missing, and the straightness was excellent, and A clean pattern characteristic β having an optical density of 4.0 or more without the exposed portion 34 1380058 5 was obtained, and an excellent light-shielding property was obtained. Example 5 A photoresist composition having the same composition ratio as that of Example 1 was prepared. In addition to Example 5, 30 parts by weight of 2-phenyl-2-(didecylamino)-1-(4-morpholinylphenyl)-butan-one, 1 part by weight, was used. 2,2, bis(p-chlorophenyl) 4,4,5,5 _tetrabenyl·ι, 2'_ two spray saliva, 丨〇 4 parts by weight of bis(diethylamino)diphenyl a ketone, and 5 parts by weight of a thiol benzothiazole thioketone as a photopolymerization initiator. 10 Using a photoresist composition solution prepared by the above method Rotary coating on an alkali-free glass, pre-baking at a temperature of about 1 ° C for 2 minutes, and then forming a coating film having a thickness of about 1.37 μm. Then, cooling the substrate at room temperature, The pressure of the interstitial mercury lamp is 8 〇mj/em2 and exposed by a reticle. The exposed substrate is sprayed by a spray method in a 0.04 % 〇11 aqueous solution, and then cleaned with clean water. After drying, it was incubated for 3 minutes in a convection oven at 220 ° C. The photoresist composition prepared above was subjected to various processes in the same manner as in Example 1. Finally, the thickness of the obtained coating film pattern was 1.1 μιη, and the pattern is not missing, the straightness is excellent, and a clean pattern feature without the contaminant of the exposed portion 20 can be obtained. The optical density is 4.0 or more, and excellent light-shielding property can be obtained. A photoresist composition having the same composition ratio as in Example 1, except that in Example 6, 60 parts by weight of a compound 35 1380058 [molar ratio 35 (phenyl methacrylate)/10 (benzene) was used as an adhesive. Ethylene)/10 (bicyclo methacrylate) Amyl ester) / 20 (glycidyl additive) / 25 (succinic anhydride additive), Mw = 10,000, acid value: 63 KOH mg / g, and double bond equivalent: 492] (this compound is through an open ring The reaction is formed by using succinic anhydride on a part of the alcohol radicals 5, wherein the alcohol radicals are added by adding glycidyl methacrylate to phenyl monomethacrylate/styrene/dicyclopentanyl acrylate. / methacrylic acid copolymer formed.) The photoresist composition prepared above was subjected to various processes in the same manner as in Example 1. Finally, the obtained coating film pattern had a thickness of 10 and the pattern was not missing. Excellent, and a clean pattern feature without exposed portions/losses can be obtained. The optical density is 4 Å or more, and excellent light blocking properties are obtained. Comparative Example 1 A photoresist composition having the same composition ratio as in Example 1 was prepared. 'Compared with Comparative Example 1, 60 parts by weight of a compound was used [molar ratio 35 (methacrylic acid vinegar) / 25 ( Glycidyl additive) / 4 〇 (succinic anhydride additive), Mw = 12, hydrazine, acid value: 89 K 〇 H mg / g, and double bond equivalent: 386] (this compound is opened The ring reaction is formed by using succinic anhydride on a part of the alcohol radicals, wherein the alcohol radicals are formed by adding methyl 20-glycidyl acrylate to methacrylate methacrylate/methacrylic acid copolymer. The alkali-soluble resin adhesive in Example 1. The photoresist composition prepared above was subjected to various processes in the same manner as in Example 1. Finally, the resulting coating film pattern was omitted due to development, and was not excellent. 36 1380058 Comparative Example 2 A photoresist composition having the same composition ratio as in Example 1 was prepared. In addition to Comparative Example 2, 60 parts by weight of a compound [molar ratio 55 (phenyl methacrylate) was used. /20(methacrylic acid)/25( Glycidyl additive), 5 Mw = 12,000, acid value: 65 KOH mg/g, and double bond equivalent: 686] (This compound is added by adding glycidyl methacrylate to methacrylic acid stearate/mercapto The acrylic copolymer was formed as the solvent-soluble resin adhesive in the example. 1 The photoresist composition prepared above was subjected to various processes in the same manner as in Example 1 and then subjected to various processes, and then developed. The development time was too long, and it was difficult to obtain a pattern. Further, the trueness of the developed pattern and the film characteristics were poor. Comparative Example 3 A photoresist composition having the same composition ratio as in Example 1 was prepared, except that Comparative Example 3 was 60 parts by weight of the compound [molar ratio 55 (phenyl methacrylate) / 40 (methacrylic acid) / 5 (glycidyl additive), Mw = 12,000, acid value: 157 KOH mg / g, and Double bond equivalent: 2858] (This compound is formed by adding glycidyl methacrylate to a mercaptopropionate/methacrylic acid copolymer), as an alkali-soluble 20 resin adhesive in the example Will be on The photoresist composition prepared as described above was subjected to various processes in the same manner as in Example 1 and then developed. Finally, the pattern was omitted due to development too fast. 37 1380058 [Simplified Schematic] FIG. 1 is a FIG. 2 is a diagram showing changes in the thickness of the photoresist composition according to a preferred embodiment of the present invention as a function of development time. [Main component symbol description] None 0

3838

Claims

1380058 X. Patent Application Scope · · · A black matrix photoresist composition for liquid crystal displays, in 1 〇〇 parts by weight of black matrix photoresist composition, including: 1) 1 to 40 parts by weight containing black a pigment coloring agent; 2) 1 to 20 parts by weight of an alkali-soluble resin adhesive represented by the following formula 1; 3) 1 to 20 parts by weight of a polyfunctional monomer having an ethylenically unsaturated double bond; 0.1 to 20 parts by weight of one photopolymerization initiator; and 5) 30 to 90 parts by weight of one solvent; [Formula 1] ABCD

(wherein R1 is hydrogen, or a radical forming a quinone imine structure or forming a five-membered cyclic carboxylic anhydride with X, and 15 R2 is selected from the group consisting of hydrogen, methyl, and hydroxyindole, R3 And R 4 may be the same or different from each other and independently hydrogen or methyl, X is selected from alkyl esters of C 丨 to Cu, (: 2 to 6: alkyl ester substituted by 1 or 2 hydroxy groups, (: 2 to (:6 via 0^ to (:3 alkoxy-substituted alkyl 39 1380058 ester, C丨 to C6 halogen-substituted alkyl ester, oxime to 0:3 alkoxylate (n =2 to 30) diol ester of alkylene, C2 and C3, phenyl substituted alkyl ester of (^ to <:6, phenyl group substituted by 0: 丨 to (6 alkyl group) (^ to alkoxy substituted stupid base, dentate substituted phenyl '^ to alkoxy alkoxy group, 5 glycidoxymethyl group, and one formed The imine structure or a group consisting of R1 - a radical formed by a five-membered ring scorpion, Y is selected from the group consisting of C alkyl to C12 alkyl, and 〇 3 to <: 6 () To a group of 10 SI group sub-alkyl vinegars, Z Ethylene, propylene, butylene, 12-phenylene, 1,2- 〇Ccc: wXcc:.x: known: 10 cyclohexylene, , and groups (where * represents The connecting portion), and a, b, c', and d represent the molar ratios of a, B, C, and D, respectively, and the range of a ranges from 1 90 to 90 ′ b ranges from 〇 to 60, c. 0 to 40, and d is in the range of 0 to 40), 15 wherein the alkali-soluble resin adhesive as shown in Formula 1 is in the range of 0 to less than 5, and it is 50 < P < 150 ' l〇〇〇<Q<2500, and 1500<(10 XP)+Q<4000 conditions' and when d ranges from 5 to 40, it is 20<P<80 '40〇<Q<i〇〇〇 And 5〇〇<(1〇xP)+q<15〇〇 conditions (p represents acid value (KOH mg/g) ' and Q represents double bond 20 equivalent) 〇40 1380058 2. The black matrix photoresist composition according to claim 1, wherein the black pigment-containing coloring agent is a carbon black and at least one coloring pigment. 3. The black matrix according to claim 2 The photoresist constitutes 5 things, Selected from the group consisting of carbon black in the SEAST 5HIISAF-HS, SEAST KH, SEAST 3HHAF-HS, SEAST NH, SEAST 3M, SEAST

10 15

20 300HAF-LS 'SEAST 116HMMAF-HS, SEAST 116MAF, SEAST FMFEF-HS, SEAST SOFEF, SEAST VGPF, SEAST SVHSRF-HS, and SEAST SSRF (available from Tokai Carbon Co., Ltd.); DIAGRAM BLACK II, DIAGRAM BLACK N339, DIAGRAM BLACK SH, DIAGRAM BLACK H, DIAGRAM LH, DIAGRAM HA, DIAGRAM SF, DIAGRAM N550M, DIAGRAM M, DIAGRAM E, DIAGRAM G, DIAGRAM R, DIAGRAM N760M, DIAGRAM LR, #2700, #2600, #2400, #2350 ' #2300 ' #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45, #45L, #25, #CF9, #95, #3030, #3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B (available from Mitsubishi Chemical Corporation); PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85 ' PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35 ' PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL 41 1380058 BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101 (available from Degussa Japan Company); and RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020' RAVEN-1000> RAVEN- 890H' RAVEN-890 ' RAVEN -880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA,

10 RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410 ' RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN -1250, 15

20 RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170 (available from Columbia Carbon Co.). 4. The black matrix photoresist composition according to claim 2, wherein a color pigment mixed with the carbon black is selected from the group consisting of Carmine 6B (CI 12490) and Phthalocyanine Green (CI). 74260), Phthalocyanine Blue (CI 74160), Mitsubishi Carbon Black ΜΑ 100, Perylene Black, BASF K0084 and K0086, Cyanine Black, Leonor Yellow (Lionol Yellow, CI 21090), Leonol Yellow GRO (C.1.21090), Benzidine Yellow 4T-564D, Mitsubishi Carbon Black MA-40 ), Victoria Pure Blue (CI 42595), CI Pigment Red (PIGMENT 42 1380058 RED) 97, 122, 149, 168, 177, 180, 192, 215; CI Pigment Green 7, 36; CI pigment (PIGMENT) 15:1, 15:4, 15:6, 22,60,64; CI pigment (PIGMENT) 83, 139; and C, I. Pigment violet

10 15

.20 (PIGMENT VIOLET) 23. 5. The black matrix photoresist composition according to claim 1, wherein at least one single system for forming the A portion of the alkali-soluble resin adhesive as shown in Formula 1 is selected from the group consisting of: unsaturated carbonic acid Unsaturated carboxylic acid esters, such as benzyl (meth)acrylate, methyl(meth)acrylate,ethylethyl acrylate (ethyl) Meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl(meth)acrylate 'methacrylic acid isobutyl vinegar (isobutyl) (meth)acrylate), t-butyl(meth)acrylate, cyclohexyl(meth)acrylate,methacrylic acid isobornic vinegar (isobornyl (meth)acrylate), ethylhexyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, A Tetrahydrofurfuryl (meth)acrylate, hydroxyethyl (meth)acrylate, methyl acrylate (2-hydroxypropyl (meth)acrylate), 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl(meth)acrylate, methyl acrylic acid (bromooctyloxy-2-hydroxypropyl) ester 43 1380058 5

15

20 (acyloctyloxy-2-hydroxypropyl (meth)acrylate), glycerol (meth)acrylate, 2-methoxyethyl (2-methoxyethyl) vinegar (2-methoxyethyl (2-methoxyethyl) Meth)acrylate, 3-methoxybutyl(meth)acrylate, ethoxydiethylene glycol (methdiethylene glycol) Acrylate), methoxytriethyleneglycol (meth)acrylate, methoxytripropyleneglycol (meth)acrylate, methacrylic acid poly(ethylene glycol) Poly(ethyleneglycol)methylether (meth)acrylate, phenoxydiethyleneglycol (meth)acrylate, methyl acrylate (p-nonylphenoxy) P-nonylphenoxypolyethylene glycol (meth)acrylate, p-nonylphenoxypolypropylene glycol (meth)acrylate, methyl methacrylate glycidyl vinegar (glycidyl (meth)acrylate), methyl acrylate Tetrafluoropropyl (meth)acrylate, methyl acrylate (1,1,1,3,3,3-hexafluoroisopropyl) ester (1,1,1,3,3,3-hexafluoroisopropyl) (meth)acrylate), octafluoropentyl (meth)acrylate, heptaprocafluorodecyl (meth)acrylate, mercaptopropene benzoate (meth)acrylate Tribromophenyl (meth)acrylate, dicyclopentanylmethacrylate, methacrylic acid dicyclopentan vinegar 44 1380058 5

10 (dicyclopentenyl methacrylate), dicyclopentenyloxyethyl acrylate, isobornylmethacrylate 'adamantylmethacrylate', acrylic acid (methyl- Α-ylmethylmethylacrylate, acrylic acid (ethyl-α-aminomethyl), ethyl propyl-acrylate Propyl α-hydroxymethylacrylate, and butyl α-hydroxymethylacrylate; aromatic vinyls, such as styrene ), α-methylstyrene '(o-, m-, p-)-ethlyl toluene ((o, m, p)-vinyltoluene), (o, m, p)-decyloxy Styrene ((o, m, p)-methoxystyrene), and (o, m, p)-gas styrene 15

((o,m,p)-chlorostyrene);Unsaturated ethers, such as vinyl methy lether, vinyl ethyl ether, and acryl glycidid (allyl glycidyl ether); unsaturated imide, such as N-phenylmaleimide, N-(4-phenylphenyl) cis-butadiene N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, and Ν-cyclohexyl cis-butyl succinimide An amine (N-cyclohexylmaleimide); and a group of maleic anhydrides such as maleic anhydride and methyl maleic anhydride. 6. The black matrix photoresist composition according to claim 1, wherein the B portion for forming the alkali-soluble resin adhesive as shown in Formula 1 45 1380058

At least one of the monolithic systems is selected from the group consisting of (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, Fumaric acid, monomethyl maleic acid, 5-norbornene-2-carboxylic acid, mono-2-(methyl) Acetyloxy) ethyl-2-phthalic acid (mono-2-((meth)acryloyloxy)ethyl phthalate), mono-2-(methacryloxy)ethyl succinate (mono-2) -((meth)acryloyloxy)ethyl succinate), and a group consisting of ω-carboxy polycaprolactone mono(meth)acrylate. 7. The black matrix photoresist composition according to claim 1, wherein the method for producing an alkali-soluble resin adhesive as shown in Formula 1 comprises the steps of: i) preparing a portion A and B of Formula 1 a polymer consisting of a monomer for forming part A of formula 1 and a monomer for forming part B by poly 15 in combination; ^ ii) a portion of polymer B prepared by step i) Partially acidic radicals, and epoxy radicals of glycidyl methacrylate, undergo a condensation reaction to prepare a polymer of Group A, B, and C of Formula 1; and iii) Part ii) Part of the hydroxyl group of the prepared polymer C moiety is reacted with a carboxylic anhydride to form part D of formula 1. 46 1380058 5

10 15

-20 8. The black matrix photoresist composition according to item 7 of the patent application, wherein the acid-proof needle of step iii) is selected from the group consisting of succinic anhydride, glutaric anhydride, and glutaric anhydride. , adipic anhydride, phthalic anhydride, hexahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride (cis-l, 2, 3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, itaconic anhydride, trimelic anhydride, And cis-5-norbornene-endo-2,3-dicarboxylic anhydride ° 9. Black matrix photoresist as described in claim 1 a composition in which, in the alkali-soluble resin adhesive as shown in Formula 1, when b ranges from 0 to less than 5, 'b ranges from 5 to 60, and when d ranges from 5 to 40, b ranges from 0 to 10. 10. The black matrix photoresist composition according to claim 1, wherein the weight average molecular weight of the test resin adhesive as shown in Formula 1 ranges from 1,000 to 200,000. 11. The black matrix photoresist composition of claim 1, wherein the polyfunctional monomer having an ethylenically unsaturated double bond comprises a compound having at least one unsaturated radical, wherein the The saturated radical can be additionally polymerized with a monomer having a boiling point of 10 ° C or more, or a monomer having a caprolactone introduced therein. 12. The black matrix photoresist composition of claim 1, wherein the photopolymerization initiator comprises at least one compound selected from the group consisting of acetophenone compounds, A group consisting of a biimidazole compound, a triazine compound, and an oxime compound. The black matrix photoresist composition according to claim 1, wherein the photopolymerization initiator further comprises 0.01 to 10 parts by weight of a photocrosslinking accelerator or 0.01 to 10 parts by weight of a hardener. 14. The black matrix photoresist composition as described in claim 1

10 15

20, wherein the solvent comprises one or more of propylene glycol monomethyl ether, ethyleneglycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol Propyleneglycol monoethyl ether acetate, diethyleneglycol dimethyl ether, cyclohexanon '2-heptanon', 3-heptanon , 2-hydroxyethylpropionate, 3-methyl-3-methoxybutylpropionate, 3-methoxy-3-propoxypropionate (ethyl-3-methoxypropionate), 3-ethoxypropionate methyl-3-ethoxypropionate, 3-ethoxypropionate, butylacetate, Amylpermate, isoamylacetate, isobutylacetate, butylpropionate, isopropylbutyrate, ethylbutyrate ,Ding Butylbutyrate, ethylpyruvate, and gamma-butyrolacetate. 48 丄卿058 15. The black matrix photoresist composition as described in claim 1 of the patent scope further comprises: 6) a first additive 'selected from a dispersant, an adhesion promoter, an antioxidant, an ultraviolet A group of 50% of a light absorber, a thermal polymerization inhibitor, and a leveling agent. 16. The black matrix photoresist composition of claim 1, further comprising: φ 7) - a second additive selected from the group consisting of a carbon black dispersant, a resin binder having a functional group, a monomer, And the group consisting of radiation-sensitive compounds is less than one. 17. A black matrix for a liquid crystal display, the method of which the method of the present invention comprises: I) coating a black matrix photoresist for a liquid crystal display according to any one of claims 16 to 16 on a side panel And the composition of the black matrix of the liquid crystal display of