201214046 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種適於形成液晶顯示器（Liquid Crystal Display ;以下稱為rLCD」）等液晶顯示元件遮光膜之可光聚合的樹脂 組成物。 【先前技術】 液晶顯示器係利用液晶分子的光學各向異性和多折射特性來顯示 影像；當施加電場時’液晶的排列發生變化，根據液晶排列的變化， 光的穿透特性也會改變。 通常液晶顯示器係將分別形成有電場生成電極的兩個基板，以形 成有兩個電極的面相對而設置，在兩個基板之間注入液晶物質後，向 兩個電極施加電壓形成電場；通過所述電場液晶分子發生移動，從而 改變光的穿透率而顯示影像。 廣泛使用之薄膜電晶體液晶顯示器（TFT_LCD)的結構例如下：具下 邻基板（又稱為陣列基板（array substrate))，該下部基板上排列有薄 膜電晶體和像素電極；上部基板（又稱為彩线光片（⑺⑽丨㈣基 板該上部基板的結構為’由塑膠或玻璃形成的基板上部重複設置有 黑色矩陣（black matrix)和紅、綠、藍三色著色層，於其上為了保護 彩色遽光片並維持表面平滑性而形成有由聚醯亞胺、聚丙稀酸醋、聚 ，基甲酸s日等材料製成之厚度i至3μηι的外保護層(的⑽⑽），該外保 ，層上形成有用於驅動液晶而施加電壓的IT〇(lndium Tin 〇硫姻錫 氧化物）透明導電層，以及液晶，填充於上部基板和下部基板之間； 的兩側面分別附著有能夠對可見光線（自然光）進行旋光偏 ,偏光片。向通過外部周邊電路轉成像麵TFT職施加電壓使 電日日體成為· (tunw)n)狀態，並使液晶處於可施加零序電壓（麵 ΓΓ: 的狀態後’絲料電壓而在液晶㈣雜資訊， 電閉（1跡0ff)，保存液晶充電器及輔助充電器中儲藏的 電何，使衫像顯不—定時間。向液晶施加電麼時液晶的排列發生變化， 201214046 光透過此時的液晶就會產生繞射。使此光線透過偏光板即得到所要的 影像。 所述彩色濾光片通常是在塑膠或者玻璃製成的透明基板上形成黑 色矩陣，而紅、綠、藍等不同顏色則是由光微影法（ph〇t〇lith〇graphy) 或印刷法、喷墨法等方法依序形成條紋狀或馬赛克狀等彩色圖案。 彩色濾光片基板中的黑色矩陣係阻斷向基板之透明像素電極以外 穿透之未經控制的光來提高對比度；紅、綠、藍的著色層可使白色光 :具特定波長的光穿透而顯色；透明導電膜可發揮作為向液晶施加電 場的通用電極（common electrode )的作用。 然而，在將上部彩色濾光片基板和下部陣列基板相結合來製造液 B曰面板時，由於彩色濾光片基板和陣列基板的結合誤差，發生漏 機率極高。 因此，為防止此種漏光，則設計黑色矩陣時便留有一定的邊緣 (margin)來設計，而這種邊緣會成為侵蝕開口率的主要原因。 為改善此一問題，近來一般係試圖將液晶顯示器的彩色濾光片形 成?了部基板（即陣列基板）而非上部基板（即彩色漶光片基板）上 來提高開口率，並減少製造步驟來降低製造成本。 【發明内容】 本發明的目的在於提供一種可光聚合的樹脂組成物，於形成硬化 膜時’。具有適當的光學密度同時降低特定金屬的含量，從而減少液晶 顯示器的驅動不良及畫質或光學性能下降。 _本'發明的另一目的在於提供一種可光聚合的樹脂組成物，在液晶 顯不器製造時，於陣列基板上形成有彩色濾光片的結構中，具有用= 形成陣列基板上的黑色矩陣及液晶胞間隙維持用間隔件。 、 本發明的再一目的在於提供一種可光聚合的樹脂組成物，對形成 可同時滿足陣列基板上的黑色矩陣功能及液晶胞間隙維持用工 能之圖案係有用的。 崎功 本發明的再一目的在於提供一種可光聚合的樹脂組成物，即使陣 列基板上形成有彩色濾光片，也不會妨礙施加之電壓的維持。 201214046[Technical Field] The present invention relates to a photopolymerizable resin composition suitable for forming a light-shielding film of a liquid crystal display element such as a liquid crystal display (hereinafter referred to as "rLCD"). [Prior Art] A liquid crystal display uses an optical anisotropy and a multi-refracting property of a liquid crystal molecule to display an image; when an electric field is applied, the arrangement of the liquid crystal changes, and the light transmission characteristics change depending on the arrangement of the liquid crystal. Generally, a liquid crystal display is provided with two substrates on which electric field generating electrodes are respectively formed, and opposite surfaces are formed to form two electrodes. After a liquid crystal substance is injected between the two substrates, a voltage is applied to the two electrodes to form an electric field; The electric field liquid crystal molecules move to change the transmittance of light to display an image. The structure of a widely used thin film transistor liquid crystal display (TFT_LCD) is as follows: a lower substrate (also referred to as an array substrate) on which a thin film transistor and a pixel electrode are arranged; an upper substrate (also referred to as an upper substrate) For the color line light film ((7)(10)丨(4) substrate, the structure of the upper substrate is 'the black matrix and the red, green and blue colored layers are repeatedly disposed on the upper portion of the substrate formed of plastic or glass, for protection thereon The color filter sheet and the surface smoothness are formed to form an outer protective layer ((10)(10)) having a thickness of i to 3 μm made of a material such as polyimide, polyacrylic acid vinegar, polyglycolic acid, and the like. An IT〇 (lndium Tin 〇 〇 锡 tin oxide) transparent conductive layer for driving a liquid crystal and a liquid crystal is formed on the layer, and a liquid crystal is filled between the upper substrate and the lower substrate; the two sides are respectively attached to the visible light The line (natural light) is optically polarized, and the polarizer is applied to the TFT through the external peripheral circuit, and the voltage is applied to the TFT (the tunw) state. Apply zero-sequence voltage (after the state of the surface: 'wire' voltage in the liquid crystal (four) miscellaneous information, electrical closure (1 trace 0ff), save the electricity stored in the liquid crystal charger and auxiliary charger, so that the shirt is not visible - The time is set. When the liquid crystal is applied with electricity, the arrangement of the liquid crystal changes, and the liquid crystal passes through the liquid crystal at 201214046. This light is transmitted through the polarizing plate to obtain the desired image. The color filter is usually in plastic. Or a black matrix formed on a transparent substrate made of glass, and different colors such as red, green, and blue are sequentially formed by photolithography, printing, inkjet, etc. a color pattern such as a mosaic or a mosaic. The black matrix in the color filter substrate blocks uncontrolled light penetrating outside the transparent pixel electrode of the substrate to improve contrast; the red, green, and blue color layers can be white. Light: a light having a specific wavelength penetrates and develops color; a transparent conductive film can function as a common electrode that applies an electric field to the liquid crystal. However, the upper color filter substrate and the lower array are used. When the column substrate is combined to produce a liquid B panel, the leakage probability is extremely high due to the combination error of the color filter substrate and the array substrate. Therefore, in order to prevent such light leakage, a certain margin is left when designing the black matrix. (margin) to design, and this edge will become the main reason for eroding the aperture ratio. In order to improve this problem, it has recently been attempted to form a color filter of a liquid crystal display to form a substrate (ie, an array substrate) instead of an upper portion. The substrate (i.e., the color slab substrate) is used to increase the aperture ratio, and the manufacturing steps are reduced to reduce the manufacturing cost. SUMMARY OF THE INVENTION An object of the present invention is to provide a photopolymerizable resin composition which is formed when a cured film is formed. Appropriate optical density simultaneously reduces the content of specific metals, thereby reducing the poor driving performance of the liquid crystal display and the deterioration of image quality or optical performance. Another object of the present invention is to provide a photopolymerizable resin composition having a color filter formed on an array substrate in the structure in which a color filter is formed on the array substrate when the liquid crystal display is manufactured. Matrix and spacer for liquid crystal cell gap maintenance. Still another object of the present invention is to provide a photopolymerizable resin composition which is useful for forming a pattern which can simultaneously satisfy the black matrix function on the array substrate and the liquid crystal cell gap maintenance work. A further object of the present invention is to provide a photopolymerizable resin composition which does not hinder the maintenance of the applied voltage even if a color filter is formed on the array substrate. 201214046
rj路ία肉妨礙所施加之電壓的維持。 丨玉J 叩校Γ脂組成物，具有充 耐受性，能夠充分發揮黑色矩陣及液 且不會妨礙所施加之電壓的維持，從 ®成物，特別是 ’不會由液晶層Rj road ία meat hinders the maintenance of the applied voltage. Saitama J Γ school's rouge composition is tolerant and can fully utilize the black matrix and liquid without hindering the maintenance of the applied voltage. From the product, especially the 'not liquid crystal layer'
晶胞間隙維持用間隔件的功能， 而能夠減少像素不良。 根據本發明-實_的可絲合的樹脂組祕，提供—種可光聚 &的樹月曰組成物，该組成物包括γΑ)黏合劑樹脂；（B)多官能單體；（〇 光聚合起始劑或光敏化劑；（D)黑色顏料；以及(E)溶劑，其令所述黑色 顏料為選自苯胺黑、茈黑(perylene black)、金屬氧化物中的一種以上。 根據本發明另一實施例的可光聚合的樹脂組成物，以所述(A)黏 合劑樹脂為100重量份為準，係含有01_99重量份的(B)多官能單體，含 有0.01-20重量份的(〇光聚合起始劑或光敏化劑，含有“㈨重量份的 (D)黑色顏料，以及含有1-400重量份的(e)溶劑。 根據本發明另一實施例的可光聚合的樹脂組成物，所述金屬氧化 物為包括選自鉻、鈽、錳中的一種以上金屬的金屬氧化物。 根據本發明另一實施例的可光聚合的樹脂組成物，所述黑色顏料 的粒度為50-150μιη。 根據本發明另一實施例的可光聚合的樹脂組成物，所述黑色顏料 進一步包括顏料混合成分。 根據本發明另一實施例的可光聚合的樹脂組成物，所述顏料混合 成分必須含有紅色顏料及藍色顏料，且含有選自黃色顏料、綠色顏料 及紫色顏料中的一種或此等之混合物。 根據本發明另一實施例的可光聚合的樹脂組成物，其特徵為以顏 料混合成分的總重量中固形物含量為基準，該顏料混合成分係含有 10-50重量％的紅色顏料、10-50重量％的藍色顏料、1-20重量％的黃色 顏料、1-20重量％的綠色顏料及1-20重量％的紫色顏料。 根據本發明另一實施例的可光聚合的樹脂組成物，以顏料混合成 分的總重量中固形物含量為基準，所述黑色顏料的含量為1〇重量％以 201214046 下。 根據本發明另一實施例的可光聚合的樹脂組成物，以可光聚合的 樹脂組成物的總重量為基準，所述顏料混合成分的含量為20-80重量％。 根據本發明另一實施例的可光聚合的樹脂組成物，所述顏料混合 成分為各個顏料分散在溶劑中的顏料分散液形態。 根據本發明另—實施例的可光聚合的樹脂組成物，所述顏料分散 液含有選自丙烯酸酯類顏料分散劑中的至少一種顏料分散劑。 根據本發明另一實施例的可光聚合的樹脂組成物，其特徵為以顏 料混合成分的總重量為基準，所述顏料分散劑的含量為3-20重量％。 根據本發明另一實施例的可光聚合的樹脂組成物，塗佈所述可光 聚合的樹脂組成物分散而製備的樹脂黑色矩陣後，經曝光及顯影而得 到的圖案’其每單位厚度3.0μηι的光學密度(OD)為3.0以上。 根據本發明的另一實施例，提供一種薄膜電晶體基板，包括黑色 矩陣其係所述可光聚合的樹脂組成物通過光微影法而形成。 根據本發明的另—實施例，提供-種薄膜電晶體基板，包括液晶 3隙維制間隔件’其係湘所述可光聚合賴脂組成 影法而形点。 根據本發明的另_實施例，提供—種薄膜電晶體基板，包括黑色 组成物朗隙維制間隔件，其係湘所述可光聚合的樹脂 組成物通過光微影法而形成。 為下=二【施例，提供-種包括所述薄膜電晶體基板作 發明的可光聚合的_組成物形成硬化膜時，既能顯示出 =的光學密度又能使金屬含量最小化，因此在製作液晶 持用間隔件’或在====板上的黑色矩陣及液晶胞間隙維 液晶胞間隙維持形成可同時滿足黑色矩陣功能及 201214046 【實施方式】 根據本發明的一實施例，提供一種可光聚合的樹脂組成物，該組 成物包括：（A)黏合劑樹脂；（B)多官能單體；（C)光聚合起始劑或光敏 化劑；（D)黑色顏料；以及(E)溶劑，所述黑色顏料為選自苯胺黑、茈黑、 金屬氧化物中的一種以上。 以下進一步詳細說明本發明。 (A)黏合劑樹脂 根據本發明的黏合劑樹脂的實例可為下述化學式1所示之主鍵中 包含丙稀酸酯基之具有多官能基團結構的樹脂化合物。 [化學式1]The cell gap maintains the function of the spacer, and the pixel defect can be reduced. According to the present invention, a splicable resin composition provides a photopolymerizable & sap composition comprising a γ Α) binder resin; (B) a polyfunctional monomer; a photopolymerization initiator or a photosensitizer; (D) a black pigment; and (E) a solvent which is one or more selected from the group consisting of nigrosine, perylene black, and metal oxide. A photopolymerizable resin composition according to another embodiment of the present invention, which comprises 0.01 to 99 parts by weight of (B) polyfunctional monomer, and contains 0.01 to 20 parts by weight based on 100 parts by weight of the (A) binder resin. a (photopolymerization initiator or photosensitizer containing "(9) parts by weight of (D) black pigment, and containing 1 to 400 parts by weight of (e) solvent. Photopolymerizable according to another embodiment of the present invention. The resin composition, the metal oxide is a metal oxide including one or more metals selected from the group consisting of chromium, lanthanum, and manganese. The photopolymerizable resin composition according to another embodiment of the present invention, the black pigment The particle size is 50-150 μηη. The photopolymerizable tree according to another embodiment of the present invention. The composition, the black pigment further comprising a pigment mixing component. According to another embodiment of the present invention, the photopolymerizable resin composition, the pigment mixing component must contain a red pigment and a blue pigment, and contains a yellow pigment, One or a mixture of the green pigment and the violet pigment. The photopolymerizable resin composition according to another embodiment of the present invention, characterized in that the pigment is mixed based on the solid content of the total weight of the pigment mixture component. The composition contains 10-50% by weight of red pigment, 10-50% by weight of blue pigment, 1-20% by weight of yellow pigment, 1-20% by weight of green pigment and 1-20% by weight of violet pigment. The photopolymerizable resin composition of another embodiment of the present invention is based on the solid content of the total weight of the pigment mixture component, and the content of the black pigment is 1% by weight under 201214046. According to another embodiment of the present invention The photopolymerizable resin composition is exemplified in an amount of from 20 to 80% by weight based on the total mass of the photopolymerizable resin composition. According to another embodiment of the present invention, the photopolymerizable resin composition is in the form of a pigment dispersion liquid in which respective pigments are dispersed in a solvent. The photopolymerizable resin composition according to another embodiment of the present invention, The pigment dispersion contains at least one pigment dispersant selected from the group consisting of acrylate pigment dispersants. The photopolymerizable resin composition according to another embodiment of the present invention is characterized by based on the total weight of the pigment mixture component The content of the pigment dispersant is from 3 to 20% by weight. According to another embodiment of the present invention, the photopolymerizable resin composition is coated with the resin black matrix prepared by dispersing the photopolymerizable resin composition. The pattern obtained by exposure and development has an optical density (OD) of 3.0 μm per unit thickness of 3.0 μm. According to another embodiment of the present invention, there is provided a thin film transistor substrate comprising a black matrix formed by the photolithographic method. According to another embodiment of the present invention, there is provided a thin film transistor substrate comprising a liquid crystal 3 spacer spacer member, wherein the photopolymerizable lysate is patterned to form a dot. According to another embodiment of the present invention, there is provided a thin film transistor substrate comprising a black composition gap-preserving spacer, wherein the photopolymerizable resin composition is formed by photolithography. When forming a cured film comprising the thin film transistor substrate as the photopolymerizable composition of the invention, it is possible to exhibit both an optical density of = and a metal content, thereby In the process of fabricating the liquid crystal holding spacer 'or the black matrix on the ==== plate and the liquid crystal cell gap, the cell gap is maintained to form the black matrix function and 201214046. [Embodiment] According to an embodiment of the present invention, A photopolymerizable resin composition comprising: (A) a binder resin; (B) a polyfunctional monomer; (C) a photopolymerization initiator or a photosensitizer; (D) a black pigment; E) a solvent, wherein the black pigment is one or more selected from the group consisting of nigrosine, indigo, and metal oxides. The invention is further described in detail below. (A) Binder Resin The resin composition according to the present invention may be a resin compound having a polyfunctional group structure containing a acrylate group in the main bond represented by the following Chemical Formula 1. [Chemical Formula 1]
(上式中R1及R3為氫原子或甲基，γ為第一酸酐的殘基，z為第二 酸酐的殘基，m:n的莫耳比為ι〇〇:〇_〇:ι〇〇。） 上述化學式1表示的化合物中，γ為選自馬來酸酐、破珀酸酐、 順-1，2,3,6-四氫鄰苯二甲酸針（cis-l,2,3,6-Tetrahydrophthalic Anhydride)、3,4,5,6-四氩鄰苯二甲酸酐（3,4,5,6- Tetrahydrophthalic Anhydride )、鄰苯二曱酸酐、衣康酸酐、l，2,4-苯三酸酐 (l，2,4-Benzenetricarboxylic Anhydride )、甲基四氫鄰苯二曱酸酐 (Methyl-Tetrahydrophthalic A.nhydride )、檸康酐（Citraconic Anhydride)、2,3-二甲基馬來酸酐（2,3-Dimethylmaleic Anhydride)、1-環戊稀-1，2-二叛酸針（l-Cyclopentene-l,2-Dicarboxylic anhydride)、順 -5-降冰片烯-内-2,3-二幾酸酐（(^5_5->1〇]±)〇1116116-611(^〇-2,3-0化31'1)〇\>^〇 Anhydride)、1，8-萘二甲酸針（i,8-Naphthalic Anhydride)中的第一酸 201214046 肝的殘基。 另外，上述化學式1表示的化合物中，z為選自均苯四甲酸二酐 (l，2,4,5-Bezenetetracarboxylic Dianhydride )、4,4’-聯苯四叛酸二針 (4,4’-Biphthalic dianhydride)、3，3’，4,4’-二苯甲酮四酸二酐 (3,3’，4,4’-Benzophenonetetracarboxyli Dianhydride)、均苯四酸二酐 (Pyromelitic Dianhydride ) 、 1,4,5,8-萘四甲酸 Sf (l，4,5,8-Naphthalenetetracarboxylic Dianhydride)、1，2,4,5-四叛酸針 (l，2,4,5-Tetracarboxylic Anhydide )、甲基降冰片稀-2,3-二叛酸酐 (Methylnorbornene-2,3-Dicarboxylic Anhydride)、4,4’-(六氟異丙烯）二醜 酸 6f (4,4,-[2,2,2-Trifluoro-l-(Trifluoromethyl)Ethylidene]Diphthalic Anhydride)' 4,4’-氧雙鄰苯二曱酸酐(4,4’-Oxydiphthalic Anhydride)及雙 (偏本二酸酐）乙二醇醋（Ethylene Glycol Bis(Anhydro Trimellitate))中 的第二酸酐的殘基。 又，化學式1表示的化合物中，當第一酸酐和第二酸酐的莫耳比 m:n為 100:0-0:100’較佳為 100:0_50:50’更佳為 1〇〇:〇_7〇:3〇,最佳為〇1〇〇 -50:50之範圍時，係有利於圖案形成時圖案顯影穩定性、硬化密度、 接力的改善。 Λ 以總樹脂組成物為準，當所述黏合劑樹脂的含量為5_8〇重量％時， 對改善所开>成的圖案的耐熱性、Rakeh、塗佈性係有利的。 具體===聚合的樹脂組成物可包括之所述_^^^ 具體實财化學式1表*的化合物，所述化學幻麵 由以下方法獲得：使下列化學式2的雙酚苐型環氧化人0 、體 (甲基）Θ稀酸反應而合成出化學式4表示的化合物，。並°化一學式3的 第二酸酐處理叫^兩财賴影性，此後再與化 _，酐或 稀酸醋反應卩料乡冑能基s，祕得化學式讀復氧丙 [化學式2] °物。 \201214046(In the above formula, R1 and R3 are a hydrogen atom or a methyl group, γ is a residue of the first acid anhydride, z is a residue of the second acid anhydride, and a molar ratio of m:n is ι〇〇:〇_〇:ι〇 〇.) Among the compounds represented by the above Chemical Formula 1, γ is selected from the group consisting of maleic anhydride, cyanoic anhydride, and cis-1,2,3,6-tetrahydrophthalic acid (cis-l, 2, 3, 6). -Tetrahydrophthalic Anhydride), 3,4,5,6-Tetrahydrophthalic Anhydride, phthalic anhydride, itaconic anhydride, 1,2,4-benzene Tris(2,4-Benzenetricarboxylic Anhydride), Methyl-Tetrahydrophthalic A.nhydride, Citracononic Anhydride, 2,3-dimethylmaleic anhydride ( 2,3-Dimethylmaleic Anhydride), 1-cyclopentene-1,2-Dicarboxylic anhydride, cis-5-norbornene-endo-2,3-di a few anhydrides ((^5_5->1〇]±)〇1116116-611(^〇-2,3-031'1)〇\>^〇Anhydride), 1,8-naphthalene dicarboxylic acid needle ( The first acid 201214046 liver residue in i,8-Naphthalic Anhydride). Further, in the compound represented by the above Chemical Formula 1, z is selected from the group consisting of pyromellitic dianhydride (1,2,4,5-Bezenetetracarboxylic Dianhydride) and 4,4'-biphenyltetrahydropyrubic acid (4,4'). -Biphthalic dianhydride), 3,3',4,4'-Benzophenone tetracarboxylic acid dianhydride (Pyromelitic Dianhydride), 1 , 4,5,8-naphthalenetetracarboxylic acid Sf (1,4,5,8-Naphthalenetetracarboxylic Dianhydride), 1,2,4,5-tetra-treasure acid (l,2,4,5-Tetracarboxylic Anhydide), A Methylnorbornene-2,3-Dicarboxylic Anhydride, 4,4'-(hexafluoroisopropene) di ugly acid 6f (4,4,-[2,2,2 -Trifluoro-l-(Trifluoromethyl)Ethylidene]Diphthalic Anhydride) 4,4'-Oxodiphthalic Anhydride and Ethylene Glycol Residue of the second anhydride in Bis (Anhydro Trimellitate). Further, in the compound represented by Chemical Formula 1, the molar ratio m:n of the first acid anhydride and the second acid anhydride is 100:0 to 0:100', preferably 100:0 to 50:50', more preferably 1 〇〇: 〇 _7〇: 3〇, preferably in the range of 〇〇1〇〇-50:50, is advantageous for pattern development stability, hardening density, and relay improvement at the time of pattern formation. Λ When the content of the binder resin is 5-8 8% by weight based on the total resin composition, it is advantageous for improving the heat resistance, Rakeh, and coatability of the formed pattern. Specifically, the polymer composition of the polymerization may include the compound of the formula *, which is obtained by the following method: the bisphenol hydrazine type epoxidation of the following chemical formula 2 0, the compound (methyl) hydrazine is reacted to synthesize a compound represented by Chemical Formula 4. And the second anhydride treatment of the formula 3 is called the two-products, and then reacts with the _, anhydride or dilute vinegar, and the chemical formula reads oxypropylene. [Chemical formula 2] ] °. \201214046
(R為氫原子或甲基) [化學式4](R is a hydrogen atom or a methyl group) [Chemical Formula 4]
(R1為氫原子或甲基) [化學式5] 9 201214046(R1 is a hydrogen atom or a methyl group) [Chemical Formula 5] 9 201214046
(R為氫原子或甲基） (B) 多官能單體 透過光而形成光阻狀態之多官能單體的具體實例有：聚丙二醇甲 基丙烯酸酯、二新戊四醇六丙烯酸酯、二新戊四醇丙烯酸酯、新戊二 醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、1,6-己二醇丙烯酸酯四乙二醇 甲基丙烯酸酯、雙苯氧基乙醇二丙烯酸酯、三羥乙基異氰尿酸三甲基 丙烯酸酯、三甲基丙烧三甲基丙稀酸酯、新戊四醇三曱基丙稀酸酯、 新戊四醇四甲基丙烯酸酯及二新戊四醇六甲基丙烯酸醋中的一種或兩 種以上。 以所述化學式1表示的化合物的為100重量份為準，所述多官能單 體的含量為0.1-99重量份時’係有利於由UV使光起始劑引起自由基反 應產生交聯結合而形成圖案’並有利於提南顏料及粒子成分的結合 力，從而增加光學密度。 (C) 光聚合起始劑或光敏化劑 所述光聚合起始劑的具體實例有肟酯類化合物：1-[9-乙基-6-(2-甲 基苯甲醯基)-9H-咔唑-3-基]-1-(0-乙醯肟）、1，2-辛烷二酮-i-[4-(苯硫基) 苯基]-2-(0-苯甲醯肟)和噻噸酮、2,4-二乙基噻噸酮、噻噸酮-4-磺酸、 二苯曱酮、4,4'-二(二乙胺基)二苯甲酮、苯乙酮、對二甲胺基苯乙酮、 二甲氧基乙醯氧基苯乙酮、2,2-二曱氧基-2-苯基苯乙酮、對甲氧基苯 乙酮、2-甲基[4-(甲硫基）苯基]-2·嗎♦基-1·丙酮、2·苯甲基-2-二乙 胺基-1-(4-嗎啉基苯基）-丁烷-1-酮、2-經基-2-甲基-1-苯基-丙烷-1-酮、 4- (2-羥基乙氧基）苯基-(2-羥基-2-丙基）_、1_羥基環己基苯基酮 201214046 等酮類；蒽酿、1,4-萘醌等醌類；1，3,5_三（三氣曱基）均三嗪(1，3,5_ 三（三氣甲基）-s-三嗪）、1，3_雙（三氣曱基）·5_(2_氣苯基）-s-三嗪、 1，3_雙（三氣苯基）-S·三嗪、苯醯甲基氣、三溴甲基苯砜、三（三氣曱 基）_s_二嗪等鹵素化合物；過氧化二（三級丁基）（Di-tert-butyl peroxide) 等過氧化物；2,4,6-三曱基苯甲醯二苯基膦氧化物等醯基膦氧化物。 以所述化學式1表示的化合物1〇〇重量份為準，所述光聚合起始劑 或光敏化劑的含量較佳為〇.〇1_2〇重量份。 (D)黑色顏料 所述黑色顏料可選自苯胺黑、茈黑、金屬氧化物中的一種以上。 所述金屬氧化物較佳含有選自鉻、鈽、錳中的一種以上金屬。由易於 使圖案顯影之觀點考量’較佳為苯胺黑、氧化猛。 所述黑色顏料的粒度較佳為5〇_ΐ5〇ηιη，更佳為80-100nm ;當進行 旋轉式及非旋轉式(spinless)塗佈時可賦予流動性，並可有效防止預烘 烤後產生表面殘留物及突起’而有利於光學密度及基板的黏著力。 以化學式1表示的化合物1〇〇重量份為準，當所述黑色顏料的含量 為1-300重量份時，可調節樹脂組成物的光學密度而較佳。 所述黑色顏料可進一步包括顏料混合成分。 所述顏料混合成分中必須含有紅色顏料及藍色顏料，可含有選自 黃色顏料、綠色顏料及紫色顏料中的一種或其等之混合物。具體上， 若考量顏料混合時的透光率及介電常數，則較佳混合有機顏料而使 用。較佳的是’必須含有紅色顏料及藍色顏料，並在此進一步混合黃 色顏料或綠色顏料。此外，可再混合顏料。 顏料的具體實例係有’但未限於：依比色值(C.L number)，紅色顏 料：C.I. 3, 23, 97，108, 122, 139, 149, 166, 168, 175, 177, 180, 185, 190, 202, 214, 215, 220, 224, 230, 235, 242, 254, 255, 260, 262, 264, 272 ;黃 色顏料：C.I. 13, 35, 53, 83, 93, 110, 120, 138, 139, 150, 154, 175, 180, 181，185, 194, 213 ;藍色顏料：C.I. 15, 15:1, 15:3, 15:6, 36, 71，75 ;綠色 顏料：C.I. 7, 36 ;紫色顏料：C.I. 15, 19, 23, 29, 32, 37。 以顏料混合成分總重量中固形物成分的含量為基準，所述顏料混 合成分中紅色顏料含量為10-50重量％、藍色顏料含量為10-50重量％、 201214046 黃色顏料含量為1-20重量％、綠色顏料含量為1_2〇重量％及紫色顏料含 量為1-20重量％。 以可光聚合的樹脂組成物總重量為準，所述顏料混合成分的含量 為20-80重量。/〇。 所述顏料混合成分係以各個顏料在溶劑中分散的顏料分散液形態 為佳。 所述顏料分散液係包括選自丙烯酸酯類顏料分散劑中的至少一種 顏料分散劑。 所述顏料分散劑係占顏料混合成分總重量的3-20重量％。 (E)溶劑 所述溶劑可選自丙二醇曱醚醋酸酯(PGMEA)、丙二醇乙醚醋酸 酯、丙二醇甲醚、丙二醇丙醚、乙酸甲賽璐蘇、乙酸乙赛璐蘇、二乙 二醇甲基醋酸酯、乙氧基丙酸乙酯、乙氧基丙酸甲酯、乙酸丁酯、乙 酸乙酯、環己酮、丙酮、甲基異丁基甲酮、二甲基甲醯胺、N，N，-二曱 基乙醯胺、N-甲基吡咯啶酮、二丙二醇甲醚、甲苯、甲賽璐蘇及乙赛 路蘇而使用。 以所述化學式1表示的化合物100重量份為準，當所述溶劑的含量 為1-400重量份時，可調節樹脂組成物的溶解性、塗佈特性以及表面特 性而較佳。 此外，根據本發明的可光聚合的樹脂組成物可根據不同的需要選 擇性地包括含有環氧基的石夕氧（silicone)系化合物。 包含含有所述環氧基的矽氧系化合物之目的在於改善樹脂黑色矩 陣對水、驗、酸及有機溶劑等化學物質的耐化學藥品性（chemieal resistance);以及改善耐熱性和黏著性等。具體上可為選自線性酚醛 樹=型環氧丙烯酸酯、雙酚A型丙烯酸酯、雙酚s型丙烯酸酯、甲醛酚 醛清漆型環氧丙烯酸酯等具有環氧基的1種以上化合，物。 以所述化學式1表示的化合物100重量份為準，當所述矽氧系化合 物的含量為G_1_8G重量份時’係可改善圖案形成後的耐熱性、化學性、 黏者性而較佳。 此外，根據本發明的樹脂黑色矩陣用可光聚合的樹脂組成物視需 12 201214046 求還可包括添加劑，添加劑的具體實例有提高黑色矩陣和塗佈基板之 間的後接力的矽烷偶合劑；以及改善塗佈表面的接觸角和殘留物等特 性的界面活性劑。 將如上所述的可光聚合的樹脂組成物分散而製造的樹脂黑色矩陣 的黏度較佳為l-5cps。於此範圍時，相對旋轉式或非旋轉式塗佈，可提 供不同的製品等級、可防止塗佈後薄膜内的殘留物及突起，還可調節 不同薄膜的不同厚度。 尚且，就塗佈如上所述之可光聚合的樹脂組成物分散而製備的樹 脂黑色矩陣後進行曝光及顯騎得之圖_光學密度而言，以3 一的 厚度為單位’係較佳為3.〇-6.〇μπι。 具體說明，在液晶顯示器中作為提高開口率等的一環，係在下部 基板’即陣列基板上形成彩色濾光片層，並在所述彩色滤光片層的R、 G、B像素之間形成黑色矩陣。此時便可使黑色矩陣的邊緣最小化，從 而最終提高開口率、增加亮度。 特別是在陣列基板上形成黑色矩陣的同時可在陣列基板上形成間 隙維持用間隔件’其乃一般稱為「柱間隔件（c〇lumn spa—」的間 隙維持關隔件。在陣列基板上形成黑色矩陣和職維持關隔件係 通過另外的圖案形成步驟形成，亦可分別形成。已知—般作為黑色矩 =之遮光膜形成用可歧合的樹脂組成物、及形成間隙維持用間隔件 的可光聚合的樹脂組成物具有不同的組成，對其所需的特性也不同。 +惟，由在陣列基板上形成彩色遽光片之LCD結構的技術發展而 需滿足以下要求：透過-種光微影步驟形成黑色矩陣和間隙維持 :間隔件，使之形成高低差(段差);在黑色矩陣上形成間 5進步使用-圖案來發揮黑色矩陣及間隙維持用間隔件的功能。 :成此用途的圖案所需之特性中的—種為可於形成圖紐進一步 ，仃其他目的之光微影步驟。由此點而言，為了發揮作為遮光膜之功 ^則根據本發明的可光聚合的樹脂組成物在滿足最小限的遮光性的 ^需滿足母皁位厚度3卿的光學密度（〇D)為3以上，以使特定金 屬(鋼、鋅）的含量最小化4為了使液晶顯示裝置的驅動不良最小 而通過對樹餘成物金屬成分之溶出實驗，使金屬成分中銅的含 13 201214046 量為i_m下、辞的含量為3Gp_p金屬成分的溶出實驗方法可 如下定義： <金屬成分溶出實驗方法> -硬化膜形成法 利用如此獲得的可光聚合的樹脂組成物通過下述方法形成硬化獏 圖案·利用&塗機以5GGrpm ’在具有乾淨表面的玻璃基板上塗佈樹脂 而形成塗佈層。塗佈後，以加熱板在l〇(TC之溫度下乾燥1〇〇秒，使 塗佈膜升>成厚1-1.5μπι。接著，通過光罩（間隙1〇〇μιη)照射3〇mJ/cm2 之照射量的紫外線等光化射線進行曝光，以曝光所得的膜使用顯影液 (0·032%ΚΟΗ水溶液，25°C)顯影（顯影時間60秒）而形成硬化臈 圖案。顯影後，放入對流烘箱在220°C下進行30分鐘的後烘烤。 -分析樣品的準備及分析方法 於後烘烤完成的玻璃基板上將硬化膜圖案切成一定面積(〇 5cinx 〇.5cm)後，將其浸潰在NMP(N-甲基D比〇各°定銅)5g中，其後在1〇〇。(3之溫 度下實施熱處理1小時。熱處理後對NMP進行萃取，並使用icp-MS(感 應耦合電漿質譜儀)設備測定溶液中的金屬含量。 倘若由可光聚合的樹脂組成物獲得的硬化膜按3.〇微米的厚度，其 光學密度（OD)係小於3.0，則增至一定厚度亦難以發揮適當的遮光 效果’作為遮光膜時並無法充分發揮遮光作用，從而無法阻斷向透明 像素以外的區域透過之無法控制的光。 若利用滿足上述特性的可光聚合的樹脂組成物，則可使用狭縫光 罩(slit mask)或乎色調光罩(half-tone mask)進行圖案化，使之具有既定 寬度的高低差而形成黑色矩陣和間隙維持用間隔件；或在形成黑色矩 陣的位置上在進一步形成間隙維持用間隔件’而在形成黑色矩陣時可 發揮間隙維持用間隔件之功能。尤其是形成所述圖案後，在後續的光 微影步驟中形成透明電極時，可以使剝離液引起的圖案最小化。 此外，如上所述液晶顯示器之影像係依此方式顯示··於兩電極（像 素電極、通用電極）對向的兩基板之間注入液晶物質，並對兩電極施 加電壓’透過電場使液晶分子運動來改變透光率《倘若在下部基板形 成的像素電極和在上部基板形成的.通用電極之間混入導電異物（金屬 201214046 氧化物）’則在下部基板形成的像素電極和在上部基板形成的通用電極 之間的電位差便無法維持在施加初始的狀態，而導致液晶分子不進行 配向或配向不均。 這些問題會導致液晶顯示器驅動時的亮點或黑點等斑點，而發生 像素不良。 為使利用可光聚合的樹脂組成物製備的黑色矩陣硬化圖案的金屬 含量最小化，具體的方法有多種，並沒有特別的限制。具體上可為變 化黑色顏料的種類及含量等方法。 以下詳細說明本發明的實施例及比較例。惟，此等實施例和比較 例係僅用以更佳地說明本發明，而非限定本發明之範圍。 <製備例ι>化學式1表示的化合物的製備 在1L四口燒瓶中混合雙酚第型環氧化合物232g、丙烯酸72g，並 將二乙胺4.56g和對苯二酚〗〇〇mg加入溶劑丙二醇甲醚醋酸酯 (PGMEA)中後’於l〇〇t予以加熱溶解。溶液係於混濁狀態中緩慢升 溫，且於iooc完全溶解。完全溶解後維持在9(rc，在此以25ml/分鐘 的速率注入氮，一直持續12小時至達到所需的酸價。測定酸價並持續 加熱授拌至酸價小於3.OmgKOH/g。然後，冷卻到室溫即製得無色透明 的雙酚第型環氧丙烯酸酯。 於由此獲得的雙酚第型環氧丙烯酸酯3〇〇g中混合12,3,6_四氫化 欧針32_57g’緩慢升溫至120°C反應20小時，從而獲得卡爾多（Card〇) 系黏合劑樹脂。 <製備例2>鹼可溶性丙烯酸黏合劑樹脂合成例 於1000ml的四口燒瓶中加入下表i所示的組成成分，在此吹入氮 氣並充分攪拌30分鐘。然後，緩慢升溫至6yc反應4小時後，再升 溫至80。(：反應2小時，即合成出鹼可溶性丙烯酸類黏合劑樹脂。下表 1中所記載的含量單位為g。 ' 15 201214046 表1] 製備例2 MAA 38.13 MMA 108.82 Sty 32.45 KBM503 11.45 起始劑 19.09 PGMEA 490.00 (註）MAA :甲基丙烯酸，MMA :曱基丙烯酸曱酯，sty :苯乙烯 KBM503 : 3-(曱基丙烯醯氧丙基)三曱氧基矽烷，Shin-Etsu Chemical 製品 起始劑：偶氮二異丁腈 PGMEA:丙二醇曱醚醋酸酯 <實施例1-8> 在所述製備例1中製備的卡爾多系化合物和所述製備例2中得到 的鹼可溶性丙烯酸黏合劑樹脂中，分別按照下表2中所示加入黑色顏 料、多官能單體（二新戊四醇六丙烯酸酯）、光聚合起始劑、溶劑（丙 二醇曱醚醋酸酯（PGMEA))和其他添加劑（氟系界面活性劑及偶合 劑）攪拌下反應3小時，從而製備了可光聚合的樹脂組成物。 其中，重量份係以總黏合劑樹脂（卡爾多系化合物和丙烯酸類黏 合劑樹脂）固形物含量為100重量份為準的含量。 16 201214046 [表2] 製備例 1 (卡爾 多系化 合物） 製備例 2 (丙烯 酸類黏 合劑） 黑色顏料 光起 始劑 溶劑 (PG ME A) 多官 能單 體 (DPH A) 添加齊|J (GPTM S) 顏料名 重量 份 比 較 例 1 $ 20 KLBK-103 100 10 215 30 '—---- 2.5 2 8 20 KLBK-103 150 10 3 8 20 KLBK-90 100 10 4 8 20 KLBK-90 150 10 1 8 20 ΑΜ-092 100 10 實 施 例 2 8 20 ΑΜ-092 150 10 3 8 20 ΑΜ-113 100 10 4 8 20 ΑΜ-113 150 10 (言主） 樹脂成分:總組成中15重量％ DPHA:二新戊四醇六丙烯酸酯 PGMEA:丙二醇甲醚乙酸酯 GPTMS:y-(縮水甘油醚）丙基三甲氧基矽烷(矽氧系化合物） KLBK-103 :Mikuni公司的碳黑顏料分散液 KLBK-90:Mikuni公司的有機顏料(RGB)分散液 AM-092:KCC公司的氧化錳黑色顏料 AM-113:KCC公司的苯胺黑色顏料 通過下述方法測定依所述比較例1-4及實施例1·4製備的可光聚 合的樹脂組成物的顯影開始時間、顯影圖案穩定性、光學密度、金屬 成分溶出量、殘留物等，其結果在下表3中示出。 (1)硬化膜形成方法 利用如此獲得的可光聚合的樹脂組成物通過下述方法形成硬化膜 17 201214046 圖案：利用旋塗機以500rpm，在具有 而形成塗佈層。塗佈後，以加熱板在ω表面^玻^基^上塗佈樹脂 塗佈膜成為。接著，_光罩（2打杨_秒，使 照射量的紫外線等光化射線進行先射遍細2之 (〇.〇32%KOH水溶液，25t )顯影f t所1的膜使用顯影液 圖案=财，放人對流烘箱在職下進行3G分鐘的後供烤。 (2) 顯影開始時間 用肉眼確認脂黑色_在玻縣板上進行塗佈·預烘烤-曝光 顯影步驟中樹脂黑色矩陣顯影而開始形成圖案的時間，該時 間即為顯影開始時間。 (3) 顯影圖案穩定性 少對樹脂黑色矩陣在玻璃基板上進行塗佈-預烘烤-曝光步驟後，在顯 影步驟中樹脂黑色矩陣顯影而開始形成圖案之後（顯影開始時間），分 不同時間進行顯影，以光學顯微鏡確認圖案的線寬及圖案的直線性。 顯影時間係以5秒鐘為單位’並確認圖案的線寬減少1μ〇ι以下的區間。 (4)光學密度 通過上述方法獲得的硬化膜係使用大塚電子股份有限公司的ΡΜΤ (光電倍增管）設備以及光學密度為2.4的參考物（reference)測定光 學密度，其結果示於表3。 (5 )金屬成分溶出量 於後烘烤完成的玻璃基板上將硬化膜圖案切成一定面積(〇.5cmx 〇.5cm)後，將其浸潰在NMP(N-甲基吡咯咬嗣)5g中，其後在100°C之溫 度下實施熱處理1小時。熱處理後對NMP進行萃取，並使用ICP-MS設 備(產品名：ELAN DRC-II，廠商：Perkin Elmer)測定溶液中的金屬含量。 (6)殘留物 利用SEM確認顯影後是否有殘留物。 18 201214046 [表3] 比較例 及 實施例 顯影開始 時間 (s) 顯影 圖案 穩定性(s) 光學密度 (/ 1 μηι) ____一 金屬成分溶出量 (ppb) _ 殘留物 鋼 鋅 比較例1 35 15 2.8 22.3 78.2 無 比較例2 38 15 3.5 28.7 90.5 無 比較例3 28 15 0.9 317.7 36.2 無 比較例4 33 15 1.2 498.6 51.2 無 實施例1 35 15 1.3 8.5 21-7 無 實施例2 75 10 1.6 8.7 29.1 有 實施例3 35 15 1.4 未檢出 15.9 無 實施例4 38 15 1.8 3.1 18.1 ----1 _無 由所述表3的結果，通過比較例1-4的金屬成分溶出實驗結果可 知，使用碳黑及有機RGB顏料的樹脂組成物在形成遮光膜之後，被檢 出的銅和鋅等金屬成分相對較多。相對於此，實施例1-4之使用苯胺黑 顏料和氧化錳黑顏料的樹脂組成物在形成硬化膜時，可顯示適當的光 ，个 密度，又可使特定金屬含量最小化，從而在液晶顯示器驅動時 會發生亮點或黑點等斑點（Sp〇t )等像素不良的問題。 為實m々，使其他評價值最小化的損傷具有最適合的條件的實施例 熟習該技藝者可對本發明進行單純變化或變更，因 變更皆屬於本發明之範圍。 k種變 【圖式簡單說明】 叙 19 201214046 【主要元件符號說明】(R is a hydrogen atom or a methyl group) (B) Specific examples of the polyfunctional monomer in which a polyfunctional monomer transmits light to form a photoresist state are: polypropylene glycol methacrylate, dipentaerythritol hexaacrylate, and Neopentyl alcohol acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol acrylate tetraethylene glycol methacrylate, bisphenoxyethanol Acrylate, trishydroxyethyl isocyanuric acid trimethacrylate, trimethylpropenyl trimethyl acrylate, neopentyl alcohol tridecyl acrylate, neopentyl alcohol tetramethacrylate And one or more of dipentaerythritol hexamethacrylate. When the content of the compound represented by the above formula 1 is 100 parts by weight, and the content of the polyfunctional monomer is 0.1 to 99 parts by weight, it is advantageous for the photoinitiator to cause a radical reaction by UV to produce cross-linking. The formation of the pattern 'is beneficial to the binding force of the pigment and particle components of the South, thereby increasing the optical density. (C) Photopolymerization initiator or photosensitizer A specific example of the photopolymerization initiator is an oxime ester compound: 1-[9-ethyl-6-(2-methylbenzylidene)-9H -oxazol-3-yl]-1-(0-acetamidine), 1,2-octanedione-i-[4-(phenylthio)phenyl]-2-(0-benzamide肟) and thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-di(diethylamino)benzophenone, benzene Ethyl ketone, p-dimethylaminoacetophenone, dimethoxyacetoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2 -methyl[4-(methylthio)phenyl]-2·?♦-l-acetone, 2·benzyl-2-diethylamino-1-(4-morpholinylphenyl)- Butan-1-one, 2-yl-2-methyl-1-phenyl-propan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl ), _, 1-hydroxycyclohexyl phenyl ketone 201214046 and other ketones; 蒽, 1,4-naphthoquinone and other steroids; 1,3,5_three (trimethyl fluorenyl) s-triazine (1,3, 5_ tris(trimethylmethyl)-s-triazine), 1,3_bis(trimethylsulfonyl)·5_(2_gasphenyl)-s-triazine, 1,3_bis (tris benzene) Base)-S·triazine, benzoquinone methyl gas, three a halogen compound such as methyl benzene sulfone or tris(trimethyl fluorenyl) _s di diazine; a peroxide such as Di-tert-butyl peroxide; 2,4,6-triazine A mercaptophosphine oxide such as benzamidine diphenylphosphine oxide. The content of the photopolymerization initiator or the photosensitizer is preferably 〇1〇2 〇 by weight based on the weight of the compound represented by the above formula 1. (D) Black Pigment The black pigment may be one or more selected from the group consisting of nigrosine, ruthenium, and metal oxides. The metal oxide preferably contains one or more metals selected from the group consisting of chromium, rhodium, and manganese. It is preferable to be aniline black and oxidized by the viewpoint of easiness in developing the pattern. The black pigment preferably has a particle size of 5 〇 ΐ 5 〇 ηηη, more preferably 80-100 nm; it imparts fluidity when subjected to spin and spinless coating, and can effectively prevent prebaking The surface residue and protrusions are generated to facilitate the optical density and the adhesion of the substrate. The amount of the compound represented by the chemical formula 1 is 1 part by weight, and when the content of the black pigment is 1 to 300 parts by weight, the optical density of the resin composition can be adjusted. The black pigment may further include a pigment mixing component. The pigment mixed component must contain a red pigment and a blue pigment, and may contain one selected from the group consisting of a yellow pigment, a green pigment, and a violet pigment, or a mixture thereof. Specifically, in consideration of the light transmittance and the dielectric constant when the pigment is mixed, it is preferred to use an organic pigment in combination. It is preferred that 'the red pigment and the blue pigment must be contained, and a yellow pigment or a green pigment is further mixed here. In addition, the pigment can be remixed. Specific examples of pigments are 'but not limited to: color number (CL number), red pigments: CI 3, 23, 97, 108, 122, 139, 149, 166, 168, 175, 177, 180, 185, 190, 202, 214, 215, 220, 224, 230, 235, 242, 254, 255, 260, 262, 264, 272; yellow pigments: CI 13, 35, 53, 83, 93, 110, 120, 138, 139, 150, 154, 175, 180, 181,185, 194, 213; blue pigment: CI 15, 15:1, 15:3, 15:6, 36, 71,75; green pigment: CI 7, 36 Purple pigment: CI 15, 19, 23, 29, 32, 37. Based on the content of the solid content in the total weight of the pigment mixture component, the red pigment content of the pigment mixture component is 10-50% by weight, the blue pigment content is 10-50% by weight, and the 201214046 yellow pigment content is 1-20. The weight %, the green pigment content is 1 to 2% by weight, and the purple pigment content is 1 to 20% by weight. The pigment mixed component is contained in an amount of from 20 to 80% by weight based on the total mass of the photopolymerizable resin composition. /〇. The pigment mixing component is preferably in the form of a pigment dispersion in which each pigment is dispersed in a solvent. The pigment dispersion liquid includes at least one pigment dispersant selected from the group consisting of acrylate-based pigment dispersants. The pigment dispersant is from 3 to 20% by weight based on the total weight of the pigment mixture component. (E) Solvent The solvent may be selected from the group consisting of propylene glycol oxime ether acetate (PGMEA), propylene glycol ethyl ether acetate, propylene glycol methyl ether, propylene glycol propyl ether, acesulfame acetate, ethyl acesulfame acetate, diethylene glycol methyl Acetate, ethyl ethoxypropionate, methyl ethoxypropionate, butyl acetate, ethyl acetate, cyclohexanone, acetone, methyl isobutyl ketone, dimethylformamide, N, N, - Dimercaptoacetamide, N-methylpyrrolidone, dipropylene glycol methyl ether, toluene, acesulfame, and cesulfuron. In the case of 100 parts by weight of the compound represented by the above Chemical Formula 1, when the content of the solvent is from 1 to 400 parts by weight, the solubility, coating properties and surface characteristics of the resin composition can be adjusted. Further, the photopolymerizable resin composition according to the present invention may optionally include an epoxy group-containing silicon compound according to various needs. The purpose of the antimony-containing compound containing the epoxy group is to improve the chemical resistance of the resin black matrix to chemicals such as water, chemicals, acids, and organic solvents, and to improve heat resistance and adhesion. Specifically, it may be one or more compounds having an epoxy group selected from the group consisting of novolacs = type epoxy acrylate, bisphenol A type acrylate, bisphenol s type acrylate, and formaldehyde novolac type epoxy acrylate. . When 100 parts by weight of the compound represented by the above Chemical Formula 1 is used, when the content of the oxime-based compound is G_1_8 G by weight, the heat resistance, chemical properties, and stickiness after pattern formation are improved. Further, the photopolymerizable resin composition for a resin black matrix according to the present invention may further include an additive as needed, and a specific example of the additive is a decane coupling agent which improves the post-contact force between the black matrix and the coated substrate; A surfactant that improves the contact angle of the coated surface and the properties of the residue. The viscosity of the resin black matrix produced by dispersing the photopolymerizable resin composition as described above is preferably from 1 to 5 cps. In this range, relatively rotary or non-rotating coatings can provide different product grades, prevent residues and protrusions in the film after coating, and can adjust different thicknesses of different films. Further, in the case of applying a resin black matrix prepared by dispersing the photopolymerizable resin composition as described above, exposure and riding are carried out. In terms of optical density, it is preferable to use a thickness of 3 3. 〇-6.〇μπι. Specifically, in the liquid crystal display, as a ring for increasing the aperture ratio or the like, a color filter layer is formed on the lower substrate 'that is, the array substrate, and is formed between the R, G, and B pixels of the color filter layer. Black matrix. At this point, the edges of the black matrix can be minimized, ultimately increasing the aperture ratio and increasing the brightness. In particular, a gap maintaining spacer can be formed on the array substrate while forming a black matrix on the array substrate. This is generally referred to as a "column spacer" (g-lumn spa-" gap-maintaining spacer. On the array substrate The formation of the black matrix and the maintenance spacer are formed by another pattern forming step, and may be separately formed. It is known that the black matrix = the disposable resin composition for forming the light-shielding film, and the gap maintaining interval are formed. The photopolymerizable resin composition of the member has a different composition and different characteristics required for it. However, the technical development of the LCD structure for forming a color light-receiving sheet on the array substrate needs to satisfy the following requirements: The photolithography step forms a black matrix and gap maintenance: spacers are formed to form a height difference (step difference); and a black matrix is formed on the black matrix to play a function of the black matrix and the gap maintaining spacers. Among the characteristics required for the pattern of this application, it is a photolithography step which can form a further pattern for further purposes, and in order to function as a light-shielding film. The photopolymerizable resin composition according to the present invention satisfies the minimum light-shielding property to satisfy the optical density (〇D) of the mother soap layer thickness of 3 or more, so that the specific metal (steel, zinc) In order to minimize the driving failure of the liquid crystal display device, the elution test of the metal component of the tree residue is carried out, so that the content of copper in the metal component is 13 201214046, and the content of the word is 3 Gp_p metal component. The dissolution test method can be defined as follows: <Metal component dissolution test method> - Curing film formation method Using the photopolymerizable resin composition thus obtained, a hardened enamel pattern is formed by the following method: using & coater at 5 GG rpm ' A coating layer is formed by coating a resin on a glass substrate having a clean surface. After coating, drying is performed at a temperature of TC at a temperature of TC for 1 sec, and the coating film is raised to a thickness of 1-1.5 μm. Then, an actinic ray such as an ultraviolet ray having an irradiation amount of 3 〇mJ/cm 2 is irradiated through a mask (gap 1 〇〇 μηη), and a developing solution (0·032% hydrazine aqueous solution, 25 ° C) is used for exposure. Development (development) After 60 seconds), a hardened enamel pattern is formed. After development, it is placed in a convection oven for post-baking at 220 ° C for 30 minutes. - Analysis sample preparation and analysis method. The cured film is formed on the post-baking glass substrate. After the pattern was cut into a certain area (〇5cinx 〇.5cm), it was immersed in 5g of NMP (N-methyl D is more than 定), and then 1 〇〇. (3 at a temperature of heat treatment) 1 hour. After the heat treatment, the NMP was extracted, and the metal content in the solution was measured using an icp-MS (inductively coupled plasma mass spectrometer) apparatus. The cured film obtained from the photopolymerizable resin composition was 3. When the optical density (OD) of the thickness is less than 3.0, it is difficult to exhibit an appropriate light-shielding effect when it is increased to a certain thickness. When the light-shielding film is used, the light-shielding effect is not sufficiently exhibited, and the transmission to the region other than the transparent pixel cannot be blocked. Light. If a photopolymerizable resin composition satisfying the above characteristics is used, it can be patterned using a slit mask or a half-tone mask to have a height difference of a predetermined width. The black matrix and the gap maintaining spacers; or the gap maintaining spacers are further formed at the positions where the black matrix is formed, and the gap maintaining spacers can function as the black matrix. In particular, after the pattern is formed, when a transparent electrode is formed in the subsequent photolithography step, the pattern caused by the stripping liquid can be minimized. In addition, as described above, the image of the liquid crystal display is displayed in this manner. The liquid crystal substance is injected between the two substrates facing the two electrodes (pixel electrode, common electrode), and a voltage is applied to both electrodes to transmit the liquid crystal molecules through the electric field. To change the light transmittance "if a conductive foreign matter (metal 201214046 oxide) is mixed between the pixel electrode formed on the lower substrate and the common electrode formed on the upper substrate", the pixel electrode formed on the lower substrate and the common electrode formed on the upper substrate The potential difference between the electrodes cannot be maintained in the initial state of application, and the liquid crystal molecules are not subjected to alignment or misalignment. These problems can cause spots such as bright spots or black spots when the liquid crystal display is driven, and pixel defects occur. In order to minimize the metal content of the black matrix hardening pattern prepared by using the photopolymerizable resin composition, there are various specific methods and are not particularly limited. Specifically, it may be a method of changing the type and content of the black pigment. Hereinafter, examples and comparative examples of the present invention will be described in detail. However, the examples and comparative examples are only intended to better illustrate the invention and not to limit the scope of the invention. <Preparation Example ι> Preparation of Compound represented by Chemical Formula 1 In a 1 L four-necked flask, 232 g of a bisphenol type epoxy compound, 72 g of acrylic acid, and 4.56 g of diethylamine and a solvent of hydroquinone were added to the solvent. In propylene glycol methyl ether acetate (PGMEA), it is heated and dissolved in l〇〇t. The solution was slowly warmed in the turbid state and completely dissolved in the iooc. After complete dissolution, it was maintained at 9 (rc, where nitrogen was injected at a rate of 25 ml/min for 12 hours until the desired acid value was reached. The acid value was measured and heating was continued until the acid value was less than 3.0 mg/g. Then, cooling to room temperature, a colorless transparent bisphenol type epoxy acrylate is obtained. The bisphenol type epoxy acrylate 3 〇〇g thus obtained is mixed with 12,3,6_tetrahydro hydride needle. 32_57g' Slowly heated to 120 ° C for 20 hours to obtain a Card® adhesive resin. <Preparation Example 2> Alkali-soluble acrylic adhesive resin Synthesis Example The following table was added to a 1000 ml four-necked flask. The composition shown here was purged with nitrogen gas and stirred well for 30 minutes. Then, the temperature was gradually raised to 6 μc for 4 hours, and then the temperature was raised to 80. (: The reaction was carried out for 2 hours to synthesize an alkali-soluble acrylic binder resin. The content unit described in the following Table 1 is g. ' 15 201214046 Table 1] Preparation Example 2 MAA 38.13 MMA 108.82 Sty 32.45 KBM503 11.45 Starting agent 19.09 PGMEA 490.00 (Note) MAA: methacrylic acid, MMA: fluorenyl methacrylate Ester, sty: styrene KBM 503 : 3-(mercapto propylene methoxypropyl) trimethoxy decane, Shin-Etsu Chemical product starter: azobisisobutyronitrile PGMEA: propylene glycol oxime ether acetate <Example 1-8> In the Carbide-based compound prepared in Preparation Example 1 and the alkali-soluble acrylic binder resin obtained in the Preparation Example 2, a black pigment and a polyfunctional monomer (dipentaerythritol) were added as shown in Table 2 below, respectively. Alcohol hexaacrylate), photopolymerization initiator, solvent (propylene glycol oxime ether acetate (PGMEA)) and other additives (fluorine-based surfactant and coupling agent) were reacted for 3 hours with stirring to prepare a photopolymerizable resin. The composition is a content of the total binder resin (Kardolin compound and acrylic binder resin) in a solid content of 100 parts by weight. 16 201214046 [Table 2] Preparation Example 1 (Caldo) Compound) Preparation Example 2 (Acrylic Adhesive) Black Pigment Photoinitiator Solvent (PG ME A) Polyfunctional monomer (DPH A) Addition | J (GPTM S) Pigment name by weight Comparative Example 1 $ 20 KLBK- 103 100 10 215 30 '— ---- 2.5 2 8 20 KLBK-103 150 10 3 8 20 KLBK-90 100 10 4 8 20 KLBK-90 150 10 1 8 20 ΑΜ-092 100 10 Example 2 8 20 ΑΜ-092 150 10 3 8 20 ΑΜ-113 100 10 4 8 20 ΑΜ-113 150 10 (speech main) Resin composition: 15% by weight of the total composition DPHA: dipentaerythritol hexaacrylate PGMEA: propylene glycol methyl ether acetate GPTMS: y- (shrinkage Glycidyl ether) propyltrimethoxydecane (oxygenated compound) KLBK-103: Carbon black pigment dispersion of Mikuni KLBK-90: Organic pigment (RGB) dispersion of Mikuni Corporation AM-092: Manganese oxide of KCC Black pigment AM-113: aniline black pigment of KCC Co., Ltd. The development start time, development pattern stability, and development pattern stability of the photopolymerizable resin composition prepared according to the above Comparative Examples 1-4 and Example 1-4 were measured by the following methods. The optical density, the elution amount of the metal component, the residue, and the like are shown in Table 3 below. (1) Method of forming a cured film The cured film was formed by the following method using the photopolymerizable resin composition thus obtained. 17 201214046 Pattern: A coating layer was formed by using a spin coater at 500 rpm. After coating, a resin coating film was coated on the ω surface by a hot plate. Next, the _mask (2 dozens of _ seconds, the irradiation amount of ultraviolet rays and other actinic rays are first shot through the fine 2 (〇. 〇 32% KOH aqueous solution, 25t) developed ft 1 film using developer pattern = Fortunately, the convection oven is used for 3G minutes of post-baking. (2) Confirmation of fat black with the development start time _ Coating on the glass plate, pre-bake-exposure development step, resin black matrix development The time at which the patterning is started, which is the development start time. (3) The development pattern is less stable. After the resin black matrix is coated on the glass substrate-prebaking-exposure step, the resin black matrix development is performed in the development step. After the patterning was started (development start time), development was performed at different times, and the line width of the pattern and the linearity of the pattern were confirmed by an optical microscope. The development time was in units of 5 seconds' and the line width of the pattern was confirmed to be reduced by 1 μ. (1) Optical density The cured film obtained by the above method is a ΡΜΤ (photomultiplier tube) device of Otsuka Electronics Co., Ltd. and a reference material having an optical density of 2.4 (refe The optical density was measured, and the results are shown in Table 3. (5) The amount of eluted metal component was cut into a certain area (〇5 cmx 〇.5 cm) on a glass substrate after post-baking, and then immersed. It was kneaded in 5 g of NMP (N-methylpyrrole bitumen), and then heat-treated at 100 ° C for 1 hour. After heat treatment, NMP was extracted and ICP-MS equipment was used (product name: ELAN DRC-II) , manufacturer: Perkin Elmer) Determination of the metal content in the solution. (6) Residues were confirmed by SEM whether there was residue after development. 18 201214046 [Table 3] Comparative Example and Example Development start time (s) Development pattern stability ( s) Optical density (/ 1 μηι) ____ One metal component dissolution (ppb) _ Residue steel zinc Comparative example 1 35 15 2.8 22.3 78.2 No comparison 2 38 15 3.5 28.7 90.5 No comparison 3 28 15 0.9 317.7 36.2 No Comparative Example 4 33 15 1.2 498.6 51.2 No Example 1 35 15 1.3 8.5 21-7 No Example 2 75 10 1.6 8.7 29.1 Example 3 35 15 1.4 Not detected 15.9 No Example 4 38 15 1.8 3.1 18.1 - ---1 _ without the results of Table 3, by comparing the gold of Example 1-4 As a result of the component elution test, it was found that the resin composition using carbon black and the organic RGB pigment had a relatively large amount of metal components such as copper and zinc after the formation of the light-shielding film. In contrast, the aniline black of Example 1-4 was used. When the resin composition of the pigment and the manganese oxide black pigment forms a cured film, it can display appropriate light and density, and the specific metal content can be minimized, so that spots such as bright spots or black spots occur when the liquid crystal display is driven (Sp 〇t) The problem of poor pixels. The present invention is susceptible to variations and modifications of the present invention, and modifications are intended to be included within the scope of the present invention. k kinds of changes [Simple description of the diagram] Syria 19 201214046 [Main component symbol description]