1330757 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種顏料型感光材料’特別有關於一 種具高耐熱性與尺寸安定性之顏料型感光材料。 【先前技術】 液晶顯示器之彩色濾光片通常包含形成黑框防止混光 _ 之黑色感光樹脂’以及濾光用之紅、綠、藍三色彩色光阻， 其中彩色光阻必須有好的光穿透度及飽和度’傳統的彩色 濾光片中使用染料來達到高穿透性及色飽和度的要求，但 是’染料的财光性與耐熱性皆不佳。為克服此問題，顏料 * 分散法光阻材料已取代染料法成為主流’隨著電視用大尺 '寸面板的發展，其所要求的高亮度使得面板溫度提高，另 外，為了追求高色飽和度，則必須降低光阻中顏料粒子的 粒徑以防止散射，這使得傳統彩色濾光片中的顏料之耐熱 鲁性不足以達到電視用液晶顯示器之要求。 此外，由於彩色濾光片之需求為高光穿透度，因此顏 料分散達奈米尺度是必需的，然而當顏料粒子達奈米尺度 時，由於表面積與表面能量增加，根據熱力學第二定律， 顏料粒子必傾向於聚集，因此，必須使用更多的分散劑才 能使顏料粒子達到有效的穩定。這些分散劑係以物理方式 吸附於顏料表面，而分散劑的増加會造成彩色光阻黏度的 上升，以及產生與光阻系統相容性的問題。 針對顏料表面改質方面’在美國專利第2005075416號 0954-A21982TWF(N2) ：P54950079TW；kelly 5 1330757 揭露一種以可聚合的界面活性劑進行顏料微粒包覆來增進 . 其分散穩定性，美國專利第6,916,861號則揭露一種以高分 子包覆的方法來增進顏料分散穩定性，然而，當使用高分 子包覆顏料微粒時，因表層樹脂容易被溶劑膨潤（swell)， 會造成顏料粒子變大與團聚，其長期儲存性不佳，且對於 而于熱性並無改善效果。 另外，在美國專利第7001936B2號中則揭露一種自分 散型顏料之製造方法，以應用於喷印用墨水（inkjet ink)， • 該方法主要在顏料表面吸附一種含胺基化合物，使顏料達 自分散功能。然而，在顏料表面先吸附含胺基化合物，極 有可能影響接下來的濕式研磨之製程安定性，或者在配方 - 過程中造成胺基化合物脫附而產生凝集。此外，含胺基化 _ 合物之熱裂解溫度低於碳黑，因此可能會降低碳黑之熱裂 解溫度，不適用於彩色濾光片之黑色矩陣。 上述之顏料表面改質方式其耐熱性皆不佳，不適用於 彩色濾光片中高耐熱彩色光阻及黑色矩陣材料的需求，因 • 此，業界亟需一種顏料型感光材料，其具有高耐熱性及尺 寸安定性，可適用於耐高溫之彩色濾光片。 【發明内容】 有鑑於此，本發明之目的在於提供一種顏料型感光材 料，其具有高耐熱性、尺寸安定性以及低色度變化，可適用於 一般液晶顯示器及可撓式顯示器之彩色濾光片。 為達上述目的，本發明提供一種顏料型感光材料，包括： 鹼可溶樹脂、多官能基單體、光起始劑、以無機烷氧縮合 0954-A21982TWF(N2)；P54950079TW：kelly 6 L330757 物包覆之顏料以及溶劑。 . 本發明之顏料型感光材料中的顏料表面具有無機烷氧 縮合物包覆，將此表面改質後的顏料與驗可溶樹脂、多官 能基單體、光起始劑以及溶劑搭配，可提高顏料型感光材 料的耐熱性與尺寸安定性，同時其在高溫下的色度變化 小，能維持色彩穩定度。 在本發明之一實施例中，鹼可溶樹脂可為含矽烷之共聚 物，其可使得以無機烷氧縮合物包覆之顏料具有更佳的分 φ 散性，並且更可進一步降低顏料型感光材料的熱膨脹係 數，使得其更具尺寸安定性，因此除了適用於一般以玻璃 為基板之顯示器，更可適用於在軟性基板上製作之可撓式 - 顯示器。 . 為了讓本發明之上述目的、特徵、及優點能更明顯易 懂，以下配合所附圖式，作詳細說明如下： 【實施方式】 φ 本發明之顏料型感光材料包括（a)鹼可溶樹脂；（b)多官 能基單體；（c)光起始劑；（d)以無機烷氧縮合物包覆之顏 料；以及（e)溶劑。其中以無機烷氧縮合物包覆之顏料係使 用一種具反應性的無機烷氧化合物作為顏料的表面改質 劑，此無機烧氧化物可利用溶膠-凝膠法（sol-gel)進行縮合 與聚合反應，形成無機烷氧縮合物包覆於顏料表面，使顏 料具有較高的耐熱性及熱穩定性，此外，亦可使顏料具有 易分散的特性。其中，顏料週遭之無機烷氧縮合物包覆層 的厚度約為2〜4nm之間，此厚度可藉由所添加的無機烷 0954-A21982TWF(N2)；P54950079TW；kelly 7 1.330757 氧化合物與顏料的比例來控制，並非限定於上述之厚度範 • 圍’其所得到的無機烷氧縮合物與顏料的重量比例可為 . 3 : 1〇〇〜60 : 100 〇 上述之無機烷氧化合物的結構如下所示： R—M —(OR ·)ηΧ3.η 其中Μ為Si或金屬，例如Ti;R為氮、Ci〜18院基(alkyl group) '芳香族經基(aryi gr0Up)、烧基乙烯基（alkyl vinyl group)、院基胺基（aikyl amine group)、统基腈（alkyl 馨 nitrile)、烧基異氰酸I旨（alkyl isocyanate)、烧基環氧基(alkyl epoxide group)或OR’ ； R’為烷基，η為1〜3的正整 數；X為鹵素、-OH、-NCO或Ci〜6烷基。此無機烷氧化 - 合物較佳為鈦烷氧化物或矽烷氧化物。 . 本發明之顏料型感光材料中的顏料可為有機顏料或無 機顏料，其中有機顏料可為紅色顏料，依色彩指數(Color Index)編號例如為 Pigment Red 122、Pigment Red 202、 Pigment Red 206 ' Pigment Red 209 ' Pigment Red 177 ' _ Pigment Red 254 等；黃色顏料例如為 Pigment Yellow 13、 Pigment Yellow 55、Pigment Yellow 119、Pigment Yellow 138 ' Pigment Yellow 139 ' Pigment Yellow 168 ' Pigment Yellow 150 等；綠色顏料例如為 Pigment Green 7、Pigment Green 36 等；藍色顏料例如為 Pigment Blue 15:3、Pigment Blue 15:4、Pigment Blue 15:6等或上述之混合顏料。無機 顏料可為黑色顏料，包括碳黑、石墨或金屬氧化物如氮化 鈦等，其中又以碳黑較常見，例如為三菱生產之碳黑 0954-A21982TWF(N2)；P54950079TW；kelly 8 1330757 LFF-MA7、LFF-MA100、HCF-#2650、MCF-88、M2650、 . MA7等；德固薩生產之Special 4A、FW-18 ;卡伯特生產 之S90B、Mogul L、M900、M1000 ;哥倫比亞生產之 RAVEN1200、RAVEN2000等。另外，為了色相或流動性 等其他因素，亦可將黑色顏料與其他彩色顏料混合使用。 上述之顏料的主要功能是提供遮光性，因此其粒徑之 控制是非常重要的，粒徑太大則光學透光度不佳；粒徑太 小會造成顏料型感光材料的熱穩定度不佳。本發明之顏料 # 型感光材料中，其顏料粒徑控制在50 nm〜500nm，其中較 佳為50nm〜150nm。在有效的控制粒徑分佈下，可達到最 高光學特性與配方儲存穩定性。 - 本發明之顏料型感光材料中的鹼可溶樹脂可為含有酸 基之壓克力高分子，其中的酸基例如為甲基丙烯酸或丙烯 酸；此外，也可使用乙稀化不館合單體、含硬烧（silane)結 構之乙烯化不飽合單體或其組合與前述之含酸基單體搭 配，形成鹼可溶樹脂，其結構如下式所示： Λ Ri R2 R3[Technical Field] The present invention relates to a pigment type photosensitive material' particularly relating to a pigment type photosensitive material having high heat resistance and dimensional stability. [Prior Art] The color filter of a liquid crystal display usually includes a black photosensitive resin that forms a black frame to prevent light mixing, and a red, green, and blue color photoresist for filtering, wherein the color photoresist must have good light penetration. Permeability and Saturation 'Dye is used in traditional color filters to achieve high penetration and color saturation requirements, but 'the dyes are poor in both light and heat resistance. In order to overcome this problem, the pigment* dispersive photoresist material has replaced the dye method as the mainstream. With the development of the large-size 'inch panel for TV, the high brightness required for the panel has increased the panel temperature, and in addition, in pursuit of high color saturation. Therefore, the particle size of the pigment particles in the photoresist must be reduced to prevent scattering, which makes the heat resistance of the pigment in the conventional color filter insufficient to meet the requirements of the liquid crystal display for television. In addition, since the demand for color filters is high light transmittance, pigment dispersion of the nanometer scale is necessary. However, when the pigment particles are on the nanometer scale, the surface area and surface energy increase, according to the second law of thermodynamics, the pigment Particles tend to aggregate, so more dispersant must be used to achieve effective stabilization of the pigment particles. These dispersants are physically adsorbed to the surface of the pigment, and the addition of the dispersant causes an increase in the viscosity of the color photoresist and a problem of compatibility with the photoresist system. In terms of pigment surface modification, 'U.S. Patent No. 2005075416 No. 0954-A21982TWF(N2): P54950079TW; kelly 5 1330757 discloses a pigmented surfactant coated with a polymerizable surfactant to enhance its dispersion stability, US Patent No. 6,916,861 discloses a method of polymer coating to improve pigment dispersion stability. However, when polymer coated pigment particles are used, the surface resin is easily swelled by the solvent, which causes the pigment particles to become larger and agglomerated. , its long-term storage is not good, and there is no improvement in heat. In addition, in U.S. Patent No. 7,001,936 B2, a method for producing a self-dispersible pigment is disclosed for use in an ink jet ink. The method mainly adsorbs an amine-containing compound on the surface of the pigment to make the pigment self-divided. Scatter function. However, the adsorption of the amine-containing compound on the surface of the pigment is highly likely to affect the process stability of the subsequent wet milling or cause agglomeration of the amine compound during the formulation-process. In addition, the amidation-containing compound has a lower thermal cracking temperature than carbon black, and thus may lower the thermal cracking temperature of the carbon black, and is not suitable for the black matrix of the color filter. The above-mentioned pigment surface modification method has poor heat resistance, and is not suitable for the demand of high heat-resistant color resist and black matrix material in color filters. Therefore, there is a need in the industry for a pigment-type photosensitive material having high heat resistance. Sex and dimensional stability, suitable for high temperature resistant color filters. SUMMARY OF THE INVENTION In view of the above, an object of the present invention is to provide a pigment-type photosensitive material which has high heat resistance, dimensional stability, and low chromaticity change, and is suitable for color filter of general liquid crystal display and flexible display. sheet. To achieve the above object, the present invention provides a pigment type photosensitive material comprising: an alkali soluble resin, a polyfunctional monomer, a photoinitiator, an aromatic alkoxy condensation 0954-A21982TWF (N2); P54950079TW: kelly 6 L330757 Coated pigments and solvents. The surface of the pigment in the pigment-type photosensitive material of the present invention is coated with an inorganic alkoxy condensate, and the surface-modified pigment is matched with a soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent. The heat resistance and dimensional stability of the pigment-type photosensitive material are improved, and the chromaticity change at a high temperature is small, and the color stability can be maintained. In an embodiment of the present invention, the alkali-soluble resin may be a decane-containing copolymer which allows the pigment coated with the inorganic alkoxy condensate to have a better dispersion and further reduce the pigment type. The thermal expansion coefficient of the photosensitive material makes it more dimensionally stable, and therefore, it is applicable to a flexible-display made on a flexible substrate, in addition to being suitable for a glass-based display. In order to make the above objects, features, and advantages of the present invention more comprehensible, the following description will be described in detail with reference to the accompanying drawings: [Embodiment] φ The pigment-type photosensitive material of the present invention comprises (a) an alkali soluble a resin; (b) a polyfunctional monomer; (c) a photoinitiator; (d) a pigment coated with an inorganic alkoxy condensate; and (e) a solvent. The pigment coated with the inorganic alkoxy condensate uses a reactive inorganic alkoxide as a surface modifier of the pigment, and the inorganic burned oxide can be condensed by a sol-gel method. The polymerization reaction forms an inorganic alkoxy condensate to coat the surface of the pigment, so that the pigment has high heat resistance and thermal stability, and the pigment can be easily dispersed. Wherein, the thickness of the inorganic alkoxy condensate coating surrounding the pigment is between about 2 and 4 nm, and the thickness can be obtained by adding the inorganic alkane 0954-A21982TWF(N2); P54950079TW; kelly 7 1.330757 oxygen compound and pigment The ratio of the inorganic alkoxy condensate obtained by controlling the ratio is not limited to the above-mentioned thickness range. The weight ratio of the inorganic alkoxy condensate to the pigment may be 3. 3 : 1 〇〇 ~ 60 : 100 〇 The structure of the above inorganic alkoxy compound is as follows Shown: R—M —(OR ·)ηΧ3.η where Μ is Si or metal, such as Ti; R is nitrogen, Ci~18 alkyl group 'aromatic base (aryi gr0Up), alkylene An alkyl vinyl group, an aikyl amine group, an alkyl nitrile, an alkyl isocyanate, an alkyl epoxide group, or an OR. '; R' is an alkyl group, η is a positive integer of 1 to 3; and X is a halogen, -OH, -NCO or Ci~6 alkyl. The inorganic alkoxylate is preferably a titanium alkoxide or a decane oxide. The pigment in the pigment type photosensitive material of the present invention may be an organic pigment or an inorganic pigment, wherein the organic pigment may be a red pigment, and the color index number is, for example, Pigment Red 122, Pigment Red 202, Pigment Red 206 ' Pigment Red 209 ' Pigment Red 177 ' _ Pigment Red 254 and the like; yellow pigments such as Pigment Yellow 13, Pigment Yellow 55, Pigment Yellow 119, Pigment Yellow 138 ' Pigment Yellow 139 ' Pigment Yellow 168 ' Pigment Yellow 150 and the like; Pigment Green 7, Pigment Green 36, etc.; blue pigments such as Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, etc. or mixed pigments as described above. The inorganic pigment may be a black pigment, including carbon black, graphite or a metal oxide such as titanium nitride, among which carbon black is more common, such as carbon black produced by Mitsubishi 0954-A21982TWF (N2); P54950079TW; kelly 8 1330757 LFF -MA7, LFF-MA100, HCF-#2650, MCF-88, M2650, .MA7, etc.; Special 4A, FW-18 produced by Degussa; S90B, Mogul L, M900, M1000 produced by Cabot; RAVEN1200, RAVEN2000, etc. In addition, black pigments may be mixed with other color pigments for other factors such as hue or fluidity. The main function of the above pigments is to provide light-shielding properties, so the control of the particle size is very important. If the particle size is too large, the optical transmittance is not good; if the particle size is too small, the thermal stability of the pigment-type photosensitive material may be poor. . In the pigment type-sensitive material of the present invention, the pigment particle diameter is controlled to be 50 nm to 500 nm, preferably 50 nm to 150 nm. The highest optical properties and formulation stability are achieved with an effective particle size distribution. - The alkali-soluble resin in the pigment type photosensitive material of the present invention may be an acid group-containing acrylic polymer, wherein the acid group is, for example, methacrylic acid or acrylic acid; in addition, an ethylation-free combination may also be used. The body, the vinylated unsaturated monomer having a silane structure or a combination thereof is combined with the acid group-containing monomer described above to form an alkali-soluble resin, and the structure thereof is as follows: Λ Ri R2 R3
其中Ri、R_2、R_3係各自獨立地選自為H或CH3 ; X為 烧基(alkyl)、苯基(benzyl)、羥基(hydroxyl)或前述之組合； nl、n2為0〜8之正整數；a、b、c為重複單元之數目，一 般在0〜1之間；R4為多環芳基、多環芳基衍生物或含石夕 0954-A21982TWF(N2);P54950079TW：kelly 9 1.330757 烧衍生物。 • 在上述之鹼可溶樹脂中，含酸基單體的莫耳比例可為 10〜50%，較佳為20〜40% ;另外，以乙烯化不飽合單體 與含矽烷（silane)結構之乙烯化不飽合單體形成之共聚合 物（copolymer)為例，其中含石夕烧(silane)結構之乙烯化不飽 合單體所佔的莫耳比例約小於20%。鹼可溶樹脂的重量平 均分子量約為1，000〜100,000苢/111〇16，較佳為6,000〜 20,000 g/mole 〇 • 鹼可溶樹脂之單體包括曱基丙烯酸酯類，例如曱基丙 烯酸甲酯（methyl (meth)acrylate)、曱基丙稀酸苯g旨（benzyl (meth)acrylate)、曱基丙烯酸乙醋（ethyl (meth)acrylate)、曱 . 基丙稀酸經乙醋（2-hydroxyethyl (meth)acrylate)、曱基丙烯 酸經丙醋（hydroxylpropyl (meth)acrylate)或甲基丙稀酸異 丁酉旨（isobutyl (methy)acrylate)等；或是丙稀酸_類，例如 丙稀酸曱酉旨（methyl acrylate)、丙稀酸苯酉旨（benzyl acrylate)、丙烯酸乙酉旨（ethyl acrylate)、丙稀酸經乙酉旨 鲁（2-hydroxyethyl acrylate)、丙烯酸經丙酉旨（hydroxylpropyl acrylate)、丙稀酸異丁酯（isobutyl acrylate)或 3-(三甲氧基 石i烧）丙基丙烯酸脂（3-(Trimethoxysilyl)propyl methacrylate) 等；或是甲基丙稀酸（MethacrylicAcid)等。 本發明之顏料型感光材料中的多官能基單體可為具有 兩個以上雙鍵之多官能基單體，而光起始劑則可在寬帶波 長之UV光曝光下釋放出自由基，使得具有兩個以上雙鍵 之多官能基單體進行交聯反應，形成網狀聚合物。光起始 0954-A21982TWF(N2)；P54950079TW；kelly 10 1330757 劑較佳為在波長400nm以下具有較高的效率，其可以是苯 - 乙酮（Acetophenone)類，例如為1-對曱硫基苯基-2-曱基-2- 嗎 1^· 基 -1 - 丙 嗣 (2-Methyl-1 -(4-(methylthio)phenyl)-2-morpholino-1 -propane )、1-經基環己基苯基酮（1-Hydroxy cyclohexyl phenyl ketone)、二乙氧苯乙酮（Diethoxyacetophenone)、2-經基-2-甲 基 -1- 苯基 -1- 丙 酮 (2-Hydroxy-2-methyl-l-phenyl-propane-l-one)、2-苯曱基 籲 _2_(二曱氨基）-1-[4_(4-嗎啉基）苯基]-1- 丁酮 (2-Benzyl-2-(dimethylamino)-l-[4-(4-morpholinyl)phenyl]-1 -butanone);安息香（Benzoin)類，例如為安息香 -(Benzoin)、安息香曱驗（Benzoin methyl ether)、Benzyl dimethyl ketar ;二苯曱酮（Benzophenone)類，例如為二笨甲 酮（Benzophenone) 、4-苯基二苯曱酮（4-Phenyl benzophenone)、經基二苯曱酮（Hydroxyl benzophenone); 硫雜蒽酮（Thioxanthone)類，例如為異丙基硫雜蒽酮 Φ (Isopropylthioxanthone) 、 2-氣硫雜 蒽 酮 (2-Chlorothioxanthone);蒽醌（anthraquinone)類，例如為 2-乙基蒽酿(2-ethylanthraquinone)。前述之光起始劑可單獨使 用或混合使用。 上述之多官能基單體例如為乙二醇二甲基丙烯酸酯 (ethylene glycol dimethacrylate)、1，4-丁二醇二丙烯酸酉旨 (l，4-butanediol diacrylate)、二甘醇雙丙稀酸酯（diethylene glycol diacrylate)、季戊四醇三丙烯酸酯（pentaerythritol 0954-A21982TWF(N2):P54950079TW:kelly 1330757 triacrylate)、乙氧基化三曱基丙炫三丙稀酸酯（ethoxylated - trimethylpropane triacrylate)、雙季戊四醇五丙稀酸酉旨 (dipentaerythritol pentaacrylate)、乙氧化季戊四醇四丙稀酸 酉旨（ethoxylated pentaerythritol tetraacrylate)、季戊四醇四丙 烯酸自旨（Pentaerythritol tetraacrylate)或雙季戊四醇六丙烤 酸酉旨（dipentaerythritol hexaacrylate)等。 本發明之顏料型感光材料中的溶劑可選自環己_ 二醇醚、乙二醇乙鍵、乙二醇丁酸、丙二醇曱_乙酸酉旨、 參或乙基-2-乙氧基乙醇乙酸酯，溶劑之重量％可為8〇〜4〇， 較佳為70〜50。 此外’在本發明之顏料型感光材料中還可視需要添力 - 其他成分，例如顏料分散劑、平坦劑、消泡劑或接著助1 .其中，顏料分散劑有助於有效的控制顏料粒徑分佈，以及 增加顏料與感光材料及驗可溶樹脂之相容性；分散南 1 了為 陰離子型、陽離子型或非離子型的界面活性劑，較佳 分子型分散劑。本發明之以無機烷氧縮合物包覆改質後: •顏料具有良好的分散穩定性，以-般高分子型分散劑 後，可得穩定的分散液。 ""77 $ 本發明之顏料型感光材料的固含量可為1〇%〜4〇% , 依塗佈方式與膜厚不同控制其固含量，若以旋轉塗佈°方式 控制膜厚在1〜1.5/xm，則固含量最奸調整在18〜28%。二 在本發明之顏料裂感光材料中，驗可溶樹脂、处 基單體、光起始劑以及以無機境氧輪合物包覆之顏料: 重量％可為20〜60%，較佳為30〜7〇%。下列表i所列: 0954-A21982TWF(N2) ： P54950079TW： kelly L330757 各成份較佳之比例範圍。 表1顏料型感光材料中各成份之比例範圍 成分 重量％ 驗可溶樹脂 6〜10 多官能基單體 4〜7 光起始劑 1〜5 表面改質之顏料 8〜20 分散劑 0.8 〜10 溶劑 80 〜40 本發明之顏料型感光材料的製備方式可先將表面改質 之顏料以分散劑分散後，再加入驗可溶樹脂、多官能基單 - 體、光起始劑和溶劑中混合均勻，最後將其他添加成份加 . 入，以高速攪拌均勻後使用。 本發明之顏料型感光材料可應用於彩色濾光片，作為 彩色光阻及黑色矩陣之材料，其製作步驟包含以旋轉塗佈 方式將彩色光阻塗佈在透明玻璃基板上，經90°C預烘烤約 • 2分鐘；再經能量100〜500mJ/cm2的紫外光源，以特定圖 案之光罩進行曝光，曝光部份產生交聯反應；接著以鹼性 水溶液予以顯影，未曝光部份被鹼液洗去，曝光部份之圖 案則保留；圖案經水洗與吹乾後再以約230°C之高溫硬烤1 小時，即可完成一次的光阻製作步驟；之後重複前述步驟 分別進行紅色、綠色和藍色光阻以及黑色矩陣等其他光阻 及相對應之圖案製作，即可完成彩色濾光片。 本發明之顏料型感光材料與含有未包覆無機烷氧縮合 0954-A21982TWF(N2)：P54950079TW；kelly 13 1.330757 物之顏料的顏料型感光材料相較之下，具有良好的耐熱 . 性、尺寸安定性與色度穩定性，其重量損失5%的溫度可 提高約20〜65°C，在1〇〇〜250°C的熱膨脹係數可降低約4 〜20 ppm/°C，色度變化(AEab)可減少約0.6〜3，因此適 用於耐高溫顯示器之彩色濾光片製作。 此外，由於本發明之顏料型感光材料中的鹼可溶樹脂 可為含矽烷之共聚物，其可使得以無機烷氧縮合物包覆之 顏料具有更佳的分散性，並且更可進一步降低顏料型感光 φ 材料的熱膨脹係數，使其更具尺寸安定性，因此除了適用 於一般以玻璃為基板之顯示器外，更可適用於在軟性基板 上製作之可撓式顯示器。此外，由於本發明之顏料型感光 . 材料中的顏料粒徑在50 nm〜500nm之間，因此可提高液 晶顯示器之色飽和度與光穿透度，適用於彩色濾光片在陣 列上（color filter on array，簡稱 COA)之製程。 以下製備例1〜5為製備以無機烷氧縮合物包覆之顏料： 【製備例1】 • 在250毫升的研磨罐加入1/2研磨罐體積之1mm直徑 的錯球，加入100 g四氫吱喃（THF)溶劑，再加入40 g紅色 顏料(PigmentRed 254,簡稱 PR254,購自 Ciba)與 5 g 無機 烷氧化合物改質劑 3-氨基丙基三乙氧基矽烷 (3-Aminopropyltriethoxysilane)，將此混合溶液以紅魔鬼研 磨機分散2小時，取出放置在250 g圓底反應瓶中，再加 入1.7 g PH值為2.1之鹽酸水溶液持續攪拌；接著，再加 入5 g無機烷氧化合物改質劑三乙氧基曱基矽烷 0954-A21982TWF(N2)；P54950079TW；kelly 1330757 (Triethoxymethyl silane，TEOS)，此 5 g TEOS 於鹽酸水溶 • 液中進行水解反應，在室溫下攪拌24小時並待THF揮發 後，以高溫（ll〇°C)熟化8小時’使縮合反應完全，即完成 具有無機烷氧縮合物包覆之紅色顏料。 【製備例2】 在250毫升的研磨罐中加入l〇〇g THF溶劑，再加入 40g紅色顏料(Pigment Red 254，購自Ciba)，將此混合溶 液以紅魔鬼研磨機分散2小時，取出放置在250 g圓底反 φ 應瓶中’再加入1.7 g PH值為2.1之鹽酸水溶液持續授拌；Wherein Ri, R_2, and R_3 are each independently selected from H or CH3; X is an alkyl group, a benzyl group, a hydroxyl group, or a combination thereof; and n1 and n2 are positive integers of 0 to 8; ; a, b, c are the number of repeating units, generally between 0 and 1; R4 is a polycyclic aryl group, a polycyclic aryl derivative or a stone containing 0954-A21982TWF (N2); P54950079TW: kelly 9 1.330757 derivative. • In the above alkali-soluble resin, the molar ratio of the acid group-containing monomer may be 10 to 50%, preferably 20 to 40%; in addition, the ethylenic unsaturated monomer and the silane-containing (silane) may be used. For example, a copolymer formed by a vinylated unsaturated monomer of a structure in which a vinylated unsaturated monomer having a silane structure accounts for less than about 20% molar ratio. The alkali-soluble resin has a weight average molecular weight of about 1,000 to 100,000 Å / 111 〇 16, preferably 6,000 to 20,000 g / mole. The monomer of the alkali-soluble resin includes a mercapto acrylate such as methacrylic acid. Methyl (meth)acrylate, benzyl (meth)acrylate, ethyl (meth)acrylate, 曱. propyl acrylate (2) -hydroxyethyl (meth)acrylate), hydroxypropyl (meth)acrylate or isobutyl (methy)acrylate; or acrylic acid, such as acryl Methyl acrylate, benzyl acrylate, ethyl acrylate, acrylic acid 2-hydroxyethyl acrylate, acrylic acid hydroxylpropyl acrylate ), isobutyl acrylate or 3-(Trimethoxysilyl) propyl methacrylate; or methyl methacrylate (Methacrylic Acid). The polyfunctional monomer in the pigment type photosensitive material of the present invention may be a polyfunctional monomer having two or more double bonds, and the photoinitiator may release a radical at a broadband wavelength of UV light exposure, A polyfunctional monomer having two or more double bonds is subjected to a crosslinking reaction to form a network polymer. Light start 0954-A21982TWF(N2); P54950079TW; kelly 10 1330757 agent preferably has higher efficiency at a wavelength below 400 nm, which may be benzene-ethone, such as 1-p-thiophenyl 2-Methyl-1 -(4-(methylthio)phenyl)-2-morpholino-1 -propane ), 1-cyclohexylcyclohexyl 1-Hydroxy cyclohexyl phenyl ketone, Diethoxyacetophenone, 2-carbo-2-methyl-1-phenyl-1-propanone (2-Hydroxy-2-methyl-l -phenyl-propane-l-one), 2-phenylhydrazinyl-2-(diamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone (2-Benzyl-2- (dimethylamino)-l-[4-(4-morpholinyl)phenyl]-1 -butanone); Benzoin, such as Benzoin, Benzoin methyl ether, Benzyl dimethyl ketar; Benzophenones, for example, Benzophenone, 4-Phenyl benzophenone, Hydroxyl benzophenone; Thioxanthone a class such as isopropyl thioxanthone Φ ( Isopropylthioxanthone), 2-Chlorothioxanthone; anthraquinone, for example 2-ethylanthraquinone. The aforementioned photoinitiators can be used singly or in combination. The above polyfunctional monomer is, for example, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylic acid. Diethylene glycol diacrylate, pentaerythritol triacrylate (pentaerythritol 0954-A21982TWF (N2): P54950079TW: kelly 1330757 triacrylate), ethoxylated - trimethylpropane triacrylate, dipentaerythritol Dipentaerythritol pentaacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate or dipentaerythritol hexaacrylate. The solvent in the pigment type photosensitive material of the present invention may be selected from cyclohexane-diol ether, ethylene glycol ethyl bond, ethylene glycol butyric acid, propylene glycol hydrazine-acetic acid hydrazine, ginseng or ethyl-2-ethoxyethanol. The acetate, the weight % of the solvent may be 8 Torr to 4 Torr, preferably 70 to 50. In addition, in the pigment-type photosensitive material of the present invention, it is also possible to add force - other components such as a pigment dispersant, a flat agent, an antifoaming agent or the like. Among them, the pigment dispersing agent contributes to effective control of the pigment particle size. Distribution, and increase the compatibility of the pigment with the photosensitive material and the soluble resin; the dispersion is an anionic, cationic or nonionic surfactant, preferably a molecular dispersant. After the modification by the inorganic alkoxy condensate of the present invention: • The pigment has good dispersion stability, and a stable dispersion can be obtained after the general polymer type dispersant. ""77 $ The pigment-type photosensitive material of the invention may have a solid content of 1% to 4% by weight, and the solid content is controlled according to the coating method and the film thickness, and the film thickness is controlled by the spin coating method. 1~1.5/xm, then the solid content is adjusted at 18~28%. 2. In the pigment-spraying photosensitive material of the present invention, the soluble resin, the monomer, the photoinitiator, and the pigment coated with the inorganic oxidizer are: the weight % may be 20 to 60%, preferably 30~7〇%. Listed below are listed: 0954-A21982TWF(N2) : P54950079TW: kelly L330757 The preferred ratio range for each component. Table 1 Proportion of the components in the pigment type photosensitive material range Component % by weight Solvent resin 6 to 10 Polyfunctional monomer 4 to 7 Photoinitiator 1 to 5 Surface modified pigment 8 to 20 Dispersant 0.8 to 10 Solvents 80 to 40 The pigment-type photosensitive material of the present invention can be prepared by dispersing the surface-modified pigment as a dispersing agent, and then adding a solvent, a polyfunctional mono-body, a photoinitiator and a solvent. Evenly, finally add other ingredients, and mix them at high speed for use. The pigment type photosensitive material of the invention can be applied to a color filter as a material of a color photoresist and a black matrix, and the manufacturing step comprises coating the color photoresist on the transparent glass substrate by spin coating at 90 ° C. Pre-baking for about 2 minutes; after exposure to an ultraviolet light source with an energy of 100 to 500 mJ/cm2, exposure is performed with a mask of a specific pattern, and the exposed portion is subjected to a crosslinking reaction; then, an alkaline aqueous solution is used for development, and the unexposed portion is exposed. The lye is washed away, and the pattern of the exposed portion is retained; the pattern is washed with water and dried, and then baked at a high temperature of about 230 ° C for 1 hour to complete the photoresist production step; then the above steps are repeated for red Color filters can be completed by making other photoresists such as green and blue photoresists and black matrices and corresponding patterns. The pigment-type photosensitive material of the present invention has good heat resistance and dimensional stability as compared with a pigment-type photosensitive material containing a pigment which is not coated with inorganic alkoxy condensate 0854-A21982TWF(N2): P54950079TW; kelly 13 1.330757. Sex and chromatic stability, the temperature loss of 5% of the temperature can be increased by about 20~65 ° C, the thermal expansion coefficient at 1 〇〇 ~ 250 ° C can be reduced by about 4 ~ 20 ppm / ° C, chromaticity change (AEab ) can be reduced by about 0.6 to 3, so it is suitable for color filter production of high temperature display. Further, since the alkali-soluble resin in the pigment type photosensitive material of the present invention may be a decane-containing copolymer, the pigment coated with the inorganic alkoxy condensate may have better dispersibility, and the pigment may be further reduced. The thermal expansion coefficient of the photosensitive φ material makes it more dimensionally stable. Therefore, it can be applied to a flexible display made on a flexible substrate, in addition to a glass-based display. In addition, since the pigment type of the pigment of the present invention is between 50 nm and 500 nm, the color saturation and light transmittance of the liquid crystal display can be improved, and the color filter is applied to the array (color). Filter on array, referred to as COA) process. The following Preparation Examples 1 to 5 are preparations of pigments coated with an inorganic alkoxy condensate: [Preparation Example 1] A 1/2 grinding tank volume of 1 mm diameter wrong sphere was added to a 250 ml grinding jar, and 100 g of tetrahydrogen was added.吱 ( (THF) solvent, followed by 40 g of red pigment (Pigment Red 254, abbreviated as PR254, available from Ciba) and 5 g of the inorganic alkoxy compound modifier 3-Aminopropyltriethoxysilane, The mixed solution was dispersed in a red devil mill for 2 hours, taken out in a 250 g round bottom reaction flask, and then 1.7 g of a hydrochloric acid aqueous solution having a pH of 2.1 was added thereto, and stirring was continued; then, 5 g of an inorganic alkoxide was further added. Agent triethoxydecyl decane 0854-A21982TWF (N2); P54950079TW; kelly 1330757 (Triethoxymethyl silane, TEOS), this 5 g TEOS was hydrolyzed in hydrochloric acid water solution, stirred at room temperature for 24 hours and treated with THF After volatilization, the mixture was aged at high temperature (11 ° C) for 8 hours to complete the condensation reaction, that is, to complete the red pigment coated with the inorganic alkoxy condensate. [Preparation Example 2] 1 g of a THF solvent was added to a 250 ml grinding jar, and 40 g of a red pigment (Pigment Red 254, available from Ciba) was added, and the mixed solution was dispersed in a red devil mill for 2 hours, and taken out. In a 250 g round bottom anti-φ bottle, add 1.7 g of hydrochloric acid aqueous solution with a pH of 2.1 for continuous mixing;
接著，加入 5.65 g TEOS (Triethoxymethyl silane)，此 TEOS 於鹽酸水溶液中進行水解反應，在室溫下攪拌24小時並 待THF揮發後，以高溫（110°C)熟化8小時使縮合反應完 全，即完成具有無機烧氧縮合物包覆之紅色顏料。 【製備例3〜5】 同製備例2之方法製備，其中製備例3所使用的TEOS 的量為4.23g ;製備例4所使用的顏料為綠色顏料(pigment Φ Green 36 ’簡稱PG36 ’購自BASF);製備例4所使用的顏 料為藍色顏料（Pigment Blue 15:6，簡稱PB15:6，購自 BASF)。 【實施例1】 取250ml的研磨罐加入1/2磨罐體積之1 mm直徑的錯 球，加入10g製備一顏料、80g溶劑丙二醇曱驗乙酸酯 (Propylene glycol monomethyl ether acetate > PGMEA)和 5.5g分散劑（講自SOLSPERSE，型號22000，0.5g以及型 0954-A21982TWF(N2)；P54950079TW：kelly 1330757 號24000，5g)，以紅魔鬼研磨機分散4小時，過濾後取出 . 分散液；於500ml三頸反應器中，氮氣環境下，加入96.7g 溶劑PGMEA、20g驗可溶樹脂、6g反應性單體 dipentaerythritol hexaacrylate 、 0.5g 光起始劑Next, 5.65 g of TEOS (Triethoxymethyl silane) was added, and the TEOS was subjected to a hydrolysis reaction in an aqueous hydrochloric acid solution, and stirred at room temperature for 24 hours and then evaporated to THF, and then aged at a high temperature (110 ° C) for 8 hours to complete the condensation reaction. A red pigment coated with an inorganic aerobic condensate is completed. [Preparation Examples 3 to 5] Prepared in the same manner as in Preparation Example 2, wherein the amount of TEOS used in Preparation Example 3 was 4.23 g; the pigment used in Preparation Example 4 was a green pigment (pigment Φ Green 36 'abbreviated as PG36' was purchased from BASF); The pigment used in Preparation Example 4 was a blue pigment (Pigment Blue 15:6, abbreviated as PB15:6, available from BASF). [Example 1] A 250 ml grinding jar was charged with a 1 mm diameter 1 mm diameter wrong sphere, and 10 g of a pigment, 80 g of solvent propylene glycol monomethyl ether acetate (PGMEA) and 5.5g dispersant (supplied from SOLSPERSE, model 22000, 0.5g and type 0954-A21982TWF (N2); P54950079TW: kelly 1330757 No. 24000, 5g), dispersed in a red devil grinder for 4 hours, filtered and taken out. Dispersion; In a 500 ml three-necked reactor, 96.7 g of solvent PGMEA, 20 g of soluble resin, 6 g of reactive monomer dipentaerythritol hexaacrylate, and 0.5 g of photoinitiator were added under nitrogen atmosphere.
Isopropylthioxanthone (ITX )和 4.5g 光起始劑 2-Benzyl-2-(dimethylamino)-l-[4-(4-morpholinyl) phenyl]-l-butanone (1369 ) ’其中驗可溶樹脂的成分包含曱 基丙烯酸曱醋（methyl (meth)acrylate)、甲基丙烯酸苯酯 參（benzyl (meth)acrylate)、曱基丙烯酸羥乙酯（2_hydroxyethyl (meth)acrylate)以及曱基丙烯酸(MethacrylicAcid)，分別佔 33%、34%、8%及25%莫耳比，於攪拌下再將前述分散液 •逐漸加入’持續檟:拌2小時，即完成本發明實施例1之顏 _ 料型感光材料。 將實施例1之顏料型感光材料以轉速6〇〇rpm，15秒以 及900rpm，20秒旋轉塗佈在透明破璃基板上，經9〇。匸預 烘烤2分鐘，再經能量150mJ/cm2的紫外光源搭配光罩進 ®行曝光，接著以〇·5%κοη驗液顯影，未曝光部份則被驗 液洗去’保留之圖案經水洗與吹乾後，再以230〇C高溫硬 烤1小時，即完成彩色光阻層。 將實施例1所製成之彩色光阻層以熱重損失儀(TGA) 分析’其重里損失5%之财熱溫度如表2所列；以熱膨脹 係數分析儀(TMA)分析，其在1〇〇〜25〇。〇下，垂直於表面 (out of plane)之熱膨脹係數如表2所列；此外，彩色光阻 層在經過230°C高溫硬烤1小時後之色度變化（△εα)也如 0954-A21982TWF(N2) :P54950079TW:kelly 1330757 表2所列。 【實施例2〜5】 實施例2〜5之顏料型感光材料以及彩色光阻層的製備 方式同實施例1，其不同在於實施例2〜5分別使用製備例2 〜5之以無機烷氧縮合物包覆的顏料。 將實施例2〜5所製得之彩色光阻層以同實施例1之方 式量測，其結果如表2所列。 【比較例1〜3】Isopropylthioxanthone (ITX) and 4.5 g of photoinitiator 2-Benzyl-2-(dimethylamino)-l-[4-(4-morpholinyl)phenyl]-l-butanone (1369 ) 'The composition of the soluble resin contains 曱Methyl (meth)acrylate, benzyl (meth)acrylate, 2_hydroxyethyl (meth)acrylate, and Methacrylic Acid, respectively, 33 %, 34%, 8%, and 25% molar ratio, and the above dispersion was gradually added to the mixture under continuous stirring for 2 hours to complete the pigment-type photosensitive material of Example 1 of the present invention. The pigment-type photosensitive material of Example 1 was spin-coated on a transparent glass substrate at a rotation speed of 6 rpm, 15 seconds, and 900 rpm for 20 seconds, and passed through 9 Torr.匸 pre-bake for 2 minutes, then use UV light source with energy of 150mJ/cm2 to match with reticle for exposure, then develop with 〇·5%κοη test solution, and the unexposed part is washed away by the test solution. After washing with water and drying, it was hard baked at 230 ° C for 1 hour to complete the color photoresist layer. The color photoresist layer prepared in Example 1 was analyzed by a thermogravimetric loss meter (TGA), and its thermal temperature of 5% of the weight loss was as listed in Table 2; analyzed by a thermal expansion coefficient analyzer (TMA), which was 〇〇~25〇. Under the armpit, the coefficient of thermal expansion perpendicular to the out of plane is listed in Table 2; in addition, the chromaticity change (△εα) of the colored photoresist layer after hard baking at 230 ° C for 1 hour is also as 0954-A21982TWF (N2): P54950079TW: kelly 1330757 Table 2 listed. [Examples 2 to 5] The pigment-type photosensitive materials of Examples 2 to 5 and the color resist layer were prepared in the same manner as in Example 1, except that Examples 2 to 5 used the inorganic alkoxides of Preparation Examples 2 to 5, respectively. Condensate coated pigment. The color resist layers obtained in Examples 2 to 5 were measured in the same manner as in Example 1, and the results are shown in Table 2. [Comparative Examples 1 to 3]
比較例1〜3之顏料型感光材料以及彩色光阻層的製 備方式同實施例1，其不同在於比較例1〜3分別使用未以 無機烷氧縮合物包覆的顏料PR254、PG36以及PB15:6。 將比較例1〜3所製得之彩色光阻層以同實施例1之方 式量測，其結果如表2所列。 表2實施例與比較例之特性比較 顏料 3-Aminopropyl triethoxysilane(g) Triethoxy methyl silane(g) 而才熱溫度 (°C) 熱膨脹係 (Ppm/°C) △Eab 實施例1 PR254 5 5 257 14.33 0.48 實施例2 PR254 0 5.65 267 13.39 0.78 實施例3 PR254 0 4.23 223 15.48 0.96 實施例4 PG36 0 5.65 261 28.55 1.43 實施例5 PB15:6 0 5.65 256 9.1 2.6 比較例1 PR254 ΝΑ ΝΑ 202 19.85 3.33 比較例2 PG36 ΝΑ ΝΑ 211 47.34 2.28 比較例3 PB15:6 ΝΑ ΝΑ 218 14.11 3.20 0954-A21982TWF(N2)；P54950079TW；kelly 17 330757 由表2可得知，利用本發明之顏料型感光材料所製得 的彩色光阻，其在重量損失5%的溫度皆較比較例高約2〇 〜65°C，在1〇〇〜250°C的熱膨脹係數則可較比較例降低約 )〜PPmrC，在高溫23(TC下1小時後之色度變化(AEab) I較比較例減少、約〇,6〜3，並且在顯影性方面與比較例相 :二到彩色據光片所需之解析度要求，這表示本發明 方面皆較含未被繼丄女定性以及色度穩定性 材料有大幅度的提升。° i覆之顏料的顏料型感光 雖然本發明已揭露較佳杂 定本發明，任何熟悉此項技蓺^如上’然其並非用以限 和範圍内，當可做些許更2，在不脫離本發明之精神 圍當視後附之申請專利範圍;斤::為；此本發明之保護範The pigment-type photosensitive materials of Comparative Examples 1 to 3 and the color resist layer were prepared in the same manner as in Example 1, except that Comparative Examples 1 to 3 used pigments PR254, PG36, and PB15 which were not coated with an inorganic alkoxy condensate, respectively: 6. The color resist layers prepared in Comparative Examples 1 to 3 were measured in the same manner as in Example 1, and the results are shown in Table 2. Table 2 Comparison of Characteristics of Examples and Comparative Examples Pigment 3-Aminopropyl triethoxysilane (g) Triethoxy methyl silane (g) Thermal temperature (°C) Thermal expansion system (Ppm/°C) ΔEab Example 1 PR254 5 5 257 14.33 0.48 Example 2 PR254 0 5.65 267 13.39 0.78 Example 3 PR254 0 4.23 223 15.48 0.96 Example 4 PG36 0 5.65 261 28.55 1.43 Example 5 PB15: 6 0 5.65 256 9.1 2.6 Comparative Example 1 PR254 ΝΑ ΝΑ 202 19.85 3.33 Comparative Example 2 PG36 ΝΑ 211 211 47.34 2.28 Comparative Example 3 PB15: 6 ΝΑ ΝΑ 218 14.11 3.20 0954-A21982TWF (N2); P54950079TW; kelly 17 330757 It can be seen from Table 2 that the color obtained by using the pigment type photosensitive material of the present invention The photoresist, which has a weight loss of 5%, is about 2 〇 to 65 ° C higher than the comparative example, and the thermal expansion coefficient at 1 〇〇 to 250 ° C can be reduced by about 〜PPmrC, at a high temperature of 23 ( The chromaticity change (AEab) I after 1 hour at TC is reduced from the comparative example, about 〜6 to 3, and in terms of developability, compared with the comparative example: the resolution requirement required for the color light film, which means Aspects of the present invention are more qualitative and The degree of stability of the material has been greatly improved. The pigment-type sensitization of the pigment of the i-coated pigment. Although the invention has been disclosed in the present invention, any of the above-mentioned techniques are not limited to the scope of the present invention. Can make a little more 2, without departing from the spirit of the invention, the scope of the patent application; Jin:: is; this protection of the invention
0954-A21982TWF(N2)；P54950079TW；kelly 13307570954-A21982TWF(N2); P54950079TW; kelly 1330757
【圖式簡單說明】 〇 【主要元件符號說明】 〇 < *»> 0954-A21982TWF(N2)；P54950079TW；kelly 19[Simple description of the diagram] 〇 [Explanation of main component symbols] 〇 <*»>0954-A21982TWF(N2);P54950079TW; kelly 19