TW571177B - Coloring composition and color filter, electrode substrate, and liquid crystal display device using the same - Google Patents

Coloring composition and color filter, electrode substrate, and liquid crystal display device using the same Download PDF

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TW571177B
TW571177B TW088117112A TW88117112A TW571177B TW 571177 B TW571177 B TW 571177B TW 088117112 A TW088117112 A TW 088117112A TW 88117112 A TW88117112 A TW 88117112A TW 571177 B TW571177 B TW 571177B
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coloring composition
liquid crystal
insulating substance
light
compound
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Chinese (zh)
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Takeshi Itoi
Yasuhiro Shima
Shinji Ito
Mizuhito Tani
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Toppan Printing Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Optical Filters (AREA)

Abstract

A coloring composition comprised a coloring material that is including titanium black, a resin, and an insulation material. The amount of insulation material is in a range of 1 to 35 weight percent based on the amount of the coloring material. The insulation material is covered over the coloring material. The insulation material is selected from a group consisting of silica, alumina, and zirconia. Beside the dispersion medium and solvent, the coloring composition further more comprised photopolymerization monomer and photopolymerization initiator or cross-linking agent and photoacid generated reagent or photopolymerization monomer and diazo-compound or azido-compound. The coloring composition with high insulation ability was suitable for manufacturing a black matrix. By using the black matrix, a high quality liquid crystal display device is provided.

Description

5428 pif 4 玖、發明說明： 本發明是有關於一種著色組成物，且特別是有關於一 種具有優良絕緣性而且應用在彩色過濾器、電極基板及液 晶顯示裝置上，用來求得高顯示品質的著色組成物。 一般的液晶顯示裝置如第2圖之細部剖面示意圖所 示，由液晶驅動用電極板31、位於液晶驅動用電極板31 之上的共通電極用電極板32、以及塡封於兩電極板間之間 隙的液晶材料33所構成。 上述液晶驅動用電極板31，是由基板31a、使每個相 應於顯示畫面的畫素相互獨立而設置的畫素電極31b、以及 通電於相應於畫面顯示信號之畫素電極31b的開關元件 31c所構成。上述共通電極用電極板32,是由透明基板32a、 位於此透明基板32a上爲了共通全畫素而設置的透明共通 電極32b所構成。 還有，如第2圖所示，在作爲顯示全彩畫面之全彩液 晶顯示裝置的情況下，彩色過瀘器34是爲了使透過共通電 極用電極板32之各畫素的透射光分別顯示各種色彩而設置 的。而且，此種液晶顯示裝置，是藉由控制相應於各畫面 顯示信號之上述開關元件31c使各畫素電極32b通電，隨 著畫素電極32b與透明共通電極32b之間電壓的不同，驅 5428 pif 4 動上述的液晶材料33，由光線的透過與否使畫面顯示。 在此液晶顯示裝置中，透射光線會隨著上述開關元件 31c設置位置的影響而顯得紊亂，這將使顯示畫面的對比度 降低’而使顯像品質劣化。爲了遮斷入射於前述位置之光 線’並且防止品質惡劣化的發生，在上述共通電極用電極 板32上設置遮光板(black matrix)35是必要的。 在此情況下，由於液晶顯示裝置之製程因素，遮光板 35與開關元件31c之間的相對位置亦會有誤差產生，因此 遮光板35必須設置於相對於開關元件31c之相對應的位置 上。此誤差發生的原因有：開關元件31c在液晶驅動用電 極板31上形成時之位置精度誤差、遮光板35在共通電極 用電極板32上形成時之位置精度誤差、兩電極板31、32 之相對誤差(最大約5//m)、上述液晶驅動用電極板31與共 通電極用電極板33在裝配組合時之組合誤差（最大約5// m)。因此，遮光板35與開關元件31c比較起來有平均10 // m(合計20 // m)的誤差。 近年來由於液晶顯示裝置有畫素縮小化且畫素密度 增大的驅勢，必須要求具有高品質且緻密化之顯示表面， 但卻因爲上述之誤差原因而無法達成。伴隨著畫素高密度 且微細化而來的問題是開口率（占有畫面顯示領域的畫素 5428 pif 4 部位的總面積之比例)以及顯示畫面明亮度的降低。 所以提高遮光板35與開關元件31c間相對位置的精密 度與增大開口率而開發的電極基板是被期盼的。如特開平 6-130218號公報所示，在陣列基板上形成遮光板的方法就 是此種技術。 在習知技藝上，遮光板是由金屬所形成，以下是其置 備方法：首先，在玻璃基板上以蒸鍍、濺鍍等真空成膜法 形成Cr、Ni、A1等之金屬薄膜，再以光阻塗布，放 上附有所需圖案的光罩後以紫外線照射，並經過顯像處理 而得到光阻圖案。之後經由蝕刻除去光阻以外的部份，再 將光阻剝離，最後得到所須的遮光板。 但是’使用由此遮光板所形成的彩色過濾器所製造的 液晶板’當其與液晶驅動電極導通時，會有液晶不動作或 錯誤動作等不當的狀況發生。在此情況下，以絕緣性物質 來取代金屬薄膜以製作遮光板是必要的，以τ將討論各種 不使用金屬膜之遮光板。 以特開平2 - 2392〇4號公報（Α)爲例，其中提出先 在聚醯亞胺樹脂中散布遮光劑，再以蝕刻法形成遮光板， 且又提出直接添加於感光性物質組成物中之遮光劑的組成 物質之分析。爲使遮光性上升’追些材料多使用碳黑，例 5428 pif 4 如在特開平4一 63870號公報（A)中，就提出在光重合化 合物中散布碳黑及有機顏料而用以形成遮光板。 而且，在上述陣列基板側形成遮光板的方法（特開平 6-130218號公報（A))中，還使用散布作爲黑色顏料的導 電性碳黑所形成的黑色護膜，或者是單獨地或兩種以上混 合地使用形成三種彩色過濾器的紅色、綠色、以及藍色護 膜以作爲擬黑色護膜，來作爲形成遮光板的遮光材料。 但是碳黑之遮光性與其他有機顏料比較起來，具有較 筒的導電性。而且爲了提局遮光性，就常在感光性樹脂中 添加s午多Ϊ灰黑’如此一^來’所形成的遮光板本身就具有導 電性。由於這個原因，利用此類材料製作的彩色過濾器也 會在液晶驅動電極導通的情況之下，會有液晶不動作或錯 誤動作等不當的狀況發生，以至於無法控制。 此外，亦有在樹脂中散布氧化金屬顏料作爲遮光劑而 製作出遮光板。但是，氧化金屬顏料對於所施加的外加電 壓具有電壓依存性、遮光性並非十分良好之缺點。 因此，由上述習知技藝得知，開發具有高絕緣性、耐 光性、遮光性、分散安定性的著色組成物，以及開發由具 有上述性質之著色組成物所製成的彩色過濾器、電極基板 及液晶顯示裝置是有必要的。 5428 pif 4 所以，本發明的主要目的乃是根據上述要點，提供具 有高絕緣性、及耐光性、遮光性、分散安定性優良的著色 組成物，以及提供由具有上述性質之著色組成物所製成的 彩色過濾器、電極基板及液晶顯示裝製。還提供遮光板與 開關元件間相對位置具高位置精密度、顯示畫面具高開口 率的電極基板與液晶顯示裝製。 本發明的發明者爲了解決前述課題，經由反覆硏究而 有此發明成果。 本發明之著色組成物，其特徵是原料爲含有鈦黑的色 劑、樹脂、以及絕緣性物質。 上述絕緣性物質的含量爲色劑含量的1〜35%重量百分 比。 本發明，是由含有被絕緣性物質被覆的鈦黑的色劑及 樹脂所組成之著色組成物，且絕緣性物質的含量爲色劑含 量的1〜35%重量百分比爲其特徵。 上述絕緣性物質是可以從二氧化矽矽酸鹽、氧化鋁及 氧化锆所組成的族群選出至少一化合物所構成。 絕緣性物質的含量爲色劑含量的1〜35%重量百分比。 上述樹脂爲感光性樹脂。 上述著色組成物，其組成包括分散劑、光重合單體、 571177 5428 pif 4 光重合開始劑以及溶液。 上述著色組成物，其組成包括分散劑、架橋劑、光酸 發生劑以及溶劑。 上述著色組成物，其組成包括分散劑’光重合單體、 重氮基系化合物、疊氮基系化合物以及溶劑。 上述樹脂爲（間）丙烯基系樹脂。 上述樹脂是由含有一個乙烯基與羥基的化合物10〜40 重量百分比、含有一個乙烯基與羧基的化合物10〜30重量 百分比、含有一個乙烯基的化合物30〜75重量百分比所組 成的乙烯基系共重合化合物1〇〇莫耳與含有異氰酸酯基及 至少一個乙烯基的化合物5〜25莫耳所組成之感光性樹脂， 其酸値爲50〜150。 上述樹脂爲感光性樹脂，其主成份的單位構造如下列 化學式（1)及/或化學式(2)所示。5428 pif 4 发明 Description of the invention: The present invention relates to a coloring composition, and in particular, to a coloring composition, an electrode substrate and a liquid crystal display device having excellent insulation properties and used to obtain high display quality. Colored composition. As shown in the detailed cross-sectional schematic diagram of FIG. 2, a general liquid crystal display device includes an electrode plate 31 for liquid crystal driving, an electrode plate 32 for a common electrode located above the electrode plate 31 for liquid crystal driving, and an electrode plate sealed between the two electrode plates. The gap is made of a liquid crystal material 33. The liquid crystal driving electrode plate 31 includes a substrate 31a, a pixel electrode 31b provided for each pixel corresponding to a display screen, and a switching element 31c energized to the pixel electrode 31b corresponding to a screen display signal. Made up. The common electrode electrode plate 32 is composed of a transparent substrate 32a and a transparent common electrode 32b provided on the transparent substrate 32a to share all pixels. In addition, as shown in FIG. 2, in the case of a full-color liquid crystal display device that displays a full-color screen, the color filter 34 is for displaying transmitted light transmitted through each pixel of the common electrode electrode plate 32 separately. Set in various colors. In addition, in this liquid crystal display device, each pixel electrode 32b is energized by controlling the above-mentioned switching element 31c corresponding to each screen display signal. As the voltage between the pixel electrode 32b and the transparent common electrode 32b is different, the 5428 is driven. pif 4 moves the liquid crystal material 33 described above, and the screen is displayed by the transmission of light. In this liquid crystal display device, the transmitted light appears to be disturbed by the influence of the position of the switching element 31c, which will reduce the contrast of the display screen and degrade the development quality. It is necessary to provide a black matrix 35 on the electrode plate 32 for the common electrode in order to block the light incident on the aforementioned position and prevent the deterioration of the quality. In this case, due to manufacturing factors of the liquid crystal display device, an error may occur in the relative position between the light shielding plate 35 and the switching element 31c. Therefore, the light shielding plate 35 must be disposed at a position corresponding to the switching element 31c. The reasons for this error are: positional accuracy error of the switching element 31c when formed on the liquid crystal driving electrode plate 31, positional accuracy error of the light shielding plate 35 when formed on the common electrode electrode plate 32, and The relative error (maximum about 5 // m), and the combined error (maximum about 5 // m) of the liquid crystal driving electrode plate 31 and the common electrode electrode plate 33 during assembly. Therefore, the light-shielding plate 35 has an error of 10 // m (total 20 // m) compared with the switching element 31 c. In recent years, liquid crystal display devices have been driven by a reduction in pixels and an increase in pixel density, which requires a high-quality and dense display surface, but this cannot be achieved due to the above-mentioned errors. The problems associated with high pixel density and miniaturization are the aperture ratio (proportion of the total area of the pixel 5428 pif 4 area occupying the pixel of the screen display area) and the decrease of the brightness of the display screen. Therefore, an electrode substrate developed to improve the accuracy of the relative position between the light shielding plate 35 and the switching element 31c and increase the aperture ratio is expected. As shown in Japanese Patent Application Laid-Open No. 6-130218, a method of forming a light-shielding plate on an array substrate is such a technique. In the conventional art, the light-shielding plate is formed of metal. The following is its preparation method: First, a metal thin film such as Cr, Ni, A1 and the like is formed on a glass substrate by a vacuum film-forming method such as evaporation and sputtering, and then Photoresist coating, putting a photomask with a desired pattern on it, and then irradiating it with ultraviolet rays, and then developing the photoresist pattern to obtain a photoresist pattern. After that, the parts other than the photoresist are removed by etching, and the photoresist is peeled off to finally obtain the required light-shielding plate. However, when a liquid crystal panel manufactured using the color filter formed by the light-shielding plate is electrically connected to the liquid crystal driving electrode, improper liquid crystal operation or erroneous operation may occur. In this case, it is necessary to fabricate a light-shielding plate with an insulating substance in place of a metal thin film. Various light-shielding plates that do not use a metal film will be discussed at τ. Take Japanese Patent Application Laid-Open No. 2-2392040 (A) as an example, in which a light-shielding agent is firstly dispersed in a polyimide resin, and then a light-shielding plate is formed by an etching method, and it is also proposed to be directly added to a photosensitive material composition. Analysis of the constituents of the opacifier. In order to improve the light-shielding property, carbon black is often used in some materials. For example, in 5428 pif 4 (Japanese Unexamined Patent Publication No. 63-63870 (A)), it is proposed to disperse carbon black and organic pigments in a photo-superposition compound to form light-shielding board. In addition, in the method for forming a light-shielding plate on the array substrate side (Japanese Patent Application Laid-Open No. 6-130218 (A)), a black protective film formed of conductive carbon black dispersed as a black pigment is also used, either alone or in combination. The red, green, and blue protective films that form the three color filters are used in combination as a pseudo-black protective film as a light-shielding material that forms a light-shielding plate. However, compared with other organic pigments, the light-shielding properties of carbon black are relatively conductive. In addition, in order to improve the light-shielding property, the light-shielding plate formed by adding the s-no-dark gray-black 'as it is' to the photosensitive resin is often electrically conductive. For this reason, color filters made of such materials can also cause improper operation such as improper operation or erroneous operation of the liquid crystal when the liquid crystal drive electrode is turned on, which makes it impossible to control. In addition, a light-shielding plate is produced by dispersing an oxidized metal pigment in a resin as a light-shielding agent. However, the oxidized metal pigment has disadvantages that the voltage applied to the applied voltage and the light-shielding property are not very good. Therefore, it is known from the above-mentioned conventional techniques to develop a coloring composition having high insulation, light resistance, light-shielding properties, and dispersion stability, and to develop a color filter and an electrode substrate made of the coloring composition having the above-mentioned properties. And a liquid crystal display device is necessary. 5428 pif 4 Therefore, the main object of the present invention is to provide a coloring composition having high insulation, light resistance, light-shielding property, and dispersion stability in accordance with the above-mentioned points, and to provide a coloring composition made of the above-mentioned properties. The completed color filter, electrode substrate, and liquid crystal display device. Electrode substrates and liquid crystal displays with high positional precision and relative position between the light-shielding plate and the switching element are also provided. In order to solve the aforementioned problems, the inventors of the present invention have made this invention through repeated investigations. The coloring composition of the present invention is characterized in that the raw materials are a toner containing titanium black, a resin, and an insulating material. The content of the insulating substance is 1 to 35% by weight based on the toner content. The present invention is a coloring composition composed of a toner and a resin containing titanium black coated with an insulating substance, and the content of the insulating substance is 1 to 35% by weight of the toner content. The insulating material is composed of at least one compound selected from the group consisting of silica silicate, alumina, and zirconia. The content of the insulating substance is 1 to 35% by weight of the toner content. The resin is a photosensitive resin. The coloring composition includes a dispersant, a photo-recombinable monomer, 571177 5428 pif 4 photo-recombination starter, and a solution. The coloring composition includes a dispersant, a bridging agent, a photoacid generator, and a solvent. The coloring composition includes a dispersant 'photoreactive monomer, a diazo-based compound, an azide-based compound, and a solvent. The resin is a (m-) acrylic resin. The above resin is a vinyl-based copolymer consisting of 10 to 40 weight percent of a compound containing a vinyl group and a hydroxyl group, 10 to 30 weight percent of a compound containing a vinyl group and a carboxyl group, and 30 to 75 weight percent of a compound containing a vinyl group A photosensitive resin composed of a compound of 100 moles and a compound containing 5 to 25 moles of an isocyanate group and at least one vinyl group has an acid hydration of 50 to 150. The resin is a photosensitive resin, and the unit structure of its main component is as shown in the following chemical formula (1) and / or chemical formula (2).

11 (1) 571177 5428 pif 411 (1) 571177 5428 pif 4

·，·.···(2) (化學式中，心及R2分別代表氫原子、碳數1〜5的丨完#····· (2) (In the chemical formula, heart and R2 respectively represent a hydrogen atom and a carbon number of 1 to 5.

以及鹵素原子，R3代表氫原子或甲基，X則代表 -S02-、-C(CF3)2-、-Si(CH3)2-、-CH2-、-C(CH3)2-、下 述化學式（3)、或是不存在。Y則代表酸去水後的殘基，z 則代表酸二水和物的殘基。其中m及η爲1以上的整數。） ......................(3) 上述著色組成物具有107Dcm以上之體積阻抗率。 此外’上述著色組成物是由色劑與樹脂配合所製成， 且此色劑是由色劑與絕緣性物質混合而成，而被絕緣性物 質所被覆。 作爲本發明的彩色過濾器，其遮光板是使用上述的著 色組成物所形成的。 作爲本發明的液晶顯示裝置，以使用上述彩色過濾器 12 571177 5428 pif 4 爲其特徵。 本發明的電極基板是由透明基板上的開關元件及畫素 電極所構成，且至少在前述開關元件之上設有前述著色組 成物所形成的遮光板。 作爲本發明的液晶顯示裝置，以使用上述電極基板爲 其特徵。 爲讓本發明之上述目的、特徵、和優點能更明顯易 懂，下文特舉一較佳實施例，並配合所附圖式，作詳細說 明如下： 圖式之簡單說明： 第1圖是液晶顯示裝置之一例，其重要部位剖面圖。 第2圖是液晶顯示裝置之另一例，其重要部位剖面圖。 圖式之標記說明： 10 :液晶顯示裝置 11 :電極基板 11a、21a、32a :透明基板 lib、31b :畫素電極 11c、31c :開關元件 12、35 :遮光板 21、32 :共通電極用電極板 13 571177 5428 pif 4 21b、34 :彩色過濾器 21c、32b :透明共通電極 33 :液晶 31 :液晶驅動用電極板 31a :基板 實施方式 以下將詳述有關本發明之說明： 本發明之著色組成物，其特徵是原料爲含有鈦黑的色 劑、樹脂、以及絕緣性物質。且上述絕緣性物質的含量爲 色劑含量的1〜35%重量百分比。 使用含有鈦黑的色劑所形成的著色組成物在成爲膜 時有高度的膜強度，且在含有少量絕緣性物質的情況下有 高絕緣性。即在含有鈦黑而不使遮光性低下時，可具有高 絕緣性。 至於樹脂，以感光性樹脂與（間）丙烯基系樹脂爲佳， 因其具有優良的分散性、耐熱性、及透明性，且其體積阻 抗率在1〇7Ω cm以上。構成（間）丙烯基系樹脂的單體，通常 由下列所列舉的化學式(4)表示：And a halogen atom, R3 represents a hydrogen atom or a methyl group, and X represents -S02-, -C (CF3) 2-, -Si (CH3) 2-, -CH2-, -C (CH3) 2-, the following chemical formula (3) or does not exist. Y represents the residue of the acid after dehydration, and z represents the residue of the acid dihydrate. Where m and η are integers of 1 or more. ) ............ (3) The coloring composition has a volume resistivity of 107 Dcm or more. In addition, the above-mentioned coloring composition is made by mixing a toner with a resin, and the toner is made of a mixture of a toner and an insulating substance, and is covered with an insulating substance. As the color filter of the present invention, a light-shielding plate is formed using the above-mentioned coloring composition. The liquid crystal display device of the present invention is characterized by using the color filter 12 571177 5428 pif 4 described above. The electrode substrate of the present invention is composed of a switching element and a pixel electrode on a transparent substrate, and a light shielding plate made of the colored composition is provided at least on the switching element. The liquid crystal display device of the present invention is characterized by using the above-mentioned electrode substrate. In order to make the above-mentioned objects, features, and advantages of the present invention more comprehensible, a preferred embodiment is given below in conjunction with the accompanying drawings for detailed description as follows: Brief description of the drawings: FIG. 1 is a liquid crystal An example of a display device is a cross-sectional view of an important part. Fig. 2 is another example of a liquid crystal display device, and a cross-sectional view of an important part thereof. Explanation of drawing symbols: 10: liquid crystal display device 11: electrode substrates 11a, 21a, 32a: transparent substrates lib, 31b: pixel electrodes 11c, 31c: switching elements 12, 35: light shielding plates 21, 32: electrodes for common electrodes Plate 13 571177 5428 pif 4 21b, 34: color filters 21c, 32b: transparent common electrode 33: liquid crystal 31: electrode plate for liquid crystal driving 31a: substrate embodiment The description of the present invention will be described in detail below: The coloring composition of the present invention The material is characterized in that the raw materials are a toner containing titanium black, a resin, and an insulating substance. In addition, the content of the insulating substance is 1 to 35% by weight of the toner content. The colored composition formed using a toner containing titanium black has a high film strength when it becomes a film, and has a high insulating property when a small amount of an insulating material is contained. That is, when titanium black is contained without lowering the light-shielding property, it can have high insulation properties. As for the resin, a photosensitive resin and an (m) acrylic resin are preferred, because of its excellent dispersibility, heat resistance, and transparency, and its volume resistivity is above 107Ω cm. The monomer constituting the (m) propylene-based resin is generally represented by the following chemical formula (4):

Ri CH2-C-COO-R2 14 (4) 571177 5428 pif 4 具體而言，可以從下列之單體所構成的（間）丙烯基系 樹脂所構成。Ri CH2-C-COO-R2 14 (4) 571177 5428 pif 4 Specifically, it can be composed of a (m) acrylic resin composed of the following monomers.

15 571177 5428 pif 4 CHs15 571177 5428 pif 4 CHs

I CH2=C-COO(CH2CH2)nOH (n=i〇R2)， CH2=CH-COO(CH2-CH2>OH (n=i〇R2) CH3 CH3 CH2二CH-COOH , CH2=C-COOH，CH2=C-CONH2，I CH2 = C-COO (CH2CH2) nOH (n = i〇R2), CH2 = CH-COO (CH2-CH2 > OH (n = i〇R2) CH3 CH3 CH2 di-CH-COOH, CH2 = C-COOH, CH2 = C-CONH2,

H CHs H CH2-C-CONH2 ? CH2=i-CON(CH3>，CH2=C-CON(CH3) CH2=CH_COO-CH2-CH2-N(CH3)2， CHb CH2-C-COO-CH2-CH2-N(CH3)2 ?H CHs H CH2-C-CONH2? CH2 = i-CON (CH3 >, CH2 = C-CON (CH3) CH2 = CH_COO-CH2-CH2-N (CH3) 2, CHb CH2-C-COO-CH2-CH2 -N (CH3) 2?

H CH2〇CO〇-(CH2)n-CH3 (11=1 〜5)， CH3 CH2二C-C00-(CH2)n-CH3 (n=l〜5)， H CHs CH2-C-COO-H ? CH2=C-COO-H， CH2=CH-COO-CH2-CH2-CH2-N(CH3)2， H CH3 CH尸0-COO-(CH2)5-CH3，CH2C-COO-(CH2)5-CH3， CHs CH2C-COO-(CH2)6-CH3, 16 571177 5428 pif 4 以上所述之化學式並非不能被限定’可以是以一個單 體來使用，或是合倂兩種類來使用，亦或爲了適應其必要 性，而使用上述單體所合成的（間）丙烯基系樹脂。 (間）丙烯基系樹脂除了上述丙烯基系單體外，亦可以選 擇下列單體··二甲胺、乙基甲基丙烯酸酯、T基丙烯酸酯、 環氧丙基甲基丙烯酸酯、丙烯腈、乙烯乙酸酯、N-乙烯吡 喀烷酮、四氫呋喃甲基丙烯酸酯。 作爲感光性樹脂，是由含有一個乙烯基與羥基的化合 物10〜40重量百分比、含有一個乙烯基與羧基的化合物 10〜30重量百分比、含有一個乙烯基的化合物30〜75重量 百分比所組成的乙烯基系共重合物100莫耳與含有異氰酸 酯基及至少一個乙烯基的化合物5〜25莫耳所組成’其酸値 爲50〜150 〇 在此舉例說明含有一個乙烯基與羥基的化合物爲何： 丙烯酸、異丁烯酸(以下以（間）丙烯酸稱之）、羥乙酯、羥辛 酯、羥丙酯、羥甲基丙烯胺、烯丙醇等。 若以含有一個乙烯基與羧基的化合物爲例，則有丙烯 酸、異丁烯酸、衣康酸等。 作爲一個含有乙烯基的化合物，有（間）丙烯酸甲酯、（間) 丙烯酸乙酯、（間）丙烯酸丙酯、（間）丙烯酸丁酯、（間）丙烯 17 571177 5428 pif 4 酸2-乙己酯、（間）丙烯酸月桂酯、（間)丙烯酸硬脂醯、（間) 丙烯酸甲氧乙酯、（間）丙烯酸乙氧乙酯、（間）丙烯酸丁氧乙 酯、（間）丙烯酸環己酯、（間）丙烯酸環氧丙酯、丙烯腈、（間） 丙烯酸丙烯甲胺等。 含有異氰酸酯基及至少一個乙烯基的化合物，是由一 分子內至少含有η個（η大於2)以上異氰酸酯基的聚異氰酸 酯化合物1莫耳、及一分子內含有一個異氰酸酯基與能夠 參與反應的官能基（例如羥基）與至少一個乙烯基的乙烯化 合物(η-1)莫耳，於40〜l〇〇°C反應而得的化合物。此外亦 有使用異氰酸酯基乙基甲基丙烯酸酯與異丁烯醯的情況。 作爲聚異氰酸酯的例子有2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、4,4’-二苯基甲烷二異氰酸酯、六甲撐二 異氰酸酯、異佛爾酮二異氰酸酯、4,4，-二苯基甲烷二異氰 酸酯水合物、甲苯二異氰酸酯水合物等。使其與聚異氰酸 酯化合物產生反應，且含有一個經基的乙烯化合物’其例 有（間）丙烯酸之2-羥基乙酯、2-羥基丙酯、2-羥基辛酯等， 以及N-羥甲基丙烯胺、烯丙醇、丙三醇二（間）丙烯酸酯、 丙三醇二（間）院基化物、丙三醇二（間）丙烯酸酯鏈烯基化 物、丁環氧丙醚（間）丙烯酸酯、苯環氧丙醚（間）丙烯酸酯、 聚乙二醇單（間）丙烯酸酯、聚乙醯（間）丙烯酸酯、四經甲基 18 571177 5428 pif 4 甲烷三（間）丙烯酸酯等。 含有一個乙烯基的化合物、含有一個乙烯基與羧基的 化合物、由含有一個乙烯基的化合物所形成的乙烯基系共 重合化合物，雖可根據習知之方法來製造，亦可由環己酮、 乙二醇乙醚乙酸鹽、二乙二醇甲醚、乙苯、乙二醇二乙醚、 二甲苯等溶劑，根據溶液重合來製造。以溶液重合的方法 製造而得到的乙烯基系共重合化合物，在藉由異氰酸酯來 導入乙烯基而形成感光性共重合化合物時，反應將變得容 易進行。而且，由使用此方法得到的感光性樹脂所組成的 著色組成物，將變得容易在玻璃基板上塗布薄膜。 含有一個乙烯基與一個羥基的化合物其在感光性樹脂 中的共重合比例爲10〜40重量百分比。若未滿10重量百分 比，之後反應所得到的感光基將減少，露光感度將下降， 且對基板的密著性變差。若超過40重量百分比，將使得顯 像容易而解像性變差。 含有一個乙烯基與羧基的化合物其在感光性樹脂中的 共重合比例爲10〜30重量百分比。若未滿1〇重量百分比， 其顯像性變差。若超過30重量百分比，將使得顯像容易而 解像性變差。 還有，含有一個乙烯基的化合物其在感光性樹脂中的 19 571177 5428 pif 4 共重合比例爲30〜75重量百分比。未滿30重量百分比時其 露光感度降低，超過75重量百分比時顯像變難而且無法穫 得圖案的解像性。 要得到感光性樹脂，對於上述乙烯基系共重合化合物 1〇〇莫耳，須有含有異氰酸酯基及至少一個乙烯基的化合物 5〜25莫耳，更適當的是以10〜20莫耳之比例與其反應，以 獲得感光性樹脂。 φ 此時，若含有一個異氰酸酯基及至少一個乙烯基的化 合物未滿5莫耳，露光感度將大幅下降，在鹼顯像前後之 膜厚度變化將變大，耐熱性、耐溶劑性將變差。在另一方 面，若超過25莫耳，曝光時將出現暈光作用、解像性變差 以及溶劑乾燥時將留下痕跡。 感光性樹脂的酸値是根據由鹼顯像液決定的顯像性之 良好與否來決定的，其適當値調整在50〜150之間。若酸値 φ 未滿50，當顯像時間太長或不顯像時，將成爲地污現像的 原因。若酸値超過150,顯像時間將縮短而無法達到工作界 限，另外還有顯像後的圖案變細，且其剖面形狀成爲倒錐 形等問題。 此感光性樹脂的主成份，是上述化學式（1)以及/或化學 式（2)所表示的單位構造。 20 571177 5428 pif 4 上述化學式（1)以及化學式（2)中，較佳而言，K及R2分別 代表氫原子及甲基，R3代表氫原子。 上述化學式（1)以及化學式（2)表示的單位構造中，具有 包含X之二酚基丙烷構造的官能基。以下將舉例說明此種 二酚基丙烷構造的官能基。 以X代表含有-C0-的二酚基丙烷基之具體例子有雙(4-羥基苯）甲酮、雙(4-羥基-3,5-二甲基苯）甲酮、雙(4-經基_3,5_ 二氯苯）甲酮等，以X代表含有-S02-之具體例子有雙(4-羥 基苯)楓、雙(4_羥基-3,5-二甲基苯）楓、雙(4-羥基-3,5-二氯 苯)楓等，以X代表含有-C(CF3)2-之具體例子有雙(4-羥基苯) 六氟丙烷、雙（4-羥基-3,5-二甲基苯）六氟丙烷、雙（4-羥基 -3,5-二氯苯）六氟丙烷等，以X代表含有-Si(CF3)2-之具體例 子有雙(4-羥基苯）二甲基矽烷、雙（4-羥基_3,5_二甲基苯）二 甲基矽烷、雙(4-羥基-3,5-二氯苯）二甲基矽烷等，以X代表 含有-CH2-之具體例子有雙(4-羥基苯）甲烷、雙(4-羥基-3,5-二甲基苯）甲烷、雙(4-羥基-3,5-二氯苯）甲烷等，以X代表 含有-C(CH3)2-的二酚基丙烷基之具體例子有2,2-雙(4-羥基 苯）丙烷、2,2-雙（4-羥基-3,5·二甲苯）丙烷、2,2-雙（4-羥基 -3,5_二氯苯）丙烷、2,2-雙(4-羥基-3-甲苯）丙烷、2,2_雙(4-羥基-3-氯苯)丙烷等，以X代表含有-0-之具體例子有雙(4- 21 571177 5428 pif 4 羥基苯）醚、雙（4-羥基-3,5-二甲苯）醚、雙(4-羥基-3,5-二氯 苯)醚等。 X亦代表含有化學式（3)這個構造的官能基，如此所形 成的雙苯酚的具體例子如下：9,9-雙(4-羥基苯）芴、9,9-雙(4-羥基-3-甲苯）芴、9,9-雙（4-羥基-3·氯苯）芴、9,9_雙（4-羥基-3-溴苯)荀、9,9-雙(4-經基-3-氟苯)芴、9,9-雙(4-經基-3,5·-二甲 苯）芴、9,9-雙（4-羥基-3,5-二氯苯）芴、9,9-雙（4-羥基-3,5-二溴苯)芴等。 若X代表不存在，則有4,4’-聯苯酚、3,3’-聯苯酚爲例。 上述化學式（1)以及化學式（2)中，Υ代表酸無水物的殘基， Ζ代表酸二無水物的殘基。 如此加入殘基Υ而得到的酸無水物有馬里苷酸、無水 琥珀酸、無水衣康酸、無水苯二甲酸、無水四氫化鄰苯二 甲酸、無水六氫化鄰苯二甲酸、無水甲基橋亞甲基四氫化 鄰苯二甲酸、無水氯菌酸、甲基四氫化無水苯二甲酸等。 加入殘基Ζ而得到的酸二無水物有無水均苯四甲酸、二苯 甲酮四羧酸二無水物、聯苯醚四羧酸二無水物等芳香族多 價羧酸無水物。 在此可供使用的並非只限定於包含上述化學式（1)以及 化學式（2)所示單位構造爲主成分的化合物，可以以一種成 22 571177 5428 pif 4 份單獨使用或以兩種以上成份混合使用。 本發明所提及的著色組成物包含的絕緣性物質是選自 於由矽酸鹽、氧化鋁及氧化锆所組成的族群中的原素。雖 然沒有特別限定其原料來源，但以矽溶胶、桂酸鈉水溶液、 鋁溶胶等液體物質或非晶質二氧化矽矽酸鹽之無機微粒爲 適當選擇。根據絕緣性物質添加程度之不同，可達成著色 組成物之絕緣性優良、表面硬度增強、機械強度增強、熱 特性增強、分散性及耐光性增加等。 在著色組成物中的絕緣性物質，若其含有鈦黑之色劑 的含量爲1〜35重量百分比，則所得到的著色組成物將具有 高絕緣性。若未滿1重量百分比，相對於體積抵抗値，見 不到明亮的添加效果。若超過35重量百分比，則有遮光性 低下、與透明基板接觸不良、及耐衝擊性等問題產生。含 有鈦黑之色劑其更適當的含量在1〜20重量百分比之間，但 更佳的狀況則在1〜10重量百分比間。即，要在少被覆量的 情況下得到高遮光性。 雖然依據著色組成物所含有絕緣性物質的多寡，可以 提高著色組成物的絕緣性，但若預先以絕緣性物質被覆色 劑，所得到的著色組成物將具更高的絕緣性。 以絕緣性物質被覆色劑的方法除了將兩者混合外，雖 23 571177 5428 pif 4 可以習知技藝爲之，但在此將敘述使用作爲絕緣性物質原 料的桂酸鈉來形成二氧化矽被覆的方法。 首先，利用1小時的時間’將色劑與顆粒粉狀物分散 在水中而得到水性漿狀物。接著，將桂酸鈉溶液加入水性 漿狀物色劑中。再者，以勻漿器均勻攪拌上述溶液以粉碎 色劑，然後加熱。之後，加入硫酸再以勻漿器均勻攪拌， 得到二氧化矽被覆。最後，將色劑過瀘後取出，乾燥後即 得到被二氧化矽被覆的色劑。 著色組成物是由樹脂配合被絕緣性物質被覆的色劑而 得。 本發明之著色組成物的較佳實施例子，是由被絕緣性 物質表面處理過的色劑、及分散劑、（間）丙烯基系樹脂，在 以溶劑均勻分散的膏狀物中，添加光重合單體光重合開始 劑、架橋劑與光酸發生劑、以及光重合單體與重氮基系、 疊氮基系化合物而得到的感光性著色組成物。此著色組成 物具有1〇7Ωοιη以上之體積抵抗率。 至於分散劑，則以非離子性界面活性劑(例如聚羥乙烯 烷基醚）、離子性界面活性劑（例如烷苯磺酸鈉、聚脂肪酸 鹽、脂肪酸鹽烷磷酸鹽、四烷基銨鹽）、有機顏料誘導體、 聚酯等爲例。可以一種類單獨使用亦或兩種類以上混合使 24 571177 5428 pif 4 用。 在光重合單體中，爲單官能基的有壬基苯二甘醇一乙 醚丙烯酸酯、2-羥基-3-苯氧基丙基丙烯酸酯、乙己基（二甘 醇一乙醚）乙酸鹽，二官能基的有三縮三丙二醇丙烯酸酯、 聚乙二醇二丙烯酸酯、四乙二醇二丙烯酸酯，三官能基的 有三羥甲丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、三（2-羥 乙基）異氰酸酯，多官能機的有三羥甲基丙烷四丙烯酸酯、 二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯等。 作爲光重合開始劑的有三氮雜苯系化合物、咪唑化合 物、二苯甲酮化合物等，在此舉例如下。作爲三氮雜苯系 化合物的有胡椒基-s-三連氮、三（三氯甲基）-s-三氮雜苯、 2-(對甲氧苯乙烯基）-4,6-雙（三氯甲基）-s-三氮雜苯、2-苯基 -4,6-雙（三氯甲基）_s-三氮雜苯、2-(對甲氧苯基）-4,6-雙（三 氯甲基）-s-三氮雜苯、2-(對氯苯基）-4,6-雙（三氯甲基三 氮雜苯、2-(4’-甲氧基-Γ-萘基)-4,6-雙（三氯甲基）-s-三氮雜 苯等。作爲咪唑系化合物的有2-(2,3-二氯苯基)-4,5-二苯咪 唑L二聚物、2-(2,3-二氯苯基）-4,5-雙(3-甲氧苯基）-咪唑 二聚物、2-(2,3-二氯苯基）-4,5-雙（4-甲氧苯基）-咪唑二聚 物、2-(2,3-二氯苯基）-4,5-雙（4-二氯苯基）-咪唑二聚物、 2-(2,3-二氯苯基）-4,5-二（2-呋喃基）-咪唑、2,2’-雙（2-氯苯 25 571177 5428 pif 4 基）-4,5,4’，5，-四苯基-1，2，-咪唑等。作爲二苯甲酮系化合物 的例子有二苯甲酮、苯甲醯安息香酸、苯甲醯安息香酸甲 酯、丙細基化二苯甲酮、4-苯甲醯-4’-甲基二苯硫化物、3,3，-二甲基-4-甲氧苯基二苯甲酮、4,4’-二甲胺二苯甲酮、4-二 甲胺安息香酸乙酯等。 作爲光酸發生劑的有三氮雜苯系化合物與鐺鹽系化合 物’在此舉例如下。三氮雜苯系化合物如前段所示。作爲 鑷鹽系化合物的有二苯碘鍚四氟硼酸酯、二苯碘鍚六氟鹵 化物、二苯碘鍚六氟砷酸鹽、二苯碘鐃三氟甲磺醯酸鹽、 二苯碘鍚三氟乙酸鹽、二苯碘鐵-P-甲苯磺酸鹽、4-甲氧苯 基苯碘鍚四氟硼酸鹽、4-甲氧苯基苯碘鍚六氟膦酸鹽等。 架橋劑是含有N-羥甲基構造的化合物，有羥甲基化尿 素、尿素樹脂、羥甲基化三聚氰胺、羥丁基化三聚氰胺、 羥甲基化鳥糞胺等爲例。亦可使用上述化合物的烷醚化合 物作爲架橋劑，具有熱安定性高的優點。上述烷醚化合物 其烷基的碳數約爲1〜5,且若以感度來考量，以六羥甲基三 聚氰胺的烷醚化合物爲最。由於上述架橋劑在曝光發生後 其酸素存在化的加熱現象，可與上述樹脂反應而形成圖案。 作爲重氮基系化合物的例子有對重氮基二苯胺的甲醛 縮合物與六氟磷酸鹽、四氟硼酸鹽、高氯酸鹽、對甲苯磺 26 571177 5428 pif 4 酸，還有與2-羥基-4-甲氧基二苯甲酮-5-磺酸反應而得到的 重氮鍚鹽。 作爲疊氮基化合物的有4,4’-二疊氮基芪、4,4’-二疊氮 基二苯甲酮、4,4’-二疊氮基苯基苯乙烯酮、4,4’-二疊氮基 二甲苯、P-亞苯基雙疊氮基。 可作爲溶劑的有甲苯、二甲苯等苯系溶劑，甲基乙二 醇一乙醚、甲基溶纖素、丁基乙二醇一乙醚等乙二醇一乙 醚類，甲基乙二醇一乙醚乙酸鹽、乙二醇一乙醚乙酸鹽、 丁基乙二醇一乙醚乙酸鹽等乙二醇一乙醚醋酸酯類，亞丙 基乙二醇單甲基醚乙酸鹽、亞丙基乙二醇單乙基醚乙酸 鹽、亞丙基乙二醇單丁基醚乙酸鹽等亞丙基乙二醇單烷基 醚醋酸酯類，二乙烯乙二醇單甲基醚、二乙烯乙二醇單乙 基醚等二乙烯乙二醇類，丙酮、甲基乙基甲酮、甲基丁基 甲酮、環己酮等甲酮系溶劑等等。依照其分散安定性適當 的選擇單獨一種或兩種類以上混合來使用。 以下說明本發明各成份之分配比例。 著色組成物的固形物，即除去溶劑部份後的比例爲 5〜45重量百分比，較佳者爲10〜35重量百分比，更適當者 爲20〜30重量百分比。在未滿5重量百分比及超過45重量 百分比的情況下，當著色組成物以自旋鍍層機與旋轉鍍層 27 571177 5428 pif 4 機等塗布裝置塗布在基板上時’難以達到所期望的薄膜厚 度，且其塗布性降低。 被被覆的色劑其比例爲樹脂的10〜25〇重量百分比，較 適當者則爲20〜150重量百分比。在未滿50重量百分比的 情況下，以此著色組成物形成的遮光板時，遮光性會降低， 如此一來，必須鍍上較厚的膜’但此舉會對液晶配向膜的 形成有所防礙而影響液晶顯示性能。當其成份超過250重 量百分比時，將造成均勻分散的困難’所形成的遮光板其 密著性與機械強度將下降。 分散劑的適當含量爲色劑的1重量百分比以上。若未 滿1重量百分比，則欠缺均勻分散性與安定性。 光重合單體之含量爲樹脂的20〜150重量百分比。 光重合開始劑之添加量爲光重合單體之5〜150重量百分 比，更適當者爲〇〜130重量百分比。光重合開始劑可以單 獨或兩種以上添加使用。 本發明的著色組成物是以上述各成份依適當方法混合 製造。例如：將(間）丙烯酸樹脂以溶劑稀釋’並加入分散劑 與被絕緣性物質所表面處理過的色劑’再以顆粒粉狀分散 機等均勻分散。所得到的分散液再依其必要性，添加光重 合單體與光重合開始劑，或是架橋劑與光酸發生劑’或是 28 571177 5428 pif 4 光重合單體與重氮基系、疊氮基系化合物，均勻混合後即 是所須的著色組成物。 由於此著色組成物具有高絕緣性，所以含有此著色組 成物所形成之遮光板的彩色過濾器，將無法與液晶驅動電 極導通。此著色組成物還具有優良的耐光性、遮光性、分 散安定性，所以使用含有此著色組成物所形成之遮光板的 彩色過濾器，可以提供具高顯示品質、能抑制錯誤動作等 不適當狀況的優良液晶顯示裝置。第2圖所示之液晶顯示 裝置爲適當的例子。 利用此著色組成物所形成之遮光板亦可設置在電極基 板的開關元件上。 今使用第1圖來說明本發明之液晶顯示裝置之一形態： 液晶顯示裝置10中，透明基板11 a上有開關元件11 c、 畫素電極lib，共同組成電極基板11。且在開關元件11c 上，設有著色組成物所形成的遮光板12。在用以驅動液晶 的電極基板11之上，配置有共通電極用電極板21，且此共 通電極用電極板21是由透明基板21 a、附於透明基板21 a 上之彩色過濾器21b、以及透明共通電極21c所構成。在電 極基板11與共通電極用電極板21間封存有液晶33。開關 元件 11c 可以 TFT(Thin Film transister)端子、MIM(Metal 29 571177 5428 pif 4H CH2〇CO〇- (CH2) n-CH3 (11 = 1 ~ 5), CH3 CH2 di-C-C00- (CH2) n-CH3 (n = 1 ~ 5), H CHs CH2-C-COO-H ? CH2 = C-COO-H, CH2 = CH-COO-CH2-CH2-CH2-N (CH3) 2, H CH3 CH 0-COO- (CH2) 5-CH3, CH2C-COO- (CH2) 5 -CH3, CHs CH2C-COO- (CH2) 6-CH3, 16 571177 5428 pif 4 The above chemical formula is not limited. It can be used as a single monomer, or a combination of two types, or In order to meet the necessity, the (m) propylene-based resin synthesized using the above monomers is used. (Intermediate) In addition to the above-mentioned propylene-based monomers, propylene-based resins can also be selected from the following monomers: dimethylamine, ethyl methacrylate, T-based acrylate, epoxypropyl methacrylate, propylene Nitrile, ethylene acetate, N-vinylpyrrolidone, tetrahydrofuran methacrylate. As a photosensitive resin, ethylene is composed of 10 to 40 weight percent of a compound containing a vinyl group and a hydroxyl group, 10 to 30 weight percent of a compound containing a vinyl group and a carboxyl group, and 30 to 75 weight percent of a compound containing a vinyl group. The base co-reform is composed of 100 moles and a compound containing 5 to 25 moles of isocyanate group and at least one vinyl group. Its acid is 50 to 150. Here is an example of a compound containing one vinyl group and a hydroxyl group: acrylic acid , Methacrylic acid (hereinafter referred to as (inter) acrylic acid), hydroxyethyl ester, hydroxyoctyl ester, hydroxypropyl ester, hydroxymethacrylamine, allyl alcohol, and the like. When a compound containing one vinyl group and a carboxyl group is taken as an example, there are acrylic acid, methacrylic acid, itaconic acid, and the like. As a vinyl-containing compound, there are methyl (m-acrylate), ethyl (m-acrylate), propyl (m-acrylate), butyl (m-acrylate), and (propylene) 17-571177 5428 pif 4 Ester, lauryl (m-acrylate), stearyl methacrylate (m-acrylate), methoxyethyl (m-acrylate), ethoxyethyl (m-acrylate), butoxyethyl (m-acrylate), cyclohexyl (m-acrylate) Esters, glycidyl (m-acrylate), acrylonitrile, acrylonitrile (m-acrylate), and the like. A compound containing an isocyanate group and at least one vinyl group is composed of a polyisocyanate compound containing at least η (η greater than 2) or more isocyanate groups in one molecule, and a molecule containing one isocyanate group and a function capable of participating in the reaction. A compound obtained by reacting a vinyl group (e.g., hydroxyl group) with at least one vinyl compound (η-1) at 40 to 100 ° C. There are also cases where isocyanate ethyl methacrylate and isobutylene fluorene are used. Examples of the polyisocyanate include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4, -Diphenylmethane diisocyanate hydrate, toluene diisocyanate hydrate, and the like. It reacts with a polyisocyanate compound, and contains a vinyl compound having a radical. Examples include 2-hydroxyethyl (m-) acrylic acid, 2-hydroxypropyl ester, 2-hydroxyoctyl ester, and N-hydroxymethyl Allyl amine, allyl alcohol, glycerol di (m) acrylate, glycerol di (m) acrylate, glycerol di (m) acrylate alkenyl, butylene oxide ether (m ) Acrylate, phenylene oxide ether (m) acrylate, polyethylene glycol mono (m) acrylate, polyethylene acetam (m) acrylate, tetramethyl 18 18 571177 5428 pif 4 methane tri (m) acrylic acid Esters, etc. A compound containing a vinyl group, a compound containing a vinyl group and a carboxyl group, and a vinyl-based co-overlap compound formed from a compound containing a vinyl group can be produced according to a conventional method, and can also be produced from cyclohexanone and ethylene Solvents such as alcohol ether acetate, diethylene glycol methyl ether, ethylbenzene, ethylene glycol diethyl ether, and xylene are produced by superposing solutions. When a vinyl-based co-superposition compound produced by a solution-superposition method is introduced into a vinyl group through an isocyanate to form a photosensitive co-superposition compound, the reaction will easily proceed. In addition, a colored composition composed of a photosensitive resin obtained by this method makes it easy to apply a thin film to a glass substrate. The total weight ratio of the compound containing one vinyl group and one hydroxyl group in the photosensitive resin is 10 to 40 weight percent. If it is less than 10% by weight, the photosensitive group obtained after the reaction will be reduced, the exposure sensitivity will be reduced, and the adhesion to the substrate will be deteriorated. If it exceeds 40% by weight, the development is easy and the resolution is deteriorated. A compound containing a vinyl group and a carboxyl group has a total weight ratio of 10 to 30% by weight in the photosensitive resin. If it is less than 10% by weight, the developability is deteriorated. If it exceeds 30% by weight, the development is easy and the resolution is deteriorated. In addition, a compound containing one vinyl group has a total weight ratio of 19 571177 5428 pif 4 in the photosensitive resin of 30 to 75 weight percent. When the weight is less than 30% by weight, the exposure sensitivity decreases, and when the weight exceeds 75% by weight, development becomes difficult and the resolution of the pattern cannot be obtained. To obtain a photosensitive resin, for the above-mentioned vinyl-based co-overlay compound 100 mol, a compound containing an isocyanate group and at least one vinyl group must be 5 to 25 mol, and more preferably 10 to 20 mol. React with it to obtain a photosensitive resin. φ At this time, if the compound containing one isocyanate group and at least one vinyl group is less than 5 moles, the exposure sensitivity will be greatly reduced, the film thickness change before and after the alkali development will become larger, and the heat resistance and solvent resistance will be poor. . On the other hand, if it exceeds 25 mols, halo effect will occur during exposure, resolution will deteriorate, and traces will remain when the solvent dries. The pH of the photosensitive resin is determined based on whether the developability is determined by the alkali developer, and the appropriate pH is adjusted between 50 and 150. If the acid 値 φ is less than 50, when the development time is too long or no development occurs, it will cause the appearance of ground pollution. If the pH is more than 150, the development time will be shortened and the working limit will not be reached. In addition, there will be problems such that the pattern after development becomes thinner and the cross-sectional shape becomes inverted cone. The main component of this photosensitive resin is a unit structure represented by the aforementioned chemical formula (1) and / or chemical formula (2). 20 571177 5428 pif 4 In the above chemical formula (1) and chemical formula (2), preferably, K and R2 represent a hydrogen atom and a methyl group, respectively, and R3 represents a hydrogen atom. The unit structure represented by the chemical formula (1) and the chemical formula (2) has a functional group containing a bisphenol propane structure containing X. The functional group of such a diphenol-based propane structure will be exemplified below. Specific examples in which X represents -C0--containing diphenolyl propanyl are bis (4-hydroxybenzo) methanone, bis (4-hydroxy-3,5-dimethylbenzo) methanone, and bis (4-quinone _3,5_ dichlorobenzene) ketone and the like, and X represents -S02-. Specific examples include bis (4-hydroxybenzene) maple, bis (4-hydroxy-3,5-dimethylbenzene) maple, Specific examples of bis (4-hydroxy-3,5-dichlorobenzene) maple, etc., where X represents -C (CF3) 2- include bis (4-hydroxybenzene) hexafluoropropane, and bis (4-hydroxy-3 , 5-Dimethylbenzene) hexafluoropropane, bis (4-hydroxy-3,5-dichlorobenzene) hexafluoropropane, etc., and X represents -Si (CF3) 2-. Specific examples include bis (4- Hydroxybenzene) dimethylsilane, bis (4-hydroxy_3,5_dimethylbenzene) dimethylsilane, bis (4-hydroxy-3,5-dichlorobenzene) dimethylsilane, etc., with X Representative examples of containing -CH2- are bis (4-hydroxybenzene) methane, bis (4-hydroxy-3,5-dimethylbenzene) methane, bis (4-hydroxy-3,5-dichlorobenzene) methane Etc. Specific examples in which X represents -C (CH3) 2- containing diphenolylpropanyl are 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5 · Xylene) propane, 2,2-bis (4-hydroxy-3,5_dichlorobenzene) propane, 2,2-bis (4-hydroxy-3-toluene) propane, 2,2-bis (4-hydroxy-3-chlorobenzene) propane, etc., with X representing a specific example containing -0 as bis (4- 21 571177 5428 pif 4 hydroxyphenyl) ether, bis (4-hydroxy-3,5-xylene) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, etc. X also represents a functional group containing the structure of chemical formula (3). Specific examples of the bisphenol thus formed are as follows: 9,9-bis (4-hydroxybenzene) fluorene, 9,9-bis (4-hydroxy-3- Toluene) fluorene, 9,9-bis (4-hydroxy-3 · chlorobenzene) fluorene, 9,9_bis (4-hydroxy-3-bromobenzene) fluorene, 9,9-bis (4-meryl-3 -Fluorobenzene) fluorene, 9,9-bis (4-Cyclo-3,5 · -xylene) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorobenzene) fluorene, 9,9 -Bis (4-hydroxy-3,5-dibromobenzene) fluorene and the like. If X is absent, there are 4,4'-biphenol and 3,3'-biphenol as examples. In the above chemical formulas (1) and (2), Υ represents a residue of an acid anhydride, and Z represents a residue of an acid dihydrate. The acid anhydrides obtained by adding the residue rhenium include maleic acid, anhydrous succinic acid, anhydrous itaconic acid, anhydrous phthalic acid, anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, and anhydrous methyl bridge. Methylenetetrahydrophthalic acid, anhydrous chloric acid, methyltetrahydroanhydrophthalic acid, etc. Examples of the acid dianhydrous obtained by adding the residue Z include anhydrous polyvalent carboxylic acids such as anhydrous pyromellitic acid, benzophenonetetracarboxylic acid dianhydride, and diphenyl ether tetracarboxylic acid dianhydride. What is available here is not limited to compounds containing the unit structure shown in the above chemical formula (1) and chemical formula (2) as the main component. It can be used alone in one of 22 571177 5428 pif 4 parts or mixed with two or more components. use. The coloring composition referred to in the present invention includes an insulating substance selected from the group consisting of silicate, alumina, and zirconia. Although the source of the raw material is not particularly limited, it is appropriately selected from liquid substances such as silica sol, sodium laurate aqueous solution, and aluminum sol, or inorganic fine particles of amorphous silica silicate. Depending on the degree of addition of the insulating substance, it is possible to achieve excellent insulation properties of the colored composition, enhanced surface hardness, enhanced mechanical strength, enhanced thermal characteristics, increased dispersibility, and increased light resistance. If the content of the insulating material in the coloring composition contains a titanium black toner in an amount of 1 to 35 weight percent, the resulting coloring composition will have high insulation properties. If it is less than 1% by weight, the bright addition effect is not seen relative to the volume resistance. If it exceeds 35 weight percent, problems such as poor light-shielding properties, poor contact with a transparent substrate, and impact resistance may occur. The more appropriate content of the titanium black-containing colorant is between 1 and 20% by weight, but more preferably between 1 and 10% by weight. That is, it is necessary to obtain a high light-shielding property with a small amount of coating. Although the insulation of the coloring composition can be improved depending on the amount of the insulating substance contained in the coloring composition, if the coloring composition is coated with the insulating substance in advance, the coloring composition obtained will have higher insulation. In addition to mixing the insulating material with the coloring agent, although 23 571177 5428 pif 4 can be used in a conventional manner, the use of sodium laurate as a raw material for the insulating material to form a silicon dioxide coating will be described here. Methods. First, the toner and granular powder are dispersed in water over a period of 1 hour to obtain an aqueous slurry. Next, a sodium laurate solution was added to the aqueous slurry toner. Furthermore, the solution was uniformly stirred with a homogenizer to pulverize the toner, and then heated. After that, sulfuric acid was added and the mixture was uniformly stirred with a homogenizer to obtain a silica coating. Finally, the toner is taken out, and the toner coated with silica is obtained after drying. The coloring composition is obtained by mixing a resin with a toner coated with an insulating substance. A preferred example of the coloring composition of the present invention is a toner, a dispersant, and an (m) acrylic-based resin treated with a surface treated with an insulating substance. A paste uniformly dispersed in a solvent is added with light. Photosensitive coloring composition obtained by superposing monomer photo-superposition initiator, bridging agent and photoacid generator, and photo-superposition monomer and diazo-based or azide-based compound. This colored composition has a volume resistivity of 107 ohms or more. As for the dispersant, non-ionic surfactants (such as polyhydroxyvinyl alkyl ether), ionic surfactants (such as sodium alkylbenzene sulfonate, poly fatty acid salts, fatty acid salts, alkyl phosphates, and tetraalkyl ammonium salts) ), Organic pigment inducer, polyester, etc. as examples. One type can be used alone or two or more types can be mixed for use with 24 571177 5428 pif 4. Among the photoreactive monomers, there are monofunctional nonylbenzenediethylene glycol monoethyl ether acrylate, 2-hydroxy-3-phenoxypropyl acrylate, ethylhexyl (diethylene glycol monoethyl ether) acetate, Trifunctional tripropylene glycol acrylate, polyethylene glycol diacrylate, tetraethylene glycol diacrylate, trifunctional trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) Isocyanate, polyfunctional machines include trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like. Triazine compounds, imidazole compounds, benzophenone compounds, and the like are used as photoregeneration initiators, and examples are given below. Examples of triazabenzene compounds include piperonyl-s-triazine, tris (trichloromethyl) -s-triazabenzene, 2- (p-methoxystyryl) -4,6-bis ( Trichloromethyl) -s-triazabenzene, 2-phenyl-4,6-bis (trichloromethyl) _s-triazabenzene, 2- (p-methoxyphenyl) -4,6- Bis (trichloromethyl) -s-triazabenzene, 2- (p-chlorophenyl) -4,6-bis (trichloromethyltriazabenzene, 2- (4'-methoxy-Γ -Naphthyl) -4,6-bis (trichloromethyl) -s-triazabenzene, etc. As the imidazole compound, 2- (2,3-dichlorophenyl) -4,5-dibenzene Imidazole L dimer, 2- (2,3-dichlorophenyl) -4,5-bis (3-methoxyphenyl) -imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-bis (4-methoxyphenyl) -imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-bis (4-dichlorophenyl) -imidazole dimer Compounds, 2- (2,3-dichlorophenyl) -4,5-bis (2-furyl) -imidazole, 2,2'-bis (2-chlorobenzene 25 571177 5428 pif 4 group) -4, 5,4 ', 5, -tetraphenyl-1,2, -imidazole, etc. Examples of benzophenone-based compounds include benzophenone, benzophenone benzoic acid, benzophenone benzoic acid methyl ester, and propyl Finely Diphenyl Ketone, 4-benzidine-4'-methyldiphenyl sulfide, 3,3, -dimethyl-4-methoxyphenylbenzophenone, 4,4'-dimethylamine benzophenone , 4-dimethylamine benzoic acid ethyl ester, etc. As the photoacid generator, there are triazine-based compounds and pan salt-based compounds. Here are examples. Triazabenzene-based compounds are shown in the previous paragraph. As tweezers The compounds are diphenyliodine, tetrafluoroborate, diphenyliodine, hexafluorohalide, diphenyliodine, hexafluoroarsenate, diphenyliodine, trifluoromethanesulfonate, diphenyliodine, trifluoromethane Acetate, diphenyliodide-P-toluenesulfonate, 4-methoxyphenylbenzylidene tetrafluoroborate, 4-methoxyphenylbenzylidene hexafluorophosphonate, etc. The bridging agent contains N -Methylol structured compounds include, for example, methylolated urea, urea resin, methylolated melamine, methylolated melamine, methylolated guanamine, etc. Alkyl ether compounds of the above compounds can also be used As a bridging agent, it has the advantage of high thermal stability. The alkyl ether compound has a carbon number of about 1 to 5, and if it is measured in terms of sensitivity, a hexamethylolmelamine The compound is the most. Due to the heating phenomenon of the bridging agent whose acid exists after exposure, it can react with the resin to form a pattern. Examples of the diazo-based compound include a formaldehyde condensate of p-diazodiphenylamine and six Fluorophosphate, tetrafluoroborate, perchlorate, p-toluenesulfonic acid 26 571177 5428 pif 4 acid, and the weight obtained by reaction with 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid Azido salts. As the azide compounds, there are 4,4'-diazide stilbene, 4,4'-diazide benzophenone, 4,4'-diazide phenylstyrene , 4,4'-diazidoxylene, P-phenylene bisazido. Examples of solvents that can be used include benzene solvents such as toluene and xylene, ethylene glycol monoethyl ether such as methyl ethylene glycol monoethyl ether, methyl lysin, butyl glycol monoethyl ether, and methyl ethylene glycol monoethyl ether. Ethylene glycol monoethyl ether acetates such as acetate, ethylene glycol monoethyl ether acetate, butyl ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Ethyl ether acetate, propylene glycol monobutyl ether acetate, and other propylene glycol monoalkyl ether acetates, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Diethylene glycols such as methyl ethers, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone. One kind or a mixture of two or more kinds may be appropriately selected and used according to the dispersion stability. The distribution ratio of each component of the present invention will be described below. The solid content of the coloring composition, that is, the proportion after removing the solvent portion is 5 to 45 weight percent, preferably 10 to 35 weight percent, and more suitably 20 to 30 weight percent. In the case of less than 5 weight percent and more than 45 weight percent, when the colored composition is coated on a substrate by a coating device such as a spin coating machine and a spin coating machine 27 571177 5428 pif 4 machine, it is' difficult to achieve the desired film thickness, And its coatability is reduced. The proportion of the coated toner is 10 to 25 weight percent of the resin, and more suitably 20 to 150 weight percent. In the case of less than 50% by weight, the light-shielding property of the light-shielding plate formed from the coloring composition will be reduced. In this case, a thicker film must be plated. However, this will affect the formation of the liquid crystal alignment film Obstruct and affect the performance of the liquid crystal display. When its content exceeds 250% by weight, it will cause difficulty in uniform dispersion, and the light-shielding plate formed will have reduced adhesion and mechanical strength. A suitable content of the dispersant is 1% by weight or more of the toner. If it is less than 1% by weight, uniform dispersion and stability are lacking. The content of the photorecombinable monomer is 20 to 150 weight percent of the resin. The addition amount of the photo-registration initiator is 5 to 150 weight percent of the photo-registration monomer, and more suitably 0 to 130 weight percent. The photoregistration initiator may be used alone or in combination of two or more. The coloring composition of the present invention is produced by mixing the above-mentioned components by an appropriate method. For example, the (inter) acrylic resin is diluted with a solvent ', a dispersant and a toner surface-treated with an insulating substance are added', and the particles are dispersed uniformly in a granular powder disperser. According to the necessity, the obtained dispersion liquid is added with a photorecombinable monomer and a photorecombination starter, or a bridging agent and a photoacid generator, or 28 571177 5428 pif 4 photoreactive monomer and a diazo-based Nitrogen-based compounds, after homogeneous mixing, are the required coloring composition. Since the coloring composition has high insulation, a color filter containing a light-shielding plate formed by the coloring composition cannot be connected to the liquid crystal driving electrode. This coloring composition also has excellent light resistance, light-shielding properties, and dispersion stability. Therefore, the use of a color filter containing a light-shielding plate formed by the coloring composition can provide inappropriate conditions such as high display quality and suppression of malfunction. Excellent liquid crystal display device. The liquid crystal display device shown in Fig. 2 is a suitable example. The light-shielding plate formed by using the colored composition may be provided on a switching element of an electrode substrate. Now, using FIG. 1, a form of the liquid crystal display device of the present invention will be described. In the liquid crystal display device 10, the transparent substrate 11 a includes a switching element 11 c and a pixel electrode lib, and together forms an electrode substrate 11. The switching element 11c is provided with a light shielding plate 12 formed of a colored composition. On the electrode substrate 11 for driving liquid crystal, a common electrode electrode plate 21 is arranged, and the common electrode electrode plate 21 includes a transparent substrate 21 a, a color filter 21 b attached to the transparent substrate 21 a, and Consists of a transparent common electrode 21c. A liquid crystal 33 is sealed between the electrode substrate 11 and the common electrode electrode plate 21. Switch element 11c can be TFT (Thin Film transister) terminal, MIM (Metal 29 571177 5428 pif 4

InsulaterMetal)端子、及可變電子端子爲例。 在開關元件11c上設有遮光板12，兩者之間的相對位 置精確誤差可以縮小，亦即，將開關元件與遮光板分別設 置在各自的基板上，再一體化裝配起來。與習知的液晶顯 示裝置相比較，可縮小遮光板12的大小，且若開關元件Ik 與遮光板可確實對應，將可遮斷入射光線。 採用包含上述設置於開關元件11c上由著色組成物所 形成的遮光板12的電極基板11所製作的液晶顯示裝置 1〇，具有較高的開口率，及高顯示品質。 實施例 以下將本發明以實施例具體說明。請注意，在實施例 與製造例中，所謂「部」，是一重量單位。 (製造例1) 將20部異丁烯酸、15部2-羥基乙基甲基丙烯酸酯、 W部甲基異丁烯酸、55部丁基異丁烯酸以300部乙基乙二 _一乙醚溶解，在氮氣的環境下加入0.75部偶氮腈後，於 7〇°C、5小時的時間穫得丙烯基樹脂。再將此樹脂以乙基乙 二醇一乙醚稀釋至20重量百分比而得到一乙基乙二醇一乙 醚稀釋液。以此作爲稀釋液①。 (製造例2) 30 571177 5428 pif 4 在四個1L的燒瓶裡放入175.0部二乙烯乙二醇二甲基 醚、43.8部2-羥基甲基丙烯酸酯、26_3部異丁烯酸、及105.1 部異丁烯酸乙酯，並於90°C加熱。接著，將事先混合溶解 的145.0部二乙烯乙二醇二甲基醚、43.8部2_羥基甲基丙 烯酸酯、26.3部異丁烯酸、105.1部異丁烯酸乙酯及2.92 部NAIPA-BMT(日本油脂社製，過氧化苯醯），以三小時的 時間滴入燒瓶，於90°C反應三個鐘頭。然後’以1〇部二乙 烯乙二醇二甲基醚溶解1·75部ΝΑΙΡΑ·ΒΜΤ後，再滴入燒 瓶持續反應一個鐘頭。之後，以20部二乙烯乙二醇二甲基 醚溶解34.3部IPDI加成化合物、0.02部辛酸錫，於燒瓶內 溫爲80°C時用1〇分鐘的時間滴入。反應兩小時後即得到感 光性樹脂，其酸値約90。最後，以乙基乙二醇一乙醚稀釋 此樹脂至20重量百分比而得到一乙基乙二醇一乙醚稀釋 液。以此作爲稀釋液②。 (製造例3) 邊於90〜100°C加熱76.1部之雙苯酚芴型環氧樹脂、 0.0015部三乙基苄基銨氯化物、0.00033部2,6-二-異丁基 苯酚、及23·7部丙烯酸，一邊攪拌使其反應並昇溫至120 °C，經過八小時的反應而得到感光性樹脂。再以乙基乙二 醇一乙醚稀釋此樹脂至20重量百分比而得到一乙基乙二醇 31 571177 5428 pif 4 一乙醚稀釋液。以此作爲稀釋液③。 (製造例4) 將異佛爾酮二異氰酸酯置於氮氣4(TC的環境下加 熱，使其與1〇〇部2-羥基乙基甲基丙烯酸酯及0.13部對苯 二酚反應三個鐘頭，而得到液狀含有一個異氰酸酯基與乙 烯基的樹脂A。接著將65部丙烯基樹脂(25部2-羥基乙基 甲基丙烯酸酯、10部異丁烯酸、25部甲基異丁烯酸酯重合 而得），與35部樹脂A以300部乙基乙二醇一乙醚溶解， 於90°C反應三小時後，得到感光性樹脂（丙烯基樹脂）。最 後以乙基乙二醇一乙醚稀釋此樹脂至20重量百分比而得到 一乙基乙二醇一乙醚稀釋液。以此作爲稀釋液④。 (製造例5) 2〇〇g雙苯酚芴型環氧樹脂，加入100gl，2,3,6-四氫化 無水苯二酸及2 kg乙基乙二醇一乙醚攪拌後，與150g二苯 甲酮四狻酸二水合物及lg溴化四乙基銨於110t反應兩個 鐘頭，得到感光性樹脂。以乙基乙二醇一乙醚稀釋此樹脂 至20重量百分比而得到一乙基乙二醇一乙醚稀釋液。以此 作爲稀釋液⑤。 (製造例6) 作爲黑色色劑的鈦黑13R(商品名：三菱material 32 571177 5428 pif 4 製）30g加入lOOg水後以顆粒製粉機分散，得到水性漿狀 物。將200g2%矽酸鈉溶液加入此水性漿狀物後以勻化器攪 拌。加入硫酸中和後，進行被覆反應處理。取出被覆處理 過的色劑，加入硫酸銨溶液攪拌，放置一日使被覆處理過 的色劑沉澱。其次，過濾出被覆處理過的色劑，水洗後使 其乾燥，得到被二氧化矽被覆的被覆黑色色劑。最後，將 此被覆黑色色劑以螢光X射線作定量分析，其結果爲，二 n 氧化矽相對於碳黑100,重量比爲2.11。此色劑將作爲被覆 色劑①。 、 (製造例7) 除了矽酸鈉溶液的溶度改爲5%，其餘製程與製造例6 相同，得到被二氧化矽被覆的被覆黑色色劑。將此被覆黑 色色劑與製造例6同樣作定量分析，其結果爲，二氧化矽 相對於碳黑1〇〇,重量比爲4.62。此色劑將作爲被覆色劑②。 馨 (製造例8) 除了矽酸鈉溶液的溶度改爲10%，其餘製程與製造例 6相同，得到被二氧化矽被覆的被覆黑色色劑。將此被覆黑 色色劑與製造例6同樣作定量分析，其結果爲，二氧化矽 相對於碳黑1〇〇,重量比爲9.83。此色劑將作爲被覆色劑③。 (製造例9) 33 571177 5428 pif 4 除了矽酸鈉溶液的溶度改爲20% ’其餘製程與製造例 6相同，得到被二氧化矽被覆的被覆黑色色劑。將此被覆黑 色色劑與製造例6同樣作定量分析，其結果爲，二氧化矽 相對於碳黑1〇〇,重量比爲19·4。此色劑將作爲被覆色劑④。 (製造例10) 除了矽酸鈉溶液的溶度改爲35% ’其餘製程與製造例 6相同，得到被二氧化矽被覆的被覆黑色色劑。將此被覆黑 色色劑與製造例6同樣作定量分析，其結果爲，二氧化矽 相對於碳黑100,重量比爲33.4。此色劑將作爲被覆色劑⑤。 (實施例1) 將上述製造例1所得到的稀釋液①3〇g與上述製造例6 所得到的被覆色劑①38g、2g分散劑SORUBAASU20000(商 品名：ZENEKA製）及30g乙基乙二醇一乙醚相互混合，以 一個鐘頭半的時間用顆粒粉狀分散機邊冷卻邊分散。 對於上述方法得到的著色樹脂l〇〇g，加入上述稀釋液 ①5〇g、作爲光重合單體的三羥甲基丙烷三甲基丙烯化合物 4.〇g、作爲光重合開始劑的胡椒基-s-三連氮5g、及作爲溶 劑的乙基乙二醇一乙醚100g，儘量攪拌，製作出形成遮光 板用的著色組成物。 將此形成遮光板用的著色組成物，以800rpm的轉速 34 571177 5428 pif 4 度來旋轉塗佈，於兩面蒸鍍有Cr的基板上鍍膜1.1微米。 將塗膜的乾燥後端面以乙酮擦拭，並於23(TC以30分鐘燒 成後，將兩面的Cr以銀電極短路，得到體積阻抗値測定用 基板。對此基板以JIS規格(C2103-1991)爲準的體積阻抗率 試驗方法進行測量，得到1〇12Ω cm的體積阻抗率。再次， 將其塗佈在KONING社製「7059」的透明玻璃基板上，形 成厚度1.0微米的薄膜，以光學濃度法測其値爲3.2。其結 果如表一所示。 再次於上述的透明基板上形成1·2微米的塗膜，於70 °C進行15分鐘的預先烘烤處理，然後在畫素部分置上能夠 遮光的mask，進行精確的調整，在曝光（150mJ/cm2)、2.5% 碳酸鈉水溶液顯像後，以水沖洗。乾燥後，再於230°C的環 境下以三十分鐘燒成而得到遮光板圖案。以光學的方法， 可以得到解像度6微米線幅以下的遮光板。 接著，爲了在形成的塗膜上製作至少1〇〇個碁盤目， 將其置入交叉切口（crosscut)再以cerrotape進行剝離 (peeling)實驗，在顯微鏡下評價碁盤目的剝離狀態，得到無 法確認全部剝離且密著性良好的高絕緣遮光板。 另一方面，使40g2-乙基己基丙烯酸酯、40g乙基甲基 丙烯酸酯、異丁烯酸、300g環己酮、及0.5g偶氮二異丁腈 35 571177 5428 pif 4 於氮氣氣流中邊攪拌邊以80°C加熱反應5個鐘頭，得到一 黏稠液體。相對於此液體100g，加入25g藍色色劑(BASF 社製，酞菁藍）、5g分散劑（ZENEKA(股份有限）製’ SORUSUPAASU24000)、100g環己酮、20g二季戊四醇六丙 烯酸酯、3g雙(二乙胺)二苯甲酮、5g聯二咪唑誘導體(保土 土谷化學（股份有限）製，B-CIM)而得到藍色感光性樹脂組 成物。 籲 若不使用藍色色劑酞菁藍，而代以紅色色劑 (CHIBAGAIGII(股份有限)製，蒽醌紅），則得到紅色感光性 樹脂組成物。同樣的，若代以綠色色劑(HEKISUTO社製， 酞菁綠），則得到綠色感光性樹脂組成物。 其次，在上述得到的遮光板圖案上，使用藍色感光性 樹脂組成物以自旋鍍層機全面塗布而得到1.5微米的乾燥 厚膜，在80°C下烘烤，並使用NIKON社製的直線對準器 φ 以超高壓水銀燈100mJ/cm2的曝光量對圖案曝光。曝光後， 以0.5重量百分比的氫氧化鈉水溶液顯像而得到藍色圖 案。以同樣的步驟，可得到紅色及綠色圖案。 (實施例2〜33) 除了被覆色劑與稀釋液分別使用表一所列的組合外， 其餘步驟與實施例1同，而得到著色樹脂。 36 571177 5428 pif 4 對於如此穫得的著色樹脂l〇〇g，分別加入表一所標示 的稀釋液50g，並根據表一所標示的份量加入光重合性單 體、光重合開始劑、光酸發生劑、架橋劑、疊氮基系化合 物及溶劑，儘量攪拌，製作出形成遮光板用的著色組成物。 上述光重合性單體是指三羥甲基丙烷三丙烯酸，光重 合開始劑是指胡椒基-s-三聯氮，光酸發生劑是指4-甲氧基 苯基苯碘氫基六氟膦酸鹽，架橋劑是指羥甲基化鳥糞胺， 疊氮基化合物是指4,4’-二疊氮基芪，溶劑是指乙基乙二醇 一乙醚。所得到的著色組成物除了形成遮光板用之外，亦 比照實施例一，測定體積抵抗値與光學濃度。結果如表一 所示。 37 571177 5428 pif 4 表一 實施例 種韜 添fin莆景fg、_ _έέ®_ 編號 被覆 稀釋液 光重合 光重合 光酸 架S劑 疊氮系 溶劑 抵抗値 光學 色齊Ij 甲.p 開力台齊Ij 發牛劑 化合物 Π cm 濃麽 1 ① ① 4.0 5.0 - - 101 1012 3.2 2 ① ② 4.0 5.0 - - - 101 1012 3.2 3 ① ③ 4.0 5.0 - - - 101 1012 3.2 4 ① ④ 4.0 5.0 - - - 101 1012 3.2 5 ω (5) 4.0 5.0 _ _ 101 1012 3.2 6 ② ① 4.0 5.0 - - - 101 1013 3.1 7 ② ② 4.0 5.0 - - - 101 1013 3.1 8 ② ③ 4.0 5.0 - - - 101 1013 3.1 9 ② ④ 4.0 5.0 - - - 101 1013 3.1 10 (2) C5) 4.0 5.0 _ _ 101 1013 3.1 11 ③ ① 4.0 5.0 - - - 101 1013 2.8 12 ③ ② 4.0 5.0 - - - 101 1013 2.8 13 ③ ③ 4.0 5.0 - - - 101 1013 2.8 14 ③ ④ 4.0 5.0 - - - 101 1013 2.8 15 ③ 4.0 5.0 _ _ 101 1013 2.8 16 ④ ① 4.0 5.0 - - - 101 1013 2.0 17 ④ ② 4.0 5.0 - - - 101 1013 2.0 18 ④ ③ 4.0 5.0 - - - 101 1013 2.0 19 ④ ④ 4.0 5.0 - - - 101 1013 2.0 20 ④ C5) 4.0 5.0 _ _ _ 101 1013 2.0 21 ⑤ ① 4.0 5.0 - - - 101 1013 1.6 22 ⑤ ② 4.0 5.0 - - - 101 1013 1.6 23 ⑤ ③ 4.0 5.0 - - - 101 1013 1.6 24 ⑤ ④ 4.0 5.0 - - - 101 1013 1.6 25 (5) (5) 4.0 5.0 _ _ _ 101 1013 1,6 26 ① ① 4.0 一 4.0 1.0 _ 101 1013 3.1 27 ① ③ 4.0 - 4.0 1.0 - 101 1013 3.1 28 ② ① 4.0 - 4.0 1.0 - 101 1013 3.1 29 ② ③ 4.0 - 4.0 1.0 - 101 1013 3.1 30 ① ① 4.0 - - - 5.0 101 1013 3.1 31 ① ③ 4.0 - - - 5.0 101 1013 3.1 32 ② ① 4.0 - - - 5.0 101 1013 3.1 33 ⑦ (3) 4.0 - - - 5.0 101 1013 3.1 38 571177 5428 pif 4 再以實施例一的方法得到遮光板圖案，並以微影法， 形成線幅6微米以下之遮光板。再如同實施例一般進行剝 離實驗，得到無法確認全部剝離且密著性良好的高絕緣遮 光板。而後，再如實施例一般，於遮光板上形成紅、藍、 綠之著色圖案。 (比較例1) 添加30g製造例1所得的稀釋液①、37.8g碳黑 MA220(商品名：三菱化學製）、0.2g 之 AMORUFASUSHIRIKA(商品名：曰本觸媒製）、2g分散齊I] SORUSUPAASU200000(商品名：ZENEKA 製）、30g 乙基乙 一醇一乙醚於顆粒粉狀分散機邊冷卻邊以一個鐘頭半分 散。 除了使用如此得到的著色樹脂100g之外，其餘皆需依 照實施例1的方法製作形成遮光板用的著色組成物，並使 用此著色組成物測定其體積抵抗値與光學濃度。所測得的 體積阻抗値爲104Ω cm，光學濃度爲2.9。 除了將曝光時間改爲l〇〇〇mj/cm 2以外，其餘步驟如同 實施例1，所得到的遮光板圖案之解像性、表面平滑性變 差，且著色組成物本身之分散性亦變差。 (比較例2) 39 5428 pif 4 加入30g製造例1所得的稀釋液①、38g鈦黑13R(商 品名：三菱 material 製）、2g 分散劑 SORUSUPAASU200000(商品名：ZENEKA 製）、30g 乙基乙 二醇一乙醚於顆粒粉狀分散機邊冷卻邊以一個鐘頭半分 散。 除了使用如此得到的著色樹脂lOOg之外，其餘皆需依 照實施例1的方法製作形成遮光板用的著色組成物，並使 用此著色組成物測定其體積抵抗値。所測得的體積抵抗値 爲104Ωαη，且其具有電壓依存性。 除了將曝光時間改爲200mJ/cm 2以外，其餘步驟如同 實施例1，得到遮光板圖案，其解像性差於15//m，且表面 平滑性、圖案形狀亦較差。 (比較例3) 加入30g製造例1所得的稀釋液①、28g鈦黑13R(商 品名：三菱 material 製）、5g 紫色色劑 RIONOGENBAIORETTO RL(商品名：東洋 INKI 製）、5g 藍 色色劑 HERIOGENBULUU L6700F(商品名：BASF 社製）、 2g 分散劑 SORUSUPAASU200000(商品名：ZENEKA 製）、 30g乙基乙二醇一乙醚於顆粒粉狀分散機邊冷卻邊以一個 鐘頭半分散。 5428 pif 4 除了使用如此得到的著色樹脂lOOg之外，其餘皆需依 照實施例1的方法製作形成遮光板用的著色組成物，並使 用此著色組成物測定其體積抵抗値與光擧濃度。所測得的 體積抵抗値爲1〇9Ωαη以上，光學濃度爲2.3。 除了將曝光時間改爲l〇〇mJ/cm 2以外，其餘步驟如同 實施例1，所得到的遮光板圖案之解像性、表面平滑性變 差，且著色組成物本身之分散性亦變差。 φ (比較例3) 加入30g製造例1所得的稀釋液①、20g鈦黑13R(商 品名：三菱 material 製）、2g 分散劑 SORUSUPAASU200000(商品名：ZENEKA 製）、48g 乙基乙 二醇一乙醚於顆粒粉狀分散機邊冷卻邊以一個鐘頭半分 散。 除了使用如此得到的著色樹脂i〇〇g之外，其餘皆需依 · 照實施例1的方法製作形成遮光板用的著色組成物，並使 用此著色組成物測定其體積抵抗値與光學濃度。所測得的 體積抵抗値爲1〇6Ωαη，光學濃度爲2.3。 除了將曝光時間改爲300mJ/cm 2以外’其餘步驟如同 實施例1，所得到的遮光板圖案之解像性、表面平滑性變 差，且著色組成物本身之分散性亦變差。 41 571177 5428 pif 4 接著，爲了在形成的塗膜上製作至少100個碁盤目， 將其置入交叉切口（crosscut)再以cerrotape進行剝離 (peeling)實驗，在顯微鏡下評價碁盤目的剝離狀態，確認其 爲20個剝離程度。 如上述，本發明之著色組成物具有高絕緣性，且具優 良之耐光性、遮光性、分散安定性及膜強度，此外，於形 成遮光板方面亦最適當。並且使用此遮光板，可以得到高 品質的液晶顯示裝置。 在透明基板上設置開關元件開關元件及畫素電極所構 成的電極基板中，由於本發明之著色組成物所形成的遮光 板製備於前述開關元件上，將簡便地提供遮光板與開關元 件間相對位置精度高、顯示畫面開口率大之電極基板及液 晶顯示裝置。 雖然本發明已以較佳實施例揭露如上，然其並非用以 限定本發明’任何熟習此技藝者，在不脫離本發明之精神 和範圍內’當可作各種之更動與潤飾，因此本發明之保護 範圍當視後附之申請專利範圍所界定者爲準。 42Insulater Metal) terminals and variable electronic terminals are examples. A light shielding plate 12 is provided on the switching element 11c, and the relative position accuracy error between the two can be reduced, that is, the switching element and the light shielding plate are respectively disposed on respective substrates, and then assembled integrally. Compared with the conventional liquid crystal display device, the size of the light shielding plate 12 can be reduced, and if the switching element Ik and the light shielding plate can correspond to each other, the incident light can be blocked. The liquid crystal display device 10 manufactured by using the electrode substrate 11 including the light-shielding plate 12 formed of the coloring composition on the switching element 11c described above has a high aperture ratio and high display quality. Examples The present invention will be specifically described below by way of examples. Note that in the examples and manufacturing examples, the "portion" is a unit of weight. (Production Example 1) 20 parts of methacrylic acid, 15 parts of 2-hydroxyethyl methacrylate, W parts of methyl methacrylic acid, and 55 parts of butyl methacrylic acid were dissolved in 300 parts of ethylethylene diethyl ether, and nitrogen After adding 0.75 parts of azocarbonitrile under the environment, the acrylic resin was obtained at 70 ° C for 5 hours. This resin was further diluted with ethyl ethylene glycol monoethyl ether to 20% by weight to obtain a diethyl ethylene glycol monoethyl ether dilution. This was used as a diluent ①. (Production Example 2) 30 571177 5428 pif 4 In four 1 L flasks, 175.0 parts of diethylene glycol dimethyl ether, 43.8 parts of 2-hydroxymethacrylate, 26-3 parts of methacrylic acid, and 105.1 parts of isobutylene were placed. Ethyl acetate and heat at 90 ° C. Next, 145.0 parts of diethylene glycol dimethyl ether, 43.8 parts of 2-hydroxymethacrylic acid ester, 26.3 parts of methacrylic acid, 105.1 parts of ethyl methacrylate and 2.92 parts of NAIPA-BMT (Nippon Oil & Fats Corporation) were mixed and dissolved in advance. Production, phenylhydrazone peroxide), dropped into the flask over a period of three hours, and reacted at 90 ° C for three hours. After that, 1.75 parts of NAIPA · BMT were dissolved with 10 parts of diethylene glycol dimethyl ether, and the reaction was continued for one hour after dripping into a flask. Thereafter, 34.3 parts of the IPDI addition compound and 0.02 part of tin octoate were dissolved with 20 parts of diethylene glycol dimethyl ether, and the solution was added dropwise over a period of 10 minutes when the internal temperature of the flask was 80 ° C. After two hours of reaction, a photosensitive resin was obtained, with an acid content of about 90. Finally, the resin was diluted with ethyl glycol-diethyl ether to 20% by weight to obtain a diethyl glycol-diethyl ether dilution. This was used as the diluent ②. (Production Example 3) 76.1 parts of bisphenol amidine epoxy resin, 0.0015 parts of triethylbenzyl ammonium chloride, 0.00033 parts of 2,6-di-isobutylphenol, and 23 were heated at 90 to 100 ° C. -7 parts of acrylic acid, reacted with stirring and heated to 120 ° C, and reacted for 8 hours to obtain a photosensitive resin. The resin was diluted with ethylethylene glycol monoethyl ether to 20% by weight to obtain monoethyl glycol 31 571177 5428 pif 4 diethyl ether diluent. This was used as a diluent ③. (Production Example 4) Isophorone diisocyanate was heated under an atmosphere of nitrogen 4 (TC), and reacted with 100 parts of 2-hydroxyethyl methacrylate and 0.13 parts of hydroquinone for three hours. To obtain a liquid resin A containing an isocyanate group and a vinyl group. Next, 65 parts of acryl-based resin (25 parts of 2-hydroxyethyl methacrylate, 10 parts of methacrylic acid, and 25 parts of methyl methacrylate were superposed to form It was dissolved in 35 parts of resin A with 300 parts of ethyl ethylene glycol monoethyl ether. After reacting at 90 ° C for three hours, a photosensitive resin (propylene-based resin) was obtained. Finally, this was diluted with ethyl ethylene glycol monoethyl ether. The resin was reduced to 20% by weight to obtain a diethyl ethylene glycol monoethyl ether diluent. This was used as the diluent ④. (Production Example 5) 200 g of a bisphenol fluorene type epoxy resin was added to 100 g, 2, 3, and 6 -After stirring with tetrahydroanhydrophthalic acid and 2 kg of ethyl glycol monoethyl ether, react with 150g of benzophenonetetraacetic acid dihydrate and lg tetraethylammonium bromide at 110t for two hours to obtain photosensitivity Resin. Dilute this resin to 20% by weight with ethyl ethylene glycol monoethyl ether to obtain ethyl ethyl ester. Alcohol-diethyl ether diluent. This was used as the diluent ⑤. (Production Example 6) Titanium Black 13R (trade name: Mitsubishi material 32 571177 5428 pif 4) as a black toner was added to 100 g of water, and dispersed in a granulating machine. An aqueous slurry was obtained. 200 g of a 2% sodium silicate solution was added to the aqueous slurry and stirred with a homogenizer. After adding sulfuric acid to neutralize, the coating reaction treatment was taken out. The coated toner was taken out and stirred with ammonium sulfate solution. After one day, the coated toner is precipitated. Secondly, the coated toner is filtered, washed with water, and dried to obtain a coated black toner coated with silicon dioxide. Finally, the coated black toner is coated. Fluorescent X-rays were used for quantitative analysis. As a result, the weight ratio of di-n silica to carbon black 100 was 2.11. This toner will be used as a coating agent ①. (Production Example 7) Except for sodium silicate solution, The solubility was changed to 5%, and the rest of the process was the same as in Manufacturing Example 6. A coated black toner coated with silicon dioxide was obtained. The coated black toner was quantitatively analyzed in the same manner as in Manufacturing Example 6. As a result, the relative density of silicon dioxide was to Black 100, weight ratio is 4.62. This colorant will be used as coating colorant ②. Xin (Production Example 8) Except that the solubility of the sodium silicate solution is changed to 10%, the rest of the process is the same as that of Production Example 6, and the second product is obtained. Silicon oxide-coated black toner. This coated black toner was quantitatively analyzed in the same manner as in Manufacturing Example 6. As a result, the weight of the silicon dioxide relative to the carbon black was 9.83. This toner was used as a coating. Toner ③. (Production Example 9) 33 571177 5428 pif 4 The same process as in Production Example 6 was performed except that the solubility of the sodium silicate solution was changed to 20%, and a coated black toner coated with silica was obtained. This coated black toner was subjected to quantitative analysis in the same manner as in Production Example 6. As a result, the weight ratio of silicon dioxide to carbon black was 19.4. This toner will serve as a coating toner ④. (Manufacturing Example 10) The same procedure as in Manufacturing Example 6 was performed except that the solubility of the sodium silicate solution was changed to 35%, to obtain a coated black toner coated with silicon dioxide. When this coated black toner was subjected to quantitative analysis in the same manner as in Production Example 6, the weight ratio of silicon dioxide to carbon black 100 was 33.4. This toner will serve as a coating toner ⑤. (Example 1) 30 g of the diluted solution ① obtained in the above-mentioned Production Example 1 and the coating agent ① obtained in the above-mentioned Production Example 6 38 g and 2 g of a dispersant SORUBAASU 20000 (trade name: manufactured by ZENEKA) and 30 g of ethyl glycol- The ethers are mixed with each other and dispersed in a granulated powder disperser for one and a half hours while cooling. To 100 g of the coloring resin obtained by the above method, 50 g of the above-mentioned diluent ①, 4.0 g of trimethylolpropane trimethylpropylene compound as a photo-recombinable monomer, and piperonyl- as a photo-recombination initiator were added. 5 g of s-triazine and 100 g of ethyl glycol monoethyl ether as a solvent were stirred as much as possible to produce a colored composition for forming a light-shielding plate. The coloring composition for forming a light-shielding plate was spin-coated at a rotation speed of 800 rpm 34 571177 5428 pif 4 degrees, and 1.1 micrometers were deposited on the substrate on which Cr was vapor-deposited on both sides. The dried end surface of the coating film was wiped with ethyl ketone, and after firing at 23 ° C for 30 minutes, Cr on both sides was short-circuited with a silver electrode to obtain a substrate for measuring volume impedance 对此. For this substrate, JIS standards (C2103- 1991) was used to measure the volume resistivity test method to obtain a volume resistivity of 1012 Ω cm. Again, this was coated on a transparent glass substrate "7059" manufactured by KONING Co., Ltd. to form a thin film having a thickness of 1.0 micron, and Its optical density was 3.2 when measured. The results are shown in Table 1. Once again, a 1.2 micron coating film was formed on the above-mentioned transparent substrate, and a pre-baking treatment was performed at 70 ° C for 15 minutes. Partly put on a mask that can block light and make precise adjustments. After exposure (150mJ / cm2), 2.5% sodium carbonate aqueous solution is developed, rinse with water. After drying, burn at 230 ° C for 30 minutes. A light-shielding plate pattern can be obtained. Optically, a light-shielding plate having a resolution of 6 micrometers or less can be obtained. Next, in order to make at least 100 panicles on the formed coating film, it is placed in a crosscut. Enter it again with cerrotape In a peeling test, the peeling state of the disk was evaluated under a microscope, and a high-insulation light-shielding plate that could not be completely peeled off and had good adhesion was obtained. On the other hand, 40 g of 2-ethylhexyl acrylate and 40 g of ethyl methacrylic acid were used. Ester, methacrylic acid, 300 g of cyclohexanone, and 0.5 g of azobisisobutyronitrile 35 571177 5428 pif 4 Heat and react at 80 ° C for 5 hours while stirring in a nitrogen gas stream to obtain a viscous liquid. Compared to this liquid 100g, add 25g blue colorant (phthalocyanine blue manufactured by BASF), 5g dispersant ('SORUSUPAASU24000' manufactured by ZENEKA (Limited)), 100g cyclohexanone, 20g dipentaerythritol hexaacrylate, 3g bis (diethylamine) Benzophenone and 5 g of biimidazole inducer (Hodogokutani Chemical Co., Ltd., B-CIM) to obtain a blue photosensitive resin composition. It is recommended that phthalocyanine blue be used instead of the blue colorant. A red toner (anthraquinone red produced by CHIBAGAIGII (limited stock)) will give a red photosensitive resin composition. Similarly, if a green toner (phthalocyanine green manufactured by HEKISUTO) is used, a green photosensitive resin will be obtained.组合 物。 Composition. Next, on the light-shielding plate pattern obtained above, a blue photosensitive resin composition was fully coated with a spin coater to obtain a dry thick film of 1.5 microns, baked at 80 ° C, and a straight line made by NIKON Corporation was used. The aligner φ exposes the pattern with an exposure amount of an ultra-high pressure mercury lamp of 100 mJ / cm2. After exposure, it is developed with a 0.5% by weight sodium hydroxide aqueous solution to obtain a blue pattern. In the same procedure, red and green patterns can be obtained. (Examples 2 to 33) Except that the coating agent and the diluent were used in the combinations listed in Table 1, the rest of the steps were the same as in Example 1 to obtain a colored resin. 36 571177 5428 pif 4 For 100 g of the coloring resin thus obtained, add 50 g of the diluent indicated in Table 1, and add the photo-reactive monomer, photo-restart initiator, and photoacid generator according to the amounts indicated in Table 1. Agent, bridging agent, azide-based compound, and solvent, stir as much as possible to produce a colored composition for forming a light-shielding plate. The photo-reactive monomer refers to trimethylolpropane triacrylic acid, the photo-recombination initiator refers to piperonyl-s-triazine, and the photoacid generator refers to 4-methoxyphenylphenyliodohydrofluorohexafluorophosphine. Acid salt, bridging agent refers to methylolated guanoamine, azide compound refers to 4,4'-diazide stilbene, and solvent refers to ethyl glycol monoethyl ether. In addition to forming a light-shielding plate, the obtained coloring composition was measured in terms of volume resistance and optical density in comparison with Example 1. The results are shown in Table 1. 37 571177 5428 pif 4 Table one of the examples of the embodiment of Tao Tian fin 莆 f fg, _ _έέ ® _ number coating diluent light superposition light superposition photoacid frame S agent azide solvent resistance 値 optical color Qi Ij A. p Qi Ij hair-boosting compound Π cm concentrated 1 ① ① 4.0 5.0--101 1012 3.2 2 ① ② 4.0 5.0---101 1012 3.2 3 ① ③ 4.0 5.0---101 1012 3.2 4 ① ④ 4.0 5.0--- 101 1012 3.2 5 ω (5) 4.0 5.0 _ _ 101 1012 3.2 6 ② ① 4.0 5.0---101 1013 3.1 7 ② ② 4.0 5.0---101 1013 3.1 8 ② ③ 4.0 5.0---101 1013 3.1 9 ② ④ 4.0 5.0---101 1013 3.1 10 (2) C5) 4.0 5.0 _ _ 101 1013 3.1 11 ③ 4.0 4.0---101 1013 2.8 12 ③ 4.0 4.0---101 1013 2.8 13 ③ 4.0 4.0-- --101 1013 2.8 14 ③ ④ 4.0 5.0---101 1013 2.8 15 ③ 4.0 5.0 _ _ 101 1013 2.8 16 ④ ① 4.0 5.0---101 1013 2.0 17 ④ ② 4.0 5.0---101 1013 2.0 18 ④ ③ 4.0 5.0---101 1013 2.0 19 ④ ④ 4.0 5.0---101 1013 2.0 20 ④ C5) 4.0 5.0 _ _ _ 101 1013 2.0 2 1 ⑤ ① 4.0 5.0---101 1013 1.6 22 ⑤ ② 4.0 5.0---101 1013 1.6 23 ⑤ ③ 4.0 5.0---101 1013 1.6 24 ⑤ ④ 4.0 5.0---101 1013 1.6 25 (5) (5 ) 4.0 5.0 _ _ _ 101 1013 1,6 26 ① ① 4.0-4.0 1.0 _ 101 1013 3.1 27 ① ③ 4.0-4.0 1.0-101 1013 3.1 28 ② 4.0-4.0 1.0-101 1013 3.1 29 ② ③ 4.0-4.0 1.0-101 1013 3.1 30 ① ① 4.0---5.0 101 1013 3.1 31 ① ③ 4.0---5.0 101 1013 3.1 32 ② ① 4.0---5.0 101 1013 3.1 33 ⑦ (3) 4.0---5.0 101 1013 3.1 38 571177 5428 pif 4 The pattern of the light-shielding plate is obtained by the method of the first embodiment, and a light-shielding plate with a line width of 6 microns or less is formed by the lithography method. Further, a peeling test was performed in the same manner as in the example, and a highly insulating light-shielding sheet having no adhesion and good adhesion was obtained. Then, as in the embodiment, red, blue, and green colored patterns are formed on the light-shielding plate. (Comparative Example 1) 30 g of the diluent ① obtained in Production Example 1, 37.8 g of carbon black MA220 (trade name: manufactured by Mitsubishi Chemical Corporation), 0.2 g of AMORUFASUSHIRIKA (trade name: manufactured by Hitachi Catalyst), and 2 g of dispersion I were added.] SORUSUPAASU200000 (trade name: manufactured by ZENEKA), 30 g of ethyl ethylene glycol monoethyl ether were semi-dispersed for one hour while cooling in a granular powder dispersing machine. Except for using 100 g of the coloring resin thus obtained, the coloring composition for forming a light-shielding plate was prepared in accordance with the method of Example 1, and the volume resistance and optical density were measured using the coloring composition. The measured volume impedance 値 was 104 Ω cm and the optical density was 2.9. Except that the exposure time was changed to 1000 mj / cm 2, the other steps were the same as in Example 1. The resolution and surface smoothness of the obtained light-shielding plate pattern were deteriorated, and the dispersibility of the coloring composition itself was also changed. difference. (Comparative Example 2) 39 5428 pif 4 was added 30 g of the diluent ① obtained in Production Example 1, 38 g of titanium black 13R (trade name: made by Mitsubishi material), 2 g of dispersant SORUSUPAASU200000 (trade name: made by ZENEKA), and 30 g of ethyl ethylene diethylene glycol. Alcohol-ether was semi-dispersed for one hour in a granular powder disperser while cooling. Except for using 100 g of the coloring resin thus obtained, the coloring composition for forming a light-shielding plate was prepared in accordance with the method of Example 1 and the volume resistance of the coloring composition was measured. The measured volume resistance 値 is 104Ωαη, and it is voltage-dependent. Except that the exposure time was changed to 200 mJ / cm 2, the other steps were the same as in Example 1 to obtain a light-shielding plate pattern, the resolution of which was worse than 15 // m, and the surface smoothness and pattern shape were also poor. (Comparative Example 3) 30 g of the dilution solution ① obtained in Production Example 1, 28 g of titanium black 13R (trade name: manufactured by Mitsubishi material), 5 g of purple toner RIONOGENBAIORETTO RL (trade name: manufactured by Toyo Inki), 5 g of blue toner HERIOGENBULUU L6700F (Trade name: manufactured by BASF), 2 g of dispersant SORUSUPAASU200000 (trade name: manufactured by ZENEKA), and 30 g of ethyl glycol monoethyl ether were dispersed in an granule powder dispersing machine for half an hour while cooling. 5428 pif 4 except for using 100 g of the coloring resin thus obtained, the coloring composition for forming a light-shielding plate was prepared in accordance with the method of Example 1, and the volume resisting radon and light lifting concentration were measured using the coloring composition. The measured volume resistance 値 was more than 109Ωαη, and the optical density was 2.3. Except that the exposure time was changed to 100 mJ / cm 2, the other steps were the same as in Example 1. The resolution and surface smoothness of the obtained light-shielding plate pattern were deteriorated, and the dispersibility of the coloring composition itself was also deteriorated. . φ (Comparative Example 3) 30 g of the diluent obtained in Production Example 1 was added, 20 g of titanium black 13R (trade name: made by Mitsubishi material), 2 g of dispersant SORUSUPAASU200000 (trade name: made by ZENEKA), and 48 g of ethyl glycol monoethyl ether Disperse the granule powder disperser for one hour while cooling. Except for using 100 g of the coloring resin thus obtained, the coloring composition for forming a light-shielding plate was prepared according to the method of Example 1, and the volume resistance and optical density were measured using the coloring composition. The measured volume resistance 値 was 106 Ωαη and the optical concentration was 2.3. Except that the exposure time was changed to 300 mJ / cm 2, the remaining steps were the same as in Example 1. The resolution and surface smoothness of the obtained light-shielding plate pattern were deteriorated, and the dispersibility of the coloring composition itself was also deteriorated. 41 571177 5428 pif 4 Next, in order to make at least 100 sacrificial disks on the formed coating film, put them into a crosscut and then perform a peeling test with cerrotape. Evaluate the peeling status of the sacrificial disks under a microscope to confirm It was 20 degrees of peeling. As described above, the colored composition of the present invention has high insulation properties, excellent light resistance, light-shielding property, dispersion stability, and film strength, and is most suitable for forming a light-shielding plate. In addition, using this light shielding plate, a high-quality liquid crystal display device can be obtained. In an electrode substrate composed of a switching element, a switching element and a pixel electrode provided on a transparent substrate, a light-shielding plate formed by the colored composition of the present invention is prepared on the aforementioned switching element. Electrode substrate and liquid crystal display device with high position accuracy and large display screen aperture ratio. Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. 'Any person skilled in the art can make various changes and decorations without departing from the spirit and scope of the present invention. Therefore, the present invention The scope of protection shall be determined by the scope of the attached patent application. 42

Claims (1)

571177 5428 pif 4 一架橋劑； 一光酸發生劑；以及 一溶劑。 5. 如申請專利範圍第1項所述之著色組成物，其中該著 色組成物更包括： 一分散劑； 一光重合單體； 一疊氮基系化合物；以及 一溶劑。 6. 如申請專利範圍第1項所述之著色組成物，其中該樹 脂爲一（間）丙烯基系樹脂。 7·如申請專利範圍第1項所述之著色組成物，其中該感 光性樹脂之酸値爲50〜1〇〇，且其是由下列物質參予反應而 得： 一乙烯基系共重合化合物，1〇〇莫耳； 一化合物曱’ 5〜25莫耳，含有異氰酸酯基及至少一個 乙烯基； 其中’ S亥乙嫌基系共重合化合物是由下列物質所形成· 一化合物乙，10〜40%重量百分比，含有一個乙烯基及 羥基； 44 571177 5428 pif 4 一化合物丙，10〜40%重量百分比，含有一個乙烯基及 羧基；以及 一化合物丁，30〜75%重量百分比，含有一個乙烯基。 8.如申請專利範圍第1項所述之著色組成物，其中該感 光性樹脂主成份的單位構造如下列化學式（1)及化學式（2) 所示：571177 5428 pif 4 a bridging agent; a photoacid generator; and a solvent. 5. The coloring composition according to item 1 of the scope of the patent application, wherein the coloring composition further comprises: a dispersant; a photoreactive monomer; an azide-based compound; and a solvent. 6. The coloring composition as described in item 1 of the scope of the patent application, wherein the resin is a (m) acrylic resin. 7. The coloring composition as described in item 1 of the scope of the patent application, wherein the acidic acid of the photosensitive resin is 50 to 100, and it is obtained by participating in the reaction of the following materials: a vinyl-based co-overlap compound 100 mol; a compound 曱 '5 ~ 25 mol, containing isocyanate groups and at least one vinyl group; wherein the' Shai ethenyl-based co-overlapping compound is formed from the following compounds · a compound B, 10 ~ 40% by weight, containing a vinyl group and a hydroxyl group; 44 571177 5428 pif 4 a compound C, 10 ~ 40% by weight, containing a vinyl group and a carboxyl group; and a compound D, 30 ~ 75% by weight, containing a vinyl group base. 8. The colored composition according to item 1 of the scope of patent application, wherein the unit structure of the main component of the photosensitive resin is as shown in the following chemical formula (1) and chemical formula (2): (1)(1) (化學式中，Ri及R2分別代表氫原子、碳數1〜5的院基、 以及鹵素原子，R3代表氫原子及甲基，X則代表-CO-、 -S02-、-C(CF3)2_、-Si(CH3)2-、-CH2-、-C(CH3)2_、_0-、下 述化學式（3)、或是不存在，Y則代表酸去水後的殘基，Z 45 5428 pif 4 則代表酸二水和物的殘基。其中m及n爲1以上的整數。） ............(3) 9. 如申請專利範圍第1項所述之著色組成物，其中該著 色組成物具有l〇7Qcm以上之體積阻抗率。 10. 如申請專利範圍第1項所述之著色組成物，其中該 著色組成物包括一色劑乙，以該樹脂與該色劑乙配合，其 中該色劑乙爲以包含鈦黑的該色劑與該絕緣性物質混合而 被該絕緣性物質所被覆。 11. 一種彩色過濾器，其中至少包括一遮光板，該遮光 是由一著色組成物所形成，該著色組成物至少包括： 一色劑，含有鈦黑； 一感光性樹脂；以及 一絕緣性物質，該絕緣性物質的含量爲該色劑含量的 1〜35重量百分比，且該絕緣性物質包括二氧化矽。 12. —種液晶顯示裝置，包括： 一液晶驅動用電極板； 一共通電極用電極板，在該共通電極用電極板上設置 有一彩色過濾器，該彩色過濾器至少包括一遮光板，該遮 46 5428 pif 4 光是由一著色組成物所形成，該著色組成物至少包括： 一色劑，含有鈦黑； 一感光性樹脂；以及 一絕緣性物質，該絕緣性物質的含量爲該色劑含 量的1〜35重量百分比，且該絕緣性物質包括二氧化矽；以 及 一液晶材料，塡封於該液晶驅動用電極板與共通電極 用電極板之間的間隙。 13.—種電極基板，由位於一透明基板上之一開關元件 與一畫素電極所備置，在該開關元件上設置有由一著色組 成物所形成之一遮光板，該著色組成物至少包括： 一色劑，含有鈦黑； 一感光性樹脂；以及 一絕緣性物質，該絕緣性物質的含量爲該色劑含量的 1〜35重量百分比，且該絕緣性物質包括二氧化矽。 H. —液晶顯示裝置，包括·· 一共通電極用電極板； 一液晶驅動用電極板，由位於一透明基板上之一開關 元件與一畫素電極所備置，在該開關元件上設置有由一著 色組成物所形成之一遮光板，該著色組成物至少包括： 47 571177 5428 pif 4 一色劑，含有鈦黑； 一感光性樹脂；以及 一絕緣性物質，該絕緣性物質的含量爲該色劑含 量的1〜35重量百分比，且該絕緣性物質包括二氧化矽；以 及 一液晶材料，塡封於該液晶驅動用電極板與該共通電 極用電極板之間的間隙。 48(In the chemical formula, Ri and R2 respectively represent a hydrogen atom, a radical of 1 to 5 carbon atoms, and a halogen atom, R3 represents a hydrogen atom and a methyl group, and X represents -CO-, -S02-, -C (CF3) 2_ , -Si (CH3) 2-, -CH2-, -C (CH3) 2_, _0-, the following chemical formula (3), or does not exist, Y represents the residue after acid dehydration, Z 45 5428 pif 4 represents the residue of acid dihydrate, and m and n are integers of 1 or more. ............ (3) 9. As described in item 1 of the scope of patent application The coloring composition, wherein the coloring composition has a volume resistivity of 107 Qcm or more. 10. The coloring composition according to item 1 of the scope of the patent application, wherein the coloring composition includes a colorant B, and the resin is mixed with the colorant B, wherein the colorant B is the colorant containing titanium black It is mixed with the insulating substance and covered with the insulating substance. 11. A color filter comprising at least a light-shielding plate formed of a coloring composition, the coloring composition comprising at least: a colorant containing titanium black; a photosensitive resin; and an insulating substance, The content of the insulating substance is 1 to 35 weight percent of the toner content, and the insulating substance includes silicon dioxide. 12. A liquid crystal display device comprising: an electrode plate for liquid crystal driving; an electrode plate for a common electrode; a color filter is provided on the electrode plate for the common electrode, and the color filter includes at least a light shielding plate, the shielding plate; 46 5428 pif 4 Light is formed by a coloring composition, which at least includes: a colorant containing titanium black; a photosensitive resin; and an insulating substance whose content is the colorant content 1 to 35 weight percent, and the insulating substance includes silicon dioxide; and a liquid crystal material sealed in a gap between the liquid crystal driving electrode plate and the common electrode electrode plate. 13. An electrode substrate provided by a switching element and a pixel electrode on a transparent substrate. A light-shielding plate formed of a coloring composition is provided on the switching element. The coloring composition includes at least : A colorant containing titanium black; a photosensitive resin; and an insulating substance, the content of the insulating substance being 1 to 35 weight percent of the content of the colorant, and the insulating substance including silicon dioxide. H. —Liquid crystal display device, including: an electrode plate for a common electrode; an electrode plate for liquid crystal driving, which is provided by a switching element and a pixel electrode on a transparent substrate, and a switching element is provided on the switching element. A shading plate formed by a coloring composition, the coloring composition includes at least: 47 571177 5428 pif 4 a colorant containing titanium black; a photosensitive resin; and an insulating substance, the content of the insulating substance is the color The content of the agent is 1 to 35 weight percent, and the insulating substance includes silicon dioxide; and a liquid crystal material is sealed in a gap between the liquid crystal driving electrode plate and the common electrode electrode plate. 48
TW088117112A 1998-10-08 1999-10-05 Coloring composition and color filter, electrode substrate, and liquid crystal display device using the same TW571177B (en)

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