1261689 九、發明說明： 【發明所屬之技術領域】 本發明係關於顏料分散液，顏料分散液之製造方法，著 色樹脂組成物，彩色濾光片，及液晶顯示裝置。更明確言 之，本發明係關於具優異消偏振性質且可形成高對比紅色 (R )圖像元件之顏料分散液，此顏料分散液之製備方法，含 此顏料分散液之著色樹脂組成物，使用此著色樹脂組成物 之彩色濾光片，及使用此彩色濾光片之液晶顯示裝置。 【先前技術】 為製造使用於液晶顯示裝置或其類似物之彩色濾光 片，習知為顏料分散方法、染色方法、電沈積方法及印刷 方法。其中由光譜性質、耐用性、圖案形狀及精確度的觀 點來看，顏料分散方法由於平均地具有優異特性而最為普 遍。 在顏料分散方法中，經由使用遮光金屬薄膜諸如鉻或氧 化鉻而將黑色基質形成於透明支承物諸如玻璃基板上。經 由旋轉塗布將其中分散有，例如，紅色顏料之著色樹脂組 成物（以下可將其中分散有紅色、藍色或綠色顏料之著色樹 脂組成物稱為「彩色抵抗劑」，同時以下可將其中分散有 黑色顏料之著色樹脂組成物稱為「黑色抵抗劑」）塗布於整 個表面上。然後使所得薄膜透過光罩曝光及藉由曝光後之 顯影，形成紅色圖像元件。經由以與前述類似之方式應用 彩色抵抗劑、曝光及顯影，形成藍色及綠色圖像元件，藉 此完成三圖像元件之形成。由於在圖像元件之間的黑色基 6 326\專利說明書(補件)\94-02\93132145 1261689 質部分為内凹，因而通常將其上形成圖像元件之表面覆蓋 透明樹脂諸如環氧樹脂或丙烯酸系樹脂，以使表面平坦。 然而，在一些情況中不設置此一保護膜。 在保護膜上方，經由濺鍍或真空沈積形成透明導電性薄 膜諸如I T 0 (銦錫氧化物）薄膜。近來有使用此顏料分散方 法於形成黑色基質的趨勢。舉例來說，黑色基質係經由塗 布其中分散有黑色顏料之著色樹脂組成物（黑色抵抗劑）， 曝光及顯影而形成。 近來之技術革新的快速進展伴隨液晶顯示裝置之螢幕 尺寸的增加，及其作為電視機之用途。為使用於電視機， 液晶顯示裝置需具有較高亮度及較寬廣的觀看角。 已使用可產生寬廣觀看角之VA(垂直配向）系統或 I P S (面内切換）系統作為液晶驅動系統。觀看角愈寬廣，則 亮度愈低。此亮度之降低一般可由增加背光燈之數目而解 決。然而，增加亮度會導致在黑色顯示器上之光泡漏，其 將導致對比降低，及依序導致圖像品質降低。因此，彩色 濾、光片亟需具有較佳的消偏振性質及較高對比。 傳統上較佳係使用二酮基吡咯并吡咯紅顏料，尤其係 C . I .顏料紅2 5 4，作為彩色濾光片之紅色圖像元件，且其 可改良亮度（參照日本公開專利第2 2 7 9 1 / 1 9 9 8號）。然而， C . I .顏料紅2 5 4由於原粒子大小及晶體顆粒形狀之各向異 性的問題而無法自由地改良對比。 習知亦將蒽S昆紅色顏料，尤其係C . I .顏料紅1 7 7，使用 作為另一紅色顏料。與C. I .顏料紅2 5 4比較，由顆粒大小 7 326\專利說明書(補件)\94-02\93132145 1261689 及顆粒形狀的觀點來看，此顏料對於改良對比更為有效。 多年來知曉一種將c . I .顏料紅1 7 7與黃色顏料混合之技術 (日本公開專利第1 4 8 7 1 2 / 1 9 9 8號），且其被廣泛地使用於 液晶顯示裝置。然而，一些黃色顏料會不利地影響對比， 此外，其之不適當的顆粒大小分佈會干擾令人滿意之對比 的達成。 關於常用於製備顏料分散液之顏料分散方法，已有一種 使用特定锆氧燒結珠粒於改良表面光澤度之方法經揭示 (曰本公開專利第1 5 5 5 7 7 / 1 9 9 5號）。熟悉技藝人士幾乎無 法想到使用前述之分散方法於改良彩色濾光片之對比。此 外，對比之改良無法僅經由將前述之分散方法應用至常用 之顏料而達成。 【發明内容】 如前所述，近來在液晶顯示裝置係普及至電視機，觀看 角變得較寬且亮度變得較高。在此一情勢下，對於具優異 消偏振性質，即較高對比之彩色濾光片的發展有持續增加 的需求。此一需求尚未完全被滿足。 因此，本發明之一目的為提供一種具優異消偏振性質且 可形成高對比紅色圖像元件之顏料分散液，此顏料分散液 之製備方法，含此顏料分散液之著色樹脂組成物，使用此 顏料分散液之彩色濾光片，及使用此彩色濾光片之液晶顯 示裝置。 本發明人為克服前述問題而進行廣泛的研究。結果，發 現可經由使用一種包含顏料、溶劑及分散劑之顏料分散液 8 326\專利說明書(補件)\94-02\93132 M5 1261689 而形成高對比紅色圖像元件3其中顏料係蒽s昆紅色顏 偶氮黃色顏料之混合物，且具有在自3 0至5 0 0奈米範 之顆粒大小，以完成本發明。 因此，在本發明之一態樣中，提供一種包含顏料、 及分散劑之顏料分散液，其特徵在於當經由使用包含 料分散液之著色樹脂組成物於玻璃基板上形成紅色圖 件時，根據以下方程式（1 )所計算之對比C : C=B/A (1) 其中A及B分別代表當將玻璃基板夾於兩偏光板之 將兩偏光板直角設置及當將兩偏光板平行設置時利用 光度計測得之光強度， 及當暴露至照明器C時利用分光光度計所測得之透 之色度X滿足以下方程式（2 ): C ^ 4 0 0 0 x - 2 0 0 0 ( 2 ) ° 在本發明之第二態樣中，亦提供一種包含顏料、溶 分散劑之顏料分散液，其特徵在於顏料包含蒽醌紅色 及偶氮黃色顏料，且具有落於自3 0至5 0 0奈米範圍内 粒大小。 在本發明之第三態樣中，亦提供一種顏料分散液之 方法，其包括當製備顏料分散液時，利用具自3 0至 米之平均顆粒大小之珠粒使顏料、溶劑及分散劑之混 分散。 在本發明之第四態樣中，亦提供一種包含本發明之 分散液的著色樹脂組成物。 326\專利說明書(補件)\94-02\93132145 9 料及 圍内 溶劑 此顏 像元 間及 亮度 射光 劑及 顏料 之顆 製備 50微 合物 顏料 1261689 在本發明之第五態樣中，亦提供一種包含顏料、溶劑、 分散劑、黏合劑樹脂、單體及光聚合引發劑系統之著色樹 脂組成物，其特徵在於當經由使用包含顏料分散液之著色 樹脂組成物於玻璃基板上形成紅色圖像元件時，根據以下 方程式（1 )所計算之對比C : OB/A (1) 其中A及B分別代表當將玻璃基板夾於兩偏光板之間及 將兩偏光板直角設置及當將兩偏光板平行設置時利用亮度 光度計測得之光強度， 及當暴露至照明器C時利用分光光度計所測得之透射光 之色度X滿足以下方程式（2 ): 4 0 0 0 x - 2 0 0 0 ( 2 ) ° 在本發明之第六態樣中，亦提供一種包括使用本發明之 著色樹脂組成物所形成之圖像元件的彩色濾光片。 在本發明之第七態樣中，亦提供一種包括彩色濾光片之 液晶顯示裝置。 本發明可產生如下所述的優異優點，以致其於工業中具 有極大潛力。 1.本發明之顏料分散液及包含顏料分散液之本發明之 著色樹脂組成物可形成具有優異消偏振性質及因此具高對 比之紅色圖像元件。 2 .根據本發明之顏料分散液之製備方法有利於此一顏 料分散液之製備。 3 .在本發明之彩色濾光片及設有此彩色濾光片之本發 10 326\專利說明書(補件)\94-02\93132145 1261689 明之液晶顯示裝置中，紅色圖像元件具有優異的消偏振 質，及因此具高對比，以致其之品質優良且可有效增加 度及觀看角，以滿足較大螢幕尺寸之需求。 【實施方式】 接下來將明確說明實施本發明之方式。 首先，將說明由本發明之顏料分散液所形成之紅色圖 元件的對比。 本發明之顏料分散液的特徵在於當經由使用包含顏料 分散液之著色樹脂組成物於玻璃基板上形成紅色圖像元 時，根據以下方程式（1 )所計算之對比C : C:B/A (1) 其中A及B分別代表當將玻璃基板夾於兩偏光板之間 將兩偏光板直角設置及當將兩偏光板平行設置時利用亮 光度計測得之光強度，及當暴露至照明器C時利用分光 度計所測得之透射光之色度X滿足以下方程式（2 ): 4 0 0 0 x - 2 0 0 0 ( 2 ) ° 紅色圖像元件係以下列方式形成。將著色樹脂組成物 塗於玻璃基板上得2微米之乾厚度，隨後再在8 0 °C下乾 1 0分鐘。於經由暴露至U V射線使樹脂固化後，在2 3 0 t 加熱3 0分鐘而進行交聯，由此形成紅色圖像元件。 當暴露至照明器C時，使用分光光度計（「U 4 1 0 0」， H i t a c h i L t d ·之產品）於測量透射光之色度。當偏光板分 直角及平行設置時，為測量光強度A及B (燭光/平方4 分），將兩偏光板緊密黏著至基板，並使用亮度光度計 326\專利說明書(補件)\94-02\93132145 11 性 像 件 及 度 光 旋 燥 下 別 1261689 (「BM-5A」 ，TOPCON 之產品）。 當C < 4 Ο Ο Ο x - 2 Ο Ο 0時，影像品質由於對比降低及於黑 顯示器上發生光洩漏而劣化。 在本發明，在對比C與色度X之間的關係係以方程 (2 - 1 )所表示較佳，方程式（2 - 2 )更佳。 C2 4 0 0 0 χ - 1 8 0 0 ( 2 - 1 ) 4000x - 1400 (2-2) 以下將說明本發明之顏料分散液的成分。 [1 ]顏料分散液 基本 接下 料分 氮黃 顏料 C. I . ’且 r 3> •顏 81、 •顏 本發明之顏料分散液具有顏料、溶劑及分散劑作為 成分，且其若需要，更包含除前述成分外之添加劑。 來將明確說明各成分。 [1 - 1 ]顏料 此處所使用之術語「顏料」係指用於使本發明之顏 散液著色之物質。在本發明，使用蒽醌紅色顏料及偶 色顏料之混合物作為顏料較佳。 關於蒽S昆紅色顏料，可使用C . I .顏料紅1 7 7、C . I . 橙5 1、C . I .顏料橙1 6 8及其類似物之一或多者。其中| 顏料紅1 7 7 ( P . R . 1 7 7 )由於可容易地轉變為微細顆粒 分散穩定性及牢度優異而尤其適當。[Technical Field] The present invention relates to a pigment dispersion liquid, a method for producing a pigment dispersion liquid, a colored resin composition, a color filter, and a liquid crystal display device. More specifically, the present invention relates to a pigment dispersion having excellent depolarization properties and capable of forming a high contrast red (R) image element, a method of preparing the pigment dispersion, a colored resin composition containing the pigment dispersion, A color filter using the colored resin composition, and a liquid crystal display device using the color filter. [Prior Art] In order to manufacture a color filter for use in a liquid crystal display device or the like, a pigment dispersion method, a dyeing method, an electrodeposition method, and a printing method are conventionally known. Among them, from the viewpoints of spectral properties, durability, pattern shape, and precision, the pigment dispersion method is most common because of the excellent average characteristics. In the pigment dispersion method, a black matrix is formed on a transparent support such as a glass substrate via using a light-shielding metal film such as chromium or chromium oxide. A colored resin composition in which, for example, a red pigment is dispersed (hereinafter, a colored resin composition in which a red, blue or green pigment is dispersed) may be referred to as a "color resist" by spin coating, and the following may be dispersed therein. A colored resin composition having a black pigment called a "black resist" is applied to the entire surface. The resulting film is then exposed through a reticle and developed by exposure to form a red image element. The formation of the three image elements is accomplished by applying a color resist, exposure and development in a manner similar to that described above to form blue and green image elements. Since the black portion 6 326 \patent specification (supplement) \94-02\93132145 1261689 between the image elements is concave, the surface on which the image element is formed is usually covered with a transparent resin such as epoxy resin. Or acrylic resin to make the surface flat. However, this protective film is not provided in some cases. Above the protective film, a transparent conductive film such as an I T 0 (indium tin oxide) film is formed by sputtering or vacuum deposition. There has recently been a tendency to use this pigment dispersion method to form a black matrix. For example, the black matrix is formed by coating a colored resin composition (black resist) in which a black pigment is dispersed, exposure and development. Recent advances in technological innovation have been accompanied by an increase in the screen size of liquid crystal display devices and their use as television sets. In order to be used in a television set, the liquid crystal display device needs to have higher brightness and a wider viewing angle. A VA (Vertical Alignment) system or an I P S (In-Plane Switching) system which can produce a wide viewing angle has been used as the liquid crystal driving system. The wider the viewing angle, the lower the brightness. This reduction in brightness can generally be resolved by increasing the number of backlights. However, increasing the brightness can result in light bubble leakage on the black display, which will result in a decrease in contrast and, in turn, a reduction in image quality. Therefore, the color filter and the light film need to have better depolarization properties and higher contrast. Conventionally, it is preferred to use a diketopyrrolopyrrole red pigment, especially C. I. Pigment Red 2 5 4 as a red image element of a color filter, and which can improve brightness (refer to Japanese Laid-Open Patent No. 2) 2 7 9 1 / 1 9 9 8). However, C.I.Pigment Red 2 5 4 cannot freely improve the contrast due to the problem of the anisotropy of the original particle size and the shape of the crystal particles. It is also known to use 蒽S Kun red pigment, especially C. I. Pigment Red 177, as another red pigment. Compared with C. I. Pigment Red 2 5 4, this pigment is more effective for improving the contrast from the viewpoint of particle size 7 326\patent specification (supplement)\94-02\93132145 1261689 and particle shape. A technique of mixing c. I. Pigment Red 177 with a yellow pigment has been known for many years (Japanese Laid-Open Patent Publication No. 1 4 8 7 1 2 / 1 9 9 8), and it is widely used in a liquid crystal display device. However, some yellow pigments can adversely affect the contrast and, in addition, their inadequate particle size distribution can interfere with the achievement of satisfactory contrast. Regarding the pigment dispersion method which is commonly used for preparing a pigment dispersion liquid, there has been disclosed a method for improving surface glossiness using a specific zirconium-oxygen sintered bead (Japanese Patent Laid-Open Publication No. 1 5 5 5 7 7 / 1 9 9 5) . Those skilled in the art can hardly think of using the aforementioned dispersion method to improve the contrast of color filters. Further, the improvement of the contrast cannot be achieved only by applying the aforementioned dispersion method to a usual pigment. SUMMARY OF THE INVENTION As described above, recently, liquid crystal display devices have spread to televisions, and the viewing angle has become wider and the brightness has become higher. In this situation, there is an increasing demand for the development of color filters having excellent depolarization properties, i.e., higher contrast. This demand has not been fully met. Accordingly, it is an object of the present invention to provide a pigment dispersion having excellent depolarization properties and capable of forming a high contrast red image element, a method of preparing the pigment dispersion, a colored resin composition containing the pigment dispersion, and the like a color filter of a pigment dispersion, and a liquid crystal display device using the color filter. The inventors conducted extensive research to overcome the aforementioned problems. As a result, it was found that a high contrast red image element 3 can be formed by using a pigment dispersion liquid containing a pigment, a solvent and a dispersing agent 8 326\patent specification (supplement)\94-02\93132 M5 1261689 A mixture of red azo-yellow pigments and having a particle size of from 30 to 500 nm to complete the present invention. Therefore, in one aspect of the invention, there is provided a pigment dispersion comprising a pigment and a dispersant, characterized in that when a red pattern is formed on a glass substrate via a colored resin composition using a dispersion of the inclusion material, The contrast calculated by the following equation (1) is C: C=B/A (1) where A and B respectively represent the two polarizing plates at right angles when the glass substrate is sandwiched between the two polarizing plates and when the two polarizing plates are arranged in parallel The intensity of the light measured by the photometer and the chromaticity X measured by the spectrophotometer when exposed to the illuminator C satisfy the following equation (2): C ^ 4 0 0 0 x - 2 0 0 0 ( 2 In the second aspect of the present invention, there is also provided a pigment dispersion comprising a pigment and a dispersing agent, characterized in that the pigment comprises a magenta and an azo yellow pigment, and has a content ranging from 30 to 50. Particle size within 0 nm range. In a third aspect of the present invention, there is also provided a method of a pigment dispersion comprising, when preparing a pigment dispersion, using a bead having an average particle size of from 30 to metre to make a pigment, a solvent and a dispersant Mixed dispersion. In a fourth aspect of the invention, there is also provided a colored resin composition comprising the dispersion of the invention. 326\Patent specification (supplement)\94-02\93132145 9 Materials and encapsulation solvent Preparation of 50 micron pigments 1261689 between the pigments and the brightness of the light and the pigments. In the fifth aspect of the invention, Provided is a colored resin composition comprising a pigment, a solvent, a dispersant, a binder resin, a monomer, and a photopolymerization initiator system, characterized in that a red pattern is formed on a glass substrate by using a colored resin composition containing a pigment dispersion For example, when compared to the component, the comparison C calculated according to the following equation (1): OB/A (1) where A and B respectively represent when the glass substrate is sandwiched between the two polarizing plates and the two polarizing plates are disposed at right angles and when The intensity of the light measured by the luminance photometer when the polarizing plates are arranged in parallel, and the chromaticity X of the transmitted light measured by the spectrophotometer when exposed to the illuminator C satisfy the following equation (2): 4 0 0 0 - 2 0 0 0 ( 2 ) ° In the sixth aspect of the invention, there is also provided a color filter comprising an image element formed using the colored resin composition of the present invention. In a seventh aspect of the invention, a liquid crystal display device including a color filter is also provided. The present invention can produce excellent advantages as described below, so that it has great potential in the industry. 1. The pigment dispersion of the present invention and the colored resin composition of the present invention comprising the pigment dispersion can form a red image element having excellent depolarization properties and thus high contrast. 2. A method of preparing a pigment dispersion according to the present invention is advantageous for the preparation of a pigment dispersion. 3. In the color filter of the present invention and the liquid crystal display device of the present invention, the red image element is excellent in the liquid crystal display device disclosed in the Japanese Patent Publication No. 10 326\Patent Specification (Supplement) Depolarization, and therefore high contrast, so that its quality is excellent and can be effectively increased in degree and viewing angle to meet the needs of larger screen sizes. [Embodiment] Next, the mode for carrying out the invention will be clearly explained. First, a comparison of the red pattern elements formed by the pigment dispersion of the present invention will be explained. The pigment dispersion of the present invention is characterized in that when a red image element is formed on a glass substrate by using a colored resin composition containing a pigment dispersion, a contrast C calculated according to the following equation (1): C: B/A ( 1) wherein A and B respectively represent the light intensity measured by the luminometer when the glass substrate is sandwiched between the two polarizing plates and the two polarizing plates are disposed at right angles and when the two polarizing plates are arranged in parallel, and when exposed to the illuminator C The chromaticity X of the transmitted light measured by the spectrophotometer satisfies the following equation (2): 4 0 0 0 x - 2 0 0 0 ( 2 ) ° The red image element is formed in the following manner. The colored resin composition was applied to a glass substrate to have a dry thickness of 2 μm, followed by drying at 80 ° C for 10 minutes. After the resin was cured by exposure to UV rays, it was crosslinked by heating at 230 ° for 30 minutes, thereby forming a red image element. When exposed to illuminator C, the chromaticity of the transmitted light is measured using a spectrophotometer ("U 4 1 0 0", H i t a c h i L t d · product). When the polarizing plates are placed at right angles and in parallel, to measure the light intensity A and B (candle/square 4 points), the two polarizing plates are closely adhered to the substrate, and the brightness photometer 326\patent specification (supplement)\94- is used. 02\93132145 11 Sexual image and light-drying under the 1261689 ("BM-5A", TOPCON product). When C < 4 Ο Ο Ο x - 2 Ο Ο 0, the image quality deteriorates due to a decrease in contrast and light leakage on the black display. In the present invention, the relationship between the contrast C and the chromaticity X is preferably expressed by the equation (2 - 1), and the equation (2 - 2) is more preferable. C2 4 0 0 0 χ - 1 8 0 0 ( 2 - 1 ) 4000x - 1400 (2-2) The composition of the pigment dispersion of the present invention will be described below. [1] The pigment dispersion is substantially followed by the nitrogen yellow pigment C. I. 'and r 3> • Yan 81, • The pigment dispersion of the present invention has a pigment, a solvent and a dispersant as components, and if necessary, It further contains additives other than the aforementioned components. The ingredients will be clearly stated. [1 - 1 ] Pigment The term "pigment" as used herein means a substance for coloring the pigment liquid of the present invention. In the present invention, a mixture of a crimson pigment and an occasion pigment is preferably used as the pigment. As for the 蒽S Kun red pigment, one or more of C.I. Pigment Red 1.7, C.I. Orange 5 1 , C.I. Pigment Orange 168 and the like can be used. Among them, Pigment Red 1 7 7 (P.R. 1 7 7 ) is particularly suitable because it can be easily converted into fine particles, which is excellent in dispersion stability and fastness.
偶氮黃色顏料之例子包括C. I .顏料黃1、C. I .顏料， C . I .顏料黃1 0、C . I .顏料黃1 2、C . I .顏料黃1 3、C . I 料黃1 4、C . I .顏料黃1 7、C . I .顏料黃5 5、C . I .顏料黃 C . I .顏料黃8 3、C . I .顏料黃9 3、C . I .顏料黃9 4、C . I 12 326\專利說明書(補件)\94-02\93132145 1261689 料黃9 5、C . I .顏料黃9 7、C . I .顏料黃1 5 Ο、C . I .顏料黃 C . I .顏料黃1 6 6、C . I .顏料1 6 7、及C . I ·顏料黃1 8 0。 單獨或以其兩者以上之組合使用。其中C . I .顏料黃8 3 顏料黃1 5 0、及C . I .顏料黃1 8 0為較佳，其中C . I .顏 1 5 0 ( P . Y . 1 5 0 )由於可容易地轉變為微細顆粒，且分散 性、光譜透射率、及牢度優異而尤其適當。 以顏料分散液中之總固體含量計之顏料的比例通常 自1 0至9 0重量％，以自3 0至9 0重量％較佳，自5 0 重量％更佳。當顏料分散液中之顏料之比例太小時，生 顏料分散液具較低之著色力，且薄膜有相對於色濃度 的傾向。另一方面，當比例太大時，分散穩定性降低 發生諸如再凝聚及增稠的問題。在本發明，術語「總 含量」係指除稍後即將說明之溶劑外的所有成分。 以偶氮黃色顏料相對於蒽S昆紅色顏料之重量比計， 紅色顏料及偶氮黃色顏料之混合比通常係自0 . 1至9 9 %，以自3至8 0重量％較佳，自5至6 0重量％更佳。當 黃色顏料之量小於前述範圍時，色相變得接近藍色， 致透射率之降低（在X Y Z色標系統中之色度Y )。另一方 當偶氮黃色顏料之量過大時，色相變得接近黃色，且 紅色圖像元件並不佳。 然而，在本發明之顏料分散液中，當將蒽醌紅色顏 偶氮黃色顏料結合使用作為顏料時，可在不會減損本 之優點的程度内結合使用另一顏料。可結合使用之另 料的例子包括異吲哚啉顏料諸如C . I .顏料黃1 3 9、C. 326\專利說明書(補件)\94-02\93132145 13 15 4、 其可 、C. I 料黃 穩定 係 ：90 成之 過厚 且會 固體 蒽醌 重量 偶氮 而導 面， 作為 料及 發明 一顏 I ·顏 1261689 料橙6 6、C . I .顏料橙6 9及C . I .顏料紅2 6 Ο，異吲哚啉酮 顏料諸如C . I .顏料黃1 Ο 9、C . I .顏料黃1 1 Ο、C . I .顏料黃 1 7 3及C · I .顏料撥6 1，及喧酞酮（q u i η o p h t h a 1 ο n e )顏料諸 如C . I .顏料黃1 3 8。此等顏料可單獨或以兩者以上之組合 使用。當結合使用另一顏料時，將其之比調整為相對於蒽 醌紅色顏料之重量為2 0重量％或以下較佳，1 0重量％或以 下特佳。 [1 - 2 ]溶劑 在本發明之顏料分散液中，溶劑具有使顏料、分散劑及 視需要添加之其他成分溶解或分散於其中，及調整其黏度 之功能。 溶劑之明確的例子包括二異丙喊、礦油精、正戊烧、戊 醚、辛酸乙酯、正己烷、***、異戊二烯、乙基異丁基醚、 硬脂酸丁酯、正辛烷、V a r s ο 1 # 2、A p c 〇 # 1 8溶劑、二異 丁烯、乙酸戊酯、乙酸丁酯、Apco稀釋劑、丁醚、二異丁 基酮、甲基環己烯、曱基壬基酮、丙醚、十二烷、Socal 溶劑No. 1及No. 2、曱酸戊酯、二己基醚、二異丙基酮、 Solveso #15、乙酸（正、第二 '第三）丁 、己稀、Shell TS28 溶劑、氣丁烷、乙基戊基酮、苯曱酸乙酯、氯戊烷、乙二 醇二***、原曱酸乙醋、曱氧曱基戊酮、曱基丁基酮、甲 基己基酮、異丁酸曱酯、苯甲腈、丙酸乙酯、曱基溶纖劑 乙酸酯、甲基異戊基酮、曱基異丁基酮、乙酸丙醋、乙酸 戊酯、甲酸戊酯、聯環己烷、二甘醇單***乙酸酯、二戊 烯、甲氧甲基戊醇、曱基戊基酮、甲基異丙基酮、丙酸丙 326\專利說明書(補件)\94-02\93132145 14 1261689 酯、丙二醇第三丁基醚 '曱基乙基酮、曱基溶纖劑、乙基 溶纖劑、乙基溶纖劑乙酸酯、卡必醇、環己酮、乙酸乙、 丙二醇、丙二醇單曱醚、丙二醇單曱醚乙酸酯、丙二醇單 ***、丙二醇單***乙酸酯、二丙二醇單***、二丙二醇 單曱醚、二丙二醇單***乙酸酯、3 -曱氧丙酸、3 -乙氧丙 酸、3 -乙氧丙酸曱6旨、3 -乙氧丙酸乙6旨、3 -曱氧丙酸曱醋、 3 -甲氧丙酸乙S旨、3 -甲氧丙酸丙S旨、3 -甲氧丙酸丁 S旨、二 甘醇二甲醚、乙二醇乙酸酯、乙基卡必醇、丁基卡必醇、 乙二醇單丁醚、丙二醇第三丁基醚、3 -曱基-3-曱氧丁醇、 三丙二醇曱基醚及乙酸3 -曱基-3 -曱氧丁酯。此等溶劑可 單獨或以其兩者以上之混合物使用。 對於本發明之整體顏料分散液中之溶劑之含量並無特 殊之限制，但其之上限通常係9 9重量％。當溶劑之含量超 過9 9重量％時，顏料及分散劑之比例變得太小而無法形成 分散液。考慮到顏料分散液之黏度，溶劑含量之下限通常 係7 0重量％，以7 5重量％較佳，8 0重量％更佳。 [1 - 3 ]分散劑 關於分散劑，適當地使用聚合物分散劑及/或顏料衍生 物。 聚合物分散劑之例子包括胺基曱酸酯分散劑、聚乙稀亞 胺分散劑、聚氧伸乙基烷基醚分散劑、聚氧伸乙基二酯分 散劑、脫水山梨糖醇脂族酯分散劑及經脂族改質之聚酯分 散劑。此一分散劑之明確例子包括「E F K A」（E F K A C h e m i c a 1 s BV 之產品）、「Disperbyk」（BYK-Chemie 之產品）、 15 326\專利說明書(補件)\94-02\93132145 1261689 rDISPARLON」 （Kusumoto chemicals 之產品）、 「SOLSPERSSE」 （Zeneca 之產品）、rKP」 （Shin—etsu Chemical 之產品）及 POLYFLOW(Kyoeisha Chemical 之產 品）。此等聚合物分散劑可單獨或以其兩者以上之組合使 用。 以顏料分散液之總固體含量計之聚合物分散劑的比例通 常係自1 0至9 0重量％，以自1 0至7 0重量％較佳，自1 0 至5 0重量％更佳。當顏料分散液中之聚合物分散劑之比例 太大時，顏料比例之相對減小導致著色力退化，且薄膜厚 度有相對於色濃度較大的傾向。另一方面，當聚合物分散 劑之比例過小時，分散穩定性降低且會產生諸如再凝聚及 增稠的問題。 顏料衍生物之例子包括偶氮、8大青素、啥σ丫 σ定酮、苯并 咪唑啶酮、喹酞酮、異吲哚啉酮、二呤°井、蒽醌、陰丹士 林、茈、紫環S ( p e r i η ο n e )及二酮基1^ D各并ϋ比咯顏料。在 本發明，使用顏料衍生物諸如蒽醌或偶氮顏料為較佳，因 其係與使用作為顏料者相似的類型。此等顏料衍生物可單 獨或以其兩者以上之混合物使用。 顏料衍生物之取代基的例子包括磺酸基、磺醯胺基或其 之第四鹽、酞醯亞胺甲基、二烷胺烷基、羥基、羧基及醯 胺基。此等取代基各係直接或經由連接基團諸如烷基、芳 基或雜環基團鏈結至顏料架構。關於顏料衍生物之取代 基，石黃酿胺基或其之第四鹽、及續酸基為較佳，石黃酸基為 更佳。可使複數個此等取代基鏈結至一顏料架構，或可使 16 326\專利說明書(補件)\94-02\93132145 1261689 用取代基之數目不同之化合物的混合物。 顏料衍生物的明確例子包括偶氮顏料之續酸衍生物及蒽 醌顏料之磺酸衍生物。 以顏料分散液之總固體含量計之顏料衍生物的比例通常 係自0. 1至2 0重量％，以自0. 5至1 5重量％較佳，自1至 1 0重量％更佳。當顏料分散液中之顏料衍生物之比例太小 時，分散穩定性降低且會產生諸如再凝聚及增稠的問題。 另一方面，當其過大時，其對分散穩定性之貢獻已經飽和， 且顏色純度有時會因此一量而降低。因此，在前述範圍外 之比例並不佳。 在本發明，即使當將聚合物分散劑及顏料衍生物結合使 用作為分散劑時，亦不會發生問題。 [1-4]另一成分 對於視需要加入於本發明之顏料分散液中之另一成分並 無特殊之限制。然而，當將本發明之顏料分散液加入於稍 後即將說明之彩色濾光片之著色樹脂組成物中時，本發明 之顏料分散液可包含一些稍後即將說明之黏合劑樹脂，由 於當製備本發明之顏料分散液時，其可提高分散穩定性。 在此情況，以顏料分散液中之全體顏料計，黏合劑樹脂 之量係自5至1 0 0重量％較佳，自1 0至8 0重量％尤佳。低 於5重量％之黏合劑樹脂之量並不足以提高分散穩定性。另 一方面，超過1 0 0重量％之量會導致顏料濃度減小，且無法 得到充分的色濃度。 [1 - 5 ]顏料之顆粒大小分佈 17 326\專利說明書(補件)\94-02\93132145 1261689 在本發明之顏料分散液中，顏料之顆粒大小係3 0奈米 或以上，50奈米或以上較佳，80奈米或以上更佳，但500 奈米或以下，3 5 0奈米或以下較佳，2 5 0奈米或以下更佳。 顆粒大小分佈之寬度半值係2 5 0奈米或以下，1 5 0奈米或 以下尤佳，1 0 0奈米或以下更佳。 在本發明，經由結合使用特定顏料及將顆粒大小調整為 落於前述預定範圍内，可達到優異的消偏振效應及高對 比。將顆粒大小，尤其係半寬度值，調整為落於前述範圍 内係相當重要，且在前述範圍之外無法達到本發明之優異 的消偏振效應及高對比。 [1 - 6 ]顏料分散液之製備方法 雖然可使用各種方法以製備本發明之顏料分散液以實 現前述之顆粒大小分佈，但透過硬球（珠粒）之碰撞使顏料 分散之珠粒研磨方法尤其適當。在此所使用之珠粒可由玻 璃、鍅氧（Z r 0 2 )、鉻及其類似物所製成。其中由锆氧製成 之珠粒由於具高比重且包含較少污染物諸如研磨粉末而為 適當。可使用於此之珠粒通常具有3 0至5 0 0微米之平均顆 粒大小，以3 0至3 0 0微米較佳，4 0至2 0 0微米更佳。平 均顆粒大小低於3 0微米之珠粒由於其之重量太小無法產 生足夠的碰撞能量而不具有足夠的分散力。另一方面，顆 粒大小大於5 0 0微米之珠粒由於珠粒間之空隙體積太大而 不適用於將顏料之形態轉變為微細顆粒。此外，各珠粒重 且顏料無可避免地會接受過多的碰撞能量，而使其很難將 顏料之顆粒大小降低至在3 0至5 0 0奈米之範圍内。 18 326\專利說明書(補件)\94-02\93132145 1261689 可將任何的分散機使用於分散處理，只要其可使用前述 之珠粒即可。其例子包括批式系統「T 0 R U S Μ I L L」（G e t z m a η η 之產品）、連續系統「禮動磨（A g l t a t o r M i 1 1 )」（A s h i z a w a Finetech 之產品）、「皮可磨（Pico mill)」 （Asada Iron Works之產品）及「Apex mega」（KEMCO之產品）。 雖然對於顏料分散液之製備步驟並無特殊之限制，但在 顏料分散液之製備過程中進行利用前述分散系統之分散。 舉例來說，經由將分散液成分諸如前述之顏料、分散劑、 溶劑及若需要之黏合劑樹脂預先混合以形成液體混合物， 然後再於前述之分散機中藉由珠粒使所得混合物分散，而 製得期望的顏料分散液。 雖然對於珠粒之使用量並無特殊之限制，但珠粒係以使 用於分散處理之分散機之容器體積之5 0至9 0體積％的量使 用較佳。當填裝於分散機器中之珠粒量太小時，其要耗費 甚長時間以得到具期望顆粒大小分佈之顏料分散液。另一 方面，當其太大時，其成為分散機的負擔，且同時珠粒會 破裂且顏料具有寬的顆粒大小分佈。 在利用具3 0至5 0 0微米之平均顆粒大小之珠粒的此種 分散前，可於輥煉機或捏合機中進行前處理諸如分散，或 利用具大至5 0 0微米或以上之平均顆粒大小的珠粒分散。 或者，可使如此製備得之顏料分散液進行後處理，例如， 利用「T.K. Filmics」（Tokushu Kika Kogyo 之產品）或 rUlti 丨 naizer」（Sugino Machine 之產品）。 [2 ]者色樹脂組成物 19 326\專利說明書(補件)\94-02\93132145 1261689 接下來將說明本發明之著色樹脂組成物。 可將本發明之顏料分散液使用於各種用途。其尤其適用 於目標在於形成，例如，彩色濾、光片之圖像元件影像的者 色樹脂組成物。除了本發明之顏料分散液之外，著色樹脂 組成物可另包含黏合劑樹脂、單體、光聚合引發劑及另一 固體成分。接下來將說明各成分。 [2 - 1 ]黏合劑樹脂 黏合劑樹脂之例子包括均聚物諸如（甲基）丙烯酸、（甲 基）丙烯酸酯、（曱基）丙烯醯胺、順丁烯二酸、（甲基）丙烯 腈、苯乙烯、乙酸乙烯酯、二氯亞乙烯及順丁烯二醯亞胺、 包含此一單體之共聚物、聚氧化乙烯、聚乙烯基吡咯啶酮、 聚醯胺、聚胺基曱酸酯、聚酯、聚醚、聚對苯二曱酸乙二 酯、乙醯基纖維素、酚醛型環氧（η 〇 v ο 1 a c )樹脂、可溶酚醛 樹脂、聚乙烯酚及聚乙烯縮丁醛。 在本發明，術語「（甲基）丙烯酸」係指丙烯酸及曱基丙 烯酸兩者。此同樣適用於（曱基）丙烯酸酯及（甲基）丙烯醯 基。術語「（共）聚合物」係指單一聚合物（均聚物）及共聚 物兩者，而術語「酸（酐）」係指酸及其之酐兩者。在本發 明，術語「丙烯酸系樹脂」係指包含（曱基）丙烯酸之（共） 聚合物及包括含羧基之（曱基）丙烯酸酯之（共）聚合物。 在前述之黏合劑樹脂中，於其之側鏈或主鏈上具有含羧 基或酚羥基之單體的丙烯酸系樹脂為較佳。使用具有此一 官能基之丙烯酸系樹脂作為黏合劑樹脂當製造彩色濾光片 時可於鹼性溶液中顯影。含羧基之丙烯酸系樹脂諸如丙烯 20 326\專利說明書(補件)\94-02\93132145 1261689 酸系（共）聚合物，及經酸酐改質之樹脂諸如苯乙烯-順丁烯 二酸酐樹脂及酚醛型環氧環氧丙烯酸酯由於可於高鹼性溶 液中顯影而為更佳。包含（曱基）丙烯酸之（共）聚合物及包 括含羧基之（曱基）丙烯酸酯之（共）聚合物為特佳。此等丙 烯酸系樹脂伴隨有其之顯影性質及透明度優異的優點，可 經由將其與各種單體結合使用而製備得不同性能之共聚 物，且其之製程可容易地控制。 使用作為黏合劑樹脂之丙烤酸系樹脂係，例如，主要包 括以下單體之（共）聚合物。 單體之例子包括經由將酸或酸酐添加至（曱基）丙烯酸 羥烷酯而製得之化合物。（曱基）丙烯酸羥烷酯包括（曱基） 丙烯酸、琥珀酸（2 -(曱基）丙烯醯氧乙）酯、己二酸（2 -丙烯 醯氧乙）酯、酞酸（2 -(曱基）丙烯醯氧乙）酯、六氫酞酸 (2 —(曱基）丙烯醯氧乙）酯、順丁烯二酸（2 -(曱基）丙烯醯氧 乙）酯、琥珀酸（2 -(曱基）丙烯醯氧丙）酯、己二酸（2 -(甲基） 丙烯醯氧丙）酯、六氫酞酸（2 -(曱基）丙烯醯氧丙）酯、酞酸 (2-(曱基）丙烯醯氧丙）酯、順丁烯二酸（2-(曱基）丙烯醯氧 丙）酯、琥珀酸（2-(曱基）丙烯醯氧丁）酯、己二酸（2-(曱基） 丙烯醯氧丁）酯、六氫酞酸（2 -(曱基）丙烯醯氧丁）酯、酞酸 (2 -（曱基）丙烯醯氧丁）酉旨、及順丁烯二酸（2 -(曱基）丙烯醯 氧丁）酯。酸（酐）包括琥珀酸（琥珀酸酐）、酞酸（酞酸酐）、 及順丁烯二酸（順丁烯二酸酐）。 待與前述單體共聚合之單體的例子包括苯乙烯單體諸 如苯乙烯、α -苯乙烯及乙烯基曱苯；含不飽和基團之羧酸 21 326\專利說明書(補件)\94-02\93132145 1261689 諸如桂皮酸、順丁烯二酸、反丁烯二酸、順丁烯二酸酐及 伊康酸；（甲基）丙稀酸酯諸如（曱基）丙稀酸曱、（曱基） 丙烯酸乙酯、（曱基）丙烯酸丙酯、（曱基）丙烯酸烯丙酯、（甲 基）丙烯酸丁酯、（曱基）丙烯酸2 -乙基己酯、（曱基）丙烯 酸羥乙酯、（曱基）丙烯酸羥丙酯、（曱基）丙烯酸苄酯、（曱 基）丙烯酸羥苯酯、及（曱基）丙烯酸甲氧苯酯，經由將内酯 諸如 ε —己内S旨、点-丙内S旨、丁内S旨及 5 -戊内酷力口至 (甲基）丙烯酸而製得之化合物；丙烯腈諸如丙烯腈及曱基 丙烯腈；丙烯醯胺諸如（甲基）丙烯醯胺、Ν -羥甲基丙烯醯 胺，Ν，Ν -二曱基丙烯醯胺、Ν -曱基丙烯醯基嗎啉、Ν，Ν -二 甲基胺乙基（曱基）丙烯酸酯、及Ν，Ν -二甲基胺乙基丙烯醯 胺；及乙烯基酯諸如乙酸乙烯酯、特十碳酸乙烯酯（ν i n y 1 versatate)、丙酸乙稀酯、桂皮酸乙稀酯及三甲基乙酸乙 稀S旨。 關於用於改良塗布於基板上之薄膜強度之黏合劑樹 脂，經由使選自以下例舉單體之至少一單體（a )與選自以下 例舉單體之至少一單體（b )共聚合而製得之丙烯酸系樹脂 為特佳。 單體（a):含苯基單體諸如苯乙烯、α -曱基苯乙烯、（曱 基）丙烯酸苄S旨、（曱基）丙烯酸羥苯酯、（曱基）丙烯酸曱氧 苯酯、羥苯基（曱基）丙烯醯胺及羥苯基（曱基）丙烯磺醯胺。 單體（b):(曱基）丙烯酸及含羧基之（曱基）丙烯酸酯諸 如琥珀酸（2 -(曱基）丙烯醯氧乙）酯、己二酸（2 -丙烯醯氧乙 酯、酞酸（2 -(曱基）丙烯醯氧乙）酯、六氫酞酸（2 -(甲基） 22 326\專利說明書(補件)\94-02\93132145 1261689 丙烯醯氧乙）酯、及順丁烯二酸（2-(曱基）丙烯醯氧乙）酯。 單體（a )通常係以1 0至9 8莫耳％之量添加，2 0至8 0莫 耳％較佳，3 0至7 0莫耳％更佳，而單體（b )通常係以2至9 0 莫耳％之量添加，2 0至8 0莫耳％較佳，3 0至7 0莫耳％更佳。 關於黏合劑樹脂，其之側鏈具有烯系雙鍵之丙烯酸系樹 脂為較佳。使用此一樹脂可改良本發明之著色樹脂組成物 的光固化性，因而使其可產生解析度及在根據本發明之第 二態樣之圖像元件與彩色濾光片之基板之間之黏著的進一 步改良。 將烯系雙鍵引入至丙烯酸系樹脂之側鏈之方法的例子 包括如說明於日本專利公告第3 4 4 4 3 / 1 9 7 5號及日本專利 公告第3 4 4 4 4 / 1 9 7 5號中之以下方法： (1 )使丙烯酸系樹脂之羧基與具有縮水甘油基或環氧環 己基及（曱基）丙烯醯基兩者之化合物反應之方法，及 (2 )使丙稀酸系樹脂之經基與氯化丙稀酸反應之方法。 明確說明，其之側鏈具有烯系雙鍵之丙烯酸系樹脂可經 由使含羧基或羥基之丙烯酸系樹脂與諸如（曱基）丙烯酸縮 水甘油S旨、稀丙基縮水甘油基醚、α -乙基丙稀酸縮水甘油 S旨、巴豆基縮水甘油基_、（異）巴豆酸縮水甘油基喊、（曱 基）丙烯酸（3，4 -環氧環己基）曱酯、氯化（曱基）丙烯酸或 (甲基）烯丙氣之化合物反應而製得。經由使含羧基或羥基 之丙烯酸系樹脂與脂環族環氧化合物諸如（曱基）丙烯酸 (3，4 -環氧環己基）曱酯反應而製得之化合物為特佳。 關於前述之預先將烯系雙鍵引入至含羧基或羥基之丙 23 326\專利說明書(補件)\94-02\93132145 1261689 烯酸系樹脂中之方法，使具有烯系雙鍵之化合物鍵結至2 至50莫耳％，以5至40莫耳％較佳之羧基或羥基通常為較 佳。以酸值計，羧基之含量係落於5至2 0 0毫克Κ Ο Η之範 圍内較佳。當酸值低於5毫克Κ Ο Η /克時，樹脂不溶於鹼 性顯影劑中。另一方面，超過2 0 0毫克Κ Ο Η /克之酸值有 時會使顯影敏感性降低。 利用G P C測得之丙烯酸系樹脂的重量平均分子量（M w )係 自1，0 0 0至1 0 0，0 0 0較佳。當重量平均分子量低於1，0 0 0 時，生成之著色樹脂組成物無法均勻地塗布。超過1 0 0，0 0 0 之重量平均分子量有使顯影性質降低的傾向。 以本發明之著色樹脂組成物之總固體含量計，黏合劑樹 脂通常係以1 0至8 0重量％之量添加，以2 0至7 0重量°/◦較 佳。 [2-2 ]單體 關於包含於著色樹脂組成物中之單體，可使用任何的可 聚合低分子化合物。具有至少一烯系雙鍵且可進行加成聚 合之化合物（以下將簡稱為「稀系化合物」）為較佳。當本 發明之著色樹脂組成物暴露至活性射線時，此一稀系化合 物經歷加成聚合及經由稍後即將說明之光聚合引發劑系統 的作用固化。在本發明，術語「單體」係指相對於所謂之 聚合物物質的物質。因此，其不僅包括狹義的單體，並且 亦包括二聚物、三聚物及寡聚物。 烯系化合物之例子包括不飽和羧酸、不飽和羧酸與單羥 基化合物之酯、脂族多經基化合物與不飽和缓酸之酯、芳 24 326\專利說明書(補件)\94-02\93132145 1261689 族多羥基化合物與不飽和羧酸之酯、經由不飽和羧酸及多 元羧酸與多羥基化合物諸如脂族多羥基化合物或芳族多羥 基化合物之酯化反應所製得之酯、及經由使聚異氰酸酯化 合物與含（曱基）丙烯醯基之羥基化合物反應而製得之具有 胺基曱酸酯架構之烯系化合物。 脂族多經基化合物與不飽和叛酸之S旨的例子包括丙稀 酸酯諸如乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、三羥 曱基丙烷三丙烯酸酯、三羥曱基乙烷三丙烯酸酯、異戊四 醇二丙烯酸酯、異戊四醇三丙烯酸酯、異戊四醇四丙烯酸 酯、二異戊四醇四丙烯酸酯、二異戊四醇五丙烯酸酯、二 異戊四醇六丙烯酸酯及甘油丙烯酸酯；及分別使用曱基丙 烯酸、伊康酸、巴豆酸、順丁烯二酸替代丙烯酸酯之丙烯 酸部分所製得之曱基丙烯酸酯、伊康酸酯、巴豆酸酯、及 順丁烯二酸酯。 芳族多羥基化合物與不飽和羧酸之酯的例子包括氫醌 二丙烯酸酯、氫醌二曱基丙烯酸酯、間苯二酚二丙烯酸酯、 間苯二酚二曱基丙烯酸酯及五倍子酚三丙烯酸酯。 經由不飽和羧酸及多元羧酸與多羥基化合物之酯化反 應所製得之酯可不一定為單一物質而係混合物。典型的例 子包括丙烯酸、酞酸及乙二醇之縮合物、丙烯酸、順丁烯 二酸及二甘醇之縮合物、曱基丙烯酸、對酞酸及異戊四醇 之縮合物、及丙烯酸、己二酸、丁二醇及甘油之縮合物。 經由使聚異氰酸酯化合物與含（曱基）丙烯醯基之羥基 化合物反應而製得之具有胺基曱酸酯架構之烯系化合物的 25 3 26\專利說明書(補件)\94-02\93132145 1261689 例子包括在脂族二異氰酸酯諸如二異氰酸己二酯或二異氰 酸三曱基己二酯，脂環族二異氰酸酯諸如環己烷二異氰酸 酯或異佛爾酮二異氰酸酯，或芳族二異氰酸酯諸如三烯 (ti~ilene)二異氰酸酯或二苯基曱烷二異氰酸酯與含（曱基） 丙烯醯基之羥基化合物諸如丙烯酸2 -羥乙酯、曱基丙烯酸 2-羥乙酯、3 -羥基三丙烯醯氧甲基）丙烷、或3 -羥 基（1，1，1 -三曱基丙烯醯氧甲基）丙烷之間的反應產物。 除前述烯系化合物外之烯系化合物的例子包括丙烯醯 胺諸如乙烯雙丙烯醯胺；烯丙基酯諸如酞酸二烯丙酯；及 含乙烯基化合物諸如酞酸二乙烯酯。 以本發明之著色樹脂組成物中之總固體含量計，單體通 常係以1 0至8 0重量％之量添加，以2 0至7 0重量％較佳。 [2-3 ]光聚合引發劑系統 當本發明之著色樹脂組成物包含稀系化合物作為前述 之單體成分時，加入具有經由直接吸收光或光敏化產生分 解反應或奪氫反應及產生聚合活性自由基之功能的光聚合 引發劑系統成分為較佳。此處所使用之「光聚合引發劑系 統成分」係指光聚合引發劑、加速劑及添加劑諸如增敏顏 料之混合物。 構成光聚合引發劑系統之光聚合引發劑的例子包括金 屬雙環戊二炼（m e t a 1 1 〇 c e n e )化合物，諸如說明於日本公開 專利第1 5 2 3 9 6 / 1 9 8 4號及第1 5 1 1 9 7 / 1 9 8 6號中之雙環戊二 烯鈦化合物；說明於日本公開專利第3 9 5 0 3 / 1 9 9 8號中之自 由基活化劑諸如六芳基二咪唑衍生物、齒曱基-s -三σ井衍生 26 326\專利說明書(補件)\94-02\93】32145 1261689 物、N -芳基-α'-胺基S茭諸如N -苯基甘月安酸、N -芳基-α -胺 基酸鹽及Ν -芳基-α -胺基酸酯；α -胺烷基苯酮化合物； 及如說明於日本公開專利第2 0 0 0 - 8 0 0 6 8號中之肟酯引發 劑。可使用於本發明之聚合引發劑的明確例子包括： 鹵曱基化三畊衍生物諸如2 - ( 4 -曱氧苯基）-4，6 -雙（三 氯曱基）-s-三畊、2-(4 -曱氧萘基）-4,6 -雙（三氯曱基）-s-三呼、2-(4 -乙氧萘基）-4,6-雙（三氯曱基）-s-三畊及 2-(4 -乙氧羰萘基）-4, 6-雙（三氣曱基）-s -三喷； 鹵曱基化呤二唑衍生物諸如2 -三氯曱基-5 - ( 2 ’ -苯并 呋喃基）-1,3,4-口号二唑、2-三氣曱基-5-[石-(2’-苯并呋 喃基）乙烯基]-1,3, 4-呤二唑、2 -三氯曱基- 5- [yS -(2， -(6” -苯并呋喃基）乙烯基）]-l，3,4-呤二唑及2 -三 氣曱基-5 -呋喃基-1 , 3，4 -呤二唑； 咪唑衍生物諸如2 - ( 2 ’ -氯苯基）-4，5 -二苯基咪唑二聚 物、2 - ( 2 ’ -氯苯基）-4，5 -雙（3 ’ -曱氧苯基）咪唑二聚物、 2 - ( 2 ’ -氟苯基）_ 4，5 -二苯基咪唑二聚物、2 - ( 2 ’ -曱氧苯 基）-4,5 -二苯基咪唑二聚物及（4’ -曱氧苯基）-4,5 -二苯 基咪嗤二聚物； 安息香烷基醚諸如安息香曱基醚、安息香苯基醚、安息 香異丁基醚及安息香異丙基醚； 蒽醌衍生物諸如2 -曱基蒽醌、2 -乙基蒽醌、2 -第三丁基 蒽西昆及1 -氯蒽醌； 二苯基酮衍生物諸如二苯基酮、米其勒（M i c h 1 e r ’ s ) 酮、2 -曱基二苯基酮、3 -曱基二苯基酮、4 -曱基二苯基酮、 27 326\專利說明書(補件)\94-02\93132145 1261689 2 -氯二苯基酮、4 -溴二苯基酮及2 -羧基二苯基酮； 苯乙酮衍生物諸如2, 2 -二曱氧基-2-苯基苯乙酮、2, 2-二乙氧基苯乙酮、1-羥環己基苯基酮、α -羥基-2-曱苯基 丙酮、1-羥基-1-甲基乙基-(對異丙苯基）酮、1-羥基-1-(對 十二基苯基）酮、2 -甲基-（4 -(甲硫基）苯基）_ 2 -嗎福17林基 -1-丙酮及1,1，1-三氯曱基-(對丁苯基）酮； 9 -氧二苯并硫派喃化合物諸如9 -氧二苯并硫派喃、2 -乙基-9 -氧二苯并硫σ底喃、2 -異丙基-9 -氧二苯并硫略喃、 2 -氯-9 -氧二苯并硫略喃、2，4 -二曱基-9 -氧二苯并硫派喃、 2,4 -二乙基-9-氧二苯并硫派喃及2，4 -二異丙基-9-氧二 本弁硫派喃， 苯曱酸酯衍生物諸如對二曱胺基苯曱酸乙酯及對二乙 胺基苯曱酸乙酯；吖啶衍生物諸如9 -苯基吖啶及9 _(對曱 氧苯基）吖啶；啡η井衍生物諸如9，1 0 -二曱基苯并啡ϋ井； 蒽酮衍生物諸如苯并蒽酮； 雙環戊二烯鈦衍生物諸如二-環戊二烯基-T i -二-氯化 物、二-環戊二烯基- Ti -雙-苯基、二-環戊二烯基-Ti-雙 -2，3，4，5，6 -五氣苯-1-基、二-環戍二稀基- Ti_雙 -2, 3, 5, 6 -四氟苯-1-基、二-環戊二烯基- Ti-雙-2, 4, 6 -三 氧苯-1-基、二_環戊二稀基-Ti_2，6_二-氟苯-1-基、二-環戊二烯基- Ti-2, 4 -二-氟苯-1-基、二-曱基環戊二烯基 -丁1-雙-2,3,4,5,6-五氟苯-1-基、二-曱基環戊二烯基_丁卜 雙-2，6 -二苯-卜基及二-環戊二稀基-Ti-2, 6 -二-說 -3-(pyl-l-基）-苯-1-基； 326\專利說明書(補件)\94-02\93 ] 32145 28 1261689 α -胺烷基苯酮化合物諸如2 -曱基-1 - [ 4 -(曱硫基 基]-2 -嗎福σ林丙-1-酮、2-节基-2 -二曱胺基-1 -（4-苯基）丁酮基-2 -二曱胺基-1-(4 -嗎福ϋ林苯J -1-酮、4 -二曱胺乙基苯曱酸酯、4 -二曱胺基異戊基 酯、4 -二乙胺基苯乙酮、4 -二曱胺基丙醯苯、2 -乙 -1，4 -二甲胺基苯甲酸酯、2, 5 -雙（4-二乙胺基亞苄J 酮、7 -二乙胺基- 3- (4 -二乙胺基苯曱醯基）薰草素、 4-(二乙胺基）查酮（chalcone);及 肟酯化合物諸如1，2 -辛二酮、1 - [ 4 -(苯硫基）苯 基]-2-（0-苯曱醯基肟）、2 -乙氧-1,2 -二苯乙酮、1 基-6-(2 -曱基苯曱醯基）-9H-咔唑-3-基]、及1-(0-肟）。 關於構成光聚合引發劑系統成分之加速劑，可使> 二烷胺基苯曱酸烷酯諸如N，N -二曱胺基苯曱酸乙酯 雜環化合物諸如2 -酼基苯并噻唑、2 -巯基苯并呤嗤 巯基苯并咪唑，及脂族多官能巯基化合物。 此等光聚合引發劑及加速劑各可單獨或以其兩者 之組合使用。 光聚合引發劑系統成分之明確例子包括如說明於 化學（Fine Chemical)」（第 20 冊，No. 4， 19 9 1 年 曰）第1 6至2 6頁之二烷基苯乙酮衍生物、安息香衍 9 -氧二苯并硫哌喃衍生物，如說明於日本公開專利 4 0 3 0 2 3 / 1 9 8 3號及日本專利公告第3 7 3 7 7 / 1 9 7 0號之 二咪唑衍生物及S -三i曱基三_衍生物，及結合使 326\專利說明書(補件)\94-02\93132145 29 )苯 嗎福琳 卜）丁 苯曱酸 基己基 ^ )環己 及 -[9-乙 乙醯基 有 N，N-，及含 及2 - 以上 「精細 3月1 生物及 第 六芳基 用雙環 1261689 戊二烯鈦、二苯并哌喃顏料、及具有胺基或胺基甲酸酯基 且可進行加成聚合之含烯系飽和雙鍵之化合物的系統。 以本發明之著色樹脂組成物之總固體含量計，光聚合引 發劑系統成分通常係以0 . 1至3 0重量％之量添加，以0 . 5 至2 0重量％較佳，0 . 7至1 0重量％更佳。當此量太小時， 其有時會導致曝光敏感性降低，而當此量太大時，未曝光 部分於顯影劑中之溶解度降低，其會引發顯影失效。 若需要，光聚合引發劑系統成分可視影像曝光源之波長 而包含增感染料，以增進反應敏感度。此種增感染料之例 子包括如說明於日本公開專利第2 2 1 9 5 8 / 1 9 9 2及 2 1 9 7 5 6 / 1 9 9 2號中之二苯并哌喃顏料、如說明於日本公開 專利第2 3 9 7 0 3 / 1 9 9 1及2 8 9 3 3 5 / 1 9 9 3號中之含雜環之薰草 素顏料；如說明於日本公開專利第2 3 9 7 0 3 / 1 9 9 1及 289335/1993號中之3 -酮基薰草素化合物；如說明於日本 公開專利第1 9 2 4 0 / 1 9 9 4號中之吡咯亞曱基顏料，及如說明 於日本公開專利第2 5 2 8 / 1 9 7 2及1 5 5 2 9 2 / 1 9 6 9號、日本專 利公告第3 7 3 7 7 / 1 9 7 0號、日本公開專利第8 4 1 8 3 / 1 9 7 2、 112681/1977、 15503/1983、 88005/1985、 56403/1984、 69/1990、 168088/1982、 107761/1993、 210240/1993 及 2 8 8 8 1 8 / 1 9 9 2號中之具有二烷胺基苯架構之著色劑。 在此等增感染料之中，較佳者為含胺基染料，於其之一 分子中同時具有胺基及苯基之化合物為更佳。特佳染料之 例子包括二苯基酮化合物諸如4，4 ’ -二曱胺基二苯基 酮、4, 4’ -二乙胺基二苯基酮、2-胺基二苯基酮、4-胺基 30 326\專利說明書(補件)\94-02\93132145 1261689 二苯基酮、4,4’ -二胺基二苯基酮、3, 3’ -二胺基二苯基 酮及3，4 -二胺基二苯基酮；及含對二烷胺苯基之化合物諸 如2 -(對二曱胺苯基）苯并唑、2 -(對二乙胺苯基）苯并鳄 唑、2 -(對二曱胺苯基）苯并[4 , 5 ]苯并鳄唑、2 -(對二曱胺 苯基）苯并[6, 7]苯并呤唑、2,5 -雙（對二乙胺苯基）-1,3, 4-:唑、2 -(對二曱胺苯基）苯并噻唑、2-(對二乙胺苯基）苯 并噻唑、2 -(對二曱胺苯基）苯并咪唑、2 -(對二乙胺苯基） 苯并咪唑、2，5 -雙（對二乙胺苯基）-1 , 3，4 -噻二唑、（對二 曱胺苯基）°比啶、（對二乙胺苯基）ϋ比啶、（對二曱胺苯基） 啥σ林、（對二乙胺苯基）啥σ林、（對二曱胺苯基）°密σ定及（對二 乙胺苯基）嘧啶。其中4, 4’ -二烷胺基二苯基酮為最佳。 此等增感染料可單獨或以其兩者以上之組合使用。 以著色樹脂組成物之總固體含量計，本發明之著色樹脂 組成物中之增感染料的比例通常係自0至2 0重量％，以自 0 . 2至1 5重量％較佳，自0 . 5至1 0重量％更佳。 [2 - 4 ]另一固體成分 本發明之著色樹脂組成物視需要可包含除前述成分外 之另一固體成分。其之例子包括表面活性劑、熱聚合抑制 劑、塑化劑、儲存安定劑、表面保護劑、黏著改進劑、及 顯影改進劑。 關於表面活性劑，可使用各種表面活性劑諸如陰離子、 陽離子、非離子及兩性表面活性劑，但非離子表面活性劑 由於較不可能對樹脂組成物之各種性質有不利影響而為較 佳。以著色樹脂組成物中之總固體含量計，表面活性劑之 31 326\專利說明書(補件)\94-02\93132】45 1261689 比例通常係自0 . 0 0 1至1 0重量％，以自0。0 0 5至1重量％ 較佳，自0 . 0 1至0 . 5重量％更佳，自0 . 0 3至0 . 3重量％最 佳。 關於熱聚合抑制劑，可使用氫酸、對曱氧S分、五倍子S分、 兒茶S分、2 , 6 -第三丁基對曱酴及/3 -萘酴。以著色樹脂組成 物中之總固體含量計，其係以在自0至3重量％之範圍内添 加較佳。 關於塑化劑，使用3大酸二辛醋、S太酸二-十二烧S旨、三 乙二醇二辛酸酯、二甲基二醇酞酸酯、磷酸三曱苯酚酯、 己二酸二辛酯、癸二酸二丁酯或三乙醯基甘油。以著色樹 脂組成物中之總固體含量計，其係以在自10重量％或以下 之範圍内添加較佳。 [2 - 5 ]著色樹脂組成物之製備 為製備本發明之著色樹脂組成物，經由將預定量之說明 於上之溶劑及黏合劑樹脂、及視需要之單體、光聚合引發 劑系統成分、及另一成分加入至前述本發明之顏料分散液 中而製得均勾分散液。由於有微細塵粉在其之形成過程中 混合於分散液或混合物中的可能性，因而將如此製得之著 色樹脂組成物過濾以將其移除較佳。 在本發明之著色樹脂組成物中，基於關於顏料分散液中 之溶劑含量所說明之相似理由，溶劑之含量落於自70重量 °/〇至9 9重量％之範圍内較佳，自7 5重量％至9 0重量％尤佳。 即使係在經由混合及分散諸如本發明之顏料分散液、溶 劑及黏合劑樹脂之成分而製得之本發明之著色樹脂組成物 32 326\專利說明書(補件)\94-02\93132145 1261689 中，包含於著色樹脂組成物中之顏料的顆粒大小分佈實質 上係與顏料分散液中之分佈相同。因此，可維持前述之顆 粒大小。 當經由使用以此一方式製備得之著色樹脂組成物於玻 璃基板上形成紅色圖像元件時，根據以下方程式（1 )所計算 之對比C : C = B/A ( 1 ) 其中A及B分別代表當將玻璃基板夾於兩偏光板之間及 將兩偏光板直角設置及當將兩偏光板平行設置時利用亮度 光度計測得之光強度，及當暴露至照明器C時利用分光光 度計所測得之透射光之色度X滿足以下方程式（2 ): C$ 4 0 0 0 x - 2 0 0 0 ( 2 )， 其中如此形成之紅色圖像元件具有高對比。 在C < 4 0 0 0 X - 2 0 0 0下，紅色圖像元件之對比低且於黑色 顯示器上發生光洩漏，而導致影像品質退化。 在本發明之著色樹脂組成物中，對比C及色度X滿足下 述的方程式（2 - 1 )較佳，下述的方程式（2 - 2 )更佳。 C$ 4 0 0 0 x- 1 8 0 0 … （2-1 ) C ^ 4 0 0 0 x - 1 4 0 0 … (2-2) [3 ]彩色濾、光片 以下將說明本發明之彩色濾光片。 彩色濾光片係經由將黑色基質設置於透明基板上，然後 再連續形成紅色、綠色及藍色影像元件（其之次序並不限於 此）而製得。在此一彩色濾光片之製造中，使用本發明之著 33 326\專利說明書(補件)\94-02\93132145 1261689 色樹脂組成物作為用於形成紅色圖像元件之塗布溶液。各 顏色之影像元件係經由將黑色抵抗劑塗布至透明基板，或 將紅色、綠色或藍色抵抗劑塗布至形成於透明基板上方之 樹脂黑色基質之表面或使用鉻化合物或另一遮光金屬材料 形成之金屬黑色基質之表面，隨後經由加熱乾燥，逐影像 地曝光，顯影及熱固化而形成。 [3 - 1 ]透明基板（支承物） 可將任何材料使用作為彩色濾光片之透明基板，只要其 係透明且具有適當強度即可。材料之例子包括由熱塑性樹 脂諸如聚酯樹脂，例如，聚對苯二曱酸乙二酯，聚烯烴樹 脂，例如，聚丙烯及聚乙烯，聚碳酸酯，聚（曱基丙烯酸曱 酯）及聚砜製成之片材；由熱固性樹脂諸如環氧樹脂，不飽 和聚酯樹脂及聚（曱基）丙烯酸系樹脂製成之片材；及各種 玻璃。其中考慮其之耐熱性，玻璃及对熱性樹脂為較佳。 若需要，可使透明基板或其上形成有黑色基質之基板進 行電暈放電處理、臭氧處理或利用矽烷偶合劑或諸如胺基 曱酸酯樹脂之樹脂之薄膜形成處理，以改良表面物性包括 黏著。透明基板之厚度通常係自0 . 0 5至1 0毫米，以自0 . 1 至7毫米較佳。當使用樹脂形成薄膜時，其之厚度通常係 自0 . 0 1至1 0微米，以自0 . 0 5至5微米較佳。 [3 - 2 ]黑色基質 利用遮光金屬薄膜或黑色基質之著色樹脂組成物將黑 色基質形成於透明基板之上。遮光金屬材料之例子包括鉻 化合物諸如金屬鉻、氧化鉻及氮化鉻，及鎳-鎢合金。材料 34 326\專利說明書(補件)\94-02\93132145 1261689 可為其之多層之堆疊。 黑色基質可經由下列步驟而形成：通常經由濺鍍形成此 一金屬遮光薄膜，透過正光阻劑於薄膜上方形成期望的圖 案，利用經由混合硝酸銨鈽（I V )及過氯酸及/或硝酸而得 之I虫刻劑姓刻絡或利用適合的ί虫刻劑14刻另一材料，然後 利用專用的釋離劑將正光阻劑剝離。 在前述情況中，經由沈積或減：鑛將此一金屬或金屬•金 屬氧化物之薄膜形成於透明基板上。接著於在此薄膜之上 形成著色樹脂組成物之薄膜後，使生成之薄膜透過具有重 複圖案諸如條紋、馬賽克或三角形之光罩曝光•顯影。亦 可經由餘刻生成之薄膜而形成黑色基質。 當使用黑色基質之著色樹脂組成物時，黑色基質係經由 使用包含黑色材料之著色樹脂組成物而形成。明確說明， 黑色基質可經由使用包含一或多種黑色材料諸如碳黑、石 墨、鐵黑、苯胺黑、花青黑及鈦黑或包含經由混合紅色、 綠色及藍色顏料或視需要選自無機或有機染料之染料而製 得之黑色材料的著色樹脂組成物，及採用與關於形成紅 色、綠色或藍色影像元件說明於下者類似之方法而形成。 [3 - 3 ]圖像元件之形成 [3 - 3 _ 1 ]薄膜之形成 將包含選自紅色、綠色及藍色材料之一有色材料（顏料） 的著色樹脂組成物塗布至其上形成有黑色基質之透明基 板。於乾燥後，將光罩置於生成之薄膜上，及透過此光罩 進行逐影像曝光，顯影及若需要之熱固化或光固化，以形 35 326\專利說明書(補件)\94·02\93132145 1261689 成影像元件，藉此形成影像元件之著色層。彩色濾光片影 像可經由對紅色、綠色及藍色之三著色樹脂組成物進行前 述之操作而形成。 彩色濾光片之著色樹脂組成物可利用旋轉器方法、環棒 式濕膜（w i r e b a r )法 '流動塗布法、口模式塗布方法、輥 塗法或喷塗法塗布至透明基板。其中由總體的觀點來看， 口模式塗布方法為較佳，因其可大大地降低塗布溶液之使 用量，且其不會受在其他情況中當使用旋轉塗布方法時將 會黏著之霧的影響，因此，可抑制外來物質的產生。 當著色樹脂組成物之薄膜太厚時，其會干擾平滑的圖案 顯影及液晶晶格形成步驟中之間隙調整，而太薄的薄膜有 時會由於提高顏料密度之困難而干擾期望顏色的表現。以 乾燥後之薄膜厚度計之薄膜的厚度係自0 . 2至2 0微米較 佳，自0. 5至1 0微米更佳，自0. 8至5微米又更佳。 [3 - 3 - 2 ]薄膜之乾燥 使用電熱板、I R烘箱、對流烘箱或其類似裝置將經由將 著色樹脂組成物塗布至透明基板而形成之薄膜乾燥較佳。 乾燥通常係分兩階段進行，即初步乾燥和藉由再加熱而乾 燥。初步乾燥條件可視溶劑成分之種類、或所使用之乾燥 機的性能視需要而選擇。乾燥時間通常係視溶劑成分之種 類或所使用之乾燥機的性能而選自在4 0至8 0 °C下1 5秒至 5分鐘之範圍，以選自在5 0至7 0 °C下3 0秒至3分鐘之範 圍較佳。 藉由再加熱而乾燥係在高於初步乾燥溫度的溫度下進 36 326\專利說明書(補件)\94-02\93132]45 1261689 行，以自5 0至2 Ο 0 °C較佳，自7 0至1 6 0 °C更佳，自 1 3 0 °C特佳。乾燥時間係視加熱溫度而異，但其係自 至1 0分鐘較佳，自1 5秒至5分鐘特佳。乾燥溫度愈 則對透明基板的黏著愈佳。過高的乾燥溫度會使黏合 脂降解及引發熱聚合，據推測其會導致顯影失效。在 下乾燥的另一種替代方式為可經由於真空室中真空乾 將薄膜乾燥。 [3-3-3]曝光步驟 經由將負基質圖案重疊於著色樹脂組成物之乾燥薄 上方，及透過此光罩圖案照射來自光源之紫外射線或 射線，而進行成影像曝光。若需要，此曝光可於將氧 層諸如聚乙烤醇層形成於著色樹脂組成物之薄膜上， 止薄膜之敏感度因氧而降低之後進行。 對於使用於成影像曝光之光源並無特殊之限制。其 包括燈光源諸如氣燈、ii素燈、鐫燈、高壓汞燈、超 汞燈、金屬ifi化物燈、中壓汞燈、低壓汞燈、碳弧及 燈；及雷射光源諸如氬離子雷射、YAG雷射、準分子霍 氮雷射、氦鎘雷射及半導體雷射。當暴露至具有特定 之光時，可使用濾光器。 [3 - 3 - 4 ]顯影步驟 於前述之成影像曝光之後，可使用包含表面活性劑 性化合物之有機溶劑或水溶液進行顯影。水溶液可進 包含有機溶劑、緩衝劑、錯合劑、或染料或顏料。 驗性化合物之例子包括無機驗性化合物諸如氫氧化 326\專利說明書(補件)\94-02\93132145 37 70至 1 0秒 高， 劑樹 南溫 燥而 膜 可見 阻斷 以防 例子 高壓 螢光 「射、 波長 及驗 一步 1261689 鈉、氫氧化鉀、氫氧化鋰、碳酸鈉、碳酸鉀、碳酸氫鈉、 碳酸氫鉀、矽酸鈉、矽酸鉀、偏矽酸鈉、磷酸鈉、磷酸鉀、 磷酸氫鈉、磷酸氫鉀、磷酸二氫鈉、磷酸二氫鉀及氫氧化 敍，及有機鹼性化合物諸如單-、二-或三乙醇胺、單-、二 -或三曱胺、單-、二-或三乙胺、單-或二異丙胺、正丁胺、 單-、二-或三異丙醇胺、乙烯亞胺、乙烯二亞胺、氫氧化 四曱銨（T M A Η )及膽鹼。此等鹼性化合物可單獨或以其兩者 以上之組合使用。 表面活性劑之例子包括非離子表面活性劑諸如聚氧伸 乙基烷基醚、聚氧伸乙基烷芳基醚、聚氧伸乙基烷基酯、 脫水山梨糖醇；(：完基酯及單甘油酯：)：完基SI ;陰離子表面活性 劑諸如烷基苯磺酸酯、烷基萘磺酸酯、烷基硫酸酯、烷基 石黃酸S旨及續酸玻拍酸S旨；及兩性表面活性劑諸如烧基甜菜 鹼及胺基酸。此等表面活性劑可單獨或以其兩者以上之組 合使用。 關於有機溶劑，可使用選自異丙醇、苯曱醇、乙基溶纖 劑、丁基溶纖劑、苯基溶纖劑、丙二醇、及二丙酮醇之一 或多種溶劑。有機溶劑可單獨或以與水溶液之組合使用。 對於顯影條件並無特殊之限制。其通常係在自1 0至5 0 °C之溫度範圍内進行，以自1 5至4 5 °C較佳，自2 0至4 0 °C特佳。可使用蘸塗顯影、噴塗顯影、刷塗顯影及超音波 顯影之任一者。 [3 - 3 - 5 ]熱固化處理 於顯影之後通常使彩色濾光片基板進行熱固化或光固 38 326\專利說明書(補件)\94-02\93132145 1261689 化處理，以熱固化處理較佳。 熱固化溫度係選自1 0 0至2 8 0 °C之範圍，以1 5 0至2 5 0 °C較佳，而熱固化時間係選自5至6 0分鐘之範圍。 於一系列的步驟後，完成一顏色的圖案化影像形成。經 由連續重複此等步驟，進行（黑色）、紅色、綠色及藍色之 圖案化，由此形成彩色濾光片。將紅色、綠色及藍色圖案 化之次序並不限於前述之次序。 本發明之彩色濾光片之另一製造方法的例子包括：（1 ) 將本發明之著色樹脂組成物塗布至基板，及經由蝕刻形成 影像元件之方法；（2 )使用本發明之著色樹脂組成物作為著 色墨水及利用印刷機直接將影像元件形成於透明基板上之 方法；（3 )使用本發明之著色樹脂組成物作為電沈積液體， 將基板浸泡於其中，及使著色薄膜沈澱於經形成為具有預 定圖案之I T 0電極上之方法；（4 )將經塗布本發明之著色樹 脂組成物之薄膜黏著至透明基板，將薄膜剝離，進行成影 像曝光，顯影形成影像元件之方法；及（5 )使用本發明之著 色樹脂組成物作為著色墨水，及利用喷墨印刷機形成影像 元件之方法。為製造彩色濾光片，視彩色濾光片之著色樹 脂組成物的組成物而採用適合於其之方法。 [3 - 4 ]透明電極之形成 於將透明電極諸如I T 0形成於影像之上，不對濾光片進 行任何進一步修改之後，將本發明之彩色濾光片使用作為 彩色顯示器、液晶顯示裝置之零件或類似的零件。為提高 其之表面平滑度及耐用性，若需要，其可於影像上方具有 326\專利說明書(補件)\94-02\93132145 39 1261689 聚醯胺或聚醯亞胺層作為面塗層。 彩色濾光片並不一定具有透明電極，例如，當將其使用 於面内切換模式（I S P模式）中時。 [4 ]液晶顯示裝置（面板） 接下來將說明液晶顯示裝置（面板）。 本發明之液晶顯示裝置通常係經由將配向層 (alignment layer)形成於本發明之彩色遽光片之上，將隔 離物喷塗於此配向層之上，將所得之彩色濾光片黏合至面 對基板而形成液晶晶格’將液晶材料注入至液晶晶格中及 接線至面對基板之電極而製得。 關於配向層，樹脂薄膜諸如聚醯亞胺為適當。為形成配 向層，通常使用照相凹版（photogravure)印刷及/或膠版 印刷方法，且通常將配向層之厚度調整至數十奈米。於經 由烘烤固化之後，使配向層暴露至UV射線或利用摩擦布摩 擦，以將其處理成可控制液晶材料之取向的表面狀態。 隔離物具有適合於與面對基板之間隙的尺寸，且具自2 至8奈米之尺寸的隔離物通常為較佳。可使用利用微影術 由透明樹脂薄膜於彩色濾光片之基板上方製得之光隔離物 (P S )替代隔離物。 關於面對基板，通常使用陣列基板，T F T (薄膜電晶體） 基板為特佳。 與面對基板之間隙係視液晶顯示裝置之使用目的而 異，但其通常係選自2至8微米之範圍。於將彩色濾光片 之基板與面對基板黏合後，利用密封劑諸如環氧樹脂密封 40 326\專利說明書(補件)\94-02\93132145 1261689 除液晶材料之填充口外的部分。此密封劑係經由暴露至 UVG射線及/或加熱固化，藉此完成在液晶晶格周圍的密 封。 於將於其周圍密封之液晶晶格切割成各面板後5將液晶 材料之填充口浸泡於在真空室中之減壓下的液晶材料中。 接者經由真空室中之Ά漏’將液晶材料注入至液晶晶格 中。通常使液晶晶格中之壓力降至1 X 1 〇_ 2至1 X 1 0 _ 7 P a，以 1 X 1 (Γ 3至1 X 1 (Γ 6 P a較佳。當減壓時，將液晶晶格加熱較佳， 且加熱溫度通常係自3 0至1 0 0 °C ，以自5 0至9 0 °C較佳。 在減壓過程中，維持熱溫度在自1 0至6 0分鐘之範圍内， 且之後將液晶材料之填充口浸泡於液晶材料中。於將液晶 材料注入至液晶晶格中之後，經由使UV固化樹脂固化將填 充口密封，由此完成液晶顯示裝置（面板）之製造。 對於液晶材料之種類並無特殊之限制，而可使用習知材 料諸如芳族化合物、脂族化合物或多環化合物。液晶可為 感膠離子或向熱性。關於向熱性液晶，已知向列、距列及 膽固醇液晶，且可使用任何一者。 (實施例） 以下將經由實施例及比較例更詳細說明本發明。然而， 應謹記本發明並不受其所限制，且其可在不脫離本發明之 範圍的範圍内作修改。在所有的指示中，組成物中之「份」 或「份數」係指「重量份」或「重量份數」^ (實施例1 ) 〈顏料分散液之製備〉 41 326\專利說明書(補件)\94-02\93132145 1261689 根據以下配方製備本發明之顏料分散液。 [顏料分散液之配方] 蒽醌紅色顏料（P。R a 1 1 7 ) (「A Τ Y - T R」，D I C之產品）： 80份 錄偶氮（Nickelazo)黃色顏料（P. Y. 150)(「E4GN」，Bayer 之產品）：2 0份 胺分散劑（「Disperbyk」，BYK-Chemie之產品）：45份 溶劑（丙二醇單曱醚乙酸酯）：5 8 0份 於將前述材料混合後，使用「T 0 R U S Μ I L L」（G e t z m a η η製 造）使所得之研磨基質分散（其係經由於容器中之珠粒的碰 撞而進行分散）。當分散時所使用之珠粒係具1 0 0微米之平 均顆粒大小的錯氧珠粒。於分散機之0 . 3 3公升容器中填充 6 5體積％之珠粒及加入1 0 0立方公分之研磨基質。在1 2米 /分鐘之周邊速度及分散時間4分鐘下進行分散處理。 〈顏料分散液之顆粒大小分佈的測量〉 利用丙二醇單甲醚乙酸酯將如此製得之顏料分散液稀 釋至5 0 0 0倍，及使用動態光散射分光光度計（「DLS 7 0 0 0」， 0 t s u k a E 1 e c t r〇n i c s之產品）測量顆粒大小。顆粒大小範 圍及半寬度值示於表1。 〈著色樹脂組成物（彩色抵抗劑）之製備〉 根據下述配方將成分混合於所得之顏料分散液中。將所 得之混合物過濾通過1微米過濾器，由此形成彩色濾光片。 [彩色抵抗劑之配方] 顏料分散液：1 0. 6份 42 326V專利說明書(補件)\94-02\93132 ] 45 1261689 溶劑（丙二醇單曱醚乙酸酯）：8 Ο , 0份 黏合劑樹脂（曱基丙烯酸苄酯/曱基丙烯酸共聚物）： 4. 7份 單體（三羥曱基丙烷三丙烯酸酯）·· 2 . 3份 光聚合引發劑系統成分1 ( 2 -酼基苯并噻唑）：0 . 8份 光聚合引發劑系統成分2 (對二曱胺基苯曱酸甲酯）：0 . 8 份 光聚合引發劑系統成分3 (米其勒酮）：0 . 8份 〈紅色圖像元件之形成〉 將所得之彩色抵抗劑旋塗於玻璃基板上得2微米之乾薄 膜厚度，隨後在8 0 °C下乾燥1 0分鐘。於暴露至U V射線以 使樹脂固化後，將基板在2 3 0 °C下加熱3 0分鐘進行交聯， 由此形成紅色圖像元件。 〈色度及對比之測量〉 使以上製得之具有紅色圖像元件之玻璃基板暴露至照 明器C，及使用分光光度計（「U4100」，Hitachi，Ltd.之 產品）測量透射光之色度。 接著將基板緊密夾於兩偏光板之間，及由利用亮度光度 計（「B Μ - 5 A」，T 〇 p c ο η之產品）所測得之當將偏光板平行 設置時之光強度Β (燭光/平方公分）對當將偏光板直角設 置時之光強度Α(燭光/平方公分）之比，使用下述方程式 (1 )計算對比。結果示於表1。 C=B/A (1) 使用利用前述測量所得之色度X，計算「4 Ο Ο Ο X - 2 0 0 0」， 43 326\專利說明書(補件)\94-02\93132145 1261689 及評估結果是否滿足以下的方程式（2 )。此等結果亦示於表 C ^ 40 OOx - 2 0 0 0 (實施例2 )Examples of azo yellow pigments include C. I. Pigment Yellow 1, C. I. Pigment, C. I. Pigment Yellow 1 0, C . I. Pigment Yellow 1 2, C. I. Pigment Yellow 1 3, C. I material yellow 1 4, C. I. Pigment Yellow 1 7 , C . I. Pigment Yellow 5 5, C. I. Pigment Yellow C. I. Pigment Yellow 8 3, C. I. Pigment Yellow 9 3, C. I. Pigment Yellow 9 4, C. I 12 326\Patent Specification (Replenishment)\94-02\93132145 1261689 Yellow Y5, C. I. Pigment Yellow 9 7 , C . I. Pigment Yellow 1 5 Ο, C. I. Pigment Yellow C. I. Pigment Yellow 1 6 6 , C . I. Pigment 1 6 7 and C. I · Pigment Yellow 1 800. Used alone or in combination of two or more thereof. Where C. I. Pigment Yellow 8 3 Pigment Yellow 1 5 0, and C. I. Pigment Yellow 180 is preferred, of which C. I. Yan 1 5 0 ( P . Y . 1 5 0 ) is particularly suitable because it can be easily converted into fine particles and is excellent in dispersibility, spectral transmittance, and fastness. The proportion of the pigment based on the total solid content in the pigment dispersion is usually from 10 to 90% by weight, preferably from 30 to 90% by weight, more preferably from 50% by weight. When the proportion of the pigment in the pigment dispersion is too small, the green pigment dispersion has a lower coloring power, and the film tends to have a relative color density. On the other hand, when the ratio is too large, the dispersion stability is lowered to cause problems such as re-agglomeration and thickening. In the present invention, the term "total content" means all ingredients except for the solvent to be described later. The mixing ratio of the red pigment and the azo yellow pigment is usually from 0 by weight of the azo yellow pigment relative to the 蒽S Kun red pigment. From 1 to 99%, preferably from 3 to 80% by weight, more preferably from 5 to 60% by weight. When the amount of the yellow pigment is less than the aforementioned range, the hue becomes close to blue, resulting in a decrease in transmittance (chromaticity Y in the X Y Z color scale system). On the other hand, when the amount of the azo yellow pigment is too large, the hue becomes close to yellow, and the red image element is not good. However, in the pigment dispersion of the present invention, when a ruthenium azo yellow pigment is used in combination as a pigment, another pigment can be used in combination without detracting from the advantages of the present invention. Examples of additional materials that can be used in combination include isoporphyrin pigments such as C. I. Pigment Yellow 1 3 9, C. 326\Patent specification (supplement)\94-02\93132145 13 15 4. It can, C. I material yellow stable system: 90% is too thick and will be solid 蒽醌 weight azo and guide surface, as a material and invention one face I · Yan 1261689 orange 6 6, C. I. Pigment Orange 6 9 and C. I. Pigment red 2 6 Ο, isoindolinone pigment such as C. I. Pigment Yellow 1 Ο 9, C. I. Pigment Yellow 1 1 Ο, C. I. Pigment Yellow 1 7 3 and C · I . The pigments are 161, and the fluorenone (q u i η o p h t h a 1 ο n e ) pigments such as C. I. Pigment Yellow 1 3 8. These pigments may be used singly or in combination of two or more. When another pigment is used in combination, the ratio thereof is adjusted to be 20% by weight or less based on the weight of the ruthenium red pigment, preferably 10% by weight or less. [1 - 2 ] Solvent In the pigment dispersion of the present invention, the solvent has a function of dissolving or dispersing a pigment, a dispersant, and other components to be added as needed, and adjusting the viscosity thereof. Clear examples of solvents include diisopropyl sulfonate, mineral spirits, n-pentyl alcohol, pentyl ether, ethyl octanoate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, positive Octane, V ars ο 1 # 2, A pc 〇# 1 8 solvent, diisobutylene, amyl acetate, butyl acetate, Apco diluent, dibutyl ether, diisobutyl ketone, methylcyclohexene, fluorenyl Mercapto ketone, propyl ether, dodecane, Socal solvent No. 1 and No. 2. Amyl decanoate, dihexyl ether, diisopropyl ketone, Solveso #15, acetic acid (positive, second 'third) butyl, hexapril, Shell TS28 solvent, gas butane, ethyl amyl ketone, Ethyl benzoate, chloropentane, ethylene glycol diethyl ether, ethyl ruthenate, decyl ketone, decyl butyl ketone, methyl hexyl ketone, decyl isobutyrate, benzonitrile, Ethyl propionate, mercapto cellosolve acetate, methyl isoamyl ketone, decyl isobutyl ketone, propyl acetate, amyl acetate, amyl formate, dicyclohexane, diethylene glycol monoethyl ether Acetate, dipentene, methoxymethylpentanol, decyl amyl ketone, methyl isopropyl ketone, propionate 326 \\ Patent Specification (supplement) \94-02\93132145 14 1261689 Ester, propylene glycol Third butyl ether 'mercaptoethyl ketone, thiol cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monoterpene ether , propylene glycol monoterpene ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoterpene ether, dipropylene glycol monoethyl ether acetate, 3-propoxypropionic acid 3-ethoxypropionic acid, 3-ethoxypropionate 曱6, 3-ethoxypropionic acid B-6, 3-methoxypropionic acid vinegar, 3-methoxypropionic acid B, 3-methoxy Propionic acid propionate, 3-methoxypropionic acid butyl, diglyme, ethylene glycol ester, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol Third butyl ether, 3-mercapto-3-hydroxybutanol, tripropylene glycol decyl ether and 3-mercapto-3-oxobutyl butyl acetate. These solvents may be used singly or in a mixture of two or more thereof. There is no particular limitation on the content of the solvent in the monolith pigment dispersion of the present invention, but the upper limit thereof is usually 99% by weight. When the content of the solvent exceeds 99% by weight, the ratio of the pigment and the dispersant becomes too small to form a dispersion. In view of the viscosity of the pigment dispersion, the lower limit of the solvent content is usually 70% by weight, preferably 75 % by weight, more preferably 80% by weight. [1 - 3 ] Dispersant As the dispersant, a polymer dispersant and/or a pigment derivative is suitably used. Examples of the polymer dispersant include an amino phthalate dispersant, a polyethyleneimine dispersant, a polyoxyethylene ethyl ether dispersion, a polyoxyethylene diester dispersant, and a sorbitan aliphatic Ester dispersant and aliphatic modified polyester dispersant. Specific examples of such a dispersing agent include "EFKA" (product of EFKAC hemica 1 s BV), "Disperbyk" (product of BYK-Chemie), 15 326\patent specification (supplement)\94-02\93132145 1261689 rDISPARLON" (product of Kusumoto chemicals), "SOLSPERSSE" (product of Zeneca), rKP" (product of Shin-etsu Chemical) and POLYFLOW (product of Kyoeisha Chemical). These polymeric dispersants may be used singly or in combination of two or more thereof. The proportion of the polymer dispersant based on the total solid content of the pigment dispersion is usually from 10 to 90% by weight, preferably from 10 to 70% by weight, more preferably from 10 to 50% by weight. When the proportion of the polymer dispersant in the pigment dispersion is too large, the relative decrease in the proportion of the pigment causes deterioration of the coloring power, and the film thickness tends to be large with respect to the color density. On the other hand, when the proportion of the polymer dispersant is too small, the dispersion stability is lowered and problems such as re-agglomeration and thickening are caused. Examples of the pigment derivative include azo, octacycline, 啥σ丫σding ketone, benzimidazolone, quinacridone, isoindolinone, bismuth well, hydrazine, indanthrene,茈, purple ring S (peri η ο ne ) and diketone 1 ^ D each ϋ 咯 咯 颜料 pigment. In the present invention, it is preferred to use a pigment derivative such as hydrazine or an azo pigment because it is of a type similar to that used as a pigment. These pigment derivatives may be used singly or in combination of two or more thereof. Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonylamino group or a fourth salt thereof, a quinone imine methyl group, a dialkylamine alkyl group, a hydroxyl group, a carboxyl group, and a guanamine group. These substituents are each attached to the pigment structure either directly or via a linking group such as an alkyl, aryl or heterocyclic group. As the substituent of the pigment derivative, the sphagnum amine or the fourth salt thereof and the acid-reducing group are preferred, and the rhein group is more preferred. A plurality of such substituents may be linked to a pigmentary structure, or a mixture of compounds having a different number of substituents may be used in the 16 326\patent specification (supplement)\94-02\93132145 1261689. Specific examples of the pigment derivative include a carboxylic acid derivative of an azo pigment and a sulfonic acid derivative of an anthraquinone pigment. The proportion of the pigment derivative based on the total solid content of the pigment dispersion is usually from 0. 1 to 20% by weight, from 0. It is preferably 5 to 15% by weight, more preferably 1 to 10% by weight. When the proportion of the pigment derivative in the pigment dispersion is too small, the dispersion stability is lowered and problems such as re-agglomeration and thickening are caused. On the other hand, when it is too large, its contribution to dispersion stability is already saturated, and the color purity sometimes decreases by an amount. Therefore, the ratio outside the aforementioned range is not good. In the present invention, even when a polymer dispersant and a pigment derivative are used in combination as a dispersing agent, no problem occurs. [1-4] Another component The other component to be added to the pigment dispersion of the present invention as needed is not particularly limited. However, when the pigment dispersion of the present invention is added to the colored resin composition of the color filter to be described later, the pigment dispersion of the present invention may contain some binder resin which will be described later, since In the case of the pigment dispersion of the present invention, it can improve dispersion stability. In this case, the amount of the binder resin is preferably from 5 to 100% by weight, particularly preferably from 10 to 80% by weight, based on the total amount of the pigment in the pigment dispersion. The amount of the binder resin of less than 5% by weight is not sufficient to improve the dispersion stability. On the other hand, an amount exceeding 100% by weight causes a decrease in the pigment concentration and a sufficient color density cannot be obtained. [1 - 5 ] Particle size distribution of pigments 17 326 \ Patent specification (supplement) \94-02\93132145 1261689 In the pigment dispersion of the present invention, the particle size of the pigment is 30 nm or more, 50 nm Preferably, 80 nm or more is preferred, but 500 nm or less, 350 nm or less is preferred, and 250 nm or less is more preferred. The half value of the width of the particle size distribution is 2,500 nm or less, preferably 150 nm or less, and more preferably 100 nm or less. In the present invention, excellent depolarization effect and high contrast can be achieved by using a specific pigment in combination and adjusting the particle size to fall within the aforementioned predetermined range. It is important to adjust the particle size, especially the half width value, to fall within the foregoing range, and the excellent depolarization effect and high contrast of the present invention cannot be achieved outside the foregoing range. [1 - 6 ] Method for Producing Pigment Dispersion Although various methods can be used to prepare the pigment dispersion of the present invention to achieve the aforementioned particle size distribution, the bead grinding method in which the pigment is dispersed by the collision of hard balls (beads) is especially appropriate. The beads used herein may be made of glass, argon (Zr 0 2 ), chromium, and the like. Among them, beads made of zirconium oxide are suitable because they have a high specific gravity and contain less contaminants such as abrasive powder. The beads which can be used herein generally have an average particle size of from 30 to 500 μm, preferably from 30 to 300 μm, more preferably from 40 to 200 μm. Beads having an average particle size of less than 30 microns are too small to produce sufficient collision energy without sufficient dispersibility. On the other hand, beads having a particle size larger than 500 μm are not suitable for converting the morphology of the pigment into fine particles because the void volume between the beads is too large. In addition, each bead weight and pigment inevitably accept excessive collision energy, making it difficult to reduce the particle size of the pigment to within the range of 30 to 500 nm. 18 326\Patent specification (supplement)\94-02\93132145 1261689 Any dispersing machine can be used for the dispersion treatment as long as it can use the aforementioned beads. Examples include the batch system "T 0 RUS Μ ILL" (product of G etzma η η), the continuous system "A gltator M i 1 1" (product of A shizawa Finetech), and "Pico can ( Pico mill) (product of Asada Iron Works) and "Apex mega" (product of KEMCO). Although the preparation step of the pigment dispersion liquid is not particularly limited, the dispersion using the aforementioned dispersion system is carried out during the preparation of the pigment dispersion liquid. For example, by dispersing a dispersion component such as the aforementioned pigment, dispersant, solvent and, if desired, a binder resin to form a liquid mixture, and then dispersing the resulting mixture by beads in the aforementioned disperser, The desired pigment dispersion is obtained. Although there is no particular limitation on the amount of the beads to be used, the beads are preferably used in an amount of from 50 to 90% by volume of the container volume of the dispersing machine for dispersion treatment. When the amount of beads packed in the dispersion machine is too small, it takes a long time to obtain a pigment dispersion having a desired particle size distribution. On the other hand, when it is too large, it becomes a burden on the dispersing machine, and at the same time the beads are broken and the pigment has a broad particle size distribution. Prior to such dispersion using beads having an average particle size of from 30 to 500 microns, pretreatment such as dispersion, or use up to 500 microns or more may be carried out in a roll mill or kneader. The average particle size of the beads is dispersed. Alternatively, the pigment dispersion thus prepared can be subjected to post-treatment, for example, using "T. K. Filmics (product of Tokushu Kika Kogyo) or rUlti 丨 naizer (product of Sugino Machine). [2] Color Resin Composition 19 326\Patent Specification (Supplement)\94-02\93132145 1261689 Next, the coloring resin composition of the present invention will be described. The pigment dispersion of the present invention can be used in various applications. It is especially suitable for a color resin composition which is intended to form, for example, an image of an image element of a color filter or a light sheet. In addition to the pigment dispersion of the present invention, the colored resin composition may further comprise a binder resin, a monomer, a photopolymerization initiator, and another solid component. Next, each component will be explained. [2 - 1 ] Examples of the binder resin binder resin include homopolymers such as (meth)acrylic acid, (meth) acrylate, (mercapto) acrylamide, maleic acid, (meth) propylene Nitrile, styrene, vinyl acetate, dichloroethylene and maleimide, a copolymer comprising the monomer, polyethylene oxide, polyvinylpyrrolidone, polyamine, polyamine hydrazine Acid ester, polyester, polyether, polyethylene terephthalate, acetonitrile cellulose, phenolic epoxy (η 〇v ο 1 ac ) resin, resol phenolic resin, polyvinyl phenol and polyethylene Butyral. In the present invention, the term "(meth)acrylic acid" means both acrylic acid and mercaptoacrylic acid. The same applies to (mercapto) acrylate and (meth) propylene sulfhydryl groups. The term "(co)polymer" refers to both a single polymer (homopolymer) and a copolymer, and the term "acid" refers to both an acid and an anhydride thereof. In the present invention, the term "acrylic resin" means a (co)polymer comprising (mercapto)acrylic acid and a (co)polymer comprising a carboxyl group-containing (fluorenyl)acrylate. Among the above-mentioned binder resins, an acrylic resin having a monomer having a carboxyl group or a phenolic hydroxyl group in its side chain or main chain is preferred. The use of an acrylic resin having such a functional group as a binder resin can be developed in an alkaline solution when a color filter is produced. Carboxyl group-containing acrylic resin such as propylene 20 326\patent specification (supplement)\94-02\93132145 1261689 acid (co)polymer, and anhydride-modified resin such as styrene-maleic anhydride resin and The phenolic epoxy epoxide acrylate is more preferred because it can be developed in a highly alkaline solution. A (co)polymer comprising (fluorenyl)acrylic acid and a (co)polymer comprising a carboxyl group-containing (fluorenyl) acrylate are particularly preferred. These acrylic resins are advantageous in that they have excellent development properties and transparency, and can be prepared by using them in combination with various monomers, and the processes thereof can be easily controlled. The acrylic acid-based resin system as a binder resin is used, for example, a (co)polymer mainly comprising the following monomers. Examples of the monomer include compounds obtained by adding an acid or an acid anhydride to a (hydroxy) hydroxyalkyl acrylate. (Hydroxyl) hydroxyalkyl acrylates include (fluorenyl) acrylic acid, succinic acid (2-(indenyl) propylene oxide), adipic acid (2-propylene oxirane), citric acid (2 - ( Mercapto) propylene oxide, hexahydrophthalic acid (2-(fluorenyl) propylene oxy) ester, maleic acid (2-(fluorenyl) propylene oxy) ester, succinic acid ( 2-(indenyl)propenyl propyl acrylate, adipic acid (2-(methyl) propylene oxypropyl) ester, hexahydrofuric acid (2-(indenyl) propylene oxypropyl) ester, citric acid (2-(indenyl) propylene oxypropyl) ester, maleic acid (2-(indenyl) propylene oxypropyl) ester, succinic acid (2-(indenyl) propylene oxy butyl) ester, Diacid (2-(indenyl) propylene oxy butyl) ester, hexahydrofuric acid (2-(indenyl) propylene oxy butyl) ester, citric acid (2-(indolyl) propylene oxybutyl) And maleic acid (2-(indenyl) propylene oxybutyl) ester. The acid (anhydride) includes succinic acid (succinic anhydride), citric acid (phthalic anhydride), and maleic acid (maleic anhydride). Examples of the monomer to be copolymerized with the aforementioned monomer include styrene monomers such as styrene, α-styrene, and vinyl fluorene; carboxylic acid containing unsaturated groups 21 326\patent specification (supplement)\94 -02\93132145 1261689 such as cinnamic acid, maleic acid, fumaric acid, maleic anhydride and itaconic acid; (meth) acrylate such as bismuth (mercapto) acrylate, Mercapto) ethyl acrylate, propyl (mercapto) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxy (meth) acrylate Ethyl ester, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, and (methoxy) methoxy acrylate, via lactones such as ε - hexane PCT, PCT/A acrylonitrile such as acrylonitrile and mercapto acrylonitrile; acrylamide such as (A) Acrylamide, hydrazine-hydroxymethyl acrylamide, hydrazine, hydrazine-dimercapto acrylamide, hydrazine-mercaptopropenyl morpholine Ν, Ν-dimethylaminoethyl (mercapto) acrylate, and hydrazine, hydrazine-dimethylaminoethyl acrylamide; and vinyl esters such as vinyl acetate, tetradecene carbonate (ν iny 1 Versatate), ethyl propionate, ethyl cinnamate and trimethylacetate. The binder resin for improving the strength of the film coated on the substrate is obtained by copolymerizing at least one monomer (a) selected from the following exemplary monomers with at least one monomer (b) selected from the following exemplary monomers; The acrylic resin obtained by polymerization is particularly preferred. Monomer (a): a phenyl group-containing monomer such as styrene, α-mercaptostyrene, (benzyl)acrylic acid, hydroxyphenyl (meth) acrylate, decyl phenyl acrylate, Hydroxyphenyl (fluorenyl) acrylamide and hydroxyphenyl (mercapto) propylene sulfonamide. Monomer (b): (mercapto)acrylic acid and carboxyl group-containing (fluorenyl) acrylate such as (2-(fluorenyl) propylene oxy ethoxide) succinic acid, adipic acid (2-propylene oxirane ethyl ester, Capric acid (2-(indenyl)propene oxime), hexahydrofurfuric acid (2-(methyl) 22 326\patent specification (supplement)\94-02\93132145 1261689 propylene oxime), And maleic acid (2-(indenyl) propylene oxide). The monomer (a) is usually added in an amount of from 10 to 98 mol%, preferably from 20 to 80 mol%. 30 to 70% of the molar % is better, and the monomer (b) is usually added in an amount of 2 to 90% by mole, preferably 20 to 80% by mole, and 30 to 70 moles. It is preferable that the binder resin has an acrylic resin having an ethylenic double bond in its side chain, and the use of the resin improves the photocurability of the colored resin composition of the present invention, thereby enabling analysis. And further improvement of adhesion between the image element according to the second aspect of the present invention and the substrate of the color filter. Examples of the method of introducing an olefinic double bond to the side chain of the acrylic resin include Japanese Patent Publication No. 3 4 4 4 3 / 1 9 7 5 and Japanese Patent Publication No. 3 4 4 4 4 / 1 9 7 5: (1) making a carboxyl group of an acrylic resin and having a glycidyl group a method of reacting a compound of both an epoxycyclohexyl group and a (fluorenyl)propenyl group, and (2) a method of reacting a radical of an acrylic resin with a chlorinated acid. The acrylic resin having an ethylenic double bond in the chain can be obtained by subjecting a carboxyl group-containing or hydroxyl group-containing acrylic resin to a glycidyl group such as (mercapto)acrylic acid, propyl glycidyl ether, and α-ethyl acrylate glycidol. S, crotonyl glycidyl _, (iso)crotonic acid glycidyl sulfonate, (mercapto)acrylic acid (3,4-epoxycyclohexyl) decyl ester, chlorinated (hydrazino) acrylate or (methyl) Prepared by reacting a compound of propylene gas by reacting a carboxyl group- or hydroxyl group-containing acrylic resin with an alicyclic epoxy compound such as (3,4-epoxycyclohexyl) decyl (meth) acrylate. The compound is particularly preferred. Regarding the aforementioned introduction of an olefinic double bond to a carboxy group Or hydroxy propyl 23 326\patent specification (supplement) \94-02\93132145 1261689 a method in an olefinic resin, which bonds a compound having an ethylenic double bond to 2 to 50 mol%, and 5 to 40 Preferably, the carboxy or hydroxy group is preferably a carboxy group or a hydroxy group. Preferably, the carboxyl group content is in the range of 5 to 200 mg Κ Η 酸 based on the acid value. When the acid value is less than 5 mg Κ Ο Η / In the case of gram, the resin is insoluble in the alkaline developer. On the other hand, an acid value of more than 200 mg Κ Η / 克 sometimes lowers the development sensitivity. The weight average molecular weight of the acrylic resin measured by GPC ( M w ) is preferably from 1,0 0 0 to 1 0 0,0 0 0. When the weight average molecular weight is less than 1,0 0 0, the resulting colored resin composition cannot be uniformly coated. A weight average molecular weight of more than 100,0 0 has a tendency to lower the developing property. The binder resin is usually added in an amount of from 10 to 80% by weight, preferably from 20 to 70% by weight, based on the total solid content of the colored resin composition of the present invention. [2-2] Monomer Any polymerizable low molecular compound can be used as the monomer contained in the colored resin composition. A compound having at least one ethylenic double bond and capable of undergoing addition polymerization (hereinafter simply referred to as "rare compound") is preferred. When the colored resin composition of the present invention is exposed to an active ray, the rare compound undergoes addition polymerization and is cured by the action of a photopolymerization initiator system which will be described later. In the present invention, the term "monomer" means a substance relative to a so-called polymer substance. Therefore, it includes not only narrowly defined monomers, but also dimers, trimers, and oligomers. Examples of the olefinic compound include an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid and a monohydroxy compound, an ester of an aliphatic poly-based compound and an unsaturated acid retardant, and an aromatic 24 326\patent specification (supplement)\94-02 \93132145 1261689 an ester of a polyhydric compound and an unsaturated carboxylic acid, an ester obtained by esterification of an unsaturated carboxylic acid and a polycarboxylic acid with a polyhydroxy compound such as an aliphatic polyhydroxy compound or an aromatic polyhydroxy compound, And an olefinic compound having an amino phthalate structure obtained by reacting a polyisocyanate compound with a hydroxy compound containing a (fluorenyl) acrylonitrile group. Examples of the aliphatic poly-based compound and the unsaturated traconic acid include acrylate such as ethylene glycol diacrylate, triethylene glycol diacrylate, trishydroxypropyl propane triacrylate, and trishydroxyl Ethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, diisopentaerythritol tetraacrylate, diisopentaerythritol pentaacrylate, diiso Pentaerythritol hexaacrylate and glycerin acrylate; and mercapto acrylate, itaconate, which are prepared by using methacrylic acid, itaconic acid, crotonic acid, maleic acid instead of the acrylic portion of the acrylate, respectively. Crotonate, and maleate. Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimercapto acrylate, resorcinol diacrylate, resorcinol dimercapto acrylate, and gallic phenol trisole. Acrylate. The ester obtained by esterification of an unsaturated carboxylic acid and a polycarboxylic acid with a polyhydroxy compound may not necessarily be a single substance but a mixture. Typical examples include condensates of acrylic acid, citric acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, methacrylic acid, condensates of citric acid and pentaerythritol, and acrylic acid, a condensate of adipic acid, butylene glycol and glycerin. 25 3 26\patent specification (supplement)\94-02\93132145 of an olefinic compound having an amino phthalate structure prepared by reacting a polyisocyanate compound with a hydroxy compound containing a (fluorenyl) acrylonitrile group Examples of 1261689 include aliphatic diisocyanates such as hexamethylene diisocyanate or tridecyl hexane diisocyanate, alicyclic diisocyanates such as cyclohexane diisocyanate or isophorone diisocyanate, or aromatic Diisocyanates such as ti~ilene diisocyanate or diphenyldecane diisocyanate and hydroxy compounds containing (fluorenyl) acrylonitrile groups such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3 - a reaction product between -hydroxytripropenyloxymethyl)propane or 3-hydroxy(1,1,1-trimercaptopropenyloxymethyl)propane. Examples of the olefinic compound other than the aforementioned olefinic compound include acrylamide such as ethylene bis acrylamide; allyl ester such as diallyl phthalate; and vinyl containing compounds such as divinyl phthalate. The monomer is usually added in an amount of from 10 to 80% by weight, preferably from 20 to 70% by weight, based on the total solid content of the colored resin composition of the present invention. [2-3] Photopolymerization Initiator System When the colored resin composition of the present invention contains a rare compound as the above-mentioned monomer component, the addition has a decomposition reaction or hydrogen abstraction reaction and polymerization activity by direct absorption of light or photosensitization. A photopolymerization initiator system component which functions as a radical is preferred. The "photopolymerization initiator system component" as used herein means a mixture of a photopolymerization initiator, an accelerator, and an additive such as a sensitizing pigment. Examples of the photopolymerization initiator constituting the photopolymerization initiator system include a metal bicyclopentane (meta 1 1 〇cene ) compound, such as described in Japanese Laid-Open Patent No. 1 5 2 3 9 6 / 1 9 8 4 and 1 a dicyclopentadienyl titanium compound in 5 1 1 9 7 / 1 9 8 6; a radical activator such as hexaaryldiimidazole derived from Japanese Laid-Open Patent Publication No. 3 9 5 03 / 1 9 9 8 Substance, dentate-s-three-sigma well derivative 26 326\patent specification (supplement)\94-02\93] 32145 1261689 substance, N-aryl-α'-amino group S such as N-phenylglycol Acid, N-aryl-α-amino acid salt and Ν-aryl-α-amino acid ester; α-aminoalkyl phenone compound; and as disclosed in Japanese Laid-Open Patent No. 2000-80 Ester ester initiator in 0 6 8 . Specific examples of the polymerization initiator which can be used in the present invention include: a halogenated tri-negative derivative such as 2-(4-oxophenyl)-4,6-bis(trichloroindenyl)-s-three tillage 2-(4-oxo-naphthyl)-4,6-bis(trichloroindenyl)-s-trisole, 2-(4-ethoxynaphthyl)-4,6-bis(trichloroindenyl) )-s-three tillage and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trimethylhydrazinyl)-s-three spray; halogenated oxadiazole derivatives such as 2-trichloro Mercapto-5 - ( 2 '-benzofuranyl)-1,3,4-oxadiazole, 2-trimethylsulfonyl-5-[stone-(2'-benzofuranyl)vinyl]- 1,3,4-oxadiazole, 2-trichloroindolyl-5-[yS-(2,-(6"-benzofuranyl)vinyl)]-l,3,4-oxadiazole and 2-tris-decyl-5-furyl-1,3,4-oxadiazole; imidazole derivatives such as 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2 - ( 2 '-chlorophenyl)-4,5-bis(3 '-nonyloxyphenyl)imidazole dimer, 2 - ( 2 '-fluorophenyl)_ 4,5 -diphenylimidazole dimerization 2,( 2 '-indolylphenyl)-4,5-diphenylimidazolium dimer and (4'-nonyloxyphenyl)-4,5-diphenyl Dimers; benzoin alkyl ethers such as benzoin decyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; anthracene derivatives such as 2-mercaptopurine, 2-ethylhydrazine醌, 2 - tert-butyl oxime and 1-chloropurine; diphenyl ketone derivatives such as diphenyl ketone, Mich 1 er ' s ketone, 2-nonyldiphenyl Ketone, 3-mercaptodiphenyl ketone, 4-nonyldiphenyl ketone, 27 326\patent specification (supplement)\94-02\93132145 1261689 2 -chlorodiphenyl ketone, 4 -bromodiphenyl Ketones and 2-carboxydiphenyl ketones; acetophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl Phenyl ketone, α-hydroxy-2-indolyl phenylacetone, 1-hydroxy-1-methylethyl-(p- cumyl) ketone, 1-hydroxy-1-(p-dodecylphenyl) ketone , 2-methyl-(4-(methylthio)phenyl)-2-pyrene 17-linyl-1-propanone and 1,1,1-trichloroindolyl-(p-butylphenyl)one; -oxydibenzothiazepine compounds such as 9-oxodibenzothiopyran, 2-ethyl-9-oxodibenzothiazepine, 2-isopropyl-9-oxodibenzo Slightly sulphate, 2-chloro-9-oxodibenzothiopyran, 2,4-dimercapto-9-oxodibenzothiopyran, 2,4-diethyl-9-oxodibenzothione And 2,4-diisopropyl-9-oxydibenzine thiopyran, a benzoate derivative such as ethyl p-nonylaminobenzoate and p-diethylaminobenzoate; Acridine derivatives such as 9-phenyl acridine and 9-(p-oxophenyl) acridine; η well derivatives such as 9,10-dimercaptobenzophenone oxime; anthrone derivatives such as benzene And anthracene; dicyclopentadienyl titanium derivatives such as di-cyclopentadienyl-T i -di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl -Ti-bis-2,3,4,5,6-penta-benzene-1-yl, di-cyclopentadienyl-ti_bis-2,3,5,6-tetrafluorophenyl-1-yl , di-cyclopentadienyl-Ti-bis-2,4,6-trioxaphenyl-1-yl, di-cyclopentadienyl-Ti_2,6-di-fluorophenyl-1-yl, di- Cyclopentadienyl-Ti-2,4-di-fluorophenyl-1-yl, bis-indolylcyclopentadienyl-but-1-bis-2,3,4,5,6-pentafluorobenzene- 1-yl, bis-fluorenylcyclopentadienyl-buteb-bis-2,6-diphenyl-buyl and di-cyclopentadienyl-Ti-2,6-di-s--3-(pyl - L-yl)-phenyl-1-yl; 326\Patent Specification (supplement)\94-02\93 ] 32145 28 1261689 α-Amine alkyl phenone compounds such as 2-indolyl-1 - [ 4 -(曱Thiothio]-2-ifosyl sulphide-1-one, 2-pyristyl-2-diamido-1-(4-phenyl)butanone-2-diguanidin-1- (4-Imfolin Benzene J -1- ketone, 4-diguanamine ethyl benzoate, 4-diaminoaminoisoamyl ester, 4-diethylaminoacetophenone, 4-II Amidoxime, 2-ethyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene J ketone, 7-diethylamino-3 (4-diethylaminophenylhydrazine), oxacin, 4-(diethylamino)chalcone; and oxime ester compounds such as 1,2-octanedione, 1-[4-]-benzene Thio)phenyl]-2-(0-phenylhydrazinyl), 2-ethoxy-1,2-diphenylethanone, 1-yl-6-(2-mercaptophenylhydrazino)-9H -oxazol-3-yl], and 1-(0-肟). As the accelerator constituting the component of the photopolymerization initiator system, > alkyl dialkylaminophenyl phthalate such as N,N-diammonium benzoate ethyl ester heterocyclic compound such as 2-mercaptobenzothiazole , 2-nonylbenzomercaptobenzimidazole, and an aliphatic polyfunctional thiol compound. These photopolymerization initiators and accelerators may each be used singly or in combination of both. Specific examples of the components of the photopolymerization initiator system include, for example, the description of Chemical (Fine Chemical) (Vol. 20, No. 4, 19 9 1 曰) Dialkyl acetophenone derivatives, benzoin 9-oxodibenzothiopyran derivatives on pages 16 to 26, as described in Japanese Patent Publication No. 4 03 3 2 3 / 1 9 8 3 and Japanese Patent Publication No. 3 7 3 7 7 / 1 9 7 No. 2 imidazole derivatives and S-Trisinyl tri-derivatives, and combinations 326\ patent specification (supplements) ) \94-02\93132145 29 ) Benzofenebine) Butylphthalic acid hexyl group ^) Cyclohexyl and - [9-Ethyl fluorenyl group has N, N-, and contains and 2 - above "Fine March 1 Biological and sixth aryl double-ring 1261689 pentadienyl titanium, dibenzopyran pigment, and a system having an amine group or a urethane group and capable of undergoing addition polymerization of an ethylenic saturated double bond-containing compound The photopolymerization initiator system component is usually 0 in terms of the total solid content of the colored resin composition of the present invention. Add 1 to 30% by weight to 0. 5 to 20% by weight is preferred, 0. 7 to 10% by weight is more preferable. When the amount is too small, it sometimes causes a decrease in exposure sensitivity, and when the amount is too large, the solubility of the unexposed portion in the developer is lowered, which causes development failure. If desired, the photopolymerization initiator system component may contain a sensitizing dye depending on the wavelength of the image exposure source to enhance the sensitivity of the reaction. Examples of such sensitizing dyes include dibenzopyran pigments as described in Japanese Laid-Open Patent Publication No. 2 2 1 5 5 8 / 1 9 9 2 and 2 1 9 7 5 6 / 1 9 9 2, as illustrated a heterocyclic-containing scavenger pigment in Japanese Laid-Open Patent Publication No. 2 3 9 7 0 3 / 1 9 9 1 and 2 8 9 3 3 5 / 1 9 9 3; as disclosed in Japanese Laid-Open Patent No. 2 3 9 3 - keto-encain-based compound of 7 0 3 / 1 9 9 1 and 289335/1993; as described in Japanese Laid-Open Patent Publication No. 1 9 2 4 0 / 1 9 94, And as disclosed in Japanese Laid-Open Patent No. 2 5 2 8 / 1 9 7 2 and 1 5 5 2 9 2 / 1 9 6 9 , Japanese Patent Publication No. 3 7 3 7 7 / 1 9 7 0, Japanese Public Patent 8 8 1 8 3 / 1 9 7 2, 112681/1977, 15503/1983, 88005/1985, 56403/1984, 69/1990, 168088/1982, 107761/1993, 210240/1993 and 2 8 8 8 1 8 A coloring agent having a dialkylaminobenzene structure in / 1 9 9 2 . Among these sensitizing dyes, an amine-based dye is preferred, and a compound having both an amine group and a phenyl group in one of the molecules is more preferable. Examples of particularly preferred dyes include diphenyl ketone compounds such as 4,4 '-diguanidinodiphenyl ketone, 4,4'-diethylaminodiphenyl ketone, 2-aminodiphenyl ketone, 4 -amino 30 326\patent specification (supplement)\94-02\93132145 1261689 diphenyl ketone, 4,4'-diaminodiphenyl ketone, 3,3'-diaminodiphenyl ketone and 3,4-diaminodiphenyl ketone; and a compound containing p-dialkylamine phenyl such as 2-(p-diamine phenyl)benzoxazole, 2-(p-diethylamine phenyl)benzene crocodile Oxazole, 2-(p-diamine phenyl)benzo[4,5]benzoxazole, 2-(p-diamine phenyl)benzo[6,7]benzoxazole, 2,5- Bis(p-diethylamine phenyl)-1,3,4-: azole, 2-(p-diamine phenyl)benzothiazole, 2-(p-diethylamine phenyl)benzothiazole, 2- ( P-diamine phenyl) benzimidazole, 2-(p-diethylamine phenyl) benzimidazole, 2,5-bis(p-diethylamine phenyl)-1,3,4-thiadiazole, ( P-diamine phenyl) ° pyridine, (p-diethylamine phenyl) anthopidine, (p-diamine phenyl) 啥 σ lin, (p-diethylamine phenyl) 啥 σ lin, (pair two Indole phenyl) Pyrimidine (p-phenyl diethylamine). Among them, 4, 4'-dialkylaminodiphenyl ketone is preferred. These sensitizing dyes may be used singly or in combination of two or more thereof. The proportion of the sensitizing dye in the colored resin composition of the present invention is usually from 0 to 20% by weight, based on the total solid content of the colored resin composition. 2 to 15% by weight is preferred, from 0. 5 to 10% by weight is more preferable. [2 - 4 ] Another solid component The colored resin composition of the present invention may contain another solid component other than the above components as needed. Examples thereof include a surfactant, a thermal polymerization inhibitor, a plasticizer, a storage stabilizer, a surface protectant, an adhesion improver, and a development improver. As the surfactant, various surfactants such as anionic, cationic, nonionic and amphoteric surfactants can be used, but nonionic surfactants are preferred because they are less likely to adversely affect various properties of the resin composition. Based on the total solid content of the colored resin composition, the ratio of surfactant 31 326\patent specification (supplement)\94-02\93132] 45 1261689 is usually from 0. 0 0 1 to 10% by weight, preferably from 0. 0 0 5 to 1% by weight, preferably from 0. 0 1 to 0. 5 wt% is better, from 0. 0 3 to 0. 3 wt% is the best. As the thermal polymerization inhibitor, hydrogen acid, anti-oxygen S, gallium S, catechu S, 2,6-t-butyl-p-quinone and /3-naphthoquinone can be used. It is preferably added in the range of from 0 to 3% by weight based on the total solid content of the colored resin composition. For the plasticizer, use 3 major acid dioctyl vinegar, S too acid di-dodecane S, triethylene glycol dicaprylate, dimethyl glycol phthalate, triterpene phosphate, hexa Dioctyl acid ester, dibutyl sebacate or triethylene glycerol. It is preferred to add it in an amount of from 10% by weight or less based on the total solid content of the colored resin composition. [2 - 5 ] Preparation of a colored resin composition To prepare a colored resin composition of the present invention, a predetermined amount of the solvent and the binder resin, and optionally a monomer, a photopolymerization initiator system component, And another component is added to the above-described pigment dispersion of the present invention to prepare a homogenous dispersion. Since the fine dust powder is mixed in the dispersion or the mixture during its formation, it is preferred to filter the colored resin composition thus obtained to remove it. In the coloring resin composition of the present invention, the solvent content is preferably in the range of from 70% by weight to 99% by weight, based on the reason for the solvent content in the pigment dispersion, from 7 5 It is especially preferred to weigh from 90% by weight. The coloring resin composition of the present invention 32 326\patent specification (supplement)\94-02\93132145 1261689 prepared by mixing and dispersing components such as the pigment dispersion liquid, the solvent and the binder resin of the present invention. The particle size distribution of the pigment contained in the colored resin composition is substantially the same as the distribution in the pigment dispersion. Therefore, the aforementioned particle size can be maintained. When a red image element is formed on a glass substrate by using the colored resin composition prepared in this manner, a comparison C calculated according to the following equation (1): C = B/A (1) where A and B respectively Representing the light intensity measured by the brightness photometer when the glass substrate is sandwiched between the two polarizing plates and the two polarizing plates are disposed at right angles and when the two polarizing plates are arranged in parallel, and when the illuminator C is exposed, the spectrophotometer is used. The measured chromaticity X of the transmitted light satisfies the following equation (2): C$ 4 0 0 0 x - 2 0 0 0 ( 2 ), wherein the red image element thus formed has a high contrast. In C < 4 0 0 0 X - 2 0 0 0, the contrast of the red image elements is low and light leakage occurs on the black display, resulting in degradation of image quality. In the colored resin composition of the present invention, the comparison C and the chromaticity X satisfy the following equation (2 - 1), and the following equation (2 - 2) is more preferable. C$ 4 0 0 0 x- 1 8 0 0 ... (2-1 ) C ^ 4 0 0 0 x - 1 4 0 0 (2-2) [3] Color filter, light sheet The following will explain the present invention. Color filter. The color filter is produced by disposing a black matrix on a transparent substrate and then continuously forming red, green, and blue image elements, the order of which is not limited thereto. In the production of such a color filter, the composition of the present invention is used as a coating solution for forming a red image element, using the 33 326 \patent specification (supplement) \94-02\93132145 1261689 color resin composition. The image elements of the respective colors are formed by applying a black resist to the transparent substrate, or applying a red, green or blue resist to the surface of the resin black matrix formed over the transparent substrate or using a chromium compound or another light-shielding metal material. The surface of the metal black matrix is then formed by heat drying, imagewise exposure, development and thermal curing. [3 - 1] Transparent substrate (support) Any material can be used as a transparent substrate of a color filter as long as it is transparent and has appropriate strength. Examples of materials include thermoplastic resins such as polyester resins, for example, polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, poly(decyl methacrylate), and poly A sheet made of sulfone; a sheet made of a thermosetting resin such as an epoxy resin, an unsaturated polyester resin, and a poly(fluorenyl)acrylic resin; and various glasses. Among them, glass and a heat-sensitive resin are preferable in consideration of heat resistance. If necessary, the transparent substrate or the substrate on which the black matrix is formed may be subjected to corona discharge treatment, ozone treatment, or a film formation treatment using a decane coupling agent or a resin such as an amino phthalate resin to improve surface physical properties including adhesion. . The thickness of the transparent substrate is usually from 0.5 to 10 mm, preferably from 0.1 to 7 mm. When a film is formed using a resin, the thickness thereof is usually from 0.01 to 10 μm, preferably from 0.05 to 5 μm. [3 - 2] Black matrix A black matrix is formed on a transparent substrate using a light-shielding metal film or a colored resin composition of a black matrix. Examples of the light-shielding metal material include chromium compounds such as metallic chromium, chromium oxide, and chromium nitride, and nickel-tungsten alloys. Material 34 326\Patent Specification (Repair)\94-02\93132145 1261689 Stacking of multiple layers. The black matrix can be formed by forming the metal light-shielding film by sputtering, forming a desired pattern over the film through the positive photoresist, using mixed ammonium nitrate (IV) and perchloric acid and/or nitric acid. The I insect engraving agent is engraved or another material is engraved with a suitable insect engraving agent, and then the positive photoresist is stripped by a special release agent. In the foregoing case, a film of a metal or metal metal oxide is formed on a transparent substrate via deposition or subtraction. Next, after forming a film of the colored resin composition on the film, the resulting film is exposed and developed through a mask having a repeating pattern such as a stripe, a mosaic or a triangle. A black matrix can also be formed by the film formed by the remainder. When a colored resin composition of a black matrix is used, the black matrix is formed by using a colored resin composition containing a black material. It is expressly stated that the black matrix may comprise one or more black materials such as carbon black, graphite, iron black, aniline black, cyanine black and titanium black via use or comprise a mixture of red, green and blue pigments or optionally selected from inorganic or A colored resin composition of a black material obtained by dyeing an organic dye, and formed by a method similar to that described above for forming a red, green or blue image element. [3 - 3] Formation of image element [3 - 3 _ 1 ] Formation of film A colored resin composition containing a colored material (pigment) selected from one of red, green and blue materials is coated thereon to form black A transparent substrate of the substrate. After drying, the photomask is placed on the formed film, and the image is exposed through the photomask, developed and thermally cured or photocured if necessary, in the form of 35 326\patent specification (supplement)\94·02 \93132145 1261689 An image component that forms the color layer of the image element. The color filter image can be formed by performing the aforementioned operations on the three colored resin compositions of red, green, and blue. The colored resin composition of the color filter can be applied to the transparent substrate by a rotator method, a w bar coating method, a flow coating method, a die coating method, a roll coating method or a spray coating method. Among them, the oral mode coating method is preferable because it can greatly reduce the amount of the coating solution used, and it is not affected by the fog which will adhere when the spin coating method is used in other cases. Therefore, the generation of foreign substances can be suppressed. When the film of the colored resin composition is too thick, it interferes with the smooth pattern development and the gap adjustment in the liquid crystal lattice forming step, and the too thin film sometimes interferes with the performance of the desired color due to difficulty in increasing the pigment density. The thickness of the film is preferably from 0.2 to 20 μm, more preferably from 0.8 to 5 μm, even more preferably from 0.8 to 5 μm. [3 - 3 - 2 ] Drying of the film It is preferable to dry the film formed by applying the colored resin composition to the transparent substrate using a hot plate, an I R oven, a convection oven or the like. Drying is usually carried out in two stages, i.e., preliminary drying and drying by reheating. The preliminary drying conditions may be selected depending on the kind of the solvent component or the performance of the dryer to be used. The drying time is usually selected from the range of 150 to 80 ° C for 15 to 5 minutes depending on the kind of the solvent component or the performance of the dryer to be used, and is selected from the group consisting of 50 to 70 ° C. A range of seconds to 3 minutes is preferred. Drying by reheating is carried out at a temperature higher than the preliminary drying temperature into the line of 36 326\patent specification (supplement)\94-02\93132] 45 1261689, preferably from 50 to 2 Ο 0 °C, Better from 70 to 1 60 °C, especially from 130 °C. The drying time varies depending on the heating temperature, but it is preferably from 10 minutes to 10 minutes, preferably from 15 seconds to 5 minutes. The drying temperature is better as the adhesion to the transparent substrate. Excessive drying temperatures can degrade the binder and initiate thermal polymerization, which is presumably cause development failure. Another alternative to underdrying is to dry the film by vacuum drying in a vacuum chamber. [3-3-3] Exposure step Imagewise exposure is carried out by superposing a negative matrix pattern over the dried thin layer of the colored resin composition and irradiating the ultraviolet rays or rays from the light source through the mask pattern. If necessary, the exposure can be carried out by forming an oxygen layer such as a layer of polyethene alcohol on the film of the colored resin composition, and the sensitivity of the film is lowered by oxygen. There is no particular limitation on the light source used for image exposure. The utility model comprises a lamp light source such as a gas lamp, a ii lamp, a xenon lamp, a high pressure mercury lamp, a super mercury lamp, a metal ifi lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc and a lamp; and a laser light source such as an argon ion mine. Shot, YAG laser, excimer homo-nitrogen laser, cadmium-cadmium laser and semiconductor laser. A filter can be used when exposed to specific light. [3 - 3 - 4 ] Developing step After the above imagewise exposure, development can be carried out using an organic solvent or an aqueous solution containing a surfactant compound. The aqueous solution may contain an organic solvent, a buffer, a binder, or a dye or pigment. Examples of the test compound include inorganic test compounds such as hydroxide 326\patent specification (supplement)\94-02\93132145 37 70 to 10 seconds high, the agent tree is warm and the film is visible to block the high pressure firefly. Light "shooting, wavelength and step 1261689 sodium, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium citrate, potassium citrate, sodium metasilicate, sodium phosphate, phosphoric acid Potassium, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate and hydroxide, and organic basic compounds such as mono-, di- or triethanolamine, mono-, di- or tridecylamine, single -, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylene diimine, tetraammonium hydroxide (TMA Η) And choline. These basic compounds may be used singly or in combination of two or more. Examples of the surfactant include nonionic surfactants such as polyoxyethylene ethyl ether, polyoxyethylene alkyl aryl Ether, polyoxyethylene ethyl acrylate, sorbitan; (: complete ester and monoglyceride ): complete SI; anionic surfactants such as alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfate, alkyl tartaric acid S and continuous acid glass S acid; and amphoteric surfactant Such as a burnt betaine and an amino acid. These surfactants may be used singly or in combination of two or more. Regarding the organic solvent, it may be selected from the group consisting of isopropanol, benzofuran, ethyl cellosolve, and butyl solution. One or more solvents of a granule, a phenyl cellosolve, a propylene glycol, and a diacetone alcohol. The organic solvent may be used singly or in combination with an aqueous solution. There are no particular limitations on the development conditions, and it is usually from 10 to 10 It is preferably carried out in a temperature range of 50 ° C from 15 to 45 ° C, preferably from 20 to 40 ° C. It can be developed by enamel coating, spray development, brush development and ultrasonic development. [3 - 3 - 5 ] Thermal curing treatment usually causes the color filter substrate to be thermally cured or photocured 38 326\patent specification (supplement)\94-02\93132145 1261689 to The heat curing treatment is preferred. The heat curing temperature is selected from the range of 100 to 28 ° C to 1 50. Preferably, the thermal curing time is selected from the range of 5 to 60 minutes. After a series of steps, the patterned image formation of one color is completed. Repeatedly repeating the steps (black) a pattern of red, green, and blue, thereby forming a color filter. The order of patterning red, green, and blue is not limited to the foregoing order. Another method of manufacturing the color filter of the present invention Examples include: (1) a method of applying the colored resin composition of the present invention to a substrate, and forming an image element by etching; (2) using the colored resin composition of the present invention as a colored ink and directly using the printing device a method of forming on a transparent substrate; (3) using the colored resin composition of the present invention as an electrodeposition liquid, immersing the substrate therein, and precipitating the colored film on the IT 0 electrode formed into a predetermined pattern; (4) adhering a film coated with the colored resin composition of the present invention to a transparent substrate, peeling the film, performing imagewise exposure, and developing to form an image element. And (5) a method of using the colored resin composition of the present invention as a colored ink and forming an image element by an ink jet printer. In order to manufacture a color filter, a method suitable for the composition of the colored resin composition of the color filter is employed. [3 - 4] The transparent electrode is formed by forming a transparent electrode such as IT 0 on the image, and after performing any further modification on the filter, the color filter of the present invention is used as a part of a color display or a liquid crystal display device. Or similar parts. In order to improve the surface smoothness and durability, if necessary, it may have a 326\patent specification (supplement)\94-02\93132145 39 1261689 polyamide or polyimide layer as a top coat on the image. The color filter does not necessarily have a transparent electrode, for example, when it is used in an in-plane switching mode (I S P mode). [4] Liquid crystal display device (panel) Next, a liquid crystal display device (panel) will be explained. The liquid crystal display device of the present invention is generally formed by coating an alignment layer on the color light-receiving sheet of the present invention, spraying the spacer on the alignment layer, and bonding the obtained color filter to the surface. A liquid crystal lattice is formed on the substrate. The liquid crystal material is injected into the liquid crystal lattice and wired to the electrode facing the substrate. As the alignment layer, a resin film such as polyimide is suitable. To form the alignment layer, a photogravure printing and/or offset printing method is usually used, and the thickness of the alignment layer is usually adjusted to several tens of nanometers. After curing by baking, the alignment layer is exposed to UV rays or rubbed with a rubbing cloth to treat it into a surface state that can control the orientation of the liquid crystal material. The spacer has a size suitable for the gap with the facing substrate, and a spacer having a size of from 2 to 8 nm is generally preferred. Instead of the spacer, a photo spacer (P S ) made of a transparent resin film over a substrate of a color filter can be used. Regarding the substrate facing, an array substrate is usually used, and a T F T (thin film transistor) substrate is particularly preferable. The gap with the facing substrate varies depending on the purpose of use of the liquid crystal display device, but it is usually selected from the range of 2 to 8 μm. After the substrate of the color filter is bonded to the facing substrate, it is sealed with a sealant such as epoxy resin 40 326\patent specification (supplement)\94-02\93132145 1261689 except for the filling portion of the liquid crystal material. This sealant is cured by exposure to UVG rays and/or heat, thereby completing the seal around the liquid crystal lattice. After the liquid crystal cell sealed around it is cut into individual panels, the filling opening of the liquid crystal material is immersed in the liquid crystal material under reduced pressure in the vacuum chamber. The liquid crystal material is injected into the liquid crystal lattice via a leak in the vacuum chamber. Usually, the pressure in the liquid crystal lattice is reduced to 1 X 1 〇 _ 2 to 1 X 1 0 _ 7 P a to 1 X 1 (Γ 3 to 1 X 1 (Γ 6 P a is preferred. When decompressing, The liquid crystal lattice is preferably heated, and the heating temperature is usually from 30 to 100 ° C, preferably from 50 to 90 ° C. During the depressurization, the thermal temperature is maintained from 10 to 6 Within a range of 0 minutes, and then the filling port of the liquid crystal material is immersed in the liquid crystal material. After the liquid crystal material is injected into the liquid crystal lattice, the filling port is sealed by curing the UV curing resin, thereby completing the liquid crystal display device ( Manufacturing of the panel. There is no particular limitation on the kind of the liquid crystal material, and a conventional material such as an aromatic compound, an aliphatic compound or a polycyclic compound may be used. The liquid crystal may be a lyotropic ion or a thermotropic property. Any of the nematic, intercalated, and cholesteric liquid crystals is known, and any of them may be used. (Examples) Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples. However, it should be understood that the present invention is not limited thereto. And it can be modified without departing from the scope of the invention. In the instructions, "parts" or "parts" in the composition means "parts by weight" or "parts by weight" ^ (Example 1) <Preparation of pigment dispersion> 41 326\Patent specification (supplement) \94-02\93132145 1261689 The pigment dispersion of the present invention is prepared according to the following formula. [Formulation of Pigment Dispersion] Crimson Pigment (P.R a 1 1 7 ) ("A Τ Y - TR", product of DIC ): 80 parts of Nickelazo yellow pigment (PY 150) ("E4GN", product of Bayer): 20 parts of amine dispersant ("Disperbyk", product of BYK-Chemie): 45 parts of solvent (propylene glycol single)曱 ether acetate): 580 parts After mixing the above materials, the obtained grinding substrate was dispersed using "T 0 RUS Μ ILL" (manufactured by Getzma η η) (which was passed through the beads in the container) Collision and dispersion.) The beads used for dispersion are oxygen-missing beads having an average particle size of 100 μm. Filled with 0.35% by volume of beads in a 0.33 liter container of the disperser and Add 1000 cubic centimeters of ground matrix at a peripheral speed of 12 m/min and dispersion Dispersion treatment was carried out in 4 minutes. <Measurement of particle size distribution of pigment dispersion liquid> The pigment dispersion thus obtained was diluted to 5,000 times with propylene glycol monomethyl ether acetate, and a dynamic light scattering spectrophotometer was used. ("DLS 7 0 0 0", product of 0 tsuka E 1 ectr〇nics) The particle size was measured. The particle size range and the half width value are shown in Table 1. <Preparation of Colored Resin Composition (Color Resistance Agent) The components were mixed in the obtained pigment dispersion liquid according to the following formulation. The resulting mixture was filtered through a 1 micron filter, thereby forming a color filter. [Color resist agent formulation] Pigment dispersion: 1 0. 6 parts 42 326V patent specification (supplement) \94-02\93132 ] 45 1261689 Solvent (propylene glycol monoterpene ether acetate): 8 Ο , 0 parts bonding Resin (benzyl methacrylate/mercaptoacrylic acid copolymer): 4. 7 parts of monomer (trihydroxydecylpropane triacrylate) · · 2.3 parts of photopolymerization initiator system component 1 ( 2 -fluorenyl Benzothiazole): 0.8 parts of photopolymerization initiator system component 2 (methyl p-carbamic acid benzoate): 0.8 parts of photopolymerization initiator system component 3 (michonone): 0.8 Parts <Formation of Red Image Element> The obtained color resist was spin-coated on a glass substrate to obtain a dry film thickness of 2 μm, followed by drying at 80 ° C for 10 minutes. After exposure to U V rays to cure the resin, the substrate was heated at 230 ° C for 30 minutes for crosslinking, thereby forming a red image element. <Measurement of Chroma and Contrast> The glass substrate having the red image element obtained above was exposed to the illuminator C, and the chromaticity of the transmitted light was measured using a spectrophotometer ("U4100", product of Hitachi, Ltd.). . Then, the substrate is tightly sandwiched between the two polarizing plates, and the light intensity when the polarizing plates are arranged in parallel is measured by a luminance photometer ("B Μ - 5 A", a product of T 〇pc ο η). (Candle/cm ^ 2 ) The ratio of the light intensity 烛 (candle / square centimeter) when the polarizing plate is set at a right angle is calculated using the following equation (1 ). The results are shown in Table 1. C=B/A (1) Calculate "4 Ο Ο Ο X - 2 0 0 0" using the chromaticity X obtained by the above measurement, 43 326\patent specification (supplement)\94-02\93132145 1261689 and evaluation Whether the result satisfies the following equation (2). These results are also shown in Table C ^ 40 OOx - 2 0 0 0 (Example 2)
以與實施例 1類似之方式，除了使用「C h r〇m〇p h t h a 1〇r e d A 3 B」（C i b a S p e c i a 1 t y C h e m i c a 1 s之產品）作為蒽S昆紅色 顏料（P · R 1 1 7 )及「E 5 G N」（B a y e r之產品）作為鎳偶氮黄色 顏料（P . Y 1 5 0 )，製備顏料分散液及著色樹脂組成物及進行 評估。結果示於表1。 (實施例3 ) 以與實施例1類似之方式，除了將使用於製備顏料分散 液之珠粒的顆粒大小改為5 0 0微米，製備顏料分散液及著 色樹脂組成物及進行評估。結果示於表1。In a similar manner to Example 1, except that "C hr〇m〇phtha 1 〇 Red A 3 B" (product of C iba S pecia 1 ty C hemica 1 s) was used as the 蒽S Kun red pigment (P · R 1 1 7 ) and "E 5 GN" (product of Bayer) as a nickel azo yellow pigment (P. Y 1 5 0 ), a pigment dispersion liquid and a coloring resin composition were prepared and evaluated. The results are shown in Table 1. (Example 3) In a manner similar to Example 1, except that the particle size of the beads used for the preparation of the pigment dispersion was changed to 500 μm, a pigment dispersion and a colored resin composition were prepared and evaluated. The results are shown in Table 1.
326\專利說明書(補件)\94-02\93132145 44 1261689 方程式 ⑵ 滿足 滿足 滿足 不滿足 4000χ- 2000 ① r—Η OD CJD y < CD ① τ—1 CD οα τ—Η CD 對比 ◦ 1400 1200 s OO ◦ 紅色圖像元件 N 寸 cd r—i I 16.4 CD CN1 (N1 0.315 i_ 0.315 0.315 0. 344 X 0. 654 0. 654 0.654 0. 653 顏料分散液中之顏料 半寬度值 § CD l 11 H 1 1,1 H g <N1 § (N1 顆粒大小(nm) < OO οα CO Od OO OO CO CO CD CD CO Od CO ί雜之平均 顆粒大小 (//m) g r_H g r—H g LO g r—H 黃色顏料 P.Y. 150 “E4GN” ◦ LO Γ r-H o .LO cu P.Y. 150 “E4GN” P.Y. 150 “E4GN” 紅色顏料 P.R. 177 “ATY-TR” P.R. 177 “Chromo-p hthalored A3B” P.R. 177 “ATY-TR” P.R. 254 Έ-ΟΓ r—1 OO CO 比車交例1 心寸 ι Να e6\s-寸 6\(φ}®)_κΜ1Ην»\9Νε 1261689 由表1，經發現經由使用經由將P. R。 1 7 7及P。Υ, 混合而製得且具有落於本發明範圍内顆粒大小的顏料 液可形成可滿足前述方程式（2 )之高對比紅色圖像元1 雖然本發明已經詳細說明並參照其之特定具體例， 悉技藝人士當明白可不脫離其之精神及範圍而於其中 各種變化及修改。 本申請案係以2 0 0 3年1 0月2 2曰提出申請之曰本I 案第2003-362113號及2004年1月提出申請之第 2004-012061號為基礎，將其之全體内容倂入本文為 資料。 (產業利用性） 本發明產生如下所述之優異優點，以致其於產業中 潛力。 1 .本發明之顏料分散液及包含顏料分散液之本發明 著色樹脂組成物可形成具有優異消偏振性質及因此具 比之紅色圖像元件。 2 .根據本發明之顏料分散液之製備方法有利於此一 料分散液之製備。 3 .在本發明之彩色濾光片及設有此彩色濾光片之 明之液晶顯示裝置中，紅色圖像元件具有優異的消偏 質，及因此具高對比，以致其之品質優良，且可有效 亮度及觀看角，以滿足較大螢幕尺寸的需求。 326\專利說明書(補件)\94-02\93132145 46 15 0 分散 牛。 但熟 進行 戸請 參考 極具 之 高對 顏 本發 振性 提而326\Patent Specification (Repair)\94-02\93132145 44 1261689 Equation (2) Satisfaction Satisfaction Satisfaction Not satisfied 4000χ- 2000 1 r—Η OD CJD y < CD 1 τ—1 CD οα τ—Η CD Contrast ◦ 1400 1200 s OO ◦ Red image element N inch cd r-i I 16.4 CD CN1 (N1 0.315 i_ 0.315 0.315 0. 344 X 0. 654 0. 654 0.654 0. 653 Pigment half-width value in pigment dispersion § CD l 11 H 1 1,1 H g <N1 § (N1 particle size (nm) < OO οα CO Od OO OO CO CO CD CD CO Od CO ί The average particle size (//m) g r_H gr—H g LO gr—H Yellow pigment PY 150 “E4GN” ◦ LO Γ rH o .LO cu PY 150 “E4GN” PY 150 “E4GN” Red pigment PR 177 “ATY-TR” PR 177 “Chromo-p hthalored A3B” PR 177 “ ATY-TR” PR 254 Έ-ΟΓ r—1 OO CO than car case 1 heart ι Να e6\s-inch 6\(φ}®)_κΜ1Ην»\9Νε 1261689 From Table 1, it was found that P. R. 1 7 7 and P. Υ, a pigment liquid prepared by mixing and having a particle size falling within the scope of the present invention can be formed to satisfy the aforementioned equation (2) High contrast red image element 1 Although the present invention has been described in detail with reference to the specific embodiments thereof, it will be understood by those skilled in the 2 0 0 3 1 1 2 2 2 曰 曰 曰 I 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 -01 -01 -01 -01 -01 -01 -01 -01 -01 -01 -01 -01 -01 -01 -01 -01 -01 。 。 (Industrial Applicability) The present invention has an excellent advantage as described below, so that it has potential in the industry. 1. The pigment dispersion of the present invention and the colored resin composition of the present invention comprising the pigment dispersion can have excellent depolarization properties and Therefore, the red image element is compared. 2. The preparation method of the pigment dispersion according to the present invention is advantageous for the preparation of the dispersion. 3. The color filter of the present invention and the color filter provided thereon In the liquid crystal display device of the Ming Dynasty, the red image element has excellent depolarization, and thus has high contrast, so that its quality is excellent, and the brightness and viewing angle can be effectively met to meet the needs of a larger screen size. . 326\Patent specification (supplement)\94-02\93132145 46 15 0 Disperse cattle. However, if you are familiar with it, please refer to the extremely high level of the hair.