200827931 九、發明說明： 【發明所屬之技術領域】 本發明關於-種非曝光程序，更具體地關於—種紫外線固化 液態預聚合物，經由改變保護膜層的成分或除了該保護膜層外， • 經由改變圓柱間隙物的成分而提昇熱穩定性。本發明亦關於一種 使用該紫外線固化液態預聚合物之液晶顯示（LCD)裝置及萝迕 該液晶顯示裝置的方法。 (; 【先前技術】 用於電路之精密圖案處理為―項影響裝置屬性及能量的重要 •因子。近年來非曝光程序已愈發重要。 _ —%為平面騎刷（In_Plane Plinting)的非曝光程序使用紫 外線固化液態預聚合物做為圖案材料。然而，紫外線固化液態預 :合物-旦熱處理便很柔弱，其中紫外咖化液態預聚合物會收 G 縮。當使用平面内印刷處理時，使用軟鑄模而形成保護膜層及做 /為本體的圓柱間隙物，或形成具保護膜層之白色滤光片層連同白 色附加結構中的圓柱間隙物，其中圓柱間隙物、保護膜層或白色 濾'光片層均會gj熱處理而收縮。此可發生於例如於圓柱間隙物上 形成校準層之後的烘焙過程期間。 、曰將苓照圖式描述紫外線固化液態預聚合物的相關技藝及製造 夜曰曰，、肩不衣置的方法。「第j圖」顯示包括白色子像素之矩形單一 像素的^圖。由料、制嫌態麟合物定型之液晶顯示裝置 5 200827931 包括彼此相對的第一及第二基板，及形成於第一及第二基板之間 的液晶層。如「第1圖」中所示，每—第—及第二基板包括複數 個像素區，其中每一像素包括紅（R)、綠（G)、藍（B)及白（w) 子像素。而且紅（R)、、綠⑹、藍⑻及白色渡光片層 12a、12b、12c及14分別形成於紅（R)、綠⑹、藍⑻及白 (W)子像素中。 除了紅（R)、綠⑹及藍⑻子像素外，具有白子 像素的結構稱為「白色附加結構」。在「第i圖」中，一矩形單一 像素被劃分為四個部分，其中紅（R)、綠（G)、藍（B)及白 子像素分別位於該矩形單-像素的四個部分，顯示白色附加結 構。紅（R)、綠⑹、藍⑻及白（w)子像素可配置為條狀， 且相應的顏色濾光片層可分別形成於子像素。 「第2A圖」至「第2C圖」顯示截面圖，描緣於矩形像素結 構中製造顏色濾光片陣列基板的方法。「第3圖」顯示截面圖= 繪烘焙校準層之後顏色濾光片陣列的收縮。 >第2A圖」’蔽光層η形成於由複數像素所定義之第— 基板Κ)上子像素的邊界中，其中每—像素包括紅（r)、綠⑹: 藍⑻及白（w)子像素。蔽光層11形成於第-基板10上子像 f的邊界中，其相應於形成於第二基板（未顯示）上的閘極線、 貧料線及薄膜電晶體。紅色濾光片層❿、綠色濾光片層（參照「第 1圖」之12b)及藍色滤光片層（參照「第1圖」之12c)分別形 6 200827931 成於第-基板1G的紅⑻、綠⑹及藍⑻子像素中。 接著將紫外線固化液態預聚合物的圖案材料層13塗佈於包括 蔽光層11及紅（R)、綠⑹及藍⑻色濾光片層i2a、既及 以之第-基板10的整個表面上。紫外線固化液態預聚合物的圖 案材料層13經紫外光而固化，其中預聚合物較一般聚合物黏，且 易受壓力而改變。 此如「第2B圖」中所示，鑄模2〇具有形成於其背部表面上的 背面（未顯示），其與圖案材料層13接觸而於圖案材料層13中形 成相應於鑄模2G之凹面及凸面的圖案請。參照「第％圖」，鱗 模20與_ 13G分離。結果，_⑽係由白色子像素所提供的 f色濾光片層14、第-基板1()(其中包括蔽光層n及紅、綠、 -色;慮光片層12a、12b、12e)的整個表面上所提供的保護膜層 15及蔽光層11上方保護膜層15之上所提供的圓柱鄕物16組 成。在完成上述步驟後，白色濾光片層I4、保護膜層及圓柱間 隙物16整合成為一本體並構成圖案13〇。 第2A圖」至「第2C圖」顯示白色子像素及其各層，盆中 白色濾光片層係於保護騎及__物的形成過程中而形成， 而非於形成白色濾、光片層做為附加顏色濾光片處理步驟中形成。 相對於圓柱間隙物16，保護膜層15及白色濾光片層14係一齊妹 圖案材料層而定型。切成_ 130表面之雜亞胺的校準声 時，該校準層便經約攝氏180度的熱處理。在此狀況下，保错膜 200827931 層由於H制化液態鮮合物之收縮而變料平坦。白色子像 素需要適當地維持白色濾'光片層的厚度⑷及保護膜層的厚度 a α* &準層18触培過糊’經由料制化液態預聚 合物敝縮，白色子像素_絲面130a較其他部分凹或縮得更 多。 【發明内容】 -種料線賴肺合物，包含3G〜6()體積％的單機能 Π單體、20〜5_積％的雙機能單體、1G〜2G體積％的三機能單體 及光起始劑。 • =種液晶顯示裝置包括彼此相對的第-及第二基板，其中每 .-該弟-及第二基板被定義為具有均勻配置的紅、綠、藍及白色 子像素；i光層’形成於第—基板之子像素以外的其他部分上； 紅、綠及藍色縣片層，分卿成於第—基板的紅、綠及藍色子 像素上；—平面化圖案層，形成於包括該蔽光層及該紅、綠及該 G色編層之第-基板的整個表面上，其中該平面化圖案層^ -包括3G〜6G體積％的單機能單體、2G〜5G 的雙機能單體、 1〇〜2〇體積％的三機能單體及光起始劑的紫外線固化液態預聚人 物組成;-薄膜電晶體陣列，形成於該第二基板上；一第—校^ 層，形成於包括該平面化圖案層之第—基板的整個表面上，及一 第二校準層，形成於包括薄膜電晶體陣列之第一基板的整個表面 上，及-液晶層，形成於該第一及第二基板之間。 200827931 -種製造液晶顯示裝置的方法，包括準備彼此相對的第—及 第二基板γ其中每-該第—及第二基板被定義為具有均勻配置的 紅、綠、監及白色子像素；於第—基板之子像素以外的其他部分 上形成-蔽光層；於第-基板的紅、綠及藍色子像素上分別形成 紅、綠及藍色縣片層；於包括該蔽光層及該紅、綠及藍色遽光 片層之第-基板的整個表面上塗佈紫外咖化液態預聚合物，其 中該紫外線固錄態縣合物係由包括3G〜6G體積％的單機能單 體、20〜50體積％的雙機能單體、1〇〜2〇體積％的三機能單體及 光起始劑組成；於該紅、綠、纽自色子像素巾形成—平面化圖 案層，以便體現紫外線固化液態預聚合物的平坦上表面；於該第 二基板上形成-薄膜電晶體陣列；及於該第—及第二基板之間形 成一液晶層。 有關本發明的特徵與實作，茲配合圖式作最佳實施例詳細說 明如下。 【實施方式】 現在將洋細參照圖式中所描緣之實施例，其中圖式中所使用 之相同編號係指相同零件。現在將參照圖式描述一種紫外線固化 液態預聚合物、使用該紫外線固化液態預聚合物做為定型材料的 液晶顯示裝置及其製造方法。 紫外線固化液態預聚合物允許經由改變或取代某些成分而使 熱處理期間某些材料的收縮最小化。現在將描述依據紫外線固化 200827931 液悲預聚合物中機能群組之數罝的固化及熱屬性。機能群組相廣、 於單體化合物與聚合物化學反應的一端。例如，單機能群組具有 單體化合物與聚合物化學反應的一端。即，雙機能群組或三機能 群組具有單體化合物與聚合物化學反應的二或三端。 ’ 「第4A圖」至「第4C圖」顯示包括單機能群組之紫外線固 化液悲預聚合物於固化過程及熱處理之後的體積改變。例如，紫 外線固化液怨預聚合物51形成於基板之上（未顯示），其中紫外 線固化液態預聚合物51包括各具有單機能群組的單體（M)，及 各具有單機能群組之作用端以做為誘發單體（M)上初始反應之 - 起始劑的光起始劑（I)。 祕i外線固化液態縣合物係經紫外線照㈣活化，每一 包括單機能群組的單體具有一作用端。如「第4B圖」中所示，在 圖案層52經紫外線照射而固化後，紫外線固化液態預聚合物的薄 、版便形成做為線性鏈結構。由於具有單機能群組之單體（M)係 从起始劑（I) *活化，每—活化端與另—單體結合，且該結合 、夂；Jc平面上条生’藉以形成線性鏈結構。在固化過程之後， 線性鏈結構便以固定間隔堆積或堆疊，其中每-線性鏈結構是水 線性鏈結構於固化過程之後水平配置，且紫外線固化液態 預來5物的薄膜經固化而形成做為_層52。 如「弟4C圖|中戶斤+，* — 7… 右貫施額外的熱處理所形成的圖案層 ’使件線性鏈結構之間轉急遽增加，導致_層52中發生整 10 200827931 體收縮。當水平配置複數線性鏈結構時，固化過程之後線性鏈結 構之間存在固定的距離。由於實施額外的熱處理，線性鏈結構之 間的距離減少導致圖案層52a的收縮。因此，包括單機能群組之 單體的紫外線固化預聚合物被固化，其中圖案層52a收縮使得固 化圖案層的體積相對於「第3圖」中所示之初始塗佈圖案層為小。 通常，固化過程中所形成的線性鏈結構被堆疊為多層，使得圖案 層的厚度大為收縮。 為克服固化過程之後因額外熱處理之紫外線固化液態預聚合 物的嚴重收縮，依據包括單機能群組之紫外線固化液態預聚合物 因結構屬性而於固化過程中收縮的假定，紫外線固化液態預聚合 物需包括具有雙機能群組或三機能群組的聚合物。若紫外線固化 液態預聚合物包括雙機能群組或三機能群組的聚合物，即使當固 化或熱處理時’紫外線固化液態預聚合物的體積仍維持固定。 弟5A圖」至弟5C圖」藏不包括分支或交連之機能群組 的紫外線固化液態預聚合物於固化過程及熱處理之後的體積改 變。如「第5A圖」中所示，紫外線固化液態預聚合物包括約3〇〜 60°/◦體積的單機能單體（M )、約2〇〜5〇%體積的雙機能單體（〇 )、 約10〜20%體積的三機能單體（τ)及光起拾劑（1)。單機能單體 (Μ)係由CH2=CHY或CH2=CXY組成，其中「X」及「γ」係 由鹵素、烧基、酯或苯基中任一組成。單機能單體（M)通常由 碳共價鍵結構的乙烯基單體組成。 11 200827931200827931 IX. Description of the Invention: [Technical Field] The present invention relates to a non-exposure procedure, and more particularly to an ultraviolet curing liquid prepolymer, by changing the composition of the protective film layer or in addition to the protective film layer, • Improve thermal stability by changing the composition of the cylindrical spacer. The present invention also relates to a liquid crystal display (LCD) device using the ultraviolet curable liquid prepolymer and a method of using the liquid crystal display device. (Previous technique) Precision pattern processing for circuits is an important factor affecting device properties and energy. Non-exposure procedures have become more and more important in recent years. _ -% is the non-exposure of In_Plane Plinting The procedure uses a UV-curable liquid prepolymer as the pattern material. However, the UV-curable liquid pre-compound is very weak after heat treatment, and the UV-gray liquid pre-polymer will shrink G. When using in-plane printing, Forming a protective film layer and a cylindrical spacer as a body using a soft mold, or forming a white filter layer with a protective film layer together with a cylindrical spacer in a white additional structure, wherein the cylindrical spacer, the protective film layer or the white The filter 'light sheet layer will be heat-treated and contracted by gj. This can occur, for example, during the baking process after forming the calibration layer on the cylindrical spacer. 曰 曰 图 描述 描述 描述 描述 描述 描述 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线Nightingale, the method of not wearing the shoulder. "Jth image" shows a rectangular image of a single pixel including white sub-pixels. The shaped liquid crystal display device 5 200827931 includes first and second substrates facing each other, and a liquid crystal layer formed between the first and second substrates. As shown in FIG. 1, each of the first and second The substrate includes a plurality of pixel regions, wherein each pixel includes red (R), green (G), blue (B), and white (w) sub-pixels, and red (R), green (6), blue (8), and white light The slice layers 12a, 12b, 12c, and 14 are formed in red (R), green (6), blue (8), and white (W) sub-pixels, respectively, except for the red (R), green (6), and blue (8) sub-pixels, which have white sub-pixels. The structure is called "white additional structure". In "ith picture", a rectangular single pixel is divided into four parts, in which red (R), green (G), blue (B) and white sub-pixels are respectively located in the rectangle. The four parts of the single-pixel display a white additional structure. The red (R), green (6), blue (8), and white (w) sub-pixels may be arranged in stripes, and the corresponding color filter layers may be formed in the sub-pixels, respectively. "2A" to "2C" show a cross-sectional view of a color filter array substrate fabricated in a rectangular pixel structure Figure 3. "Picture 3" shows the cross-section = shrinking of the color filter array after baking the calibration layer. > 2A" "The mask layer η is formed on the first substrate defined by the complex pixels" In the boundary of a pixel, each pixel includes red (r), green (6): blue (8), and white (w) sub-pixels. The mask layer 11 is formed in the boundary of the sub-image f on the first substrate 10, which corresponds to a gate line, a lean line, and a thin film transistor formed on the second substrate (not shown). The red filter layer ❿, the green filter layer (refer to "12" in Fig. 1) and the blue filter layer (refer to "12c" in Fig. 1) are respectively shaped 6 200827931 into the first substrate 1G Red (8), green (6), and blue (8) sub-pixels. Next, the pattern layer 13 of the ultraviolet-curable liquid prepolymer is applied to the entire surface including the mask layer 11 and the red (R), green (6), and blue (8) color filter layers i2a, and the first substrate 10. on. The patterned material layer 13 of the UV-curable liquid prepolymer is cured by ultraviolet light, wherein the prepolymer is more viscous than the general polymer and is susceptible to pressure changes. As shown in FIG. 2B, the mold 2 has a back surface (not shown) formed on the back surface thereof, which is in contact with the pattern material layer 13 to form a concave surface corresponding to the mold 2G in the pattern material layer 13 and The pattern of the convex surface please. Referring to "% map", scale 20 is separated from _ 13G. As a result, _(10) is an f-color filter layer 14 provided by a white sub-pixel, a first substrate 1 (which includes a light-shielding layer n and red, green, and color; a light-sensitive sheet layer 12a, 12b, 12e). The protective film layer 15 provided on the entire surface and the cylindrical material 16 provided on the protective film layer 15 above the light shielding layer 11 are composed. After the above steps are completed, the white filter layer I4, the protective film layer and the cylindrical spacer 16 are integrated into a body and constitute a pattern 13A. 2A to 2C show white sub-pixels and their layers. The white filter layer in the basin is formed during the formation of the protection ride and the __ object, instead of forming a white filter and a photo layer. Formed as an additional color filter processing step. With respect to the cylindrical spacer 16, the protective film layer 15 and the white color filter layer 14 are shaped by a layer of a pattern material. The calibration layer is heat treated at approximately 180 degrees Celsius when calibrated to the surface of the imino imine. Under this condition, the layer of the miscored film 200827931 is flattened due to shrinkage of the H-made liquid fresh compound. The white sub-pixel needs to properly maintain the white filter 'thickness of the light-film layer (4) and the thickness of the protective film layer a α* & the quasi-layer 18 touch paste paste' via the materialized liquid prepolymer collapse, white sub-pixel _ The silk surface 130a is more concave or contracted than other portions. SUMMARY OF THE INVENTION - The seed line is a lung compound comprising 3G~6()% by volume of a single functional monomer, 20~5% by weight of a dual function monomer, and 1G to 2G by volume of a trifunctional monomer. And photoinitiator. • The liquid crystal display device includes first and second substrates opposite to each other, wherein each of the second and second substrates is defined as a red, green, blue, and white sub-pixel having a uniform configuration; On the portion other than the sub-pixel of the first substrate; the red, green, and blue county layers are divided into red, green, and blue sub-pixels of the first substrate; the planarization pattern layer is formed to include the a light shielding layer and the entire surface of the red, green and the first substrate of the G color layer, wherein the planarization pattern layer comprises a 3G to 6G volume% single function unit, and a 2G to 5G dual function sheet a body, a 1% to 2% by volume of a trifunctional monomer and a UV-curable liquid prepolymerized person of a photoinitiator; a thin film transistor array formed on the second substrate; a first layer On the entire surface of the first substrate including the planarization pattern layer, and a second alignment layer formed on the entire surface of the first substrate including the thin film transistor array, and a liquid crystal layer formed on the first surface Between the second substrates. 200827931 - A method of manufacturing a liquid crystal display device comprising: preparing first and second substrates γ opposite to each other, wherein each of the first and second substrates is defined as a red, green, and white sub-pixel having a uniform configuration; Forming a light shielding layer on a portion other than the sub-pixel of the first substrate; forming red, green, and blue county layers on the red, green, and blue sub-pixels of the first substrate; including the light shielding layer and the The ultraviolet curable liquid prepolymer is coated on the entire surface of the first substrate of the red, green and blue calendering sheets, wherein the ultraviolet fixation state is composed of a single functional monomer including 3G to 6G by volume. 20~50% by volume of a dual functional monomer, 1〇~2〇% by volume of a trifunctional monomer and a photoinitiator; forming a planarized pattern layer in the red, green and neon sub-pixel sub-pixels, To form a flat upper surface of the ultraviolet curable liquid prepolymer; to form a thin film transistor array on the second substrate; and to form a liquid crystal layer between the first and second substrates. The features and implementations of the present invention are described in detail with reference to the preferred embodiments. [Embodiment] The embodiments described in the drawings are now referred to, and the same reference numerals are used in the drawings to refer to the same parts. A liquid crystal display device using ultraviolet curable liquid prepolymer, using the ultraviolet curable liquid prepolymer as a sizing material, and a method of manufacturing the same will now be described with reference to the drawings. Ultraviolet curing of liquid prepolymers allows for the minimization of shrinkage of certain materials during heat treatment by altering or substituting certain ingredients. The curing and thermal properties of the functional groups in the liquid-cold prepolymer based on UV-curing 200827931 will now be described. The functional group is broad at one end of the chemical reaction between the monomer compound and the polymer. For example, a single functional group has one end of a chemical reaction of a monomeric compound with a polymer. That is, the dual function group or the trifunctional group has two or three ends in which the monomer compound chemically reacts with the polymer. ''Fig. 4A'' to '4C' show the volume change of the UV-curable liquid pre-polymer containing the single-energy group during the curing process and heat treatment. For example, the ultraviolet curable liquid pre-polymer 51 is formed on a substrate (not shown), wherein the ultraviolet-curable liquid prepolymer 51 includes monomers (M) each having a single function group, and each having a single function group The working end serves as a photoinitiator (I) which induces the initiator of the initial reaction on the monomer (M). The external solidified liquid state compound is activated by ultraviolet light (four), and each monomer including a single functional group has an active end. As shown in "Fig. 4B", after the pattern layer 52 is cured by ultraviolet irradiation, the thin and plate-form of the ultraviolet-curable liquid prepolymer is formed into a linear chain structure. Since the monomer (M) having a single functional group is activated from the initiator (I)*, each of the activated ends is combined with another monomer, and the combination, enthalpy; Jc plane is formed to form a linear chain structure. After the curing process, the linear chain structure is stacked or stacked at regular intervals, wherein each linear chain structure is a horizontal arrangement of the water linear chain structure after the curing process, and the film of the ultraviolet curing liquid pre-extracting material is solidified to form _ layer 52. For example, "Development of the pattern layer formed by the additional heat treatment by the right side of the 4C picture|中中斤+,*-7..." causes a sharp increase in the linear chain structure between the pieces, resulting in the occurrence of the whole body of the 2008 layer. When the complex linear chain structure is configured horizontally, there is a fixed distance between the linear chain structures after the curing process. Due to the implementation of the additional heat treatment, the reduction in the distance between the linear chain structures causes the shrinkage of the pattern layer 52a. Therefore, including the single function group The monomeric ultraviolet curing prepolymer is cured, wherein the pattern layer 52a is shrunk such that the volume of the cured pattern layer is small relative to the initial coating pattern layer shown in "Fig. 3". Usually, the linear chain structures formed during the curing process are stacked in a plurality of layers such that the thickness of the pattern layer is largely shrunk. To overcome the severe shrinkage of the UV-cured liquid prepolymer after additional curing by the heat treatment process, UV-cured liquid prepolymers are based on the assumption that the UV-curable liquid prepolymer comprising a single functional group shrinks during curing due to structural properties. It is necessary to include a polymer having a dual function group or a triple function group. If the UV-curable liquid prepolymer comprises a polymer of a dual function group or a trifunctional group, the volume of the UV-curable liquid prepolymer remains fixed even when cured or heat treated. The 5A map to the 5C map contains volume changes of the UV-curable liquid prepolymer that does not include the branch or crosslinked functional group after the curing process and heat treatment. As shown in "Fig. 5A", the ultraviolet curable liquid prepolymer comprises a single functional monomer (M) of about 3 〇 to 60 ° / ◦ volume, and a double functional monomer of about 2 〇 to 5 〇 % by volume. ), about 10 to 20% by volume of the three functional monomer (τ) and the light pickup (1). The single functional monomer (Μ) is composed of CH2=CHY or CH2=CXY, wherein "X" and "γ" are composed of any of halogen, alkyl, ester or phenyl. The single functional monomer (M) usually consists of a vinyl monomer having a carbon covalent bond structure. 11 200827931
或 DGDMA 雙機能單體（D)係由HDDA (1，6_己二醇醋） (二甘醇丙烯酸醋）組成。例如，雙機能單體（D)具有下列化學 方程式1 〇 [化學方程式1]Or DGDMA dual functional monomer (D) consists of HDDA (1,6-hexanediol vinegar) (diethylene glycol acrylate vinegar). For example, the dual function monomer (D) has the following chemical equation 1 〇 [Chemical Formula 1]
而且’二機能單體（T)係由1_ (四氫_亞甲基_2)乙烯基丙 細酉夂酉日（1- (tetrahydro_methylenefuran-2-yl) vinyl acrylate)或 3- (2-奥噻唑丁 _3 ) 丁烷4，3_二烯_2丙烯酸酯（3_ (2-oxooxazolidin-3-yl) buta_l，3-dien-2-yl acrylate)組成。例如， 三機能單體（T)具有下列化學方程式2及3。 [化學方程式2]Moreover, the 'two functional monomer (T) is derived from 1-(tetrahydro-methylenefuran-2-yl) vinyl acrylate or 3- (2-) Thiazolidine _3 ) Butane 4,3-diene acrylate (3_(2-oxooxazolidin-3-yl) buta_l, 3-dien-2-yl acrylate). For example, the trifunctional monomer (T) has the following chemical equations 2 and 3. [Chemical Equation 2]
[化學方程式3][Chemical Equation 3]
12 200827931 光起始劑（i)包括於包含單機能單體（M)、雙機能單體（D) 及三機能單體（T)之總重量的！〜3重量％中。光起始劑係由 lrgacure369{2-苯曱基-2-(二曱苯胺）小線型）苯基]小丁醇} (2 benzyl 2- ( dimethylamino ) -l-[4- ( morpholinyl ) phenyl]_l_butanone)、Irgacure 819{苯基二（2,4,6_三甲基苯甲酸）} (phenyl bis (2,4,6_trimethyl benzoyl))或 Irgacure 184{1-囊氧環己 烧苯基酮} (l_hydtoxycyclohexyl phenyl ketone)之任一組成。 光起始劑(I)係佔約1〜3%重量，其中光起始劑為芳香 酮基材料或麟化氫氧化物基材料。例如，Irgacure 819為鱗化氫氧 化物基材料，Irgacure 184及Irgacure 369為芳香酮基材料，其可 以相同基材料替代。 光起始劑（I)為單一作用端產生起始劑。然而，光起始劑（工） 可由雙作用端產生起始劑取代，以便獲得分支或交連結構。為避 免降低反應速度，紫外線固化液態預聚合物可包括具有雙作用端 的光起始劑及具有單一作用端的光起始劑，Irgacure 369{2-苯曱基 _2_ ( 一甲苯胺）小[4-(線型）苯基]-1-丁醇}、Irgacure 819{苯基 二（2,4,6-三甲基苯甲酸）}或Irgacure 184{1-囊氧環己烧苯基酮} 其中任一。 在塗佈紫外線固化液態預聚合物200做為基板（未顯示）上 薄膜之後，紫外光便施予紫外線固化液態預聚合物。因而，任意 配置於紫外線固化液態預聚合物中的單體及光起始劑被活化，使 13 20082793112 200827931 Photoinitiator (i) is included in the total weight of single functional monomer (M), dual functional monomer (D) and three functional monomer (T)! ~3 wt% in the middle. The photoinitiator is composed of 2r benzyl 2-( dimethylamino ) -l-[4- ( morpholinyl ) phenyl] _l_butanone), Irgacure 819 {phenyl bis (2,4,6-trimethyl benzoyl)} or Irgacure 184 {1-cyanoxyl phenyl ketone} Any composition of (l_hydtoxycyclohexyl phenyl ketone). The photoinitiator (I) is present in an amount of from about 1 to 3% by weight, wherein the photoinitiator is an aromatic ketone based material or a lithiated hydroxide based material. For example, Irgacure 819 is a scaly hydroxide based material, and Irgacure 184 and Irgacure 369 are aromatic ketone based materials which can be replaced by the same base material. The photoinitiator (I) produces a starter for a single working end. However, the photoinitiator can be replaced by a double acting end initiator to obtain a branched or crosslinked structure. In order to avoid reducing the reaction rate, the UV-curable liquid prepolymer may include a photoinitiator having a double-acting end and a photoinitiator having a single acting end, and Irgacure 369 {2-benzoinyl-2-(i-toluidine) is small [4] - (linear) phenyl]-1-butanol}, Irgacure 819 {phenyl bis(2,4,6-trimethylbenzoic acid)} or Irgacure 184 {1-cyanoxanthone phenyl ketone} Either. After the ultraviolet curable liquid prepolymer 200 is applied as a film on a substrate (not shown), the ultraviolet light is applied to the ultraviolet curable liquid prepolymer. Thus, the monomer and photoinitiator which are optionally disposed in the ultraviolet curable liquid prepolymer are activated to make 13 200827931
得單機能單體（Μ)、雙機能單體（d)及 一線上，進而形成線性鏈結構。相斟A single-function monomer (Μ), a dual-function monomer (d), and a line can be formed to form a linear chain structure. Relative
耶乐儿圖」T咖，即使於經由固化而形成圖案層 施額外熱處理，相__之_交連部分有助I 相鄰線性鏈之__:。在相鄰雜鏈巾無交連的部分，分支便 支樓娜線性鏈之間的間隙。結果，圖案層21G的體積保^實^ 上固定。尤其是’對於線性鏈依序堆積之圖案層210的結構而言貝 可使交連及分支之厚度的改變最小化。 ° 為下列原因，紫外線固化液態預聚合物包括約30〜60%體積 的單機能單體CM)、約20〜50%體積的雙機能單體（D)及約^ 〜2〇°/。體積的三機能單體（τ)。隨著機能群組的數量增加，交連及 分支的數量亦經由機能群組之活化而增加。經由固化過程之後的 名頁外熱處理，紫外線固化液態預聚合物的收縮最小化。然而，與 由立曰加機能群組的數量，黏性亦增加。因而，當經由提供鱗模择 構而形成圖案時，例如，應用於塗佈紫外線固化液態預聚合物後 之基板的軟鑄模，機動性及反應速度降低，難以於基板上獲得所 需的圖案。因此，紫外線固化液態預聚合物的黏性增加受侷限為 14 200827931 最大值。提供紫外線固化液態預聚合物約20%體積以上的三機能 單體使得形成所需的圖案。 為限制黏性的增加，紫外線固化液態預聚合物可包括雙機能 單體及三機能單體，以確保熱穩定性。雙機能單體及三機能單體 經由紫外光的活化而協助產生分支及交連。雙機能單體、三機能 單體以及單機能單體的使用提供較僅使用單機能單體更大的熱穩 定性。 ( 當僅使用雙機能單體及三機能單體時，使用紫外線照射而活 化各單體的反應速度由於大量機能群組而降低。在此方面，紫外 • 線固化液態預聚合物必然需要單機能單體。經由提供約3〇%至約 ' 6〇%體積的單機能單體，可改進反應速度及獲得適當黏性。 紫外線固化液態預聚合物依據下列步驟而用於圖案形成。首 先，準備一鑄模結構，使得鑄模結構的背後表面具有一背面，且 該背後表面上具有凹面及凸面部分。 (J ； 相對於鑄模結構，將基板塗佈上述紫外線固化液態預聚合 物。接著，鑄模結構被導入接觸紫外線固化液態預聚合物，接著 固化’使得相應於鑄模結構之凹面及凸面部分的預定圖案形成於 备、外線固化液態預聚合物的表面。之後，鑄模結構便與紫外線固 化液態預聚合物的預定圖案分離。 如上述說明’紫外線固化液態預聚合物可應用於非曝光過程 及禱模結構之過程。例如，在以紫外線固化液態預聚合物塗佈基 15 200827931 板之後’預定圖案可經由印刷而形成於紫外線固化液態預聚合物 中。 如第5A圖」中所示’當紫外線固化液態預聚合物用於具有 白色附加結構的液晶齡裝置巾時，自色濾光#層及保護膜層可 經由紫外、_化液態預聚合物而同步形成。此外，陳間隙物及 自色濾光片層與賴膜層可經由紫外線固化㈣預聚合物而形 成。 r , . 「々片 第6圖」顯示一截面圖，描繪使用紫外線固化液態預聚合 物的液晶顯示裝置。如「第6圖」中所示，液晶顯示裝置包括做 _ 為圖案層的紫外線固化液態預聚合物。液晶顯示裝置包括彼此相 對的第一基板100及第二基板（未顯示），及形成於第一與第二基 板之間的液晶層，其中第一基板1〇〇包括均勻配置的紅、綠、藍 及白色子像素。 而且’第一基板1〇〇包括蔽光層m，其形成於子像素之外的 t 其他部分中。紅、綠及藍色濾光片層112分別置於紅、綠及藍色 子像素中，且平面化圖案層210形成於包括蔽光層ln及紅、綠 及監色濾光片層112的整個表面上。平面化圖案層21〇係由上述 紫外線固化液態預聚合物形成。 平面化圖案層210係經由應用包括約3〇〜6〇%體積的單機能 單體（M)、約20〜50〇/〇體積的雙機能單體（D)及約1〇〜2〇%體 積的三機能單體（T)之絷外線固化液態預聚合物的塗佈而形成。 16 200827931 如果平面化圖案層2K)係以上述紅、綠、藍及白色子像素形成， 平面化圖*層210便做為白色子像素中白色濾光片層η;，亦做為 其他區中保護膜層114。如圖式中所示，平面化圖案層210具有蔽 光層111上方的凸出部分，使得平面化圖案層21〇可做為圓柱間 隙物115。 - II柱間祕115及平面化圖案層21〇可於不同步驟中形成。 在此狀況下，平面化_層於基板之圓柱間隙物之區之外的整個 (表面上平坦形成。如圖式中所示’複數層經由平面化圖案層加 而一同形成，使其可減少第一基板100的步驟數量。 - 相對於具有顏色遽光片陣列之第-基板而準備具有薄膜電晶 體陣列的第二基板。薄膜電晶體陣列包括閘極及資料線，其於每 一子像素、鄰近閘極及倾叙交錯的_電晶體及職於每一 子像素中像素電極的邊界彼此交錯。該像素電極可與每一子像素 中像素電極交替。那麼’第一校準層118便形成於包括平面化圖 案層210之第一基板1〇〇的整個表面上，且第二校準層（未顯示） 可軸於包括晶斷狀第二紐錄面上。 在第6圖」中’平面化圖案層21〇於校準層形成之後，具 有相應於紅、綠、藍及白色子像素的平坦上表面。經由形成平面 化圖案層210,可提供減於白色子像素的白色滤光片層ιΐ3及保 護膜層114，以使包括蔽光層m的第一基板1〇〇平面化。在固化 平面化圖*層210之後’平面化圖案層加中交連及密閉改進。 17 200827931 =而’平面化圖案層21G維持其體積不因其高熱穩定性而實質收 鈿卩使於平面化圖案層21〇形成後實施額外熱處理以形成校準 ^ 相應於白色子像素的部分亦不會凹下或收縮，使得平面化 圖案層210維持均勻的厚度。 其次’液晶層形成於包括顏色濾光片陣列的第一基板1〇〇與 祕薄膜電晶體陣列的第二基板（未顯示）之間。為形成液晶層^ 魏人口之密封劑形成於第—或第二基板上，且液晶材料施予具有 ( 岔封劑的基板。第一及第二基板接著彼此結合。在另一方法中， 具入口之賴劑形成於第-或第二基板上，且第—及第二基板彼 此結合。藉使用毛細現象及壓力差，液晶材料經由入口而注入苐 一及第二基板之間的空間。 如上述，紫外線固化液態預聚合物及使用紫外線固化液態預 聚合物的液晶顯示裝置具有下列優點。第一，可避免預定的圖案 部分因熱處理而收縮。第二，紫外線固化液態預聚合物可用於一 ^ 起形成白色濾光片層、保護膜層及圓柱間隙物，其中紫外線固化 液態預聚合物包括預定比例的雙機能單體、三機能單體及單機能 ， 單體。因而，即使於使用紫外線固化液態預聚合物形成圖案之後 實施熱處理，亦可避免具有分支或交連結構的紫外線固化液態預 聚合物之體積免於收縮或減少，藉以體現具耐熱的紫外線固化液 態預聚合物。紫外線固化液態預聚合物的使用避免白色子像素部 分收縮或凹下，藉以提供高品質的圖像裝置及避免組織間隙。 18 200827931 賴本發明以前述之概實施_露如上，然其並非用以限 疋本發明，任何熟習相像技藝者，在不脫離本發明之精神和範圍 内’當可作些許之更動與潤飾，因此本發明之專利保護範圍須視 本說明書所附之申請專利範圍所界定者為準。 【圖式簡單說明】 - 第1圖為具有白色子像素之矩形單一像素的示意圖。 第2A圖至第2C圖顯示截面圖，描繪製造矩形像素結構之顏 Ο 色濾光片陣列基板的方法。 第3圖顯示截面圖，描繪烘焙校準層之後顏色濾光片陣列之 - 收縮。 第4A圖至第4C圖顯示包括單機能群組之紫外線固化液態預 聚合物於固化過程及熱處理之後的體積改變。 第5A圖至第5C圖顯示包括分支或交連之機能群組的紫外線 固化液態預聚合物於固化過程及熱處理之後的體積改變。 I). 弟6圖顯示截面圖，描繪使用紫外線固化液態預聚合物的液 - 晶顯示裝置。 【主要元件符號說明】 ίο、1〇〇 第一基板 11 ^ 111 蔽光層 112 紅、綠及藍色濾光片層 12a 紅（R)色濾光片層 19 200827931 12b 綠（G)色濾光片層 12c 藍（B)色濾光片層 13 圖案材料層 130 圖案 130a 圖案表面 14、113 白（W)色濾光片層 14a 白色濾光片層的厚度 15、114 保護膜層 15a 保護膜層的厚度 16、115 圓柱間隙物 18、118 校準層 20 鑄模 51 > 200 紫外線固化液態預聚合物 52、52a、210 圖案層 D 雙機能單體 I 光起始劑 Irgacure 184、Irgacure 369、Irgacure 819 M 光起始劑 單機能單體 T 三機能單體 20The yule diagram, even if the additional layer is applied to the pattern layer by curing, the __ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In the portion where the adjacent strands are not interconnected, the branches are the gaps between the linear chains of the towers. As a result, the volume of the pattern layer 21G is fixed. In particular, for the structure of the pattern layer 210 in which the linear chains are sequentially stacked, the change in the thickness of the cross-links and the branches can be minimized. ° For the following reasons, the UV-curable liquid prepolymer comprises about 30 to 60% by volume of the single functional monomer CM), about 20 to 50% by volume of the dual functional monomer (D) and about 2 to 2 〇 °. Volumetric three-function monomer (τ). As the number of functional groups increases, the number of connections and branches also increases through the activation of functional groups. The shrinkage of the UV-curable liquid prepolymer is minimized by an external heat treatment after the curing process. However, the viscosity is also increased with the number of functional groups. Therefore, when a pattern is formed by providing a scale mold selection, for example, a soft mold applied to a substrate coated with an ultraviolet curing liquid prepolymer, the mobility and the reaction speed are lowered, and it is difficult to obtain a desired pattern on the substrate. Therefore, the viscosity increase of the UV-curable liquid prepolymer is limited to a maximum of 14 200827931. The UV-curable liquid prepolymer is provided in an amount of about 20% by volume or more of the trifunctional monomer to form the desired pattern. In order to limit the increase in viscosity, the UV-curable liquid prepolymer may include a dual function monomer and a trifunctional monomer to ensure thermal stability. The dual functional monomer and the trifunctional monomer assist in branching and cross-linking via activation of ultraviolet light. The use of dual-function monomers, three-function monomers, and single-function monomers provides greater thermal stability than using only single-function monomers. (When only dual-functional monomers and tri-functional monomers are used, the reaction rate for activating each monomer using ultraviolet irradiation is reduced due to a large number of functional groups. In this respect, UV-curable liquid prepolymers necessarily require a single function. The monomer can improve the reaction rate and obtain appropriate viscosity by providing about 3% to about '6% by volume of a single functional monomer. The ultraviolet curing liquid prepolymer is used for pattern formation according to the following steps. First, prepare a mold structure such that the back surface of the mold structure has a back surface, and the back surface has a concave surface and a convex portion. (J; the substrate is coated with the ultraviolet curing liquid prepolymer relative to the mold structure. Then, the mold structure is Introducing the contact ultraviolet curing liquid prepolymer, followed by curing 'so that a predetermined pattern corresponding to the concave and convex portions of the mold structure is formed on the surface of the external and external solidified liquid prepolymer. Thereafter, the mold structure is combined with the ultraviolet curing liquid prepolymer The predetermined pattern is separated. As explained above, 'ultraviolet-cured liquid prepolymer can be applied to non- The process of the exposure process and the structure of the prayer pattern. For example, after the liquid prepolymer coating base 15 200827931 is cured by ultraviolet light, the 'predetermined pattern can be formed in the ultraviolet curable liquid prepolymer via printing. As shown in Fig. 5A When the UV-curable liquid prepolymer is used for a liquid crystal age device having a white additional structure, the self-color filter layer and the protective film layer can be simultaneously formed via ultraviolet, liquidated prepolymer. The material and the self-color filter layer and the film layer can be formed by ultraviolet curing of the (four) prepolymer. r , . "Brush chart 6" shows a cross-sectional view depicting a liquid crystal display device using ultraviolet curing liquid prepolymer As shown in "Fig. 6," the liquid crystal display device includes an ultraviolet curing liquid prepolymer which is a pattern layer. The liquid crystal display device includes a first substrate 100 and a second substrate (not shown) opposed to each other, and is formed. a liquid crystal layer between the first and second substrates, wherein the first substrate 1 〇〇 includes uniformly arranged red, green, blue, and white sub-pixels. And 'the first substrate 1 〇 A masking layer m is formed, which is formed in other portions of t other than the sub-pixels. The red, green, and blue color filter layers 112 are respectively disposed in the red, green, and blue sub-pixels, and the planarization pattern layer 210 is formed. The entire surface of the mask layer ln and the red, green and color filter layers 112 is formed. The planarization pattern layer 21 is formed of the above-mentioned ultraviolet-curable liquid prepolymer. The planarization pattern layer 210 is applied via an application. 3〇~6〇% of the single functional monomer (M), about 20~50〇/〇 volume of the dual functional monomer (D) and about 1〇~2〇% of the volume of the three functional monomer (T) Formed by the coating of the external solidified liquid prepolymer. 16 200827931 If the planarization pattern layer 2K) is formed by the above red, green, blue and white sub-pixels, the planarization map layer 210 is white as a white sub-pixel. The filter layer η; also serves as the protective film layer 114 in other regions. As shown in the figure, the planarization pattern layer 210 has a convex portion above the light shielding layer 111, so that the planarization pattern layer 21 can be used as the cylindrical spacer 115. - The inter-column fins 115 and the planarization pattern layer 21 can be formed in different steps. In this case, the planarization layer is formed entirely outside the region of the cylindrical spacer of the substrate (the surface is flatly formed. As shown in the figure, the plural layers are formed together by the planarization pattern layer, so that it can be reduced The number of steps of the first substrate 100. - preparing a second substrate having a thin film transistor array with respect to the first substrate having the color filter array. The thin film transistor array includes a gate and a data line at each sub-pixel The adjacent gates and the staggered interleaved _ transistors and the boundaries of the pixel electrodes in each sub-pixel are interlaced with each other. The pixel electrodes can alternate with the pixel electrodes in each sub-pixel. Then the first calibration layer 118 is formed. On the entire surface of the first substrate 1A including the planarization pattern layer 210, and the second alignment layer (not shown) may be axially included on the second blank surface of the crystal cut. In FIG. The patterned layer 21 has a flat upper surface corresponding to the red, green, blue, and white sub-pixels after the alignment layer is formed. By forming the planarization pattern layer 210, a white filter layer ι 3 that is reduced by the white sub-pixel can be provided. And The film layer 114 is configured to planarize the first substrate 1 including the light shielding layer m. After curing the planarization pattern * layer 210, the 'planar pattern layer is added to the intermediate junction and the sealing is improved. 17 200827931 = and 'planarization The pattern layer 21G maintains its volume without being substantially contracted by its high thermal stability so that an additional heat treatment is performed after the planarization pattern layer 21 is formed to form a calibration. The portion corresponding to the white sub-pixel does not be recessed or shrunk, so that The planarization pattern layer 210 maintains a uniform thickness. Next, a liquid crystal layer is formed between the first substrate 1 including the color filter array and the second substrate (not shown) of the secret film transistor array. The sealant of the Wei population is formed on the first or second substrate, and the liquid crystal material is applied to the substrate having the sealant. The first and second substrates are then bonded to each other. In another method, the inlet is applied. Formed on the first or second substrate, and the first and second substrates are bonded to each other. By using a capillary phenomenon and a pressure difference, the liquid crystal material is injected into the space between the first substrate and the second substrate via the inlet. The external solidified liquid prepolymer and the liquid crystal display device using the ultraviolet curable liquid prepolymer have the following advantages. First, the predetermined pattern portion can be prevented from shrinking due to heat treatment. Second, the ultraviolet curable liquid prepolymer can be used for one. Forming a white filter layer, a protective film layer and a cylindrical spacer, wherein the ultraviolet curing liquid prepolymer comprises a predetermined ratio of a dual function monomer, a trifunctional monomer, and a single function, a monomer. Therefore, even if the ultraviolet curing liquid is used The heat treatment after the prepolymer is patterned can also avoid the shrinkage or reduction of the volume of the ultraviolet curing liquid prepolymer having a branched or crosslinked structure, thereby reflecting the heat-resistant ultraviolet curing liquid prepolymer. The use avoids shrinkage or depression of the white sub-pixel portion, thereby providing a high quality image device and avoiding tissue gaps. 18 200827931 The invention is described in the foregoing, and is not intended to limit the invention. Therefore, the scope of patent protection of the present invention is defined by the scope of the claims appended hereto. [Simplified Schematic] - Figure 1 is a schematic diagram of a rectangular single pixel with white sub-pixels. 2A to 2C are cross-sectional views showing a method of manufacturing a color filter array substrate of a rectangular pixel structure. Figure 3 shows a cross-sectional view depicting the shrinkage of the color filter array after baking the calibration layer. Figures 4A through 4C show volume changes of the UV-curable liquid prepolymer comprising a single functional group after curing and heat treatment. Figures 5A through 5C show volume changes of the UV-curable liquid prepolymer comprising branching or cross-linking functional groups after curing and heat treatment. I). Figure 6 shows a cross-sectional view depicting a liquid crystal display device using a UV-cured liquid prepolymer. [Description of main component symbols] ίο, 1〇〇 first substrate 11 ^ 111 light shielding layer 112 red, green and blue color filter layer 12a red (R) color filter layer 19 200827931 12b green (G) color filter Light sheet layer 12c Blue (B) color filter layer 13 Pattern material layer 130 Pattern 130a Pattern surface 14, 113 White (W) color filter layer 14a White filter layer thickness 15, 114 Protective film layer 15a Protection Film thickness 16,115 Cylindrical spacers 18,118 Calibration layer 20 Mold 51 > 200 UV-curing liquid prepolymer 52, 52a, 210 Pattern layer D Dual function monomer I Photoinitiator Irgacure 184, Irgacure 369, Irgacure 819 M photoinitiator single function monomer T three function monomer 20