1286144 九、發明說明： 【發明所屬之技術領域】 本發明有關一種可輻射固化之分支聚胺酯以及含此分支 聚胺醋之輻射可固化之墨水組成物。 【先前技術】 薄膜電晶體液晶顯示器（TFT LCD)的彩色濾光片為一般液 晶顯示器中的重要元件之一，其主要功用是將白色背光轉換紅 色(R)、綠色(G)、藍色(B)等三原色，得以形成顯示器全彩化 目的。目前彩色濾光片的製作是以旋轉塗佈的方式，將光^劑 塗佈於玻璃基板上，預烘烤、經過光罩曝光、隨後顯影的製程， ’重複三次後依序將RGB三種顏色蝕刻在玻璃基板上，該種製程 不僅步驟繁瑣，且將近有90%的光阻液會在旋轉塗佈以及顯影 時損失、浪費，造成製造成本負擔。有鐘於此，而發展出喷墨 技術取代傳統的旋轉塗佈法。此喷墨技術是將紅色(R)、綠色 (G)、藍色(B)彩色顏料墨水喷塗於基板上，再經由熱或yy光 照射固化，隨後經過平坦化製程，完成彩色濾光片的製作。此 種喷墨技術不需要如旋轉塗佈法中的光阻劑塗佈、預烘烤、光 罩曝光、隨後顯影等製程。與傳統方法相較，此種喷墨方法可 大幅降低設備成本、簡化製程、減少廢液並提升彩色墨水材料 _ 的運用效率。 ’ 雖然以喷墨技術製造衫色渡光片的方法具有簡化製程、環 保且省料等諸多優勢，但仍有其開發困難度，因為傳統彩色光 阻劑製程一般選用高分子量之感光樹脂達成成品的耐熱性、附 者力等物性要求，然而喷墨法彩色渡光片製作時難以將傳統彩 色光阻劑改良作成喷墨頭使用的喷墨交聯油墨。 / 在過去相關研究中，佳能(Canon)公司曾發表相關製程， 例如美國專利號US 6162510中揭示一種水性感光基環氧樹脂 組合成墨水以喷墨方式製作彩色濾光片。而中華民國公開公報 2004-11026號專利中述及交聯型UV感光樹脂作為水性墨水之 1286144 份有限公司生產的季戊四醇三丙烯酸酯（商品名為Ai® 2884) 〇 _ 本發明中用以製備分枝聚胺酯之含至少三個經基之單體 包含各種多元醇，例如三羥曱基丙烷(TMP)、甘油、季戊四醇、 ，二季戊四醇、山梨糖醇、及其他具樹枝狀多羥基之單體。該等 單體可利用環氧乙烷、環氧丙烷、己内酯等進行鏈延長改質， 將更有助於控制型態及分子量。另用利用伸乙二胺加上環氧乙 • 烧或壤氧丙烧早體進行反應所形成之含4個經基官能基之化 合物亦可使用。 本發明之具有樹枝狀結構之分枝聚胺酯由於具有較高分 % 子量以及較多的丙浠酸基供輻射固化並交聯，而可提高物性、 接者性及财熱性’且在南固形份之下，具有較低黏性可賦予流 動性，因此使用在喷印用途時，不會因黏度問題導致喷嘴阻 塞。此外，由於具有高固形份，因此可藉由較少的喷印次數即 可達到所需厚度。且由於本發明之具有樹枝狀結構之分枝聚胺 酯易形成氬鍵之胺酯基結構，可進一步提升物性及耐熱性。 本發明組成物中所用的丙烯酸單體(B)，可舉例如單、二 -、三-或多-官能基單體。單官能基單體可舉例如丙烯酸2一苯 氧基乙基酯、丙烯酸四氳呋喃基酯、丙烯酸異冰片酯、曱基丙 鲁 烯酸異冰片酯、丙烯酸2-(2_乙氧基乙氧基）乙酯、丙烯酸異 癸酯、丙烯酸月桂基酯及甲基丙烯酸月桂基酯。二官能基單體 可舉例如二丙婦酸二丙二醇醋、二丙稀酸1，6-己二醇醋、二 甲基丙稀酸1，6_己^~醇酿、二丙稀酸^丙二醇醋、二甲基丙 歸酸二乙二醇酯、二甲基丙婦酸6二醇酯、二丙稀酸三乙二醇 酯、二甲基丙烯酸三乙二醇酯、二丙烯酸四乙二醇酯、二甲基 4 丙烯酸四乙二醇醋。三官能基或多官能基單體可舉例如三丙烯 酸二(經甲基）丙醋、二甲基丙稀酸三(幾甲基）丙醋、四丙稀酸 雙(三(經甲基）丙酯）、五丙埽酸二季戊四醇酯及六丙烯酸二季 戊四醇酯等。此等丙烯酸基單體可單獨使用或混合兩種以上使 1286144 用。 本發明組成物中所用的光起始劑(c)為在受到可見光、紫 外光、遠紫外光、電子束以及X射線等輻射光照射下，其分子 結構會發生裂解產生如游離基、陽離子或陰離子等活性位點， 而與具有樹枝狀結構之分枝聚胺酯（A)與丙烯酸單體(B)進行 聚合反應者。 光起始劑（C)實例可舉例如咪唑類如2,2’-雙（2-氯苯 基)-4,4’，5,5’-肆(4-甲氧基羰基苯基)-1，2’-二咪唑、2,2’-雙 (2-氯苯基)-4,4’，5,5’-肆(4-乙氧基羰基苯基）-1，2’-二咪 唑、2,2’-雙（2-氣苯基）-4,4’，5,5’-肆（4-苯氧基羰基苯 基)-1，2’-二咪唑、2,2’-雙(2,4-二氯苯基)-4,4’，5, 5’-肆(4-甲氧基羰基苯基）-1，2’-二咪唑、2,2’-雙（2,4-二氯苯 基)-4,4’，5,5’-肆(4_乙氧基羰基苯基)-1，2’-二味唑、2,2’-雙 (2, 4-二氯苯基)-4,4’，5, 5’-肆(4-苯氧基羰基苯基)-1，2’-二 咪唑、2, 2’-雙(2,4, 6-三氯苯基)-4, 4’，5,5’-肆(4-甲氧基羰基 苯基)-1，2’-二咪唑、2, 2’-雙(2,4, 6-三氯苯基)-4,4’，5,5’-肆 (4-乙氧基羰基苯基)-1，2’-二咪唑、2,2’-雙(2, 4, 6-三氯苯 基)-4,4’，5,5’-肆(4-苯氧基幾基苯基)-1，2’-二味峰、2,2’-雙 (2-溴苯基)-4,4’，5,5’-肆(4-甲氧基幾基苯基）-1，2’-二味 唑、2,2’-雙（2-溴苯基）-4,4’，5,5’-肆（4-乙氧基羰基苯 基)-1，2’-二咪唑、2,2’-雙(2-溴苯基)-4,4’，5, 5’-肆(4-苯氧 基羰基苯基）-1，2’-二咪唑、2, 2’-雙（2,4-二溴苯 基)-4,4’，5,5’-肆(4-甲氧基羰基苯基)-1，2’-二咪唑、2,2’-雙 (2,4-二溴苯基)-4, 4’，5, 5’-肆(4-乙氧基羰基苯基H，2’-二 咪唑、2,2’-雙(2,4-二溴苯基)-4,4’，5, 5’-肆(4_苯氧基羰基苯 基)-1，2’-二咪唑、2,2’-雙(2,4, 6-三溴苯基)-4,4’, 5, 5’-肆 (4-甲氧基羰基苯基)-1，2’-二咪唑、2,2’-雙(2,4, 6-三溴苯 基)-4,4’，5,5’-肆(4-乙氧基羰基苯基)-1，2’-二咪唑、2, 2’-雙 (2, 4, 6-三溴苯基)-4,4’，5, 5’-肆(4-苯氧基羰基苯基)-1，2’- 1286144 二咪唑、2, 2’-雙(2-氰基苯基)-4,4’，5, 5’-肆(4-甲氧基羰基苯 基)-1，2’-二咪唑、2, 2’-雙(2-氰基苯基)-4,4’，5, 5’-肆(4-乙 氧基羰基苯基）-1，2’-二咪唑、2,2’-雙（2-氰基苯 基)-4,4’，5, 5’-肆(4-苯氧基羰基苯基H，2’-二咪唑、2,2’-雙 (2-甲基苯基)-4,4’，5,5’-肆(4-甲氧基羰基苯基)-1，2’-二咪 唑、2,2’-雙(2-甲基苯基）-4,4’，5,5’-肆(4-乙氧基羰基苯 基)-1，2’-二咪唑、2, 2’-雙(2-甲基苯基)-4,4’，5, 5’-肆(4-苯 氧基羰基苯基）-1，2’-二咪唑、2,2’-雙（2-乙基苯 基)-4,4’，5, 5’-肆(4-甲氧基羰基苯基)-1，2’-二咪唑、2,2’-雙 (2-乙基苯基)-4, 4’，5,5’-肆(4-乙氧基羰基苯基)-1，2’-二咪 唑、2,2’_雙(2-乙基苯基)-4,4’，5,5’_肆(4-苯氧基羰基苯 基)-1，2’-二咪唑、2, 2’-雙(2-苯基苯基)-4,4’，5, 5’-肆(4-甲 氧基羰基苯基）-1，2’-二咪唑、2, 2’-雙（2-苯基苯 基)-4,4’，5, 5’-肆(4-乙氧基羰基苯基)-1，2’-二咪唑、2,2’-雙 (2-苯基苯基)-4,4’，5,5’-肆(4-苯氧基羰基苯基)-1，2’-二咪 唑、2, 2’-雙(2-氯苯基)-4,4’，5, 5’-四苯基-1，2’-二咪唑、 2, 2’_雙(2,4-二氯苯基)-4,4’，5, 5’-四苯基-1，2’-二咪唑、 2, 2’-雙(2,4,6-三氯苯基)-4,4’，5, 5’-四苯基-1, 2’-二咪唑、 2, 2’-雙(2-溴苯基)-4,4’，5, 5’-四苯基-1，2’-二咪唑、2,2’-雙 (2,4-二溴苯基)-4,4’，5,5’_四苯基-1，2’-二咪唑、2,2’-雙 (2,4, 6-三溴苯基)-4,4’，5, 5’-四苯基-1,2’-二咪唑、2,2’-雙 (2-氰基苯基)-4,4’，5,5’-四苯基-1，2’-二味唾、2, 2’-雙(2,4-二氰基苯基）-4,4’，5,5’_四苯基-1，2’-二咪唑、2,2’-雙 (2,4, 6-三氰基苯基)-4,4’，5, 5’-四苯基-1，2’-二味〇坐、2, 2’-雙(2-甲基苯基)_4,4’，5,5’-四苯基-1，2’-二咪唑、2,2’-雙 (2,4-二甲基苯基)-4,4’，5, 5’-四苯基-1，2’-二咪唑、2,2’-雙 (2,4,6-三甲基苯基)-4,4’，5, 5’-四苯基-1，2’-二味嗤、2,2’-雙（2-乙基苯基)-4,4’，5, 5，-四苯基-1，2’-二咪唑、2,2’-雙 (2,4-二乙基苯基)-4,4’，5, 5’-四苯基-1，2’-二咪唑、2,2’-雙 1286144 (2,4, 6-三乙基苯基)-4,4’，5, 5’-四苯基—12，—二味唾 一 雙（2-苯基苯基)-4,4，，5,5，-四苯基-丨’ 2，—二咪唑、2 2，’錐 (2,4-二苯基苯基)-4,4’，5,5,-四苯基—丨，2，—二咪唑、2 = ， (2,4, 6-三苯基苯基)-4,4，，5, 5’-四苯基—i，2，—二咪唑^ = 及其類似衍生物;較好為2, 2’-雙(2-氣苯基)_4,4，，5, 5，_^ t 乙氧基幾基苯基）-1，2’-二咪唆、2,2，-雙（2一、拿笑 基)-4,4，，5,5，-肆(4-乙氧基羰基笨基)_1，2，’—二咪唾、一= (2,4-一氣本基）-4,4’，5, 5-四本基-1，2’一二咪峻、2 2，—雔 (2,4, 6-二氯苯基)-4,4，5,5 -四笨基一 1，2’-二咪唾、2 2，-雔 (2,4-一漠苯基)-4,4，，5, 5-四笨基-1，2’-二味唾及2 2，—雜 _ (2,4, 6-二>臭苯基)-4,4,5, 5 -四表基—1，2’—二咪唾。又可舉 如苯偶因（Benzoin)類光起始劑例如苯偶因、苯偶因甲基鍵、 苯偶因乙基醚、苯偶因異丙基醚、笨偶因異丁基喊、甲基一2'一 笨甲醯基苯甲酸酯等以及其類似衍生物。又可舉例如苯乙1網類 結構例如2, 2-二甲氧基-2-苯基笨乙酮、2-經基一2一甲基一1 一^ 基丙-1-酮、1_(4-異丙基苯基)-2-羥基-2-甲基丙一 1—酮、4—(2 一 經基乙氧基）苯基-(2-經基-2-丙基）嗣、2, 2-二甲氧基苯乙 嗣、2, 2-二乙氧基苯乙酮、2-甲基-(4-甲硫基苯基)—2-嗎啉基 -1-丙-1-酮、2-苄基_2-二甲胺基-1 -(4-嗎琳基苯基）丁一 1 一 | _、1-羥基環己基苯基酮、2,2’ -二甲氧基一ι 2-二苯基乙一卜 鲷、4-疊氮基苯乙酮、4-疊氮基亞苄基苯乙酮等以及類似衍生 物。又可舉例如二苯甲酮類如二苯甲酮、4,4，-雙(二甲胺基） 二苯甲酮、4,4’ -雙(二乙胺基)二苯甲酮、3,3’ _二甲基-4-甲氧基二苯甲酮等及其類似衍生物。具有α-二酮結構之光起始 劑，例如二乙醯基甲酸酯、二苯甲醯基甲酸酯、甲基苯甲醯基 甲酸酯等以及類似衍生物。具有多核醌結構之光起始劑如蒽 醌、2-乙基蒽酿、2-第三丁基蒽醌、1，4-萘醌等及類似衍生物。 黃_類以3111:11〇肪)結構之光起始劑如黃明、琉代黃酮、2,4-二乙基硫代黃酮、2-氣硫代黃酮等及類似衍生物。具有重氮結 1286144 構之光起始劑如4—重氮二苯基胺、4-重氮-4’ -甲氧基二苯基 胺、4-疊氮基_3-甲氧基二苯基胺等以及類似衍生物。具有三 唤結構之光起始劑如2-(2’ -11 夫味基亞乙基)-4, 6-雙(三氯甲 基)-s-三嗪、2-(3’，4’ -二甲氧基苯乙烯基)-4, 6-雙(三氣甲 基)-s-三嗪、2-(4’ -甲氧基萘基)_4,6-雙（三氯甲基)—s一三 唤、2-(2’ -溴-4’ -甲基苯基)-4, 6-雙(三氯甲基)-3一三嗪、 2- (2’ _隹吩基亞乙基)-4, 6-雙（三氯曱基)-s-三嗪等以及類 似衍生物。 除了上述所列舉之光起始劑以外，亦可使用4-重氮基苯 甲醛、疊氮基芘、雙(2, 6-二甲氧基苯甲醯基)2,4,4-三甲基戊 _ 基鱗氧化物、N-苯基硫代吖唆酮、三苯基芘鑌高氯酸鹽等以及 類似衍生物。該等光起始劑可單獨使用亦可混合兩種以上使 用。 本發明組成物中可使用之接著助劑(D)包含具有乙稀基官 能基之梦烷類如乙烯基三氣乙烷、乙烯基三甲氧基發烷、乙烯 基三乙氧基石夕烷；含環氧官能基之石夕烷類如2-(3,4-環氧基環 己基)-乙基三甲氧基砍烧、3-縮水甘油氧基丙基三甲氧基梦 烷、3-縮水甘油氧基丙基甲基二乙氧基砍烷、3-縮水甘油氧基 丙基^乙氧基每，含甲基丙稀酿^氧基之烧類例如3-甲基 丙烯醯氧基丙基甲基二甲氧基石夕烷、3-甲基丙烯醯氧基丙基三 甲氧基砍娱;、3-甲基丙烯醯氧基丙基甲基二乙氧基梦烧、3-甲基丙烯醯氧基丙基三乙氧基石夕烷；含丙烯醯氧基之發烷類如 3- 丙烯醯氧基丙基三甲氧基矽烷；含胺基官能基之矽烷類如 N- (2-胺基乙基)_3-胺基丙基甲基二甲氧基發烧、N- (2-胺基乙 基)-3-胺基丙基三甲氧基石夕烷、N-(2-胺基乙基)-3-胺基丙基 .二乙氧基發烧、3-胺基丙基三甲氧基發烧、3-胺基丙基三乙氧 基發烧、3-三乙氧基砍烧基-N-(l，3-二甲基亞丁基）丙基胺、 N-苯基-3-胺基丙基三甲氧基石夕烷、N-（乙烯基苄基)-2-胺基丙 基三甲氧基石夕烷鹽酸鹽；含脲基官能基之砍烷類如3-脲基丙 ⑧ 12 1286144 基三乙氧基石夕烧；含氯丙基官能基之發烧類如3-氯丙基三甲 氧基石夕烷；含氫硫基官能基之石夕烷類如3-氫硫基丙基甲基二 •甲氧基矽烷、3-氫硫基丙基三甲氧基矽烷；含硫醚官能基之梦 烷類如雙(三乙氧基石夕烷基丙基）四硫醚；含異氰酸酯基官能基 之石夕烷類如3-異氫酸酯基丙基三乙氧基石夕烷。使用量約為墨 水組成物總重之0〜3重量。/〇。 本發明組成物中可使用之著色劑(E)可使用具有耐熱性之 有機顏料，例如C· I·顏料黃(Pigment Yellow) 83、C. L顏料 黃110、C· I·顏料黃138、C· I·顏料黃139、C. I.顏料黃150 及C.I·顏料黃155;C.I·顏料撥71;C.I·顏料紫19及C.I. 顏料紫23 ; C· I·顏料紅48:1、C· I·顏料紅48:2、C. L顏料紅 48:3、C· I·顏料紅48:4、C· I·顏料紅 122、C. I.顏料紅 177、 C· I·顏料紅202、C· I·顏料紅206、C· I·顏料紅207、C· I.顏 料紅209、C· I·顏料紅224及C· I·顏料紅254 ; C· I·顏料藍 15:3、C· I·顏料藍15:4及C· I·顏料藍15:6 ; C· I.顏料綠7及 C· I·顏料綠36 ; C· I·顏料棕23及C· I·顏料棕25 ; C· I·顏料 黑 1 及 C· I·顏料黑 7。（C· I 為 The Society of Dyers and Colourists Co·所制定公佈）。上述著色劑可單獨使用或可組 合兩種以上使用。使用量約為墨水組成物總重之5〜40%。 本發明組成物中使用之分散劑(F)係Avecia公司所生產 的S32000，是一種陽離子型聚(烧基亞胺），與有游離羧基的羥 基硬脂酸酯(hydroxy stearate)反應形成醯胺。添加後經砂輪機 研磨可幫助著色劑穩定分散。使用量約為著色劑(E)的3〇重量 %。 本發明組成物中使用之溶劑(G)係用以獲得保持液態並控 制組成物在適宜喷霧之黏度。所用的溶劑只要是可溶解或分散 上述組成物中所含之成分、且不參與反應且具有適當揮發性即 〇 可使用的溶劑舉例如：（聚)伸烧二醇單烷基醚如乙二醇單 13 1286144 單己其醇單正丁基醚、三乙二醇單甲基醚、三乙二醇 基鍵:丙-醢：醇翠甲基醚、丙二醇單乙基鍵、丙二醇單正丙 鍵、，一丁基醚、二丙二醇單甲基縫、二丙二醇單乙1286144 IX. Description of the Invention: [Technical Field] The present invention relates to a radiation curable branched polyurethane and a radiation curable ink composition comprising the branched polyurethane. [Prior Art] The color filter of a thin film transistor liquid crystal display (TFT LCD) is one of the important components in a general liquid crystal display, and its main function is to convert a white backlight into red (R), green (G), blue ( B) The three primary colors can be used to form a full color display. At present, the color filter is produced by spin coating, applying a photoresist to a glass substrate, pre-baking, exposing through a reticle, and then developing, "repeating three times and sequentially RGB three colors. Etching on a glass substrate is not only cumbersome, but nearly 90% of the photoresist is lost and wasted during spin coating and development, resulting in a manufacturing cost burden. There is a clock here, and inkjet technology has been developed to replace the traditional spin coating method. The inkjet technology is to spray red (R), green (G), blue (B) color pigment ink on a substrate, and then cure by heat or yy light irradiation, and then through a planarization process to complete the color filter. Production. Such ink jet technology does not require processes such as photoresist coating, prebaking, reticle exposure, and subsequent development in a spin coating process. Compared to conventional methods, this inkjet method can significantly reduce equipment costs, simplify processes, reduce waste, and improve the efficiency of color ink materials. Although the method of making shirt color by inkjet technology has many advantages such as simplified process, environmental protection and material saving, it still has difficulty in development, because the traditional color photoresist process generally uses high molecular weight photosensitive resin to achieve the finished product. However, it is difficult to improve the conventional color resist as an inkjet crosslinked ink used in an ink jet head. / In the past related research, Canon has published a related process. For example, a water-based photosensitive epoxy resin synthetic ink disclosed in US Pat. No. 6,162,050 is an ink jet ink filter. In the Republic of China Publication No. 2004-11026, a cross-linked UV-sensitive resin is used as a pentaerythritol triacrylate (trade name: Ai® 2884) produced by 1286144 parts of water-based ink. The monomer containing at least three vials of the polyurethane comprises various polyols such as trishydroxypropylpropane (TMP), glycerin, pentaerythritol, dipentaerythritol, sorbitol, and other dendritic polyhydroxyl monomers. These monomers can be modified by chain extension using ethylene oxide, propylene oxide, caprolactone, etc., and will be more useful for controlling the type and molecular weight. Further, a compound having four radical functional groups formed by a reaction using ethylenediamine or epoxy bromide or a oxyfluoride can also be used. The branched polyurethane having the dendritic structure of the present invention has higher molecular weight and more propionate groups for radiation curing and cross-linking, thereby improving physical properties, acceptability and finerification' and is in the south solid shape. Below the part, the lower viscosity gives the fluidity, so when used for printing purposes, the nozzle will not be blocked due to viscosity problems. In addition, since it has a high solid content, the desired thickness can be achieved with a small number of printing times. Further, since the branched polyurethane having a dendritic structure of the present invention easily forms an amine ester group structure of an argon bond, physical properties and heat resistance can be further improved. The acrylic monomer (B) used in the composition of the present invention may, for example, be a mono-, di-, tri- or poly-functional monomer. The monofunctional monomer may, for example, be 2-phenoxyethyl acrylate, tetrafurfuryl acrylate, isobornyl acrylate, isobornyl decyl urethane, 2-(2-ethoxy acrylate) Oxy)ethyl ester, isodecyl acrylate, lauryl acrylate and lauryl methacrylate. The difunctional monomer may, for example, be dipropylene glycol dipropylene glycol vinegar, dipropylene dihydrogen acid 1,6-hexanediol vinegar, dimethyl propylene acid 1,6-hexanol alcohol, dipropylene acid ^ Propylene glycol vinegar, diethylene glycol diethylene glycol ester, dimethyl propylene glycol acid 6 glycol ester, dipropylene glycol triethylene glycol ester, triethylene glycol dimethacrylate, tetraethyl acrylate Glycol ester, dimethyl 4 acrylate tetraethylene glycol vinegar. The trifunctional or polyfunctional monomer may, for example, be di(methyl)propyl acrylate, tris(monomethyl)propane dimethyl dimethyl acrylate or bis (trimethyl) methacrylate Propyl ester), dipentaerythritol pentapropionate, dipentaerythritol hexaacrylate, and the like. These acrylic monomers may be used alone or in combination of two or more for use in 1286144. The photoinitiator (c) used in the composition of the present invention is subjected to irradiation with visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like, and its molecular structure is cleaved to generate, for example, radicals, cations or An active site such as an anion, and a polymerization reaction with a branched polyurethane having a dendritic structure (A) and an acrylic monomer (B). Examples of the photoinitiator (C) include, for example, imidazoles such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-fluorene (4-methoxycarbonylphenyl)- 1,2'-diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl)-1,2'-di Imidazole, 2,2'-bis(2-phenylphenyl)-4,4',5,5'-indole (4-phenoxycarbonylphenyl)-1,2'-diimidazole, 2,2' - bis(2,4-dichlorophenyl)-4,4',5,5'-indole (4-methoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis ( 2,4-Dichlorophenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl)-1,2'-dioxazol, 2,2'-bis (2, 4-dichlorophenyl)-4,4',5,5'-indole (4-phenoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis (2,4, 6 -trichlorophenyl)-4,4',5,5'-indole (4-methoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis(2,4,6- Trichlorophenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis (2, 4, 6-three Chlorophenyl)-4,4',5,5'-indole (4-phenoxyphenyl)-1,2'-di-smell, 2,2'-bis(2-bromophenyl) -4,4',5,5'-anthracene (4-methoxybenzylphenyl)-1 , 2'-dioxazol, 2,2'-bis(2-bromophenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl)-1,2'-di Imidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-indole (4-phenoxycarbonylphenyl)-1,2'-diimidazole, 2, 2' - bis(2,4-dibromophenyl)-4,4',5,5'-indole (4-methoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis ( 2,4-Dibromophenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl H,2'-diimidazole, 2,2'-bis(2,4-di) Bromophenyl)-4,4',5,5'-indole (4-phenoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis(2,4,6-tribromo Phenyl)-4,4',5,5'-indole (4-methoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis(2,4,6-tribromobenzene -4,4',5,5'-indole (4-ethoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis(2,4,6-tribromophenyl) -4,4',5,5'-indole (4-phenoxycarbonylphenyl)-1,2'- 1286144 diimidazole, 2,2'-bis(2-cyanophenyl)-4, 4',5,5'-indole (4-methoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis(2-cyanophenyl)-4,4',5, 5'-肆(4-ethoxycarbonylphenyl)-1,2'-di Azole, 2,2'-bis(2-cyanophenyl)-4,4',5,5'-indole (4-phenoxycarbonylphenyl H,2'-diimidazole, 2,2'- Bis(2-methylphenyl)-4,4',5,5'-indole (4-methoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis(2-A Phenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis(2-methylphenyl)- 4,4',5,5'-indole (4-phenoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis(2-ethylphenyl)-4,4', 5, 5'-肆(4-methoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis(2-ethylphenyl)-4, 4',5,5'-肆(4-Ethoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis(2-ethylphenyl)-4,4',5,5'-肆(4-benzene Oxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis(2-phenylphenyl)-4,4',5,5'-indole (4-methoxycarbonylphenyl) -1,2'-diimidazole, 2,2'-bis(2-phenylphenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl)-1,2 '-Diimidazole, 2,2'-bis(2-phenylphenyl)-4,4',5,5'-indole (4-phenoxycarbonylphenyl)-1,2'-diimidazole, 2, 2'-bis(2-chlorophenyl)-4,4 ,5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1 , 2'-diimidazole, 2, 2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2, 2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2,4-dibromophenyl) -4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2,4,6-tribromophenyl)-4,4',5, 5 '-Tetraphenyl-1,2'-diimidazole, 2,2'-bis(2-cyanophenyl)-4,4',5,5'-tetraphenyl-1,2'-diflavor Saliva, 2, 2'-bis(2,4-dicyanophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis (2 ,4,6-Tricyanophenyl)-4,4',5,5'-tetraphenyl-1,2'-disaccharide, 2,2'-bis(2-methylphenyl) _4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2,4-dimethylphenyl)-4,4',5, 5'- Tetraphenyl-1,2'-diimidazole, 2,2'-bis(2,4,6-trimethylphenyl)-4,4',5,5'-tetraphenyl-1,2' - Dimiso, 2,2'-bis(2-ethylphenyl)-4,4',5,5,-tetraphenyl-1,2'-diimidazole, 2,2'- (2,4-diethylphenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-double 1286144 (2,4,6-triethyl) Phenyl)-4,4',5,5'-tetraphenyl-12,-di-sodium bis(2-phenylphenyl)-4,4,5,5,-tetraphenyl-丨' 2,-diimidazole, 2 2, 'cone (2,4-diphenylphenyl)-4,4',5,5,-tetraphenyl-indole, 2,-diimidazole, 2 = , (2,4,6-triphenylphenyl)-4,4,5,5'-tetraphenyl-i,2,-diimidazole^ and its derivatives; preferably 2, 2' - bis(2-phenylphenyl)_4,4,,5,5,_^ t ethoxylated phenyl)-1,2'-diimidine, 2,2,-double (2, take笑基)-4,4,,5,5,-肆(4-ethoxycarbonylphenyl)_1,2,'-diimidine, one = (2,4-one gas base)-4,4 ',5,5-four-base-1,2'-two-micron, 2 2,-雔(2,4,6-dichlorophenyl)-4,4,5,5-tetraphenyl-one , 2'-dimethine, 2 2,-雔 (2,4-a-diphenyl)-4,4,5,5-tetraphenyl-1,2'-di-salt and 2 2,- Miscellaneous _ (2,4,6-di> stinyl phenyl)-4,4,5,5-tetra-substyl-1,2'-diimyral. Further, a Benzoin photoinitiator such as a benzoin, a benzoin methyl bond, a benzoin ethyl ether, a benzoin isopropyl ether, a styrene, and an isobutyl group are mentioned. Methyl-2'-stupylmethyl benzoate and the like and similar derivatives thereof. Further, for example, a phenylethyl group 1 network structure such as 2,2-dimethoxy-2-phenyl acetophenone, 2-transyl-2-methyl-1 propyl propan-1-one, 1_( 4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-monoethyloxy)phenyl-(2-yl-2-yl)anthracene, 2 , 2-dimethoxyphenylacetamidine, 2,2-diethoxyacetophenone, 2-methyl-(4-methylthiophenyl)-2-morpholinyl-1-propan-1- Ketone, 2-benzyl-2-dimethylamino-1 -(4-morphinylphenyl)butyl-1, _, 1-hydroxycyclohexyl phenyl ketone, 2,2'-dimethoxy Io 2-diphenylethylidene, 4-azidoacetophenone, 4-azidobenzylideneacetophenone, and the like, and the like. Further, for example, benzophenones such as benzophenone, 4,4,-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 3 , 3' _ dimethyl-4-methoxybenzophenone and the like and similar derivatives. A photoinitiator having an α-diketone structure, such as diethyl phthalate, benzoyl methacrylate, methyl benzhydrylcarboxylate or the like, and the like. A photoinitiator having a polynuclear fluorene structure such as anthraquinone, 2-ethyl oxime, 2-tert-butyl fluorene, 1,4-naphthoquinone or the like and the like. The yellow starter is a light starter such as Huang Ming, deuterated flavonoids, 2,4-diethylthioflavonoids, 2-oxothioflavonoids and the like and the like. Photoinitiator having a diazo knot 1286144 structure such as 4-diazodiphenylamine, 4-diazo-4'-methoxydiphenylamine, 4-azido-3-methoxybenzobenzene Alkylamines and the like and similar derivatives. A photoinitiator having a triple-call structure such as 2-(2'-11-fusinoethylene)-4,6-bis(trichloromethyl)-s-triazine, 2-(3', 4' -dimethoxystyryl)-4,6-bis(trimethylmethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl) —s-three-, 2-(2'-bromo-4'-methylphenyl)-4,6-bis(trichloromethyl)-3-triazine, 2-(2' _ phenyl) Ethyl)-4,6-bis(trichloroindenyl)-s-triazine and the like and similar derivatives. In addition to the photoinitiators listed above, 4-diazobenzaldehyde, azidopurine, bis(2,6-dimethoxybenzylidene) 2,4,4-trimethyl can also be used. A ketone oxide, N-phenylthioxanthone, triphenylsulfonium perchlorate, and the like, and the like. These photoinitiators may be used singly or in combination of two or more. The auxiliaries (D) which can be used in the composition of the present invention comprise a dreamane having a vinyl functional group such as vinyl triethane, vinyl trimethoxy ketone, vinyl triethoxy oxalate; An epoxy group-containing alkane such as 2-(3,4-epoxycyclohexyl)-ethyltrimethoxy chopping, 3-glycidoxypropyltrimethoxymethane, 3-shrinkage Glyceroxypropylmethyldiethoxy decane, 3-glycidoxypropyl ethoxylate, m-propyl propylene oxide such as 3-methyl propylene methoxy propyl Methyl dimethoxy oxetane, 3-methyl propylene methoxy propyl trimethoxy oxime; 3-methyl propylene methoxy propyl methyl diethoxy dream, 3-methyl Propylene methoxy propyl triethoxy oxalate; propylene oxy group-containing olefins such as 3- propylene methoxy propyl trimethoxy decane; amine functional group-containing decanes such as N- (2- Aminoethyl)- 3-aminopropylmethyldimethoxy-lower, N-(2-aminoethyl)-3-aminopropyltrimethoxy-infraline, N-(2-amino Ethyl)-3-aminopropyl. Diethoxy fever, 3-aminopropyltrimethoxy fever 3-aminopropyltriethoxylate, 3-triethoxydecyl-N-(l,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyl Trimethoxy oxetane, N-(vinylbenzyl)-2-aminopropyltrimethoxy oxalate hydrochloride; sulfhydryl group-containing decanes such as 3-ureidopropane 8 12 1286144 a triethoxy zebra; a chloropropyl functional group-like fever such as 3-chloropropyltrimethoxy oxalate; a thiol-containing functional group such as 3-hydrothiopropylmethyl Bis-methoxydecane, 3-hydrothiopropyltrimethoxydecane; sulfanyl functional group-containing montanes such as bis(triethoxysulphate) tetrasulfide; isocyanate-containing functional groups Alkaloids such as 3-isohydroester propyl triethoxy oxalate. The amount used is about 0 to 3 by weight based on the total weight of the ink composition. /〇. The coloring agent (E) which can be used in the composition of the present invention can be an organic pigment having heat resistance such as C.I. Pigment Yellow 83, C. L Pigment Yellow 110, C·I·Pig Yellow 138, C·I·Pigment Yellow 139, CI Pigment Yellow 150 and CI·Pigment Yellow 155; CI·Pigment Dial 71; CI·Pigment Violet 19 and CI Pigment Violet 23; C·I·Pigment Red 48:1, C·I· Pigment Red 48:2, C. L Pigment Red 48:3, C·I·Pigment Red 48:4, C·I·Pigment Red 122, CI Pigment Red 177, C·I·Pigment Red 202, C·I· Pigment Red 206, C·I·Pigment Red 207, C·I. Pigment Red 209, C·I·Pigment Red 224, and C·I·Pigment Red 254; C·I·Pigment Blue 15:3, C·I· Pigment Blue 15:4 and C·I·Pigment Blue 15:6; C·I. Pigment Green 7 and C·I·Pigment Green 36; C·I·Pigment Brown 23 and C·I·Pigment Brown 25; C· I·Pigment Black 1 and C·I·Pigment Black 7. (C·I is an announcement made by The Society of Dyers and Colourists Co.). The above colorants may be used singly or in combination of two or more. The amount used is about 5 to 40% of the total weight of the ink composition. The dispersing agent (F) used in the composition of the present invention is S32000 produced by Avecia, which is a cationic poly(alkylenimine) which reacts with a hydroxy stearate having a free carboxyl group to form a guanamine. . Grinding with a grinder after addition can help the colorant to be stably dispersed. The amount used is about 3% by weight of the colorant (E). The solvent (G) used in the composition of the present invention is used to obtain a liquid state and to control the viscosity of the composition at a suitable spray. The solvent to be used may be any solvent which can dissolve or disperse the components contained in the above composition, and does not participate in the reaction and has appropriate volatility, for example, a (poly) extender diol monoalkyl ether such as ethylene. Alcohol mono 13 1286144 monohexyl alcohol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol-based bond: C-indole: alcohol methyl ether, propylene glycol monoethyl bond, propylene glycol mono-propyl Bond, monobutyl ether, dipropylene glycol monomethyl sequestration, dipropylene glycol monoethyl
li鍵、^二醇單c基鍵、乙二醇單正丙基鍵、乙二醇單正丁 =鍵=醇ί!基醚、二乙二醇單乙細、二乙二醇單正 單乙； 基鍵 C二醇，丙基鍵、二丙二醇單正丁基越:三 二基醚乙酸醋、乙二醇單乙基醚乙酸醋、丙二 及丙二醇單乙基邮酸si;其他如二乙二醇 嗔擎Μ敍· κ曰醇甲基乙基醚、二乙^一醇一乙基鍵及四氫11 夫 例如甲基乙基酮、環己網、2_細及3_庚^ 鉍基丙酸甲醋及2_羥基丙酸乙輯；酷類包含 乙Λ魄乙醋、3一甲氧基丙酸甲醋、3〜甲氧基丙酸 #曰乙氧基丙酸甲酯、3_乙氧基丙酸乙酯、乙氧基乙酸乙 :备f基乙酸乙醋、2-羥基一3-甲基丁酸甲酯、乙酸3-甲基一3一 氧基I基酯、丙酸3-甲基-3-甲氧基丁基酯、乙酸乙酯、乙 =正丁醋、乙酸異丁醋、甲酸異戊醋、乙酸異戊醋、丙酸正丁 』、1[酸異丙醋、丁酸乙醋、丁酸正丁醋、丙酮酸甲S旨、丙酮 乙S曰、丙_酸正丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯及2一 代丁酸乙自曰，方香族碳氫化物如甲苯及一甲笨；酿胺類如 N-甲基吼咯燒酮(醜p)、N，N一二甲基甲醯胺及N，N—二甲基乙醯 胺等。 上述溶劑可單獨使用或組合兩種以上使用。溶劑之添加量 並無特別限制’只要可達所需黏度即可，但一般約佔組成物總 重之5至60重量％。 、他 本發明將以下列實施例以及調配例進一步說明本發明，惟 該等實施例以及調配例僅用以說明本發明而不用以限制本發 明之範圍。 下列實施例中，所用之ΤΜΡ為購自拜耳公司，經基數為3 ,· 1286144 之季戊四醇係購自Perstorp的產品Poly〇1 pp 50，_ ^數為4 ;糖/甘油為起始齊! p〇改質之混合物，為陶氏公司^ f的產品Voranol 280，理論羥基值為7 ;肊11;〇111 P5〇〇係購 自P^storp公司，分子量為議克/莫耳、經價約為56〇至 口克K0H/克’理論經基數為μ。TDI為日本三井化學公司 之產οα，季戊四醇三丙烯酸酯則為新力美科技股份有限公司生 產的AgiSyn® 2884。觸媒則使用Air pr〇duct公司之τ-12。 [實施例1] 2克TDI置於配備有冷凝管及溫度感應器之反應瓶Li bond, ^diol single c-based bond, ethylene glycol mono-n-propyl bond, ethylene glycol mono-n-butyl = bond = alcohol, ether, diethylene glycol, monoethylene, diethylene glycol, single positive B; base bond C diol, propyl bond, dipropylene glycol mono-n-butyl group: tridyl ether acetate vinegar, ethylene glycol monoethyl ether acetate vinegar, propylene glycol and propylene glycol monoethyl phytate si; Diethylene glycol 嗔 Μ · 曰 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四^ Mercaptopropionic acid methyl vinegar and 2_ hydroxypropionic acid B series; cool class contains acetamidine acetate, 3-methoxypropionic acid methyl vinegar, 3~ methoxypropionic acid #曰 ethoxy propionate A Ester, ethyl 3-ethoxypropionate, ethoxyacetic acid B: ethyl acetate acetate, methyl 2-hydroxy-l-methylbutanoate, 3-methyl-3-methoxyl acetate Ester, 3-methyl-3-methoxybutyl propionate, ethyl acetate, B = n-butyl vinegar, isobutyl vinegar, isovaleric acid, isovaleric acid, n-butyl propionate, 1 [Acetic acid isopropyl vinegar, ethyl butyrate, butyric acid butyrate, pyruvate, S, acetone, S, propyl, n-propyl, ethyl acetate Acid methyl ester, ethyl acetate ethyl acetate and 2 generations of butyric acid ethyl bromide, square aromatic hydrocarbons such as toluene and one of the stupid; amines such as N-methylpyrrolidone (ugly p), N, N-dimethylformamide and N,N-dimethylacetamide. The above solvents may be used singly or in combination of two or more. The amount of the solvent to be added is not particularly limited as long as the desired viscosity is obtained, but it is usually about 5 to 60% by weight based on the total weight of the composition. The invention is further illustrated by the following examples and examples, which are intended to illustrate the invention and not to limit the scope of the invention. In the following examples, the oxime used was purchased from Bayer, and the pentaerythritol with a base of 3, · 1286144 was purchased from Perstorp as Poly 〇 1 pp 50, _ ^ 4; the sugar / glycerin was the starting point! p 〇 之 之 , 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶The theoretical base number is μ from 56 〇 to 克 K0H / gram. TDI is produced by Japan's Mitsui Chemicals Co., Ltd., and pentaerythritol triacrylate is AgiSyn® 2884 produced by Xinlimei Technology Co., Ltd. The catalyst uses the τ-12 of Air pr〇duct. [Example 1] 2 g of TDI was placed in a reaction bottle equipped with a condenser tube and a temperature sensor
中，緩慢滴加482· 8克AgiSyn® 2884，使溫度先升溫至60°C 持續60分鐘後，再升溫至65ΐ持續6〇分鐘。隨後，加入〇· 3 克12，^度維持在65°C維持60分鐘。最後加入24克ΤΜΡ , 升溫至JO°C並保持在該溫度直至藉滴定測試到NC〇%=〇%為 止。獲得本發明之具有樹枝狀結構之分枝聚胺酯1，其結構式 如下：Medium, slowly add 482. 8 g of AgiSyn® 2884, and then warm the temperature to 60 ° C for 60 minutes, then heat to 65 ΐ for 6 〇 minutes. Subsequently, 〇·3 g was added, and the degree was maintained at 65 ° C for 60 minutes. Finally, 24 g of hydrazine was added and the temperature was raised to JO ° C and maintained at this temperature until the NC〇%=〇% was tested by titration. The branched polyurethane 1 having a dendritic structure of the present invention is obtained, and its structural formula is as follows:
[實施例2] 將90· 0克TDI置於配備有冷凝管及溫度感應器之反應瓶 15 1286144 中，緩慢滴加464· 0克AgiSyn® 2884，使溫度先升溫至6(TC 持續60分鐘後，再升溫至65°C持續60分鐘。隨後，加入0. 3 克T-12 ’溫度維持在65乞維持6〇分鐘《最後加入46. 0克 PP50 ’升溫至7〇°c並保持在該溫度直至藉滴定測試到NC0%=0% 為止。獲得本發明之具有樹枝狀結構之分枝聚胺酯2。 [實施例3] f 82· 0克TDI置於配備有冷凝管及溫度感應器之反應瓶 中’緩慢滴加424· 0克AgiSyn® 2884，使溫度先升溫至60°C 持續60分鐘後，再升溫至6fC持續6〇分鐘。隨後，加入〇. 3 克Τ-12 ’溫度維持在65°c維持6〇分鐘。最後加入94. 〇克 Voranol 280，升溫至7(TC並保持在該溫度直至藉滴定測試到 NCO%=0%為止。獲得本發明之具有樹枝狀結構之分枝聚胺酯3。 [實施例4] f 89· 5克TDI置於配備有冷凝管及溫度感應器之反應瓶 中’缓慢滴加461· 5克AgiSyn® 2884，使溫度先升溫至60°C 持續60分鐘後，再升溫至65°c持續6〇分鐘。隨後，加入〇· 3 克T-12，溫度維持在65°C維持60分鐘。最後加入49. 0克 P500 ’升溫至70°C並保持在該溫度直至藉滴定測試到NC0%=0% 為止。獲得本發明之具有樹枝狀結構之分枝聚胺酯4。 [調配例1] 將實施例1至4中所製得之具有樹枝狀結構之分枝聚胺酯 1至4以下表1所示的量與表1所列的成分經充分混合後，經 砂輪機研磨辅以適當分散劑將粒徑分布控制在2〇〇咖以下，獲 得墨水組成物1至4。 表1 調配例1 調配例2 調配例3 調配例4 墨水組成 物1 墨水組成 物2 墨水組成 物3 墨水組成 物4 分枝聚胺酯1 10 一 1286144[Example 2] 90. 0 g of TDI was placed in a reaction bottle 15 1286144 equipped with a condenser tube and a temperature sensor, and 464·0 g of AgiSyn® 2884 was slowly added dropwise to raise the temperature to 6 (TC for 60 minutes). After that, the temperature was raised to 65 ° C for 60 minutes. Then, 0.3 g of T-12 'temperature was maintained at 65 乞 for 6 〇 minutes. Finally, 46.0 g of PP50 was heated to 7 ° C and kept at The temperature was up to NC0% = 0% by titration. The branched polyurethane having the dendritic structure of the present invention was obtained. [Example 3] f 82 · 0 g of TDI was placed in a condenser and a temperature sensor In the reaction flask, slowly add 424·0 g of AgiSyn® 2884, and then warm the temperature to 60 °C for 60 minutes, then heat up to 6 fC for 6 minutes. Then, add 〇. 3 gΤ-12 'temperature maintenance Maintained at 65 ° C for 6 〇 minutes. Finally, 94. VVoranol 280 was added, and the temperature was raised to 7 (TC and kept at this temperature until NCO% = 0% by titration test. The dendritic structure of the present invention was obtained. Polyurethane 3. [Example 4] f 89· 5 g of TDI was placed in a reaction flask equipped with a condenser and a temperature sensor' Slowly add 461·5g of AgiSyn® 2884 to warm the temperature to 60°C for 60 minutes, then raise the temperature to 65°C for 6 minutes. Then, add 〇·3 g of T-12 and maintain the temperature at 65. °C was maintained for 60 minutes. Finally, 49.0 g of P500' was heated to 70 ° C and maintained at this temperature until NC0% = 0% by titration. The branched polyurethane 4 having a dendritic structure of the present invention was obtained. [Preparation Example 1] The branched polyurethane having the dendritic structure prepared in Examples 1 to 4 was 1 to 4, and the amounts shown in Table 1 were thoroughly mixed with the components listed in Table 1, and then ground by a grinder. The particle size distribution was controlled to 2 or less with a suitable dispersing agent to obtain ink compositions 1 to 4. Table 1 Formulation Example 1 Formulation Example 2 Formulation Example 3 Formulation Example 4 Ink Composition 1 Ink Composition 2 Ink Composition 3 ink composition 4 branched polyurethane 1 10 a 1286144
TPGDA:三丙二醇二丙稀酸g|，新力美科技股份有限公司產品。 KBM50^3-。甲基丙烯醯氧基丙基三乙氧基魏，日本信越公司TPGDA: Tripropylene glycol dipropylene acid g|, Xinlimei Technology Co., Ltd. products. KBM50^3-. Methyl propylene methoxy propyl triethoxy Wei, Japan Shin-Etsu Corporation
Igacure 907 : 2-甲基-(4_甲基噻吩基)_2_嗎啉基一丨丙+ _，Ciba公司產品。 PMA :丙二醇單甲基醚乙酸醋。 。广上述所得之墨水組成物1至4塗佈在玻璃片上，經70〜1〇〇 C，烘烤1〇〇〜300秒，經1〇〇mJ/cm2曝光，再經2⑽〜25〇它進 烘烤20〜30分鐘，再將經塗佈之破璃片含浸在各種溶劑 、PM、NMP、TMAH 2.38%)5〜15分鐘或暴露在各種環境 空氣t 170¾，10〜20分鐘），測試其耐黃變性(^Eab)，复 結果列於下表2。 /、 2。又對經塗佈之玻璃片進行錯筆硬度測試，結果亦示於下表Igacure 907: 2-methyl-(4-methylthienyl)_2_morpholinyl-indenyl- propyl, a product of Ciba. PMA: propylene glycol monomethyl ether acetate vinegar. . The above-obtained ink compositions 1 to 4 are coated on a glass sheet, baked at 70 to 1 〇〇C, baked for 1 to 300 seconds, exposed through 1 〇〇mJ/cm 2 , and then passed through 2 (10) to 25 Torr. Bake for 20~30 minutes, then dip the coated granules in various solvents, PM, NMP, TMAH 2.38%) for 5~15 minutes or expose to various ambient air t 1703⁄4, 10~20 minutes), test it Yellowing resistance (^Eab), the complex results are listed in Table 2 below. /, 2. The coated glass piece was tested for the wrong pen hardness and the results are also shown in the table below.
墨水組成 物3 墨水組成 物4 17 1286144Ink composition 3 Ink composition 4 17 1286144
丙二醇單甲基 謎(PM) <3 =3 =3 =3 N-甲基11 比洛烧 酮(NMP) <3 =3 =3 =3 氳氧化四甲銨 (TMAH) 2.38% <3 =3 =3 =3 空氣中170°C <3 =3 =3 =3 鉛筆硬度 (5〇〇g) B 4B 4B 4B 由上述試驗可知，以實施例1所得之聚胺酯1所調配之墨 水組成物1其比例雖僅有10. Owt%，但聚胺酯1本身結構中所 具有的9個丙烯酸官能基卻可提供極佳的耐熱性以及耐化性 (△EabS3)。另外，在整個系統中均呈單一相，顯示本發明之 組成物有很高相容性。 依據本發明之分支聚胺酯為可輻射固化高度交聯之樹 脂’使用該樹脂作為光阻液的主要成分，可將顏料牢固在玻璃 基板上’可提升成膜後之耐光性、耐化性以及耐熱性。若又配 合適當分散劑可適當控制所調配之墨水組成物之表面張力以 及黏度’使墨水組成物喷印到玻璃基板時可均勻迅速地擴散開 來，避免膜厚不均或漏光。在光阻劑調配物中，整個系統呈單 一油相’亦即系統呈現很高的相容性，而可用作為極優異之噴 墨輻射可固化之墨水組成物。 ' 【圖式簡單說明】 【主要元件符號說明】Propylene glycol monomethyl mystery (PM) <3 =3 =3 =3 N-methyl 11 pirone (NMP) <3 =3 =3 =3 Tetramethylammonium oxide (TMAH) 2.38% < 3 = 3 = 3 = 3 170 ° C in air < 3 = 3 = 3 = 3 Pencil hardness (5 〇〇 g) B 4B 4B 4B From the above test, the ink prepared by the polyurethane 1 obtained in Example 1 was prepared. The composition 1 has a ratio of only 10. Owt%, but the nine acrylic functional groups in the structure of the polyurethane 1 itself provide excellent heat resistance and chemical resistance (ΔEabS3). In addition, a single phase throughout the system shows a high compatibility of the compositions of the present invention. The branched polyurethane according to the present invention is a radiation curable highly crosslinked resin. The resin is used as a main component of the photoresist, and the pigment can be firmly adhered to the glass substrate to improve light resistance, chemical resistance and heat resistance after film formation. Sex. If the appropriate dispersant is used, the surface tension and viscosity of the formulated ink composition can be appropriately controlled. When the ink composition is printed on the glass substrate, it can be uniformly and rapidly diffused to avoid uneven film thickness or light leakage. In the photoresist formulation, the entire system exhibits a single oil phase, i.e., the system exhibits high compatibility, and can be used as an extremely excellent ink radiation curable ink composition. ' [Simple diagram description] [Main component symbol description]