201111454 六、發明說明： 【發明所屬之技術領域】 本毛明係關於在使用喷墨方式形成既 用的彩色濾光片爾# s 疋圖案像素時，所使 九片用熱硬化性喷墨墨水。 【先前技術】201111454 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a thermosetting inkjet ink for nine sheets when a color filter er# 疋 疋 pattern pixel is formed by an inkjet method. . [Prior Art]
近年來隨個人I w人電細的發達、尤其是 達，對液晶顯示器、特 仃動用個人電腦的發 傾向。 顯示器的需求有增加之 此種液晶顯示器的彩声 ⑹、及辆之3原備有紅⑻、綠 個像素所對應之電極進行⑽/⑽:吏aR、G及B的各 ΛΛ^,, 而使液晶進行作為快門 ，乍’光通過R、G^的各個像素則執行彩色顯示。 I知所進行的彩色縣R製造方法，有如染色法。該染 色法係首先在玻璃基板上形成屬於染色用材料的水溶性高 /刀子材料，再將其湘光學微影步驟*圖案化為所需形狀 後’將所獲得之圖案浸潰於染色浴中，獲得經著色的圖案。 藉由重複實施3次，形成R、G及B的像素。又，其他方法 有如顏料分散法。該方法係首先在基板上形成分散了顏料的 感光性樹脂層，藉由對其施行圖案化，獲得單色圖案。再進 一步重複施行此項步驟3次，形成R、〇及B的像素。再另 一方法係有如電鍍法’或者使顏料分散於熱硬化樹脂中並施 行R、G及B的3次印刷後，再使樹脂熱硬化的方法等。 099117156 4 201111454 然而’因為任—方法均施行R、G及b等3色 而同一步驟必需重複3次，而有導致成本提高的色’因 為重複同樣的步驟，因有經濟效益降低的問題。且因 作為解決料問題點的彩色㈣狀製造方法，在 獻1中記載有：將含有熱硬化性樹脂的著色墨水利文 方式《人抵於基板上’藉由施行加熱而形成像素部。、墨 [先行技術文獻] [專利文獻] [專利文獻1]日本專利特開平9-21910號公報 【發明内容】 (發明所欲解決之問題） 習知當使用熱硬化性樹脂形成彩色濾光片的 般係利用酸成分與環氧成分的聚合及/或交聯反應^時’-因為酸成分與環氧齡的反聽㈣高，因而 ^ ’ ::，漸上升’導致保存安定性出現問 二 占度=上=則有損及利用噴墨方式施行的墨二2 f以及衫喷輕生的可紐。再者 與環氧成分的聚合及/或交敎μ η 胸"成刀 的耐藥性u之問題。時，亦有所獲得之著色層 =彩色遽 '光片的色特性方面，近年來尤其在彩色電視 部八=^’要求色域重現性、高對比及高輝度，但若像素 ^的耐樂性不足，則造成像素部龜裂舆色彩變化，因而有 099117156 201111454 導致所獲得之彩色濾光片的輝度與色純度降低之可能性。 近年來因為對彩色濾光片的高輝度、高色純度化之需求， 因而要求該噴墨墨水中所含顏料的細微化、高濃度化。隨著 顏料的細微化與顏料濃度提高，在該喷墨墨水中所含的顏料 量與顏料分散劑量亦必需跟著增加。然而，若使彩色濾光片 用喷墨墨水中所含的顏料與顏料分散劑之量增加，則黏結劑 等對硬化膜的膜物性具有助益的成分將相對性地減少，結果 有該墨水的硬化性降低，以及硬化膜的密接性與表面硬度降 低等問題。又，若提高顏料濃度，則促進墨水的乾燥，利用 喷墨朝黑矩p車内所吐出的墨水發生乾燥不均，而有像素的平 坦性惡化㈣題。若像素的平坦性惡化，則有輝度與色純度 降低的問題。 有鑑於上述實情，本發明係欲達成下述第丨與第2目的。 本發明之第1目的在於提供：可實現保存安定性與硬化性 均優異、熱硬化後的補性優異、色域魏性佳之彩色遽光 片的彩色濾光片用熱硬化性噴墨墨水。 再者’本發明之第2目的在於提供：即便提高顏料濃度， 熱硬化後的密接性、表面硬度、及平坦性仍優異之彩色濾光 片用熱硬化性噴墨墨水。 (解決問題之手段） 本發明者等人經深入鑽研，結果發現，彩色滤光片用喷墨 墨水的熱硬化性黏結成分，藉由组合使用：具有乙稀性不飽 099117156 6 201111454 和鍵的多官能基單體；以及使至少含有含環氧基之單體與含 脂環式煙之單體的單體群進行共聚合而獲得之丙稀酸^共 聚物；則可解決上述目的，遂完成本發明。本發明中，係將 具有乙稀性不飽和鍵的多官能基單體利用作為熱硬化性黏 ; 結劑成分，#使噴墨墨水進行硬化時，藉由熱使該多官能基 . 單體進行聚合及/或交聯反應。 更具體而言’為了達成上述第i目的，提供下述第夏彩色 濾、光片用熱硬化性噴墨墨水。 即，本發明的第1彩色濾、光片用熱硬化性喷墨墨水，係含 有多官能基性單體、減_脂、·、顏料分散劑及溶 者’其特徵為’上述多官能基性單體係〗分子内具有4個以 上乙烯性不飽和鍵的化合物，且上_結_料使至少^ 有(A)具有環氧基與乙烯性不飽和_含環氧基單體、師3) 二有月曰％式煙基與乙烯性不飽和鍵之含脂豸式煙的單體的 單體群’進行共聚合而成的丙烯酸系共聚物。、 •第1噴墨墨水中，上述丙烯聚物中，上述 产 • 氧基單體係總共聚合成分中之20重量％〜80重量％，且= =含脂環式烴的單體係總共聚合成分+之2G重量％〜如重 !%，此由墨水的保存安定性與低黏度化、或硬化媒的耐藥 性、及色域重現性等觀點而言，係屬較佳。 ，第1彩色濾、光片用熱硬化性嘴墨墨水中，上述(B)含脂環 式經的單體係從硬化膜的耐藥性、色域重現性等觀點而+, 099117156 ， 201111454 較佳為具有架橋脂環式烴基。所謂架橋(bridged)脂環式烴基 係指脂環式烴基内具有橋接構造，且分子内具有多環構造的 多環狀脂肪族烴基。 再者，為了達成上述第2目的，提供下述第2彩色濾光片 用熱硬化性喷墨墨水。 即，本發明的第2彩色濾光片用熱硬化性喷墨墨水，係含 有多官能基性單體、黏結劑樹脂、顏料、顏料分散劑及溶劑 者，其特徵為，上述多官能基性單體係1分子内具有4個以 上之乙烯性不飽和鍵的化合物，且上述黏結劑樹脂係含有： 使至少含有（A)具有環氧基與乙烯性不飽和鍵的含環氧基單 體、與(B)具有脂環式烴基與乙烯性不飽和鍵之含脂環式烴 的單體的單體群，進行共聚合而成的丙烯酸系共聚物；以及 不同於上述丙烯酸系共聚物的環氧樹脂。 第2喷墨墨水中，上述丙烯酸系共聚物較佳係上述由至少 含有(A)含環氧基單體與(B)含脂環式烴的單體之單體群進 行共聚合而成的共聚物所具有的環氧基之1個以上，與具有 羧基及乙烯性不飽和鍵的含羧基單體(C)進行反應而成的丙 烯酸系共聚物。此情況，在丙烯酸系共聚物的側鏈具有乙烯 性不飽和鍵，因為亦可與上述多官能基性單體進行交聯，故 從熱硬化後的密接性、表面硬度、及平坦性均優異，且耐 ITO形成性亦優異的觀點而言，屬較佳。 第2喷墨墨水中，從與墨水中之各成分間之相溶性、墨水 099117156 8 201111454 熱硬化後的密接性、表面硬度等觀點而言，較佳係上述丙烯 酸系共聚物中，上述(A)含環氧基單體為總共聚合成分中之 20重量％~80重量％，且上述(B)含脂環式烴的單體為總共聚 合成分中20重量％〜80重量％。 第2喷墨墨水中，上述(B)含脂環式烴的單體係具有架橋 脂環式烴基，從墨水熱硬化後的表面硬度、耐溶劑性等觀點 而言，屬較佳。 第2喷墨墨水中，上述多官能基性單體、上述丙烯酸系共 聚物、及上述環氧樹脂的含有比例，係上述環氧樹脂相對於 上述多官能基性單體與上述丙烯酸系共聚物之和的重量比 (環氧樹脂/(多官能基性單體+丙烯酸系共聚物))為0.25〜4， 且上述丙烯酸系共聚物相對於上述多官能基性單體的重量 比（丙烯酸系共聚物/多官能基性單體）為0.125〜8，由墨水熱 硬化後的密接性、表面硬度、及平坦性優異等觀點而言，屬 較佳。 (發明效果） 本發明的第1彩色濾光片用熱硬化性喷墨墨水，可實現保 存安定性及硬化性均優異、熱硬化後的财藥性優異、以及色 域重現性良好的彩色濾光片。 再者，本發明之第2彩色濾光片用熱硬化性喷墨墨水，係 熱硬化後的密接性、表面硬度、及平坦性均優異。 【實施方式】 099117156 9 201111454 <第1喷墨墨水> 本發明的第1彩色濾光片用熱硬化性噴墨墨水，係含有多 官能基性單體、減·m、顏料、賴分散劑及溶劑的彩 色濾光片用熱硬化性噴墨墨水，其特徵為，上述多官能基性 單體係1分子内具有4個以上之乙稀性不飽和鍵的化合物， 且上述黏結劑樹脂係使至少含有（A)具有環氧基與乙烯性不 飽和鍵的含環氧基單體、與⑻具有脂環式烴基與乙婦性不 飽和鍵之含脂環式烴的單體的單體群，進行共聚合而成的丙 烯酸系共聚物。 本發明的彩色滤光片用熱硬化性喷墨墨水中，作為熱硬化 性黏結成分並非以習知之環氧樹脂及酸成分為主體，而是藉 由2口使用· 1分子内具有4個以上之乙稀性不飽和鍵的多 :此基性單H，及錢少含彳含環減賴與含脂環式烴的 單體之單體群’進打共聚合而成的丙烯酸系共聚物；則可實 現保存安定性及硬純餐異、熱硬化後的耐優異、色 域重現性佳的彩色濾光片。 再者’本發明中’因為使用熱硬化性樹脂，故不需要光照 射等特別的附加設備，亦具有生產性高的優點。 作為熱硬化性黏結成分，藉由組合使用使^分子内具有4 =以上之乙烯性减和鍵㈣官能基性單體，與使至少含有 s裒氧基之單體及含脂環式煙之單體的單體群進行共聚合 而成的丙烯㈣共聚物，便料揮上述效果的理由 ，推測如 099117156 201111454 下。 作為熱硬化性黏結成分，若將習知的環氧樹脂與酸成分使 用為主體’則因為酸成分與環氧樹脂的反應性非常高，因而 經時性地出現黏度逐漸上升，而有保存安定性的問題。又， ·' 亦有耐藥性不足的問題。 : 相對於此，本案的熱硬化性黏結成分並非利用習知的環氧 樹脂及酸成分之聚合及/或交聯反應，而是組合使用於側鏈 具有環氧基與脂環式烴的丙烯酸共聚物、與1分子内具有4 個以上之乙烯性不飽和鍵的多官能基性單體，利用藉由熱所 進行之乙烯性不飽和鍵的聚合及/或交聯反應，以及利用藉 由熱所進行之環氧基的聚合及/或交聯反應。 本案中’因為本質上未利用環氧基與酸成分的反應，且不 使在環氧基與酸成分共存，因而環氧基不易進行反應，使保 存安定性優異。 於側鏈具有環氧基與脂環式烴的丙烯酸共聚物，係環氧基 ' 藉由熱產生反應而進行聚合及/或交聯，且因具有脂環式烴 . 而硬化性優異，且因具有脂環式烴而亦不致因熱經歷造成變 黃，故色域重現性良好。 另一方面’ 1分子内具有4個以上之乙烯性不飽和鍵的多 S此基性單:ϋ，係藉由進行熱聚合，可獲得高交聯密度的高 硬度塗膜。 本發明巾，藉由料於峨具有縣基錢環式烴的丙稀 099117156 11 201111454 酸共聚物、與1分子内具有4個以上之乙烯性不飽和鍵的多 官能基性單體之組合的相乘效應’則可實現保存安定性優 異，並因為硬化性而熱硬化後的对藥性亦優異、且色域重現 性佳的彩色濾光片。 本發明的彩色濾光片用熱硬化性喷墨墨水係至少含有：多 官能基性單體、黏結劑樹脂、顏料、顏料分散劑及溶劑，視 需要尚可含有其他的成分。以下’針對本發明之彩色濾光片 用熱硬化性喷墨墨水所使用的各成分進行說明。 <多官能基性單體> 本發明中，多官能基性單體係使用1分子内具有4個以上 之乙烯性不飽和鍵的化合物。此處所謂「乙烯性不飽和鍵」 係指能進行自由基聚合的碳原子間之雙鍵，具有此種乙烯性 不飽和鍵的官能基，可例示如：乙烯基(ch2=ch_)、（甲基) 丙稀基(CH2=CH-CH2-及 CH2=C(CH3)-CH2·)、（甲基）丙稀酿 基(CH2=CH-CO-及 CH2=C(CH3)-CO-)、（甲基）丙烯醯氧基 (CH2=CH-COO-及 CH2=C(CH3)-COO-) 、 及 -COO-CH=CH-COO-等。本發明所使用的多官能基性單體 中，具有乙烯性不飽和鍵的官能基若具有4個以上，則可具 有單獨1種、亦可組合具有2種以上。又，本發明所使用的 多官能基性單體可單獨使用1種、亦可組合使用2種以上。 其中’作為乙烯性不飽和鍵，從利用熱聚合及/或交聯進行 的硬化膜之硬化性之觀點而言，較佳係具有4個以上之（甲 099117156 12 201111454 基）丙烯醯氧基、及/或（甲基）丙烯醯基。另外，本發明中， 將丙烯酸酯、與甲基丙烯酸酯統稱為「（曱基）丙烯酸酯」。 其他亦同。 本發明中’從墨水黏度的觀點而言多官能基性單體的分子 -量，較佳係2000以下、更佳1〇〇〇以下。 _ 1分子内具有4個以上之乙烯性不飽和鍵的化合物，可舉 例如·四羥曱基曱烧四（曱基）丙烯酸醋、季戊四醇四（甲基) 丙烯酸酯、二季戊四醇四（甲基）丙烯酸酯、二(三羥甲基丙烷) 四（甲基）丙烯酸g旨、烧基改f二季戊四醇四（甲基）丙稀酸 酯、五（甲基）丙烯酸二季戊四醇單羥酯、二季戊四醇六（甲基） 丙稀、一季戊四醇五（曱基）丙烯酸酯、烧基改質二季戊 四醇五（甲基）丙埽酸酉旨、胺基曱酸乙醋六（？基）丙稀酸醋、 聚醋六（曱基）丙烯酸酿、_酸改質二季戊四醇五（甲基）丙 烯酸酯等。 其他尚可舉例如：季戊四醇四己内醋四（甲基）丙稀酸醋、 甘/由四（曱基）丙稀酸酯、二（三經曱基丙烧）四己内酯四（甲 基）丙烯酸酯、二（三羥甲基乙烷）四（甲基）丙烯酸酯、二（三 羥甲基丁烷）四（甲基）丙烯酸酯、二（三羥甲基己烷）四（曱基） 丙稀酸酿、二(三經曱基辛烧)四（f基）丙稀酸S旨、三季戊四 醇六（甲基)丙稀酸g旨、三季戊四醇七（甲基)丙婦酸酯、三季 戊四醇八（甲基）丙稀酸醋、三季戍四醇聚環氧院七（甲基）丙 稀酸醋及該等的環氧乙炫加成物、環氧服加成物等。進一 099117156 13 201111454 步可舉例如：乙氧基化季戊四醇四（曱基）丙烯酸酯、新戊二 醇寡丙烯酸酯、1，4-丁二醇寡丙烯酸酯、丨，6_己二醇纂丙烯 酸酯、三羥甲基丙烷寡聚丙烯酸酯、季戊四醇募丙烯酸酯、 胺基曱酸乙酯丙烯酸酯、環氧基丙烯酸酯等。 再者，尚可舉例如：陸（甲基丙烯醯氧基乙基)環三磷腈(例 如共榮公司化學股份有限公司製Γρρζ」）、二季戊四醴五丙 烯酸酯六亞曱基二異氰酸酯•胺基曱酸乙酯預聚物（例如共 榮公司化學股份有限公司製「UA_51〇H」）等。 1分子内具有4個以上之乙烯性不飽和鍵的多官能基性單 體之含有量，係相對於墨水的固形份，較佳在5重量％〜80 重量％範圍内、更佳在1〇重量％〜6〇重量％範圍内。其理由 係若少於上述範圍，則有硬化膜的硬化性 、耐藥性不足之 虞。又’若多於上述範圍，則有無法重現所需色彩的可能性。 再者’ 1分子内具有4個以上之乙烯性不飽和鍵的多官能 基性單體之含有量，係在除了後述顏料與顏料分散劑以外的 固形伤中’車乂佳含有1〇〜9〇重量％、更佳含有2〇〜重量％， 從土 K的低黏度化、保存安定性、硬化膜的硬化性、及财藥 性等觀點而言’屬較佳。另外，本發明中，所謂「固形份」 係才曰除了 W丨外所含的全部成分，諸如餘化合物等亦涵括 於固形份中。 本毛明中，夕B能基性單體雖使用1分子内具有4個以上 之乙烯&不飽和纟麵化合物’但在*損及本發明效果的前提 099117156 14 201111454 下’於適田確保低It度化、喷墨吐出之目的下，亦可併用1 分子内具有2〜3個之乙埽性不飽和鍵的化合物。此情況下， 亦在多官能基性單體全量中^分子内具有4個以上之乙稀 性不飽和鍵的化合物較佳含有50重量％以上、更佳含有達 :%重量％以上。本發明中，在多官能基性單體全量中，工分 ： 子内具有4個以上之乙稀性不飽和鍵的化合物較佳為1〇〇 重量％。 作為亦可併㈣分子内具有2〜3個之乙烯性殘和鍵之 化合物，較佳係具有2〜3個（曱基）丙烯醯基的化合物，可舉 例如：三羥曱基丙烷三（甲基）丙烯酸酯、三羥曱基乙烷三（甲 基）丙烯酸酯、丙三醇三（曱基）丙烯酸酯、季戊四醇三（甲美) 丙烯酸酯、烷基改質二季戊四醇三（曱基）丙烯酸酯、磷酸三 (曱基）丙烯酸酯、異三聚氰酸參（丙烯醯氧基乙基）酿、異三 I氰k參（甲基丙稀醯氧基乙基）醋等，惟並不僅侷限於节 等，可適當選擇使用各種（曱基）丙烯酸醋類。 ^ . <黏結劑樹脂> . 本發明所使用的黏結劑樹脂，係使至少含有(Α)具有产氧 基與乙烯性不飽和鍵的含環氧基單體、以及(Β)具有脂#式 烴基與乙烯性不飽和鍵的含脂環式烴的單體之單體群，進> 共聚合而成的丙烯酸系共聚物。 本發明所使用的丙烯酸系共聚物若使至少含有（Α)具# $ 氧基與乙烯性不飽和鍵的含環氧基單體、以及(Β)具有 099117156 15 201111454 式煙基與乙烯性不飽和鍵的含脂環式烴的單體之單體群，進 行共聚合’則可使各單體進行無規的共聚合，亦可依成為嵌 段共聚物的方式進行共聚合。 藉由含有（A)具環氧基與乙烯性不飽和鍵的含環氧基單體 作為共聚合成分，可使丙烯酸系共聚物含有環氧基。藉此， 可造成利用熱所進行的反應性提升，以及提升硬化膜硬化性 之作用。作為(A)具有環氧基與乙烯性不飽和鍵的含環氧基 單體，可舉例如：（甲基）丙烯酸環氧丙酯、（甲基）丙烯酸甲 基環氧丙酯、（甲基）丙烯酸3,4-環氧基環己酯、（甲基）丙烯 酸3，4_環氧基環己基曱酯等。其中，本發明中較佳可使用（曱 基）丙稀酸壞氧丙醋。 (Α)含ί哀氧基單體可單獨使用！種、亦可混合使用2種以 上。 丙稀酸系共聚物中，上述⑷含環氧基單體的含有量係只 要能使上述黏結劑樹脂具有所需之硬化膜的硬化適性便 可，在總共聚合成分中’較佳係2〇〜8〇重量％、更佳％〜％ 重量％、特佳40〜60重量％。其理由係藉由使上述含有量在 上述範_ ’可形成硬化膜的硬倾、以及與其他成分間之 相溶性優異物。 藉由含有⑻具有脂環式烴基與乙烯性不飽和鍵的含脂環 早體作為共聚合成分，則使丙稀酸系共聚物含有脂環 式烴基。藉此，可造成硬化膜硬化性之提升，以及不易因孰 099117156 201111454 經歷而發生變黃的作用。具有脂環式烴基與乙烯性不飽和鍵 的含脂環式烴的單體，可舉例如：（曱基）丙烯酸環己酯、（曱 基）丙烯酸環己基甲酯、（曱基）丙烯酸3_環己烯基曱酯、（曱 基）丙烯酸4-異丙基環己酯、（曱基）丙烯酸丨_曱基環己酯、（曱 基）丙烯酸2-曱基環己酯、（曱基）丙烯酸3_曱基環己酯、（曱 基）丙烯酸4-曱基環己酯、（甲基）丙烯酸乙基環己酯、（曱 基）丙烯酸4-乙基環己酯、（曱基）丙烯酸2_第三丁基環己酯、 (曱基）丙烯酸4-第三丁基環己酯、（曱基）丙烯酸曱酯、（甲基） 丙烤I 3,3,5-二曱基壤己g旨、（甲基）丙烯酸環庚g旨、（甲基） 丙烯酸環辛酯、（曱基）丙烯酸環壬酯、（曱基）丙烯酸環癸酯、 (甲基）丙烯酸異稻酯、（曱基）丙烯酸二環戊酯、（曱基）丙烯酸 二環戊烯酯、（曱基）丙烯酸二環戊烯氧酯、（甲基）丙烯酸金 剛烷酯、（曱基）丙烯酸2-烷基-2-金剛烷酯、（曱基）丙烯酸3_ 羥基-1-金剛烷酯、（甲基）丙烯酸1_全氟金剛烷酯等。而（曱 基）丙烯酸2-烷基-2-金剛烷酯具體可舉例如：（曱基）丙烯酸 2-曱基-2-金剛烷酯、及（曱基）丙烯酸2-乙基_2·金剛烷酯等。 作為上述含脂環式烴的單體’從抑制因熱經歷所造成的變 黃、以及不使色域重現性降低的觀點而言，較佳為具有架橋 脂環式烴基與乙烯性不飽和鍵之含脂環式烴的單體。作為具 有架橋脂環式烴基與乙稀性不飽和鍵之含脂環式烴的單 體，從（曱基）丙烯酸異β酿、（曱基）丙烯酸二環戊酯、（曱基) 丙烯酸二環戊烯酯、（甲基）丙烯酸二環戊烯氧酯、（曱基）丙 099117156 17 201111454 烯酸金剛烷酯、（甲基）丙烯酸2-烷基-2-金剛烷酯、（曱基）丙 烯酸3-經基金剛烷酯、及（甲基）丙烯酸丨_全氟金剛烷酯 所構成群組中選擇之1種以上，係從抑制因熱經歷所造成的 變黃、以及不使色域重現性降低的觀點而言屬較佳。其中， 特別在本發明中，較佳可使用（曱基）丙烯酸二環戊酯、（曱基) 丙婦酸金剛烧g旨、（甲基）丙烯酸2_烷基_2_金剛烷酯。 (B)含脂環式烴的單體可單獨使用i種、亦可混合使用2 種以上。 丙烯酸系共聚物中’上述(B)含脂環式烴的單體之含有 里’係/、要能使上述黏結劑樹脂具有所需之硬化膜的硬化適 性便可’在總共聚合成分中，較佳係2q〜⑽重量％、更佳 30〜70 重詈％、 特佳40〜60重量％。其理由係藉由使上述含 有里在上述範圍内，可形成硬化膜的硬化性、以及與其他成 分間之相溶性優異物。 、 上述内烯酸系共聚物係在不損及本發明效果、且能確保彩 “片的各細部所必要之性能（例如硬度、透明性等）之 下亦可更進一步使用使除了上述(Α)含環氧基單體與上述 3 I %式煙的單體料之可進行共聚合的單體進行共聚 〇而成者。此種單體具體可舉例如：（曱基)丙烯酸甲酉旨、（甲 、-丁S曰（曱基）丙稀酸稀丙S旨、（甲基）丙稀酸經乙 ^ (甲基）丙烯酸2_二曱胺基乙酯、（甲基）丙烯酸2-乙基己 西曰（甲基）丙烯酉交2_經乙酿等；Ν-曱基順丁稀二醢亞胺、Ν_ 099117156 18 201111454 環己基順丁烯二醯亞胺等之N取代順丁烯二醯亞胺類等。 上述(A)含環氧基單體及上述(B)含脂環式烴的單體以外 的其他可進行共聚合單體之含有量，係在總共聚合成分中， 較佳含有〇重量％〜50重量％、更佳0重量％〜30重量％、特 佳0重量％〜20重量％。 本發明的丙烯酸系共聚物中，從抑制變黃的觀點而言，較 佳係不未含有芳香環。又，本發明的丙烯酸系共聚物中，從 使保存安定性良好的觀點而言，較佳係實質上不含有由（甲 基）丙烯酸所衍生的構成單位等酸成分。本發明的丙烯酸系 共聚物中，所謂「實質上不含有酸成分」係指刻意不使用 含有羧基等酸成分的單體作為共聚合成分的丙烯酸系共聚 物。 再者，上述丙烯酸系共聚物的重量平均分子量並無特別的 限定，較佳係1，000〜30,000、更佳係3000〜20,000。若上述 丙烯酸系共聚物的重量平均分子量小於1，000，則有對作為 彩色濾光片細部的硬化層所要求之強度、耐溶劑性等物性不 足之虞。反之，若上述丙烯酸系共聚物的重量平均分子量大 於30,000,則有容易發生黏度上升之虞，而有藉喷墨方式從 吐出喷頭吐出時的吐出量安定性、與吐出方向之直進性變差 之虞，且有長期保存的安定性惡化之虞。此處，重量平均分 子量可利用凝膠滲透色層分析儀(GPC)，依標準聚苯乙烯換 算值求得。 099117156 19 201111454 本發明所使用之丙婦酸系共聚物的合成方法，只要屬 上述各單體依所需比例含有的方式進行共聚合之方法 可，可使用-般的聚合方法。具體而言有如使上述各單體盘 聚合起始劑溶解或分散於溶射之後，再料聚合的方法、。 上述丙烯酸系共聚物的含有量係相對於墨水的固形份，較 佳在5重量％〜80重量％範圍内、更佳在1〇重量％〜6〇重旦 〇/〇範圍内。若少於上述範圍，則有缺乏硬化膜的硬化性、容 易出現龜裂之虞。又’若多於上述範圍，财容祕生黏度 上升之虞，在藉喷墨方式從吐出噴頭中吐出時的吐出量安定 性與吐出方向之直進性惡化之虞，且有長期保存的安定性變 差之虞。又，上述丙稀酸系共聚物的含有量，從保存安定性、 硬化膜的硬化性、耐藥性、色域$現性之觀點㈣，在除了 後述顏料與顏料分散劑以外的固形份中，較佳含有〜如 重量％、更佳含有20〜80重量％。 再者，本發明所使用的上述多官能基性單體相對於上述黏 結劑樹脂的含〇匕率，係只要能達成所需的墨水適性、硬化 膜之硬化舰便可，在上_色熱魏財墨墨水 中所含有的多g能基性單體與黏結劑樹脂之重量比（多官能 基性單體/點結劑樹脂；）’較佳係在1〇/9〇〜9〇/】〇範圍内，其 中從墨水的低黏度化、保存安定性、噴墨時的吐出安定性、 硬化膜的硬化性、畴性、色域重現性等觀點而言，較佳在 20/80〜80/20範圍内。 099117156 20 201111454 <顏料> 本發明所使用的顏料可使用公知顏料。本發明中可使用的 有機顏料具體例，如下表1與表2所示。 [表1] 顏料 色彩索引編號 1 3 12 13 14 15 16 17 20 24 31 55 60 61 65 71 73 74 81 83 93 95 97 98 色素黃 100 101 104 106 108 109 110 113 114 116 117 119 120 126 127 128 129 138 139 150 151 152 153 154 155 156 166 168 175 180 185 213 214 1 5 13 14 16 17 色素撥 24 34 36 38 40 43 46 49 51 61 63 64 71 73 21 099117156 201111454 [表2]In recent years, it has become more and more developed, especially in the case of personal computers, and has a tendency to use liquid crystal displays and personal computers. The color sound of the liquid crystal display (6), and the 3 (3) and green pixels corresponding to the display of the display are increased by (10)/(10): 吏aR, G, and B, and The liquid crystal is made to function as a shutter, and the light is transmitted through each of the pixels of R and G^. I know that the color county R manufacturing method is similar to the dyeing method. The dyeing method firstly forms a water-soluble high/knife material belonging to a dyeing material on a glass substrate, and then patterns the obtained optical lithography step* into a desired shape, and then dipped the obtained pattern into the dye bath. , to obtain a colored pattern. The pixels of R, G, and B are formed by repeating three times. Also, other methods are like pigment dispersion. In this method, a photosensitive resin layer in which a pigment is dispersed is first formed on a substrate, and patterned to obtain a monochromatic pattern. This step is repeated three more times to form pixels of R, 〇, and B. Still another method is a method such as an electroplating method or a method in which a pigment is dispersed in a thermosetting resin and three times of printing of R, G, and B is performed, and then the resin is thermally cured. 099117156 4 201111454 However, 'there are three methods of R, G, and b, and the same step must be repeated three times, and there is a color that causes an increase in cost because the same steps are repeated because of the problem of reduced economic efficiency. Further, in the color (four) shape manufacturing method as a problem of solving the problem, in the first embodiment, a coloring ink containing a thermosetting resin is used to form a pixel portion by heating by heating. [Patent Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 9-21910 (Summary of the Invention) It is known that a color filter is formed using a thermosetting resin. The general use of the polymerization and / or cross-linking reaction of the acid component and the epoxy component ^ - because the acid component and the epoxy age of the anti-hearing (four) is high, so ^ ' ::, gradually rising 'results in preservation stability The second occupancy = upper = is detrimental to the ink 2 2 f that is carried out by the ink jet method and the light-hearted button. Furthermore, the problem of the polymerization of the epoxy component and/or the exchange of 敎μ chest " At the same time, the color layer of the color layer is also obtained. In recent years, especially in the color television department, the color gamut is required to have color gamut reproducibility, high contrast and high luminance, but if the pixel is resistant to Insufficient music results in a color change in the cracked portion of the pixel, and thus there is a possibility that the luminance and color purity of the obtained color filter are lowered by 099117156 201111454. In recent years, there has been a demand for high luminance and high color purity of color filters, and thus it is required to make the pigment contained in the inkjet ink finer and higher in concentration. As the pigment is refined and the pigment concentration is increased, the amount of pigment contained in the inkjet ink and the amount of pigment dispersion must also increase. However, when the amount of the pigment and the pigment dispersant contained in the inkjet ink for the color filter is increased, the component which contributes to the film properties of the cured film, such as a binder, is relatively reduced, and as a result, the ink is used. The hardenability is lowered, and the adhesion of the cured film and the surface hardness are lowered. Further, when the pigment concentration is increased, the drying of the ink is promoted, and the ink discharged into the vehicle by the ink jet is unevenly dried by the ink, and the flatness of the pixel is deteriorated (4). If the flatness of the pixel is deteriorated, there is a problem that luminance and color purity are lowered. In view of the above facts, the present invention is intended to achieve the following objectives and objectives. A first object of the present invention is to provide a thermosetting inkjet ink for a color filter which is excellent in both storage stability and curability, and which is excellent in complementation after thermosetting and has a good color gamut. In addition, the second object of the present invention is to provide a thermosetting inkjet ink for a color filter which is excellent in adhesion, surface hardness, and flatness after heat curing, even if the pigment concentration is increased. (Means for Solving the Problem) The inventors of the present invention have intensively studied and found that the thermosetting adhesive component of the inkjet ink for a color filter is used in combination by having a mixture of ethylene and 099117156 6 201111454 and a bond. a polyfunctional monomer; and an acrylic acid copolymer obtained by copolymerizing a monomer group containing at least an epoxy group-containing monomer and an alicyclic cigarette-containing monomer; The present invention has been completed. In the present invention, a polyfunctional monomer having an ethylenically unsaturated bond is used as a thermosetting adhesive; a binder component, #, when the inkjet ink is hardened, the polyfunctional group is made by heat. The polymerization and/or crosslinking reaction is carried out. More specifically, in order to achieve the above object i, the following summer color filter and thermosetting inkjet ink for light sheet are provided. In other words, the first color filter and the thermosetting inkjet ink for a light sheet of the present invention contain a polyfunctional monomer, a minus-lipid, a pigment dispersant, and a solvent which is characterized by the above-mentioned polyfunctional group. Sexual single system: a compound having four or more ethylenically unsaturated bonds in the molecule, and the upper layer has at least (A) having an epoxy group and an ethylenic unsaturated group containing an epoxy group. 3) An acrylic copolymer obtained by copolymerizing a monomer group of a monomer containing a hydrazine-type ketone group and an ethylenically unsaturated bond. In the first inkjet ink, in the above propylene polymer, 20% by weight to 80% by weight of the total polymerization component of the above-mentioned oxy-oxide-only system, and = = total polymerization of a single system containing an alicyclic hydrocarbon The component 2 + 2% by weight to 5% by weight is preferred from the viewpoints of storage stability and low viscosity of the ink, resistance to the curing medium, and color gradation reproducibility. In the thermosetting ink ink for the first color filter or the light sheet, the (B) alicyclic-containing single system is derived from the viewpoints of resistance of the cured film, color gradation reproducibility, and the like, 099117156, 201111454 preferably has a bridged alicyclic hydrocarbon group. The bridged alicyclic hydrocarbon group refers to a polycyclic aliphatic hydrocarbon group having a bridged structure in an alicyclic hydrocarbon group and having a polycyclic structure in a molecule. Further, in order to achieve the above second object, the following thermosetting inkjet ink for a second color filter is provided. In other words, the thermosetting inkjet ink for a second color filter of the present invention contains a polyfunctional monomer, a binder resin, a pigment, a pigment dispersant, and a solvent, and is characterized by the above polyfunctionality. a compound having four or more ethylenically unsaturated bonds in one molecule of a single system, and the above-mentioned binder resin contains: an epoxy group-containing monomer having at least (A) an epoxy group and an ethylenically unsaturated bond And (B) an acrylic copolymer obtained by copolymerizing a monomer group of an alicyclic hydrocarbon-containing monomer having an alicyclic hydrocarbon group and an ethylenically unsaturated bond; and a copolymer different from the above-mentioned acrylic copolymer Epoxy resin. In the second inkjet ink, the acrylic copolymer is preferably obtained by copolymerizing a monomer group containing at least (A) an epoxy group-containing monomer and (B) an alicyclic hydrocarbon-containing monomer. One or more epoxy groups of the copolymer, and an acrylic copolymer obtained by reacting a carboxyl group-containing monomer (C) having a carboxyl group and an ethylenically unsaturated bond. In this case, since the side chain of the acrylic copolymer has an ethylenically unsaturated bond, since it can be crosslinked with the above polyfunctional monomer, it is excellent in adhesion, surface hardness, and flatness after heat curing. It is preferable from the viewpoint of excellent ITO formation resistance. In the second inkjet ink, the above-mentioned (A) is preferably the above-mentioned (A) in terms of the compatibility with each component in the ink, the adhesion after heat curing of the ink 099117156 8 201111454, the surface hardness, and the like. The epoxy group-containing monomer is 20% by weight to 80% by weight based on the total polymerization component, and the above (B) alicyclic hydrocarbon-containing monomer is 20% by weight to 80% by weight based on the total polymerization component. In the second ink-jet ink, the (B) alicyclic hydrocarbon-containing single system has a bridged alicyclic hydrocarbon group, and is preferable from the viewpoints of surface hardness and solvent resistance after heat curing of the ink. In the second inkjet ink, the content ratio of the polyfunctional monomer, the acrylic copolymer, and the epoxy resin is the epoxy resin relative to the polyfunctional monomer and the acrylic copolymer. The weight ratio of the sum (epoxy resin / (polyfunctional monomer + acrylic copolymer)) is 0.25 to 4, and the weight ratio of the above acrylic copolymer to the above polyfunctional monomer (acrylic The copolymer/polyfunctional monomer) is preferably 0.125 to 8, and is excellent in terms of adhesion, surface hardness, and flatness after heat curing of the ink. (Effect of the Invention) The thermosetting inkjet ink for a first color filter of the present invention is excellent in both storage stability and hardenability, excellent in chemical properties after heat curing, and color filter excellent in color gamut reproducibility. Light film. Further, the thermosetting inkjet ink for a second color filter of the present invention is excellent in adhesion, surface hardness, and flatness after heat curing. [Embodiment] 099117156 9 201111454 <First Inkjet Ink> The thermosetting inkjet ink for a first color filter of the present invention contains a polyfunctional monomer, a minus m, a pigment, and a dispersion. A thermosetting inkjet ink for a color filter of a coloring agent and a solvent, characterized in that the polyfunctional one-system has a compound having four or more ethylenically unsaturated bonds in one molecule, and the above-mentioned binder resin A single monomer containing at least (A) an epoxy group-containing monomer having an epoxy group and an ethylenically unsaturated bond, and (8) an alicyclic hydrocarbon-containing monomer having an alicyclic hydrocarbon group and an ethylarene-unsaturated bond. A group of acrylic copolymers obtained by copolymerization. In the thermosetting inkjet ink for color filters of the present invention, the thermosetting adhesive component is not mainly composed of a conventional epoxy resin or an acid component, but is used in two ports. More than the ethylidene unsaturated bond: the basic single H, and the lesser-containing oxime-containing ring-reducing acrylic copolymer with the monomer group of the alicyclic hydrocarbon-containing monomer The color filter which preserves stability and hard-smelling meal, excellent resistance after heat hardening, and good color gamut reproducibility can be realized. Further, in the "invention", since a thermosetting resin is used, special additional equipment such as light irradiation is not required, and the productivity is high. As a thermosetting adhesive component, a combination of four or more ethylene-reducing bond-functional groups, and a monomer containing at least s-methoxy group and alicyclic-type smoke are used in combination. The reason why the propylene (tetra) copolymer obtained by copolymerization of a monomer group of monomers is used for the above effects is presumed to be as follows: 099117156 201111454. When the conventional epoxy resin and the acid component are used as the main component of the thermosetting adhesive component, since the reactivity of the acid component and the epoxy resin is very high, the viscosity gradually rises over time, and the stability is preserved. Sexual problem. Also, · 'There is also a problem of insufficient drug resistance. In contrast, the thermosetting adhesive component of the present invention is not used in the polymerization and/or crosslinking reaction of a conventional epoxy resin and an acid component, but is used in combination with an acrylic acid having an epoxy group and an alicyclic hydrocarbon in a side chain. a copolymer, a polyfunctional monomer having four or more ethylenically unsaturated bonds in one molecule, using a polymerization and/or crosslinking reaction of an ethylenically unsaturated bond by heat, and utilizing The polymerization and/or crosslinking reaction of the epoxy group carried out by heat. In the present invention, since the reaction between the epoxy group and the acid component is not utilized in nature, and the epoxy group and the acid component are not coexisted, the epoxy group is less likely to react, and the storage stability is excellent. An acrylic copolymer having an epoxy group and an alicyclic hydrocarbon in a side chain, wherein the epoxy group is polymerized and/or crosslinked by a heat generation reaction, and has an alicyclic hydrocarbon, and is excellent in hardenability, and Because of the alicyclic hydrocarbons, it does not cause yellowing due to thermal experience, so the color gamut reproducibility is good. On the other hand, a polystyrene coating film having a high crosslink density can be obtained by thermal polymerization by a polystyrene having four or more ethylenically unsaturated bonds in one molecule. The towel of the present invention is prepared by a combination of a propylene 099117156 11 201111454 acid copolymer having a county-based cyclamate hydrocarbon and a polyfunctional monomer having 4 or more ethylenically unsaturated bonds in one molecule. The multiplication effect is a color filter which is excellent in storage stability, excellent in chemical properties after heat hardening, and excellent in color gamut reproducibility. The thermosetting inkjet ink for color filters of the present invention contains at least a polyfunctional monomer, a binder resin, a pigment, a pigment dispersant, and a solvent, and may contain other components as needed. Hereinafter, each component used in the thermosetting inkjet ink for color filters of the present invention will be described. <Polyfunctional monomer> In the present invention, a compound having four or more ethylenically unsaturated bonds in one molecule is used in the polyfunctional single system. Here, the "ethylenically unsaturated bond" means a double bond between carbon atoms capable of radical polymerization, and a functional group having such an ethylenically unsaturated bond, and examples thereof include a vinyl group (ch2=ch_), Methyl) propyl (CH2=CH-CH2- and CH2=C(CH3)-CH2·), (methyl) propylene (CH2=CH-CO- and CH2=C(CH3)-CO- ), (meth) propylene oxime (CH2=CH-COO- and CH2=C(CH3)-COO-), and -COO-CH=CH-COO-. In the polyfunctional monomer used in the present invention, when the number of the functional groups having an ethylenically unsaturated bond is four or more, it may be used alone or in combination of two or more. Further, the polyfunctional monomer to be used in the invention may be used singly or in combination of two or more. Among them, as the ethylenically unsaturated bond, from the viewpoint of the curability of the cured film by thermal polymerization and/or crosslinking, it is preferred to have four or more (methyl 099117156 12 201111454-based) acryloxy group, And / or (meth) acrylonitrile. Further, in the present invention, the acrylate and the methacrylate are collectively referred to as "(fluorenyl) acrylate. Others are the same. In the present invention, the molecular weight of the polyfunctional monomer is preferably 2,000 or less, more preferably 1 Å or less, from the viewpoint of ink viscosity. _ 1 compound having four or more ethylenically unsaturated bonds in the molecule, and examples thereof include tetrakis(hydroxy) sulfonium tetrakis(indenyl) acrylate vinegar, pentaerythritol tetra(meth) acrylate, dipentaerythritol tetra(methyl) Acrylate, bis(trimethylolpropane) tetra(meth)acrylic acid g, calcined f dipentaerythritol tetrakis(methyl) acrylate, pentaerythritol pentasyl monohydroxyl ester, two Pentaerythritol hexa(methyl) propylene, pentaerythritol penta(indenyl) acrylate, alkyl modified dipentaerythritol penta(methyl)propionate, amino hexanoic acid hexaacetate Vinegar, polyacetate (indenyl) acrylic acid, _ acid modified dipentaerythritol penta (meth) acrylate, and the like. Other examples are: pentaerythritol tetrahexyl vinegar tetrakis (meth) acrylic acid vinegar, gansu / tetrakis(mercapto) acrylate, bis (tris-propyl propyl) tetracaprolactone four (a Acrylate, bis(trimethylolethane)tetrakis(meth)acrylate, bis(trimethylolbutane)tetra(meth)acrylate, bis(trimethylolhexane)tetra Mercaptoic acid, acrylic acid, bis(tris-decyl octyl), tetrakis(f-based) acrylic acid S, tripentaerythritol hexa(methyl) acrylate, g-tripentaerythritol, succinate Acid ester, tripentaerythritol octa (meth) acrylic acid vinegar, tristaerythritol polyepoxy sulphate seven (meth) acrylic acid vinegar, and these epoxy ethoxylate adducts, epoxy oxide adducts Wait. Further, the steps of 099117156 13 201111454 include, for example, ethoxylated pentaerythritol tetrakis(meth) acrylate, neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate, hydrazine, 6-hexanediol hydrazine acrylate Ester, trimethylolpropane oligoacrylate, pentaerythritol acrylate, amino phthalate acrylate, epoxy acrylate, and the like. Further, for example, terenium (methacryloxyethyl)cyclotriphosphazene (for example, Γρρζ manufactured by Kyoei Chemical Co., Ltd.), dipentaerythritol hexamethacrylate diisocyanate • Amino decanoic acid ethyl ester prepolymer (for example, "UA_51〇H" manufactured by Kyoei Chemical Co., Ltd.). The content of the polyfunctional monomer having 4 or more ethylenically unsaturated bonds in one molecule is preferably in the range of 5% by weight to 80% by weight, more preferably 1%, based on the solid content of the ink. Weight %~6〇% by weight. If the reason is less than the above range, the cured film may have insufficient curability and chemical resistance. Further, if it is more than the above range, there is a possibility that the desired color cannot be reproduced. In addition, the content of the polyfunctional monomer having four or more ethylenically unsaturated bonds in one molecule is contained in a solid wound other than the pigment and the pigment dispersant described later. The weight %, more preferably 2% by weight to weight %, is preferable from the viewpoints of low viscosity of soil K, storage stability, hardenability of cured film, and property. Further, in the present invention, the "solid portion" means that all components contained in addition to W, such as the residual compound, are also included in the solid portion. In the present invention, the B-based basic monomer has four or more ethylene & unsaturated kneading compounds in one molecule, but the premise of the damage of the present invention is 099117156 14 201111454. For the purpose of grading and inkjet discharge, a compound having 2 to 3 ethylidene unsaturated bonds in one molecule may be used in combination. In this case, the compound having four or more ethylenically unsaturated bonds in the total amount of the polyfunctional monomer is preferably contained in an amount of 50% by weight or more, more preferably up to 5% by weight or more. In the present invention, in the total amount of the polyfunctional monomer, the compound having 4 or more ethylenically unsaturated bonds in the subunit is preferably 1% by weight. As a compound which may have 2 to 3 ethylene residues and bonds in the molecule, it is preferably a compound having 2 to 3 (fluorenyl) acrylonitrile groups, and examples thereof include trishydroxypropyl propane III ( Methyl)acrylate, trihydroxydecylethane tri(meth)acrylate, glycerol tris(decyl)acrylate, pentaerythritol tris(methyl) acrylate, alkyl modified dipentaerythritol tris(yl) ) acrylate, tris(mercapto) acrylate, isomeric cyanuric acid (propylene oxyethyl), iso-I-cyano-k-xyl (methyl propyl methoxyethyl) vinegar, etc. It is not limited to the knot, etc., and various (mercapto) acrylic vinegars can be appropriately selected and used. ^ . <Adhesive Resin> The binder resin used in the present invention contains at least an epoxy group-containing monomer having an oxy group and an ethylenically unsaturated bond, and (脂) has a fat. An acrylic copolymer obtained by copolymerizing a monomer group of an alicyclic hydrocarbon-containing monomer having an alkyl group and an ethylenically unsaturated bond. The acrylic copolymer used in the present invention contains an epoxy group-containing monomer having at least an oxime having an ethoxy group and an ethylenically unsaturated bond, and (Β) having a nicotine group of 099117156 15 201111454 and an ethylene group. When a monomer group of a saturated bond alicyclic hydrocarbon-containing monomer is subjected to copolymerization, each monomer can be randomly copolymerized, or copolymerized as a block copolymer. The acrylic copolymer may contain an epoxy group by containing (A) an epoxy group-containing monomer having an epoxy group and an ethylenically unsaturated bond as a copolymerization component. Thereby, it is possible to cause an increase in reactivity by heat and an effect of improving the hardenability of the cured film. The (A) epoxy group-containing monomer having an epoxy group and an ethylenically unsaturated bond may, for example, be a glycidyl (meth)acrylate or a methyl glycidyl (meth)acrylate. 3) 4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl decyl (meth) acrylate, and the like. Among them, (mercapto)acrylic acid acetoacetic acid is preferably used in the present invention. (Α) Containing oxime oxy-monomer can be used alone! It is also possible to use two or more kinds in combination. In the acrylic copolymer, the content of the epoxy group-containing monomer (4) is such that the above-mentioned binder resin can have a desired curing property of the cured film, and is preferably a total of 2 in the total polymerization component. 8% by weight, more preferably % to % by weight, particularly preferably 40 to 60% by weight. The reason for this is that the above-mentioned content is in the above-mentioned range, and it is possible to form a hard surface of the cured film and an excellent compatibility with other components. When the (8) alicyclic ring-containing precursor having an alicyclic hydrocarbon group and an ethylenically unsaturated bond is contained as a copolymerization component, the acrylic acid copolymer contains an alicyclic hydrocarbon group. Thereby, it can cause an increase in the hardenability of the cured film, and it is not easy to cause yellowing due to the experience of 99 099117156 201111454. The alicyclic hydrocarbon-containing monomer having an alicyclic hydrocarbon group and an ethylenically unsaturated bond may, for example, be cyclohexyl (meth) acrylate, cyclohexyl methyl (meth) acrylate or (mercapto) acrylate 3 _cyclohexenyl decyl ester, 4-isopropylcyclohexyl (decyl) acrylate, 丨-nonylcyclohexyl (mercapto) acrylate, 2-mercaptocyclohexyl (decyl) acrylate, (曱3) decyl cyclohexyl acrylate, 4-mercaptocyclohexyl (meth) acrylate, ethyl cyclohexyl (meth) acrylate, 4-ethylcyclohexyl (decyl) acrylate, (曱Acrylic acid 2_t-butylcyclohexyl ester, 4-tert-butylcyclohexyl (decyl)acrylate, decyl (meth) acrylate, (methyl) propyl I 3,3,5-two曱 壤 壤 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Rice ester, dicyclopentanyl (mercapto) acrylate, dicyclopentenyl (mercapto) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, ( Yl) acrylate, 2-alkyl-2-adamantyl acrylate, (Yue-yl) acrylic acid 3_ hydroxy-1-adamantyl acrylate, (meth) acrylic acid alkyl ester 1_ perfluoro adamantyl and the like. Specific examples of 2-alkyl-2-adamantyl (meth) acrylate include 2-mercapto-2-adamantyl (meth) acrylate and 2-ethyl _2 (fluorenyl) acrylate. Adamantyl ester and the like. As the above-mentioned alicyclic hydrocarbon-containing monomer', from the viewpoint of suppressing yellowing due to heat history and not lowering color gamut reproducibility, it is preferred to have a bridged alicyclic hydrocarbon group and ethylenic unsaturation. A monomer containing an alicyclic hydrocarbon. As an alicyclic hydrocarbon-containing monomer having a bridged alicyclic hydrocarbon group and an ethylenically unsaturated bond, from (mercapto)acrylic iso-beta, (cyclo)acrylic acid dicyclopentanyl ester, (mercapto)acrylic acid Cyclopentenyl ester, dicyclopentenyl (meth) acrylate, (mercapto) propene 099117156 17 201111454 adamantyl olefinate, 2-alkyl-2-adamantyl (meth) acrylate, fluorenyl One or more selected from the group consisting of acrylic acid 3-carbonated alkyl alkanoate and fluorinated (meth) acrylate-perfluoroadamantyl ester, which suppresses yellowing caused by heat history and does not cause color change. It is preferable from the viewpoint of a reduction in domain reproducibility. Among them, in particular, in the present invention, (fluorenyl) dicyclopentanyl acrylate, (fluorenyl) propyl gallic acid, and (meth)acrylic acid 2-alkyl-2_adamantyl ester are preferably used. (B) The alicyclic hydrocarbon-containing monomer may be used singly or in combination of two or more. In the acrylic copolymer, the above-mentioned (B) alicyclic hydrocarbon-containing monomer may be contained in the total polymerization component, in order to enable the above-mentioned binder resin to have a desired hardening property of the cured film. It is preferably 2q to (10)% by weight, more preferably 30 to 70% by weight, and particularly preferably 40 to 60% by weight. The reason for this is that the above-mentioned range is contained, and the curable property of the cured film and the compatibility with other components are excellent. Further, the above-mentioned internal olefinic acid copolymer can be further used in addition to the above (Α, without impairing the effects of the present invention and ensuring the performance (for example, hardness, transparency, etc.) necessary for each fine portion of the color sheet. The epoxy group-containing monomer is copolymerized with a monomer which can be copolymerized with the monomer of the above-mentioned 3 I % cigarette, and the monomer may specifically be, for example, (mercapto)acrylic acid. , (A, -, 曰S曰(fluorenyl) acrylic acid succinyl propyl, (meth) acrylic acid via ethyl (meth) acrylate 2 bis guanidinoethyl ester, (meth) acrylate 2 -ethylhexyl hydrazine (methyl) propylene hydrazine 2_ by ethyl acetate; Ν-mercapto cis-butyl diimide imine, Ν _ 099117156 18 201111454 cyclohexyl maleimide, etc. The content of the copolymerizable monomer other than the (A) epoxy group-containing monomer and the (B) alicyclic hydrocarbon-containing monomer is the total polymerization component. Preferably, it contains 〇% by weight to 50% by weight, more preferably 0% by weight to 30% by weight, particularly preferably 0% by weight to 20% by weight. In the acrylic copolymer of the present invention, it is preferred that the acrylic copolymer of the present invention does not substantially contain the aromatic ring from the viewpoint of suppressing yellowing. In the acrylic copolymer of the present invention, the term "substantially no acid component" means that a monomer containing an acid component such as a carboxyl group is not used as a copolymerization component. Further, the weight average molecular weight of the acrylic copolymer is not particularly limited, but is preferably 1,000 to 30,000, more preferably 3,000 to 20,000. If the weight average molecular weight of the above acrylic copolymer is smaller than In the case of 1,000, the physical properties such as strength and solvent resistance required for the hardened layer as the fine portion of the color filter are insufficient. On the other hand, if the weight average molecular weight of the acrylic copolymer is more than 30,000, the viscosity tends to occur. After the rise, there is a problem that the discharge amount stability and the straightness in the discharge direction are deteriorated when the ink is ejected from the discharge head, and there is a long-term guarantee. The stability of the storage is deteriorated. Here, the weight average molecular weight can be obtained by a gel permeation chromatography (GPC) according to a standard polystyrene conversion value. 099117156 19 201111454 The method for synthesizing the substance may be a method of copolymerizing in such a manner that each of the above monomers is contained in a desired ratio, and a general polymerization method may be used. Specifically, the above-mentioned respective monomer disk polymerization initiators are dissolved or dispersed. The method of repolymerizing after the spraying, the content of the acrylic copolymer is preferably in the range of 5 wt% to 80 wt%, more preferably 1 wt% to 6 wt%, based on the solid content of the ink. If it is less than the above range, there is a lack of hardenability of the cured film and prone to cracking. In addition, if it is more than the above-mentioned range, the viscosity of the financial secret is increased, and the stability of the discharge amount and the straightness of the discharge direction when the ink is ejected from the discharge nozzle are deteriorated, and the stability of long-term storage is maintained. The difference is worse. In addition, the content of the above-mentioned acrylic acid-based copolymer is in a solid content other than the pigment and the pigment dispersant described later from the viewpoints of storage stability, curability of the cured film, chemical resistance, and color gamut (4). Preferably, it contains, for example, % by weight, more preferably 20 to 80% by weight. Furthermore, the ruthenium content of the above polyfunctional monomer used in the present invention relative to the above-mentioned binder resin is as long as it can achieve the desired ink suitability and hardening of the cured film. The weight ratio of the poly-g-based monomer to the binder resin contained in Wei Cai ink (polyfunctional monomer/junction resin;) is preferably at 1〇/9〇~9〇/】〇 In the range, from the viewpoints of low viscosity of ink, storage stability, discharge stability at the time of inkjet, hardenability of cured film, domain property, color gradation reproducibility, etc., it is preferably 20/80 to 80. /20 range. 099117156 20 201111454 <Pigment> As the pigment used in the present invention, a known pigment can be used. Specific examples of the organic pigment which can be used in the present invention are shown in Tables 1 and 2 below. [Table 1] Pigment color index number 1 3 12 13 14 15 16 17 20 24 31 55 60 61 65 71 73 74 81 83 93 95 97 98 Pigment yellow 100 101 104 106 108 109 110 113 114 116 117 119 120 126 127 128 129 138 139 150 151 152 153 154 155 156 166 168 175 180 185 213 214 1 5 13 14 16 17 Pigment dial 24 34 36 38 40 43 46 49 51 61 63 64 71 73 21 099117156 201111454 [Table 2]
氧化鈦 再者，可使用的 錯、黃色錯、鋅黃、鐵丹、録紅、群青:鐵藍 鈷綠、伽、欽黑、合成鐵黑、碳黑等。 另外，該等顏料可單獨❹、亦可混合❹2種以上 鋅華、硫酸 氧化鉻綠、 ^者"本心月所使用之顏料的分散平均粒徑，係在使用該 衫色濾、光片用熱硬化性喷墨墨水形成彩色濾光片的著色層 時，若此進行所需發色，則並無特別的限定，通常較佳在 O-Gl/xm〜0·30μηι範圍内，更佳在 O.Ol/xm〜O.lOjLtm 範圍内。其 099117156 22 201111454 理由係當使用本發明之彩色濾光片用熱硬化性喷墨墨水形 成彩色濾光片之著色層時，可形成輝度、對比均優異的著色 層。另外，上述顏料的分散平均粒徑可利用光散射方式的粒 度分佈測定裝置進行測定。 本發明的喷墨墨水中，顏料含有量係在形成彩色濾光片的 著色層時，若能進行所需發色下，則並無特別的限定，依照 所使用之顏料種類而異，並無特別的限定。顏料的含有量係 在墨水的固形份中，較佳在5重量％〜70重量％範圍内、其 中更佳在10重量％〜60重量％範圍内。上述顏料的含有量不 管多或少於上述範圍，均有欠缺喷墨墨水的黏度安定性、或 分散粒徑無法在適當範圍内的可能性。 本發明的喷墨墨水中，上述顏料(P)與顏料以外的固形份 (V)之調配重量比（P/V)，係從墨水的吐出性能、防止墨水潰 壞、及所得之膜物性的均衡等觀點而言，較佳為0.25〜1.2、 更佳0.5〜1.2。若P/V比過低，則為了獲得充分著色力便必 需使附著於像素形成區域中的墨水液滴量增多，因而有發生 從像素形成區域出現墨水潰壞等問題的情況。反之，若P/V 比過高，則有吐出喷頭發生堵塞或飛行彎曲等吐出性能降 低、或膜表面粗糙等問題的情況。 <顏料分散劑> 在本發明的彩色濾光片用熱硬化性喷墨墨水中，為了使顏 料能良好地分散，而調配入顏料分散劑。作為顏料分散劑可 099117156 23 201111454 使用例如：陽離子系、陰離子系、非離子系、兩性、聚矽氧 系等界面活性劑等。界面活性劑中，較佳係如下所例示的高 分子界面活性劑（高分子分散劑）。又，亦可更進一步使用特 殊丙烯酸系聚合體等分散輔助樹脂。 即，較佳係使用例如：聚氧乙烯月桂基醚、聚氧乙烯硬脂 醚、聚氧乙烯油基醚等聚氧乙烯烷基醚類；聚氧乙烯辛基苯 醚、聚氧乙烯壬基苯醚等聚氧乙烯烷基苯醚類；聚乙二醇二 月桂酸酯、聚乙二醇二硬脂酸酯等聚乙二醇二酯類；山梨糖 醇酐脂肪酸酯類；脂肪酸改質聚酯類；三級胺改質聚胺基甲 酸酯類等高分子界面活性劑。 上述顏料分散劑的含有量係相對於墨水的固形份整體，較 佳為5〜50重量％，更佳係相對於固形份整體為10〜30重量 %。 <溶劑> 本發明的彩色濾光片用熱硬化性喷墨墨水中，為了將該墨 水調製成高濃度液或能馬上從喷頭中吐出狀態，而調配入溶 劑。 為了將本發明的彩色濾光片用熱硬化性喷墨墨水調製成 保存用高濃度墨水或能立即施行塗佈之濃度的墨水，若屬於 能將固形份適當地溶解及分散的溶劑便可，其餘並無特別的 限定。 溶劑可舉例如乙二醇單乙醚、二乙二醇二乙醚般之二醇醚 099117156 24 201111454 類；乙二醇單曱醚醋酸酯般之二醇醚酯類；二乙二醇單曱醚 般之二醇寡聚醚類；二乙二醇單曱醚醋酸酯、二乙二醇單丁 醚醋酸酯般之二醇寡聚醚酯類；醋酸乙酯'苯曱酸丙酯般之 脂肪族或芳香族酯類；碳酸二乙酯般之二羧酸二酯類；3-曱氧基丙酸曱酯般之烷氧基羧酸酯類；乙醯醋酸乙酯般之酮 羧酸酯類；乙醇、異丙醇、酚般之醇類或酚類；二乙醚、茴 香醚般之脂肪族或芳香族醚類；2-乙氧基乙醇、1-曱氧基-2-丙醇般之烷氧基醇類；二乙二醇、三丙二醇般之二醇寡聚物 類；醋酸2-乙氧基乙酯般之烷氧基醇酯類；丙酮、曱基異 丁酮般之酮類等。 再者，本發明的彩色濾光片用熱硬化性喷墨墨水中因為含 有顏料，故從顏料的分散性、分散安定性之觀點而言，最好 使用不含有羥基者作為溶劑。 溶劑較佳者可例示如：乙二醇單丁醚醋酸酯、二乙二醇單 丁醚醋酸酯、二乙二醇單乙醚醋酸酯、二乙二醇二乙醚、二 乙二醇二丁醚、己二酸二乙酯、草酸二丁酯、丙二酸二甲酯、 丙二酸二乙酯、琥珀酸二曱酯、及琥珀酸二乙酯等。又，該 等溶劑係與醋酸3-曱氧基丁酯或丙二醇單甲醚醋酸酯 (PGMEA)般之習知即使用於調製顏料分散液的高分散性之 溶劑相混合、或者未混合而直接使用作為分散溶劑，則可調 製顏料分散液。 再者，因為在溶劑中有水分混入的情況時，於溶劑中亦有 099117156 25 201111454 水分子的羥基存在，因而有發生與使用具有羥基之溶劑時同 樣問題之虞。所以，為了從酸-環氧基間的交聯反應系統中 實質排除水分，因而最好使用與水間的混合性較低之有機溶 劑而調製喷墨墨水。從該觀點而言，調製喷墨墨水用的溶劑 對水之溶解性，係相對於液溫20°C水100重量份，較佳在 20重量份以下。 列舉作為具體例的上述溶劑中，因為二乙二醇單丁醚醋酸 酯並不具有羥基，且對液溫20°C水100重量份的溶解性亦 顯示6.5重量份的較低水混合性，因而特佳。 溶劑係相對於含有該溶劑的喷墨墨水全量，通常依40〜95 重量％比例使用以調製喷墨墨水。若溶劑過少，喷墨墨水的 黏度高，當形成喷墨墨水時，從喷墨喷頭的吐出變得困難。 反之，若溶劑過多，則從既定墨水層形成部位發生墨水潰 壞，導致可堆積於該墨水層形成部位的墨水累積量變得不 足，乾燥後的膜厚過薄，隨之將無法獲得充分的穿透濃度。 <熱聚合起始劑> 本發明中，因為利用熱使上述乙烯性不飽和鍵進行聚合或 交聯反應而硬化，因而亦可含有熱聚合起始劑。作為使乙稀 性不飽和鍵進行熱硬化的熱聚合起始劑，可使用例如：過氧 化苯曱醯等各種過氧化物；偶氮雙丁腈等偶氮系化合物；鑌 鹽、具有三_化曱基的三讲化合物、疊氮化合物、酿重氮、 肟酯化合物、三芳香基單烷基硼酸酯化合物等。 099117156 26 201111454 上述熱聚合起始劑可單獨使用1種、亦可使用2種以上的 混合。本發明所使用之熱聚合起始劑的調配量，係上述多官 能基性單體每100重量份，通常在0.1〜10重量份範圍内， 較佳0.5〜5重量份。若熱聚合起始劑的調配量未滿0.1重量 份，則硬化不足，有無法形成強韌塗膜之虞。反之，若熱聚 合起始劑的調配量超過10重量份，則有墨水保存安定性差 劣之虞。 <硬化劑•促進劑> 本發明中，在使丙烯酸共聚物中的環氧基能效率佳地進行 反應之目的下，亦可含有環氧硬化劑·促進劑。作為環氧硬 化劑·促進劑係可使用例如：未改質脂肪族聚胺、改質脂肪 族聚胺、未改質芳香族聚胺、改質芳香族聚胺、改質脂環式 聚胺、未改質脂環式聚胺、未改質聚胺基醯胺、改質聚胺基 醯胺、三級胺、酸酐、醯肼衍生物、二氰二醯胺與其衍生物、 硼氫錯合物、有機金屬錯合物、鑌鹽類、聚硫醇、酚曱醛縮 合物、酚與其衍生物、具有羥基的其他化合物、異氰酸酯、 嵌段異氰酸酯、酮亞胺、咪唑與其衍生物等。 上述硬化劑•促進劑可單獨使用1種、亦可使用2種以上 的混合。本發明所使用的硬化劑•促進劑之調配量，係上述 丙烯酸系共聚物每100重量份，通常在0.1〜10重量份範圍 内，較佳0.5〜5重量份。若硬化劑·促進劑的調配量未滿 0.1重量份，則硬化不足，有無法形成強韌塗膜之虞。反之， 099117156 27 201111454 若硬化劑·促進劑的調配量超過10重量份，則有墨水保存 安定性差劣之虞。 <其他成分> 再者’本發明的彩色濾光片用熱硬化性噴墨墨水中，視需 要亦可調配入其他1種或2種以上之添加劑。此種添加劑可 例示如下述者： a) 填充劑：例如玻璃、氧化鋁等； b) 密接促進劑：例如乙烯基三曱氧基矽烷、乙烯基三乙氧 基石夕烧、乙稀基參(2-曱氧基乙氧基)石夕烧、N-(2-胺乙基)_3_ 胺丙基曱基二甲氧基石夕烧等； c) 均塗劑：例如聚氧化伸烷系界面活性劑、脂肪酸自旨系界 面活性劑、特殊丙烯酸系聚合體、乙烯醚系聚合體等乙烯系 聚合體等； 幻抗凝聚劑.例如聚丙稀酸納等。 <墨水之製造方法> 本發明的彩色濾光片用熱硬化性喷墨墨水，亦可將各成分 投入至溶劑中並混合，使固形成分溶解或分散而進行製造。 然而，若將顏料與樹脂等其他成分一起直接投入於溶劑整 體中並授拌混合’大多無法使顏料充分分散於溶劑中。在 此，通常準備顏料分散性與分散安定性良好的溶劑，並在其 中將顏料與分散劑-起投入，再利用溶解器等施行充分授 拌’而調製顏料分散液。純，將峨得之顏料分散液，與 099117156 28 201111454 除了顏料以外的成分一起投入於溶劑中，並 —*八m n ⑺’谷解器等施 仃充刀a拌混合，則可形成本發明的噴墨墨水。 作為投入顏料分散液的其餘溶劑，亦可使用具有"炊 洛劑整體組成中扣除了顏料分散液調製時所使用21二的 組成者，經稀釋至最終濃度而完成喷墨墨水。 73之 祖八私、六4几 人’亦可將顏 枓刀政液杈入於較少量溶劑中而調製為高濃度噴黑黑 A 濃度喷墨墨切錄财，並在即將制料稀 度才使用於噴墨方式。 本發明之彩色濾、光U熱硬化时墨墨水_途，係 用於利用噴墨方式形成彩色濾光片的著色層時，但其中最好 使用於要求色域重現性良好且高輝度的著色層之形成。 另外，本發明並不僅侷限於上述實施形態。上述實施形雖 僅止於例㈣已’舉凡具有與本㈣申請糊範圍所記_ ，術思想實質上屬於同—構造，並達到⑽仙效果者，不 官何者均涵括於本發明技術範疇内。 <第2喷墨墨水> 本《月的第2彩色遽光片用熱硬化性喷墨墨水，係含有： 夕B月b基f生單體、黏結劑樹月旨、顏料、顏料分散劑及溶劑的 彩^慮光片用熱硬化性噴墨墨水，其特徵為，上述多官能基 陸單體係1分子内具有4個以上之乙烯性不飽和鍵的化合 物且上述黏結劑樹脂含有：使至少含有⑷具有環氧基與 烯!·生不飽和鍵的含環氧基單體、與⑻具有脂環式烴基與 099117156 29 201111454 乙烯性不飽和鍵之含脂環式烴的單體的單體群，進行共聚合 而成的丙烯酸系共聚物；以及不同於上述丙烯酸系共聚物的 環氧樹脂。 本發明的彩色濾光片用熱硬化性喷墨墨水中，係藉由熱硬 化性黏結成分組合使用1分子内具有4個以上之乙烯性不飽 和鍵的多官能基性單體，與使至少含有含環氧基單體與含脂 環式煙的單體進行共聚合而得成之丙烯酸系共聚物、及不同 於該丙烯酸系共聚物的環氧樹脂，則即使提高顏料濃度，仍 可貫現具有熱硬化後的密接性、表面硬度、及平坦性均優異 之著色層的彩色濾光片。 再者，本發明中，因為使用熱硬化性樹脂，故不需要光照 射等特別的附加設備，亦具有生產性較高的優點。 藉由組合使用1分子内具有4個以上之乙烯性不飽和鍵的 多官能基性單體’使至少含有含環氧基單體及含脂環式烴之 單體並經共聚合而獲得的丙烯酸系共聚物，以及不同於該丙 烯酸系共聚物的環氧樹脂等3種作為熱硬化性黏結成分，則 發揮上述效果的理由係推測如下。 即’丙烯酸系共聚物的環氧基以及不同於其的環氧樹脂， 係藉由利用熱聚合起始劑（或熱）而進行開環並聚合及/或交 聯，而提升硬化膜的密接性。又，藉由導入於丙烯酸系共聚 物中的脂環式烴，使硬化膜的表面硬度及耐溶劑性優異。此 處’藉由組合在1分子内具有4個以上之乙烯性不飽和鍵的 099117156 30 201111454 多官能基性單體，則使硬化膜的交聯密度上升，而更加提升 表面硬度，並提升對玻璃等基材的濕潤擴展性，使平坦性優 異。而且’藉由該等3成分的相乘效果’即便提高顏料濃度 的情況，推測仍可實現熱硬化後的密接性、表面硬度、及平 坦性均優異之著色層。 第2喷墨墨水係如同第1喷墨墨水，至少含有：多官能基 性早體、作為黏結劑樹脂的丙稀酸糸共聚物與環氧樹脂、顏 料、顏料分散劑、以及溶劑，且視需要亦可含有其他成分。 以下，針對第2喷墨墨水所使用各成分進行說明。有關與第 1喷墨墨水同樣的事項則省略記載，僅強調與第1喷墨墨水 不同之事項並進行說明。關於第1喷墨墨水所記載的事項， 在不屬於後述差異點的前提下，均爰引於關於第2喷墨墨水 的說明中。 <多官能基性單體> 第2噴墨墨水中’係使用與在第1噴墨墨水令所使用之多 官能基性單體相同者。 第2喷墨墨水中’從表面硬度及密接性之觀點而言，作為 乙烯性不飽和麵亦為具有4個以上之(甲基)丙烯醯氧基 及/或（甲基）丙烯醯基。 多官能基性單體的分子量係在第2噴墨墨水中，較佳亦為 與第1喷墨墨水同樣的範圍。即，多官能基性單體的分子 量’係從墨水黏度與硬化膜平坦性的觀點而言，較佳在2〇〇〇 099117156 31 201111454 以下、更佳在1000以下。 第2喷墨墨水中，！分子内具有4個以上之乙馳不飽和 鍵的多宫能基性賴之含有量，係姆於墨水_形份，較 佳在0.5重量％〜30重量％範圍内、更佳在5 〇重量％〜加重 量％範圍内。若少於上述範圍，則有因賴擴展性降°低而使 平坦性劣化、及表面硬度劣化之虞。又，若多於上述範圍， 則因與丙烯酸系絲物含有量間之均衡賴係，而有墨水硬 化膜的耐溶劑性劣化之虞。 <黏結劑樹脂> 第2喷墨墨水較用的麟賴脂係含有：使至少含有⑷ 含環氧基單體與⑻含料式煙之單體的單料，進行共聚 合而成的丙賴系共聚物；與不同於上述丙烯酸系共聚物的 環氧樹脂。 [丙烯酸系共聚物] 第2喷墨墨水中，係使用與在第1喷墨墨水中所使用的丙 烯酸系共聚物相同者。 因為丙婦酸系共聚物含有環氧基，故具有提升對墨水附著 面的也接性、以及使與其他成分間之相溶性良好的作用。 再者’因為丙烯酸系共聚物含有脂環式烴基，故具有提升 硬化膜的硬化性、提升表面硬度、以及使耐溶劑呈良好的作 用。 作為上述含脂環式烴的單體，其中從硬化膜的表面硬度及 099117156 32 201111454 耐溶劑性之觀點而言’較佳係具有架橋脂環式烴基與乙烯性 不飽和鍵的含脂環式烴之單體。作為具有架橋脂環式烴基與 乙烯性不飽和鍵的含脂環式烴之單體，對第丨喷墨墨水而言 係屬較佳者’係由硬化膜的平坦性、表面硬度及耐溶劑性之 觀點而言，亦屬較佳。 其中’尤其是第2噴墨墨水中，較佳可使用例如（甲基）丙 烯酸二環戊酯、（曱基）丙稀酸1-金剛烧酯、（甲基）丙烯酸2_ 金剛烷酯。 丙烯酸系共聚物中，上述(B)含脂環式烴之單體的含有 量，只要能具有上述黏結劑樹脂所需的硬化膜表面硬度及耐 溶劑性便可，如同第1喷墨墨水的情況，在總共聚合成分中 較佳為20〜80重量％、更佳30〜70重量％、特佳4〇〜6〇重量 %。 第2喷墨墨水+，較佳係使至少含有(A)具環氧基與乙烯 性不飽和鍵的含環氧基單體及(B)具有脂環式烴基與乙烯性 不飽和鍵的含脂％式烴的單體之單體群進行共聚合而成的 共聚物中所具有的環氧基之1個以上，與(c)具有叛基及乙 烯性不飽和鍵的含敌基單體進行反應而成的丙烯酸系共聚 物。 此種情、况’在丙烯酸系4聚物的側鏈上具有乙稀性不飽和 鍵’因為該丙烯酸系共聚物與上述多官能基性單體一起利用 乙烯性不飽和鍵進行聚合及/或交聯反應，故熱硬化後的密 099117156 33 201111454 接性、表面硬度、及平坦性均優異，且耐IT〇形成性 異。 . '、優 另外’所謂「耐ΙΤ0形成性」係指當在透明電極膜(例如 ιτο)形成時，使㈣墨水製祕料料被硬化的層（以下 稱「硬化層」）時，不易發生皴折與龜裂，且相鄰層g不易發 =與龜裂•當使用喷墨墨水形成彩色據光片的著 色層時’在基板上形成著色層後，視需要在其上㈣成伴護 膜’然後再形成透明電極膜，但在該透㈣極_成時將有 透明電_表面上發生皺折的問題i明電__成方法 有如真空驗法、舰法、離子蒸鍍Μ，但不管何種方法 均必需在減I環境下對基板施行加熱。例如當施行作為透明 電極膜具代表性的Ι1Ό膜之真空蒸鑛成膜時，成為底層的 者色層料護膜係暴露於高溫及由真空所造成的超低壓 下。可二為若由墨水所形成的著色層㉔化層㈣於此種超 2坠冋溫條件下’則因為硬化層進賴膨脹_而發生敏 而使透明電極料鄰接層發生錢，躺而在其表面上 龜裂。若透明電極膜表面發生皺折或龜裂，在發 处阻率局部性地提高而導致斷線，發生餘像，甚至成 *、、、顯不不良的肇因。所以，若耐ΙΤΟ形成性優異，則可獲 得降低了顯示不良的高輝度彩色濾光片。 、〔（）-有緩基與乙烯性*飽和鍵的含叛基單體，具體 可舉例如：甲基㈣酸、丙烯酸、巴錢、衣康酸、順;婦 099117156 34 201111454 二酸、反丁烯二酸、〇Κ羥基曱基）丙烯酸、（曱基）丙烯醯氧 基乙基琥珀酸單酯、（曱基）丙烯醯氧基酞酸單酯等。其中， 本發明較佳係可使用丙烯酸、曱基丙烯酸、及順丁烯二酸， 特佳可使用丙烯酸、甲基丙稀酸。 ； 使至少含有（Α)含環氧基單體與(Β)含脂環式烴的單體並 : 進行共聚合而成的共聚物所具有之環氧基之1個以上，與(c) 含羧基單體進行反應而成的丙烯酸系共聚物中，共聚物側鏈 所具有的環氧基其中一部分被使用於與(C)含羧基單體間的 反應’而成為具有於侧鏈具有乙烯性不飽和鍵的重複單位。 此種丙烯酸系共聚物中，於側鏈具有乙烯性不飽和鍵的重 複單位之含有量，較佳係在共聚物的總重複單位中為10〜80 莫耳％ '更佳20〜60莫耳％。其理由係藉由使含有量在上述 範圍内，可提升與多官能基性單體間之反應性，尤其可形成 耐ΙΤΟ形成性優異者。 另外，具有於侧鏈具有乙烯性不飽和鍵之重複單位的丙烯 .酸系共聚物中，作為於側鏈具有環氧基的重複單位之含有 . 量，係在共聚物的總重複單位中，較佳為10〜70莫耳％、更 佳20〜40莫耳％，又，作為於側鏈含有脂環式烴的重複單位 之含有量，係在共聚物的總重複單位中，較佳為10〜70莫耳 %、更佳20〜50莫耳％，此由硬化膜的密接性、表面硬度、 及耐ΙΤΟ形成性等觀點而言屬較佳。 第2噴墨墨水中，上述丙烯酸系共聚物的含有量係相對於 099117156 35 201111454 墨水的固形份，較佳在G.5重量％〜3〇重量_内、更佳 在U)重量％〜15重量％範圍内。若少於上述範圍，則有黑 水硬化膜的耐溶劑性惡化之虞。反之，若㈣^ 有表面硬度心化之虞。又，上述丙烯酸系共聚物的含有量， 係在除了後述顏料與顏料分散劑以外的固形份 有10〜70重量％、更佳含有队 為3 〇重：!；/〇，此由表面硬度的 親點而&屬較佳。 [環氧樹脂] 本發明中，併用作為黏結劑樹脂的環氧樹脂，係不同於上 述於側鏈具有環氧基㈣烯酸系共㈣之樹脂。本發明所使 用的環氧樹脂係從由噴墨墨水卿成的像素之耐溶劑性、密 接性等膜物性觀點而言，較佳…分子中具有⑽以上環氧 基。環氧基係只要屬於具有環氧構造的基便可，可例示如環 氧丙基、環氧乙絲、環氧基環己基等。 壤乳樹脂係從提高硬化膜的交聯密度、利用低黏度化而提 升喷墨吐出性能的觀點而言，聚笨乙烯換算的重量平均分子 里較佳係3〇〇〇〜20000、更佳4〇〇〇〜15000。 若上述環氧樹脂的分子量小於3〇〇〇，則作為彩色濾光片 的細部之硬化層所要求的強度、耐溶劑性等物性容易不足， 反之，若該分子量大於20000，則容易發生黏度上升，依喷 墨方式從吐出喷頭中吐出時，有吐出量安定性與吐出方向之 直進性變差之虞，或者有長期保存的安定性變差之虞。 099117156 36 201111454 並1::脂若為在一分子中含有2個以上之環氧基，則其餘 、”，、特別的限制，可使用例如： 、 型環氧樹脂、漠化雙盼A型環氧阶、雙二:雙_ 二苯醚型環⑽ &魏㈣、雙盼S购氧樹脂、 /氧紹日、氫_環氧樹脂、萘型環氧樹脂、聯笨 氣⑽9、第型環氧樹脂喝祕清漆型環氧樹脂、鄰甲 漆㈣氧樹脂、參料基甲烧型環氧飽旨、三官能 j環氧樹脂、四祕基乙燒型環氧樹脂、二環戊二歸_ ^乳樹脂、氫化雙紛A型環氧樹脂、物A含核多元醇型 :氧树知、聚丙二醇型環氧樹脂、環氧丙基醋型環氧樹脂、 衣氧丙基胺型環氧樹脂、乙二酿型環氧樹脂、脂環型環氧樹 脂、雜環型環氧樹脂等。Titanium oxide In addition, it can be used in the wrong, yellow, yellow, iron, red, ultramarine: iron blue cobalt green, gamma, black, synthetic iron black, carbon black and so on. In addition, the pigments may be used alone or in combination with two or more kinds of zinc silicate, chromic oxychromate green, and the dispersed average particle size of the pigment used in the present month. When the coloring layer of the color filter is formed of a thermosetting inkjet ink, the desired color development is not particularly limited, and it is usually preferably in the range of O-Gl/xm to 0.30 μm, and more preferably. In the range of O.Ol/xm~O.lOjLtm. The reason is that when the coloring layer of the color filter is formed using the thermosetting inkjet ink for a color filter of the present invention, a coloring layer excellent in luminance and contrast can be formed. Further, the dispersed average particle diameter of the above pigment can be measured by a light scattering type particle size distribution measuring apparatus. In the inkjet ink of the present invention, when the pigment content is in the coloring layer forming the color filter, it is not particularly limited as long as it can perform the desired color development, and it does not vary depending on the type of the pigment to be used. Special restrictions. The content of the pigment is preferably in the range of from 5% by weight to 70% by weight, more preferably from 10% by weight to 60% by weight, based on the solids of the ink. The content of the above pigment is not particularly large or less than the above range, and there is a possibility that the viscosity stability of the inkjet ink is insufficient or the dispersed particle diameter cannot be within an appropriate range. In the inkjet ink of the present invention, the blending weight ratio (P/V) of the pigment (P) to the solid component (V) other than the pigment is based on the discharge performance of the ink, the prevention of ink collapse, and the resulting film properties. From the viewpoint of balance and the like, it is preferably 0.25 to 1.2, more preferably 0.5 to 1.2. When the P/V ratio is too low, in order to obtain sufficient coloring power, it is necessary to increase the amount of ink droplets adhering to the pixel formation region, and thus there is a problem that ink collapse occurs from the pixel formation region. On the other hand, if the P/V ratio is too high, there is a problem that the discharge head is clogged, the discharge performance such as flight bending is lowered, or the surface of the film is rough. <Pigment Dispersant> In the thermosetting inkjet ink for color filters of the present invention, a pigment dispersant is blended in order to disperse the pigment well. As the pigment dispersing agent, for example, a surfactant such as a cationic system, an anionic system, a nonionic system, an amphoteric or polyfluorene-based system can be used. Among the surfactants, a high molecular surfactant (polymer dispersant) exemplified below is preferred. Further, a dispersion auxiliary resin such as a special acrylic polymer may be further used. That is, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc.; polyoxyethylene octyl phenyl ether, polyoxyethylene fluorenyl group are preferably used. Polyoxyethylene alkyl phenyl ethers such as phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid upgrading Polymeric surfactants such as polyesters; tertiary amine modified polyurethanes. The content of the above pigment dispersant is preferably from 5 to 50% by weight based on the total solid content of the ink, more preferably from 10 to 30% by weight based on the total solid content. <Solvent> In the thermosetting inkjet ink for color filters of the present invention, a solvent is prepared in order to prepare the ink into a high-concentration liquid or to discharge it immediately from the head. In order to prepare a high-concentration ink for storage or a concentration at which the coating can be applied immediately, the color filter for a color filter of the present invention is a solvent capable of appropriately dissolving and dispersing a solid portion. The rest are not particularly limited. The solvent may, for example, be ethylene glycol monoethyl ether, diethylene glycol diethyl ether glycol ether 099117156 24 201111454; ethylene glycol monoterpene ether acetate glycol ether ester; diethylene glycol monoterpene ether Glycol oligoethers; diethylene glycol monoterpene ether acetate, diethylene glycol monobutyl ether acetate-like diol oligopolyether esters; ethyl acetate propyl benzoate-like aliphatic Or aromatic esters; diethyl carbonate-like dicarboxylic acid diesters; 3-oxooxypropionate-like alkoxy carboxylates; ethyl acetate-like ketone carboxylates Ethanol, isopropanol, phenolic alcohols or phenols; diethyl ether, anisole-like aliphatic or aromatic ethers; 2-ethoxyethanol, 1-decyloxy-2-propanol Alkenyl alcohols; diethylene glycol, tripropylene glycol-like glycol oligomers; 2-ethoxyethyl acetate-like alkoxy alcohol esters; acetone, mercapto-isobutyl ketone-like ketones Wait. Further, since the thermosetting inkjet ink for color filters of the present invention contains a pigment, it is preferable to use a solvent containing no hydroxyl group from the viewpoint of dispersibility of the pigment and dispersion stability. The solvent is preferably exemplified by ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol dibutyl ether. , diethyl adipate, dibutyl oxalate, dimethyl malonate, diethyl malonate, dinonyl succinate, and diethyl succinate. Further, these solvents are similar to those of 3-decyloxybutyl acetate or propylene glycol monomethyl ether acetate (PGMEA), even if the solvent for dissolving the high dispersibility of the pigment dispersion is mixed or not directly mixed. When used as a dispersion solvent, a pigment dispersion can be prepared. Further, when water is mixed in the solvent, the hydroxyl group of the water molecule of 099117156 25 201111454 is also present in the solvent, so that the same problem occurs when a solvent having a hydroxyl group is used. Therefore, in order to substantially exclude water from the cross-linking reaction system between the acid-epoxy groups, it is preferred to prepare an ink-jet ink using an organic solvent having a low miscibility with water. From this point of view, the solubility of the solvent for preparing the inkjet ink with respect to water is preferably 100 parts by weight or less based on 100 parts by weight of water at 20 °C. In the above-mentioned solvent as a specific example, since diethylene glycol monobutyl ether acetate does not have a hydroxyl group, and solubility in 100 parts by weight of water at a liquid temperature of 20 ° C also shows a low water miscibility of 6.5 parts by weight, Therefore, it is especially good. The solvent is usually used in an amount of 40 to 95% by weight based on the total amount of the inkjet ink containing the solvent to prepare an inkjet ink. If the amount of the solvent is too small, the viscosity of the inkjet ink is high, and when the inkjet ink is formed, discharge from the inkjet head becomes difficult. On the other hand, if the amount of the solvent is too large, ink collapse occurs from the portion where the ink layer is formed, and the amount of accumulated ink that can be deposited on the portion where the ink layer is formed becomes insufficient, and the film thickness after drying is too thin, so that sufficient wear cannot be obtained. Penetration concentration. <Thermal polymerization initiator> In the present invention, the above-mentioned ethylenically unsaturated bond is hardened by polymerization or crosslinking reaction by heat, and thus a thermal polymerization initiator may be contained. As the thermal polymerization initiator for thermally curing the ethylenically unsaturated bond, for example, various peroxides such as benzoquinone; an azo compound such as azobisbutyronitrile; and a phosphonium salt having three The three-membered compound of the sulfhydryl group, the azide compound, the diazonium diamine, the oxime ester compound, the triaryl monoalkyl borate compound, and the like. 099117156 26 201111454 The above-mentioned thermal polymerization initiator may be used singly or in combination of two or more. The amount of the thermal polymerization initiator used in the present invention is usually from 0.1 to 10 parts by weight, preferably from 0.5 to 5 parts by weight, per 100 parts by weight of the above-mentioned multifunctional base monomer. When the amount of the thermal polymerization initiator is less than 0.1 part by weight, the hardening is insufficient, and there is a possibility that a tough coating film cannot be formed. On the other hand, if the amount of the thermal polymerization initiator is more than 10 parts by weight, there is a difference in ink storage stability. <Hardener/Accelerator> In the present invention, an epoxy hardener/accelerator may be contained for the purpose of efficiently performing the reaction of the epoxy group in the acrylic copolymer. As the epoxy hardener/accelerator, for example, unmodified aliphatic polyamine, modified aliphatic polyamine, unmodified aromatic polyamine, modified aromatic polyamine, modified alicyclic polyamine can be used. , unmodified alicyclic polyamine, unmodified polyamine amide, modified polyamine amide, tertiary amine, acid anhydride, hydrazine derivative, dicyandiamide and its derivatives, boron hydride Compounds, organometallic complexes, phosphonium salts, polythiols, phenolic furfural condensates, phenols and derivatives thereof, other compounds having hydroxyl groups, isocyanates, blocked isocyanates, ketimines, imidazoles and derivatives thereof. The above-mentioned hardener/accelerator may be used singly or in combination of two or more kinds. The amount of the curing agent/accelerator used in the present invention is usually from 0.1 to 10 parts by weight, preferably from 0.5 to 5 parts by weight, per 100 parts by weight of the above acrylic copolymer. When the amount of the curing agent/accelerator is less than 0.1 part by weight, the curing is insufficient, and there is a possibility that a tough coating film cannot be formed. On the other hand, if the amount of the hardener/accelerator is more than 10 parts by weight, there is a problem that the ink is poor in stability. <Other components> Further, the thermosetting inkjet ink for color filters of the present invention may be blended with one or more other additives as needed. Such an additive can be exemplified as follows: a) a filler: for example, glass, alumina, etc.; b) an adhesion promoter: for example, vinyl trimethoxy decane, vinyl triethoxy sulphur, and ethylene ginseng ( 2-methoxyethoxyethoxy), sinter, N-(2-aminoethyl)_3_aminopropyl decyldimethoxy sulphide, etc.; c) co-coating agent: for example, polyoxyalkylene-based interfacial activity An agent, a fatty acid-based surfactant, a special acrylic polymer, a vinyl polymer such as a vinyl ether polymer, or the like; a magical anti-coagulant such as sodium polyacrylate. <Manufacturing Method of Ink; The thermosetting inkjet ink for color filter of the present invention may be produced by putting each component into a solvent and mixing it, and dissolving or dispersing the solid component. However, if the pigment is directly introduced into the solvent together with other components such as a resin and mixed, it is often impossible to sufficiently disperse the pigment in the solvent. Here, a solvent having good pigment dispersibility and dispersion stability is usually prepared, and a pigment and a dispersing agent are put thereinto, and a pigment dispersion liquid is prepared by performing a sufficient dosing with a dissolver or the like. Pure, the pigment dispersion of Chad, and 099117156 28 201111454, in addition to the components other than the pigment, is put into the solvent, and -8 mn (7) 'glutinator or the like is mixed and mixed, then the invention can be formed Inkjet ink. As the remaining solvent to be used for the pigment dispersion, it is also possible to use a composition having a composition of 21 in which the pigment dispersion is prepared by subtracting the entire composition of the pigment dispersion, and diluting to a final concentration to complete the inkjet ink. 73 ancestor eight private, six or four people 'can also be immersed in a small amount of solvent in the 枓 枓 knife solution into a high concentration of black and black A concentration inkjet ink cut recording, and is about to be thin It is used in inkjet mode. In the color filter and the light U heat-curing of the present invention, the ink ink is used for forming a coloring layer of a color filter by an inkjet method, but it is preferably used for a color gamut having good reproducibility and high luminance. Formation of a colored layer. Further, the present invention is not limited to the above embodiment. Although the above-mentioned embodiment is only used in the case of (4), it has the same meaning as the scope of the application (4), and the idea is essentially the same-structure, and achieves the effect of (10) cents, which is not included in the technical scope of the present invention. Inside. <Second inkjet ink> The thermosetting inkjet ink for the second color calender sheet of the present month contains: BB month b-based monomer, binder, pigment, pigment dispersion A thermosetting inkjet ink for use in a coloring agent and a solvent, characterized in that the polyfunctional base system has a compound having four or more ethylenically unsaturated bonds in one molecule, and the binder resin contains An alicyclic hydrocarbon-containing monomer having at least (4) an epoxy group-containing monomer having an epoxy group and an olefin group; and (8) an alicyclic hydrocarbon group having an alicyclic hydrocarbon group and an ethylenically unsaturated bond of 099117156 29 201111454; The monomer group is an acrylic copolymer obtained by copolymerization; and an epoxy resin different from the above acrylic copolymer. In the thermosetting inkjet ink for color filters of the present invention, a polyfunctional monomer having four or more ethylenically unsaturated bonds in one molecule is used in combination with a thermosetting adhesive component, and at least An acrylic copolymer containing an epoxy group-containing monomer and a monomer containing an alicyclic cigarette, and an epoxy resin different from the acrylic copolymer, even if the pigment concentration is increased, It is a color filter of a color layer which is excellent in adhesion, surface hardness, and flatness after thermosetting. Further, in the present invention, since a thermosetting resin is used, special additional equipment such as light irradiation is not required, and the productivity is high. By using a polyfunctional monomer having four or more ethylenically unsaturated bonds in one molecule in combination to obtain at least an epoxy group-containing monomer and an alicyclic hydrocarbon-containing monomer and copolymerizing it. The reason why the above effects are exhibited by the three types of the acryl-based copolymer and the epoxy resin different from the acryl-based copolymer as the thermosetting adhesive component is presumed as follows. That is, the epoxy group of the acrylic copolymer and the epoxy resin different therefrom are opened and polymerized and/or crosslinked by using a thermal polymerization initiator (or heat) to enhance the adhesion of the cured film. Sex. Moreover, the surface hardness and solvent resistance of the cured film are excellent by the alicyclic hydrocarbon introduced into the acrylic copolymer. Here, by combining 099117156 30 201111454 polyfunctional monomers having 4 or more ethylenically unsaturated bonds in one molecule, the crosslinking density of the cured film is increased, and the surface hardness is further increased, and the pair is improved. The wettability of a substrate such as glass is excellent in flatness. Further, even when the pigment concentration is increased by the multiplication effect of the three components, it is presumed that the coloring layer excellent in adhesion, surface hardness, and flatness after thermosetting can be obtained. The second inkjet ink is, like the first inkjet ink, contains at least a polyfunctional precursor, a bismuth acrylate copolymer as a binder resin, an epoxy resin, a pigment, a pigment dispersant, and a solvent, and It may also contain other ingredients. Hereinafter, each component used in the second inkjet ink will be described. The same matters as those of the first inkjet ink will be omitted, and only the matters different from those of the first inkjet ink will be described. The matters described in the first ink-jet ink are referred to in the description of the second ink-jet ink on the premise that they do not belong to the difference point described later. <Polyfunctional monomer> The second inkjet ink is used in the same manner as the polyfunctional monomer used in the first inkjet ink. In the second inkjet ink, from the viewpoint of surface hardness and adhesion, the ethylenically unsaturated surface also has four or more (meth) acryloxy groups and/or (meth) acrylonitrile groups. The molecular weight of the polyfunctional monomer is preferably in the second inkjet ink, and is preferably in the same range as the first inkjet ink. Namely, the molecular weight of the polyfunctional monomer is preferably from 2 〇〇〇 099117156 31 201111454 or less, more preferably 1,000 or less from the viewpoint of ink viscosity and cured film flatness. In the second inkjet ink,! The content of the polyglycolic group having more than 4 kinds of ethylenically unsaturated bonds in the molecule is preferably in the range of 0.5% by weight to 30% by weight, more preferably 5 parts by weight. %~ plus weight% range. When it is less than the above range, the flatness is deteriorated and the surface hardness is deteriorated because the spreadability is lowered. In addition, when it is more than the above range, the solvent resistance of the ink hardened film is deteriorated due to the balance with the content of the acrylic fiber. <Adhesive Resin> The lining of the second inkjet ink contains a monomer which contains at least (4) an epoxy group-containing monomer and (8) a monomer containing a flue-containing cigarette, and is copolymerized. a propylene-based copolymer; and an epoxy resin different from the above-mentioned acrylic copolymer. [Acrylic copolymer] The second inkjet ink is the same as the acrylic copolymer used in the first inkjet ink. Since the buprophytic acid copolymer contains an epoxy group, it has an effect of improving the adhesion to the ink adhesion surface and the compatibility with other components. Further, since the acrylic copolymer contains an alicyclic hydrocarbon group, it has the effect of improving the hardenability of the cured film, improving the surface hardness, and making the solvent resistant. As the above-mentioned alicyclic hydrocarbon-containing monomer, from the viewpoint of the surface hardness of the cured film and the solvent resistance of 099117156 32 201111454, it is preferred to have a alicyclic ring having a bridged alicyclic hydrocarbon group and an ethylenically unsaturated bond. Hydrocarbon monomer. As a monomer having an alicyclic hydrocarbon group having a bridged alicyclic hydrocarbon group and an ethylenically unsaturated bond, it is preferred for the second inkjet ink. 'The flatness, surface hardness and solvent resistance of the cured film. From a sexual point of view, it is also preferable. Among them, in particular, in the second ink-jet ink, for example, dicyclopentanyl (meth)acrylate, 1-adamantyl ester of (mercapto)acrylic acid, and 2-adamantyl (meth)acrylate can be preferably used. In the acrylic copolymer, the content of the (B) alicyclic hydrocarbon-containing monomer may be as long as the surface hardness and solvent resistance of the cured film required for the above-mentioned binder resin, as in the case of the first inkjet ink. In the case of the total polymerization component, it is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, particularly preferably 4 to 6% by weight. The second inkjet ink + is preferably one containing at least (A) an epoxy group-containing monomer having an epoxy group and an ethylenically unsaturated bond, and (B) having an alicyclic hydrocarbon group and an ethylenically unsaturated bond. One or more epoxy groups contained in a copolymer obtained by copolymerizing a monomer group of a monomer having a fat % hydrocarbon, and (c) an ester-containing monomer having a rebel group and an ethylenically unsaturated bond An acrylic copolymer obtained by the reaction. In this case, 'having an ethylenically unsaturated bond in the side chain of the acrylic 4-mer because the acrylic copolymer is polymerized together with the above polyfunctional monomer using an ethylenically unsaturated bond and/or Cross-linking reaction, so the heat-hardened dense 099117156 33 201111454 excellent in adhesion, surface hardness, and flatness, and resistance to IT formation. In the case where a transparent electrode film (for example, ιτο) is formed, a layer in which the (4) ink secret material is hardened (hereinafter referred to as "hardened layer") is less likely to occur.皴 与 与 , , , , , , , , , , = = = = = = = = • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • The film 'then re-forms the transparent electrode film, but there will be a problem of wrinkles on the surface of the transparent electric_the surface of the film. The method is like vacuum test, ship method, ion evaporation, However, in any case, it is necessary to heat the substrate in a reduced I environment. For example, when vacuum vapor deposition of a ruthenium film which is a representative of a transparent electrode film is carried out, the layer of the color layer is exposed to a high temperature and an ultra-low pressure caused by a vacuum. The second is that if the coloring layer formed by the ink layer (4) is under the condition of the super 2 falling temperature, the sensitivity of the hardened layer depends on the expansion, so that the transparent electrode material is adjacent to the layer, and lies. Cracked on its surface. If the surface of the transparent electrode film is wrinkled or cracked, the resistivity is locally increased at the surface of the electrode, resulting in disconnection, and an afterimage occurs, and even a cause of *, and is not bad. Therefore, if the formation resistance is excellent, a high-intensity color filter with reduced display defects can be obtained. , [() - a tetamine-containing monomer having a slow-base group and an ethylenic-saturated bond, and specific examples thereof include methyl (tetra) acid, acrylic acid, barley, itaconic acid, and cis; and women 099117156 34 201111454 diacid, anti Butenedioic acid, decyl hydroxy fluorenyl acrylic acid, (fluorenyl) acryloxyethyl succinic acid monoester, (mercapto) acryloxy decanoic acid monoester, and the like. Among them, acrylic acid, mercaptoacrylic acid, and maleic acid can be preferably used in the present invention, and acrylic acid or methyl acrylic acid can be preferably used. And at least one or more epoxy groups of the copolymer containing at least (Α) an epoxy group-containing monomer and a (fluorene) alicyclic hydrocarbon-containing monomer: (c) In the acrylic copolymer obtained by reacting a carboxyl group-containing monomer, a part of the epoxy group which the side chain of the copolymer has is used for the reaction with the (C) carboxyl group-containing monomer, and has ethylene in the side chain. The repeat unit of the unsaturated bond. In the acrylic copolymer, the content of the repeating unit having an ethylenically unsaturated bond in the side chain is preferably 10 to 80 mol% in the total repeating unit of the copolymer, and more preferably 20 to 60 mol. %. The reason for this is that the content is in the above range, and the reactivity with the polyfunctional monomer can be improved, and in particular, it is excellent in the formation resistance. Further, in the propylene-acid copolymer having a repeating unit having an ethylenically unsaturated bond in a side chain, the amount of the repeating unit having an epoxy group in the side chain is in the total repeating unit of the copolymer. It is preferably 10 to 70 mol%, more preferably 20 to 40 mol%, and further, the content of the repeating unit containing the alicyclic hydrocarbon in the side chain is preferably in the total repeating unit of the copolymer, preferably 10 to 70% by mole, more preferably 20 to 50% by mole, which is preferable from the viewpoints of adhesion of the cured film, surface hardness, and resistance to ruthenium formation. In the second inkjet ink, the content of the acrylic copolymer is a solid content of the ink of 099117156 35 201111454, preferably G. 5 wt% to 3 wt%, more preferably U) wt% 15 Within the weight% range. If it is less than the above range, the solvent resistance of the black water cured film may deteriorate. On the other hand, if (4)^ has a surface hardness, it will be entangled. Further, the content of the acrylic copolymer is 10 to 70% by weight, and more preferably 3 parts by weight, in addition to the pigment and the pigment dispersing agent described later, and the weight is 3: It is preferred to kiss and & [Epoxy Resin] In the present invention, an epoxy resin used as a binder resin in combination with a resin having an epoxy group (tetra)enoic acid group (four) in the side chain is used. The epoxy resin used in the present invention is preferably an epoxy group of (10) or more in terms of film properties such as solvent resistance and adhesion of a pixel formed by inkjet ink. The epoxy group may be a group having an epoxy structure, and examples thereof include an epoxy group, an epoxy group, and an epoxycyclohexyl group. From the viewpoint of improving the crosslink density of the cured film and improving the ink jet discharge performance by using a low viscosity, the weight average molecular weight of the polystyrene resin is preferably from 3 to 20,000, more preferably 4 〇〇〇~15000. When the molecular weight of the epoxy resin is less than 3 Å, the physical properties such as strength and solvent resistance required for the hardened layer of the fine portion of the color filter are likely to be insufficient. On the other hand, if the molecular weight is more than 20,000, the viscosity is likely to increase. When the ink is discharged from the discharge nozzle by the ink jet method, the stability of the discharge amount and the straightness of the discharge direction are deteriorated, or the stability of long-term storage is deteriorated. 099117156 36 201111454 And 1: If the fat contains two or more epoxy groups in one molecule, the rest, ",, special restrictions, for example:, type epoxy resin, desertified double-awaiting type A ring Oxygen, double: double _ diphenyl ether ring (10) & Wei (four), double hope S oxygen resin, / oxygen, Japan, hydrogen _ epoxy resin, naphthalene epoxy resin, joint stupid (10) 9, first type Epoxy resin, secret varnish type epoxy resin, o- lacquer (4) oxy-resin, ginseng-based epoxy-type epoxy, trifunctional j epoxy resin, sulphur-based epoxy resin, dicyclopentane _ ^ Latex resin, hydrogenated double A type epoxy resin, substance A containing nuclear polyol type: oxygen tree, polypropylene glycol type epoxy resin, epoxy propyl vinegar type epoxy resin, oxypropylamine type Epoxy resin, ethylene glycol epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, and the like.
更具體而言，可例示如：商品名EpiK〇TE 828(Japan Ερ〇π Resins公司製）等雙酚A型環氧樹脂；商品名epik〇te 8〇7(Japan Epoxy Resins 公司製）、商品名 YDF-175S(東都化 成公司製）等雙酚F型環氧樹脂；商品名YDB_715(東都化成 公司製）等溴化雙酚A型環氧樹脂；商品名EPICLON EXA1514(大日本油墨化學工業公司製）等雙酚S型環氧樹 脂；商品名YDC-1312(東都化成公司製）等氫醌型環氧樹 脂；商品名EPICLON EXA4032(大曰本油墨化學工業公司製) 等萘型環氧樹脂；商品名EPIKOTE YX4000H(Japan Epoxy Resins公司製）等聯苯型環氧樹脂；商品名EPIKOTE 157S70(Japan Epoxy Resins公司製）等雙紛A型紛醒·清漆糸 099117156 37 201111454 環氧樹脂；商品名 EPIKOTE 154(Japan Epoxy Resins 公司 製）、商品名YDPN-638(東都化成公司製）等酚酚醛清漆型環 氧樹脂；商品名YDCN-701(東都化成公司製）等曱酚酚醛清 漆型環氧樹脂；商品名EPICLONHP-7200(大日本油墨化學 工業公司製）等二環戊二烯酚型環氧樹脂；商品名EPIKOTE 1032H60(Japan Epoxy Resins公司製）等參羥苯基甲烧型環 氧樹脂；商品名VG3101M80(三井化學公司製）等三官能基 型壞氧樹脂；商品名 EPIKOTE l〇31S(Japan Epoxy Resins 公司製）等四苯酴基乙烧型環氧樹脂；商品名Denacol EX-411 (Nagase化成工業公司製）等四官能基型環氧樹脂；商 品名ST-3000(東都化成公司製）等氫化雙酚a型環氧樹脂； 商品名EPIKOTE 190P(Japan Epoxy Resins公司製）等環氧丙 基酯型環氧樹脂；商品名ΥΗ-434(東都化成公司製）等環氧 丙基胺型環氧樹脂；商品名YDG-414(東都化成公司製）等乙 二醛型環氧樹脂；商品名EHPE3150(Daicel化學工業公司製） 等脂環式環氧樹脂；商品名EPOLEAD® GT-401(Daicel化學 工業公司製）等脂環式多官能環氧化合物；異氰酸三環氧丙 基醋（TGIC)等雜環型環氧樹脂等等。又，視需要亦可混合入 作為環氧反應性稀釋劑的商品名Ne〇t〇hto E(東都化成公司 製)等。 該等環氧樹脂之中’較佳係商品名EHPE3150(Daicel化學 工業公司製）等脂環式環氧樹脂、及EpikOTE 157S70(Japan 099117156 38 201111454More specifically, a bisphenol A type epoxy resin such as EpiK〇TE 828 (made by Japan Ερ〇π Resins Co., Ltd.); a product name epik〇te 8〇7 (made by Japan Epoxy Resins Co., Ltd.), and a product are exemplified. A bisphenol F-type epoxy resin such as YDF-175S (made by Tohto Kasei Co., Ltd.); a brominated bisphenol A type epoxy resin such as YDB_715 (made by Tohto Kasei Co., Ltd.); and the trade name EPICLON EXA1514 (Daily Ink Chemical Industry Co., Ltd.) A bisphenol S-type epoxy resin such as a bisphenol S-type epoxy resin; a hydrogenated epoxy resin such as YDC-1312 (manufactured by Tohto Kasei Co., Ltd.); and a naphthalene epoxy resin such as EPICLON EXA4032 (manufactured by Otsuka Ink Chemical Industry Co., Ltd.) A biphenyl type epoxy resin such as EPIKOTE YX4000H (made by Japan Epoxy Resins Co., Ltd.); a product name EPIKOTE 157S70 (made by Japan Epoxy Resins Co., Ltd.), etc. A type Awakening · varnish 糸 099117156 37 201111454 Epoxy resin; Phenolic novolac type epoxy resin such as EPIKOTE 154 (made by Japan Epoxy Resins Co., Ltd.) and YDPN-638 (made by Tohto Kasei Co., Ltd.); phenol novolac type epoxy resin such as YDCN-701 (made by Tohto Kasei Co., Ltd.) ; A dicyclopentadiene phenol type epoxy resin such as EPICLONHP-7200 (manufactured by Dainippon Ink and Chemicals Co., Ltd.); a hydroxyphenyl-based epoxy resin such as EPIKOTE 1032H60 (manufactured by Japan Epoxy Resins Co., Ltd.); Quaternary-type epoxy resin such as VG3101M80 (manufactured by Mitsui Chemicals Co., Ltd.); trade name: EPIKOTE l〇31S (made by Japan Epoxy Resins Co., Ltd.), etc.; trade name: Denacol EX-411 (Nagase formation) Hydrogenated bisphenol a type epoxy resin such as ST-3000 (made by Tohto Kasei Co., Ltd.), etc.; and epoxy propyl group, such as EPIKOTE 190P (made by Japan Epoxy Resins Co., Ltd.), etc. Epoxy epoxide type epoxy resin; trade name: ΥΗ-434 (made by Tohto Kasei Co., Ltd.) and other epoxy propyl type epoxy resin; trade name YDG-414 (made by Dongdu Chemical Co., Ltd.) and other glyoxal type epoxy resin; EHPE3150 (made by Daicel Chemical Industry Co., Ltd.) and other alicyclic epoxy resin; trade name EPOLEAD® GT-401 (Daicel Chemical Industry Co., Ltd.) and other alicyclic polyfunctional epoxy compounds; isocyanate triepoxypropyl vinegar ( TGIC) and other heterocyclic epoxy Resin and so on. Further, if necessary, a trade name of Ne〇t〇hto E (manufactured by Tohto Kasei Co., Ltd.), which is an epoxy reactive diluent, may be mixed. Among these epoxy resins, an alicyclic epoxy resin such as EHPE3150 (made by Daicel Chemical Industry Co., Ltd.) and EpikOTE 157S70 (Japan 099117156 38 201111454) are preferred.
Epoxy Resins公司製）等雙酚A型酚醛清漆系環氧樹脂，其 中更佳係商品名EHPE3150(Daicel化學工業公司製）等脂環 式氧樹脂。 該等環氧樹脂可僅單獨使用1種，亦可併用2種以上。 ； 上述環氧樹脂的含有量係相對於墨水的固形份，較佳為 - 2·〇重置％〜35重量％、更佳5‘0重量％〜3〇重量％。若環氧 樹脂的含有量過少，則有無法獲得充分熱硬化性的情況。反 之，若環氧樹脂的含有量過多，則發生硬化不良。 再者，本發明所使用的上述多官能基性單體、上述丙烯酸 系八聚物、及上述環氧樹脂的含有比例，若能形成所需之密 接性、表面硬度及平坦性，則並無特別的限定，❻上述環氧 樹脂相對於上述多官能基性單體與上述丙稀酸系共聚物之 和的重量比[環氧樹脂/(多官能基性單體+丙稀酸系共聚物)] 為0.25〜4,且上述丙烯酸系共聚物相對於上述多官能基性 單體的重量比（丙稀酸系共聚物/多官能基性單體）為 .⑽〜8 ’從密接性、表面硬度、平坦性、耐溶雜及保存 •安紐的觀點而言屬較佳。其中，較佳係上述環氧樹脂相對 於上述多官能基性單體與上述丙稀酸系共聚物之和的重量 1匕[環氧樹脂/(上述多官能基性單體+上述丙_系共聚物)] :0·3〜卜且上述丙烯酸系共聚物相對於上述多官能基性單 體的重量比(上述丙婦酸系共聚物/上述多官能基性單體）為 099117156 39 201111454 <顏料> 第2喷墨墨水中，係使用與第1喷墨墨水所使用的顏料相 同者。 顏料的含有量係在形成彩色濾光片的著色層時，若能進行 所需之發色，則並無特別的限定，視所使用顏料的種類而有 所差異，並無特別的限定。第2喷墨墨水中，為了達成提高 顏料濃度的第二目的，而將含有量設為較高。具體而言，顏 料含有量係在墨水的固形份中，較佳為20重量％〜70重量％ 範圍内、其中更佳為30重量％〜60重量％範圍内。 <顏料分散劑> 第2喷墨墨水中，係使用與第1喷墨墨水所使用的顏料分 散劑相同者。 <溶劑> 第2喷墨墨水中，係使用與第1喷墨墨水所使用的溶劑相 同者。 <熱聚合起始劑> 第2喷墨墨水中，為了藉由利用熱使上述乙烯性不飽和鍵 進行聚合或交聯反應而使其硬化，可使用與第1喷墨墨水所 使用的熱聚合起始劑相同者。 再者，為了藉由利用熱使上述環氧樹脂及上述丙烯酸系共 聚物中的環氧基進行聚合或交聯反應而使其硬化，故亦可含 有熱聚合起始劑。作為此種熱聚合起始劑並無特別的限制， 099117156 40 201111454 而酸酐係從俾左6 祕 ’、女疋性高、發熱量少的觀點而言屬較隹。 酸酐可舉例如. 灿 夕疋羧酸酐，具體可舉例如：酞酸酐、衣康 酸酐、璩珀酸酐、於由 ^ mm 酐榉康酸酐、十二烯基琥珀酸酐、均丙三甲 酸酐、順丁烯二 酐、六氫酞酸酐、二甲基四氫酞酸酐、腐 植θ夂肝、曱基内亞 甲基四虱苯酐等脂肪族或脂環族二羧酸二 苯A:肪族t元鲮酸二酐;均苯四T酸酐、偏苯三酸酐、二 醋、酸軒等芳香族多元羧酸奸；乙二醇雙偏苯三酸 2 Μ偏苯三酸®旨等含喊酸酐，且亦可使用由卞售羧 酸酐所形成的環氧樹S旨硬化劑。 2嘴墨墨水所使用之熱聚合起始劑的調配量，係在墨水 的固形份中’較佳在〇 1 重里/0〜5·0重罝％範圍内，其中更 旦、尚1.15重量％〜3.〇重量％範圍内。若熱聚合起始劑的含有 ’則有硬化不足、無法形成_塗膜之虞。反之，若 熱^合起㈣的含有量過多，财保存安定性差劣之虞。 <墨水之製造方法> 第2噴墨墨水可依照盘· 迄n ^第1嘴墨墨水的方法同樣之順 序進仃製造。 #=’第2喷墨墨水的用途亦與第1嘴墨墨水相同，特隹 錢用於要求色域魏性佳且高輝度的著色層之形成。 [貫施例] 以下例示實施例，針對本發明更進一步進行且祕明。 實施例“列係有關第1噴墨墨水的實驗。另一方面， 099117156 201111454 實施例B系列係有關第2喷墨墨水的實驗。 <實施例A系列> 依照以下的順序’施行實施例A1〜A9、及比較例A1〜A9。 1_顏料分散液之調製 將顏料、顏料分散劑及溶劑依下述比例進行混合，並添加 直仅0.5mm的一氧化錐球珠200重量份，使用塗料授摔5| (淺田鐵工公司製)施行3小時分散，調製得顏料分散液。 (1) 紅色顏料分散液之調製 [顏料分散液之組成] • C.I.色素紅254 : 4.5重量份 • C.I.色素紅177 : 7.5重量份 • C.I.色素黃150 : 3.0重量份 •顏料分散劑（商品名：Disperbykl6卜 BYK-Chemie · Japan 製，溶劑中的固形份30重量％) : 30重量份 • BDGAC(二乙二醇單丁醚醋酸酯广55重量份 (2) 綠色顏料分散液之調製 [顏料分散液之組成] • C.I.色素綠36 : 10重量份 • C.I.色素黃150 : 5重量份 •顏料分散劑（商品名：Disperbykl61，BYK-Chemie · Japan 製，溶劑中的固形份3〇重量％) : 30重量份 • BDGAC(二乙二醇單丁醚醋酸酯）：55重量份 099117156 42 201111454 (3)藍色顏料分散液之調製 [顏料分散液之組成j • C.I.色素藍15 : 6 : 9.5重量份 • C.I.色素紫23 : 〇·5重量份 • ： Disperbykl61 » BYK-Chemie · Japan 製’溶劑中的固形份30重量％) : 20重量份 • BDGAC(二乙二醇單丁醚醋酸酯）：7〇重量份 2.丙稀酸糸共聚物之合成 在具備氣體導入管、溫度計、冷凝器及授拌機的反應容器 中’裝填^一乙二醇單丁醚醋酸酯(BDGAC)l50重量份，並 利用氮氣進行取代，加熱至1〇〇。〇。在其中將甲基丙烯酸環 氧丙酯（GMA)50重量份、曱基丙稀酸二環戊酯pcpMA)50 重量份、及己酸過氧化第三丁基·2_乙酯1〇重量份的混合 液，歷時2小時滴下。 待滴下結束後，藉由在l〇〇°C下進行3小時反應，而獲得 GMA/DCPMA共聚物（溶液）。 同樣地，將曱基丙烯酸1-金剛烷酯(ADΑΜΑ)、曱基丙烯 酸2-甲基-2-金剛烷酯（MADΑΜΑ)、曱基丙烯酸苄酯 (BzMA)，依下表3所示比例合成丙烯酸系共聚物。 針對所獲得之丙烯酸系共聚物a-Ι〜a-5，使用GPC測定裝 置(Tosoh(股）製，HLC-8220GPC)並依聚苯乙烯標準的條件， 測定重量平均分子量(Mw) 099117156 43 201111454 [表3] 丙稀酸系 樹脂 .- _ , 共聚合物組成 ------ -----^ 分子量 丫丞内締酸 環氧丙酷 甲基丙烯酸 二環戊酯 50 甲基丙烯酸 金剛烷酯 甲#基丙烯酸2-甲— 基-2-合剛^酷 a-1 ------- 50 a-2 30 70 一 3000 12000 a-3 a-4 ------- 65 40 — — 35 — 6000 a-5 60 15000 OJ 35 80ΠΠ 3.墨水之調製 將依上述所獲得之丙烯酸系共聚物(a-1〜a-5)、多官能基性 單體(b-Ι〜b_3)、及溶劑(BDGAC)，鮮表4所示進行調配， 調製得實施例A1〜A9时墨墨水。又’依下表5所示進行 °周配而5周製得比較例A1〜A9的喷墨墨水。 接著，將作為紅色墨水的上述紅色顏料分散液與上述樹脂 組成物充分混合，並依顏料(P)與除了顏料以外的固形份⑺ :調配重量比_為0.6、以及混合液中的固形份為2〇重 里％之方式’添加BDGAC’調製得彩色渡光片㈣硬化性 喷墨墨水。 將^為、綠色墨水的上述綠色顏料分散液與上述樹脂組成 物充T混合，並依顏料(P)與除了顏料以外的固形份(V)之調 里比(P/V)為0.7、以及混合液中的固形份為2〇重量％ 弋添加BDGAC，調製得彩色濾光片用熱硬化性喷墨 墨水。 將作為齄色墨水的上述藍色顏料分散液與上述樹脂組成 099117156 201111454 物充分混合，並依顏料(p)與除了顏料以外的固形份(v)之調 配重量比(P/V)為0.25、以及混合液中的固形份為20重量％ 之方式，添加BDGAC，調製得彩色濾、光片用熱硬化性噴黑 墨水。 多官能基性單體係使用b-Ι :二季戊四醇六及五丙烯酸醋 混合物（產品名：Aronix M403，五丙烯酸酯5〇〜60%，東亞 合成製）、b-2:二(三羥甲基丙烷）四丙烯酸酯（產品名：Aronix M408，東亞合成製）。使用b-3 :異三聚氰酸EO改質二及 二丙婦酸S旨（產品名：Aronix M315，東亞合成公司製）。 [表4] ^施例 A1 A2 A3 A4 A5 A6 A7 A8 A9 紅色顏料分散液 50 50 50 — _ 綠色顏料分散液 — — — 54.9 54,9 54.9 監巴顔科分者 t液 — —— — — 40 40 40 丙烯酸樹脂 a-1 4.2 — 一 3.6 一 一 7.1 3.-2 — 6.2 一 — 5.3 — 一 10 5 a-3 a-4 7.2 — — 6.2 — 12.3 a-5 —. — — __ _ 乙烯性不飽和單體 b-1 3.8 一 0.8 3.2 — 0.6 6.5 一 1.25 b-2 — 1.8 — — 1.5 — — 3.1 b-3 —_ 一 — — 一 _ _ 溶劑 BDGAC 42 42 42 38.3 38.3 38.3 46.4 46.4 46.4 [表5] :匕較伤 A1 A2 A3 A4 A5 A6 A7 A8 A9 紅色顏料分散液 50 50 50 一 一 一 _ — 綠色顏料分叙液 — 一 — 54.9 54,9 54 9 — 藍色顏料分ϊί：液 一 — 一 一 40 40 40 丙烯酸樹脂 a-1 一 一 — 一 — 一 一 a-2 一 —— 一 — 一 6.2 一 —. _ a-3 一 — — —— 一 一 一 一 12.3 a-4 4.2 一 — 3.6 — — 7.1 — — a-5 — 6.2 — — 5.3 一 一 10.5 一 乙烯性不飽和單體 b-1 3.8 一 一 3.2 一 6.5 一 b-2 一 1.8 一 一 1.5 一 一 3.1 一 b-3 — 一 0.8 一 — 0,6 一 一 1.25 溶劑 BDGAC 42 42 42 38.3 38.3 38.3 46.4 46.4 46.4 099117156 45 201111454 針對所獲得之各彩色滤光片用熱硬化性喷墨墨水施行評 估。針對色度、耐NMP性、耐Ν_性、表面硬度，依如 下述形成樹脂硬化膜並施行評估。評仕处里上士 △〆 1 n、，口禾如表6所示。 (塗膜之形成） 在厚0.7mm玻璃基板(Corning公司製’ 1737)上利用旋 塗機施行上述各噴墨墨水的塗佈。 然後，在90Ϊ：加熱板上騎1〇分鐘預烤^其後，在無塵 烤相内，依2〇〇。〇施行30分鐘加熱而施行後烘烤，再依24〇t： 施行30分鐘加熱而施行後烘烤，形成著色層。 [評估方法] (1) 保存安定性 將所獲付之各喷墨墨水5Gg分取於麵瓶巾，在密閉狀態 下於60C下放置1週。測定放置後的喷墨墨水黏度。 [評估基準] 〇·黏度測定值差在放置前後未滿5%。 △:黏度測定值差在放置前後為5%以上且未滿1〇%。 X :黏度測定值差在放置前後達10%以上。 (2) 色度 使用顯微分光光度計(Olympus光學公司製「OPS-SP200」） 測定在C光源下的色度(γ、χ、y)。 (3) 耐NMP性 使已形成著色層的基板在NMP溶液中浸潰30分鐘，再 099117156 46 201111454 測定浸潰前後的色差。 [評估基準] 〇：NMP浸潰前後的色差在2以下。 △ : NMP浸潰前後的色差超過2且在5以下。 . X : NMP浸潰前後的色差超過5。 . (4)耐 NaOH 性 將已形成著色層的基板，在10%NaOHaq溶液中浸潰15 分鐘，再測定浸潰前後的色差。 [評估基準] 〇：在10%NaOHaq溶液中浸潰前後的色差為2以下。 △:在10%NaOHaq溶液中浸潰前後的色差超過2且在5以 下。 X .在10%NaOHaq溶液中浸潰前後的色差超過5。 (5)表面硬度(鉛筆硬度） 針對上述彩色濾光片層表面的錯筆硬度，根據JIS κ 5400-1990 8.4.1，利用「鉛筆刮痕試驗」施行評估。 099117156 47 201111454 [表6]A bisphenol A type novolak type epoxy resin such as Epoxy Resins Co., Ltd., and an alicyclic oxygen resin such as EHPE 3150 (manufactured by Daicel Chemical Industry Co., Ltd.) is more preferable. These epoxy resins may be used alone or in combination of two or more. The content of the epoxy resin is preferably -2·〇% by weight to 35% by weight, more preferably 5'0% by weight to 3% by weight, based on the solid content of the ink. If the content of the epoxy resin is too small, sufficient thermosetting property may not be obtained. On the other hand, if the content of the epoxy resin is too large, hardening failure occurs. Further, the content ratio of the polyfunctional monomer, the acrylic octam, and the epoxy resin used in the present invention does not have the required adhesion, surface hardness and flatness. In particular, the weight ratio of the above epoxy resin to the sum of the above polyfunctional monomer and the above acrylic copolymer [epoxy resin / (polyfunctional monomer + acrylic copolymer) ) is 0.25 to 4, and the weight ratio of the acrylic copolymer to the polyfunctional monomer (acrylic copolymer/polyfunctional monomer) is (10) to 8 'from adhesion, It is preferred from the viewpoint of surface hardness, flatness, resistance to impurities and preservation. Preferably, the weight of the epoxy resin relative to the sum of the polyfunctional monomer and the acrylic copolymer is 1 匕 [epoxy resin / (the above polyfunctional monomer + the above-mentioned C-system) Copolymer)]: 0·3~b and the weight ratio of the above acrylic copolymer to the above polyfunctional monomer (the above-mentioned propylene-based copolymer/the above-mentioned polyfunctional monomer) is 099117156 39 201111454 <Pigment> The second inkjet ink is the same as the pigment used in the first inkjet ink. When the coloring layer of the color filter is formed, the coloring of the color filter is not particularly limited, and the color of the pigment to be used is not particularly limited, and is not particularly limited. In the second inkjet ink, in order to achieve the second object of increasing the pigment concentration, the content is made high. Specifically, the pigment content is in the solid portion of the ink, preferably in the range of 20% by weight to 70% by weight, more preferably 30% by weight to 60% by weight. <Pigment Dispersant> The second inkjet ink is the same as the pigment dispersant used in the first inkjet ink. <Solvent> The second inkjet ink is the same as the solvent used for the first inkjet ink. <Thermal polymerization initiator> In the second inkjet ink, in order to cure the above-mentioned ethylenically unsaturated bond by heat or crosslinking reaction, it is possible to use the same as the first inkjet ink. The thermal polymerization initiator is the same. Further, in order to cure the epoxy group in the epoxy resin and the acrylic copolymer by polymerization or crosslinking reaction by heat, a thermal polymerization initiator may be contained. There is no particular limitation on such a thermal polymerization initiator, and the acid anhydride is relatively low from the viewpoint of high licking and low calorific value. The acid anhydride may, for example, be a phthalic anhydride, and specific examples thereof include phthalic anhydride, itaconic anhydride, milic anhydride, phthalic anhydride, dodecenyl succinic anhydride, propylene terephthalate, and cis. Aliphatic or alicyclic dicarboxylic acid diphenyl A such as olefinic anhydride, hexahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, humic θ 夂 liver, decyl methylene tetraphthalic anhydride: aliphatic t 鲮Acid dianhydride; aromatic polycarboxylic acid such as tetraphenyltetrahydroanhydride, trimellitic anhydride, diacetic acid, acid sulphate; ethylene glycol trimellitic acid 2 fluorene trimellitic acid® The epoxy tree S formed by the sale of a carboxylic anhydride is a hardener. 2 The amount of the thermal polymerization initiator used in the ink of the ink is in the range of the solid content of the ink, preferably in the range of 〇1 重量 /0~5·0 罝%, of which more than 1.15% by weight ~3.〇% by weight. If the content of the thermal polymerization initiator is ', there is insufficient hardening and it is impossible to form a film. On the other hand, if the content of the heat (4) is too large, the stability of the wealth preservation is inferior. <Manufacturing Method of Ink> The second ink-jet ink can be produced in the same order as the method of the disk-to-n-first nozzle ink. #=' The use of the second inkjet ink is also the same as that of the first nozzle ink, and it is used for the formation of a coloring layer which requires good color gamut and high luminance. [Examples] The following examples are given to further illustrate and clarify the present invention. EXAMPLES "Experiment on the first inkjet ink. On the other hand, 099117156 201111454 Example B series is an experiment on the second inkjet ink. <Example A series> Example was carried out in the following order A1 to A9, and Comparative Examples A1 to A9. Preparation of 1_Pigment Dispersion Liquid The pigment, the pigment dispersant, and the solvent were mixed in the following ratio, and 200 parts by weight of a oxidized cone bead of only 0.5 mm was used, and used. Paint Dispersion 5| (made by Asada Iron Works Co., Ltd.) was dispersed for 3 hours to prepare a pigment dispersion. (1) Preparation of red pigment dispersion [composition of pigment dispersion] • CI Pigment Red 254: 4.5 parts by weight • CI Pigment Red 177 : 7.5 parts by weight • CI Pigment Yellow 150 : 3.0 parts by weight • Pigment Dispersant (trade name: Disperbykl 6 Bu BYK-Chemie · Made in Japan, 30% by weight of solid content in solvent) : 30 parts by weight • BDGAC (two Ethylene glycol monobutyl ether acetate 55 parts by weight (2) Preparation of green pigment dispersion [composition of pigment dispersion] • CI pigment green 36 : 10 parts by weight • CI pigment yellow 150 : 5 parts by weight • Pigment dispersant (Product Name: Disperb Ykl61, manufactured by BYK-Chemie · Japan, solid content in solvent (3% by weight): 30 parts by weight • BDGAC (diethylene glycol monobutyl ether acetate): 55 parts by weight 099117156 42 201111454 (3) Blue pigment dispersion Modulation of liquid [Composition of pigment dispersion liquid j • CI Pigment Blue 15 : 6 : 9.5 parts by weight • CI Pigment Violet 23 : 〇 · 5 parts by weight • : Disperbykl61 » BYK-Chemie · Japan's solid content in solvent 30 weight %) : 20 parts by weight • BDGAC (diethylene glycol monobutyl ether acetate): 7 parts by weight 2. Synthesis of bismuth acrylate copolymer in a gas introduction tube, thermometer, condenser and mixer The container was filled with 50 parts by weight of ethylene glycol monobutyl ether acetate (BDGAC) and replaced with nitrogen, and heated to 1 Torr. In this case, 50 weight of glycidyl methacrylate (GMA) was used. a mixture of 50 parts by weight of thioglycolic acid dicyclopentanyl ester (pcpMA) and 1 part by weight of butyl hexanoic acid hexanoate and 1 liter of ethyl hexanoate. The mixture was dripped for 2 hours. A GMA/DCPMA copolymer (solution) was obtained by carrying out a reaction at 3 ° C for 3 hours. Similarly, 1-adamantyl methacrylate (ADΑΜΑ), 2-methyl-2-adamantyl methacrylate (MADΑΜΑ), benzyl methacrylate (BzMA) were synthesized according to the ratios shown in Table 3 below. Acrylic copolymer. With respect to the obtained acrylic copolymer a-Ι~a-5, a weight average molecular weight (Mw) was determined using a GPC measuring apparatus (manufactured by Tosoh Co., Ltd., HLC-8220GPC) under the conditions of polystyrene standards. 099117156 43 201111454 [Table 3] Acrylic resin.- _ , Copolymer composition ------ -----^ Molecular weight 丫丞 缔 缔 环氧 环氧 环氧 环氧 环氧 酷 酷 50 50 50 50 Adamantane A #基基基2-甲基-2-合刚^酷 a-1 ------- 50 a-2 30 70 a 3000 12000 a-3 a-4 ------ - 65 40 — — 35 — 6000 a-5 60 15000 OJ 35 80ΠΠ 3. The ink is prepared by the acrylic copolymer (a-1 to a-5) obtained above, and the polyfunctional monomer (b- Ι~b_3) and solvent (BDGAC) were prepared as shown in Table 4, and the inks of Examples A1 to A9 were prepared. Further, the inkjet inks of Comparative Examples A1 to A9 were prepared by performing the above-described weeks and 5 weeks as shown in Table 5 below. Next, the red pigment dispersion liquid as the red ink is sufficiently mixed with the above resin composition, and the solid content (7) of the pigment (P) and the pigment other than the pigment is adjusted to a ratio of 0.6, and the solid content in the mixed solution is 2 〇 里 % ' ' ' ' 添加 添加 添加 添加 添加 ' ' ' ' BD BD BD BD BD BD BD BD BD BD The green pigment dispersion liquid of the green ink and the above-mentioned resin composition are T-mixed, and the ratio (P/V) of the pigment (P) to the solid content (V) other than the pigment is 0.7, and The solid content in the mixed solution was 2% by weight. BDGAC was added to prepare a thermosetting inkjet ink for color filters. The above-mentioned blue pigment dispersion liquid as a ochre ink is sufficiently mixed with the above-mentioned resin composition 099117156 201111454, and the weight ratio (P/V) of the pigment (p) to the solid content (v) other than the pigment is 0.25. And the solid content in the mixed liquid was 20% by weight, and BDGAC was added to prepare a color filter and a thermosetting black ink for a light sheet. The polyfunctional single system uses b-Ι: dipentaerythritol hexa- and pentad vinegar mixture (product name: Aronix M403, pentaacrylate 5〇~60%, manufactured by Toagosei), b-2: bis (trishydroxyl) Propane) tetraacrylate (product name: Aronix M408, manufactured by Toagosei Co., Ltd.). Use b-3: octa-ocyanuric acid EO modified di- and di-butanic acid S (product name: Aronix M315, manufactured by Toagosei Co., Ltd.). [Table 4] ^Example A1 A2 A3 A4 A5 A6 A7 A8 A9 Red pigment dispersion 50 50 50 — _ Green pigment dispersion — — — 54.9 55 54.9 Bahama Branch Division t liquid — —— — — 40 40 40 Acrylic resin a-1 4.2 — 3.6 7.1 7.1 3.-2 — 6.2 I— 5.3 — 1 10 5 a-3 a-4 7.2 — — 6.2 — 12.3 a-5 —. — — __ _ Vinyl Unsaturated monomer b-1 3.8 - 0.8 3.2 - 0.6 6.5 - 1.25 b - 2 - 1.8 - 1.5 - - 3.1 b - 3 - _ A - _ _ Solvent BDGAC 42 42 42 38.3 38.3 38.3 46.4 46.4 46.4 [Table 5]: 匕 匕 A1 A2 A3 A4 A5 A6 A7 A8 A8 A9 Red pigment dispersion 50 50 50 1-1 — Green pigment liquids—1—54.9 55 54 — Blue pigment distribution ϊ: Liquid one - one 40 40 40 Acrylic resin a-1 one one - one - one a one one - one - one 6.2 one -. _ a-3 one - —— one one one one 12.3 a-4 4.2 I— 3.6 — — 7.1 — — a-5 — 6.2 — — 5.3 One to one 10.5 ethylenically unsaturated monomer b-1 3.8 I.3.2 a 6.5 a b-2 a 1.8 a one 1.5 a one 3.1 a b-3 — a 0.8 a — 0, 6 a 1.25 solvent BDGAC 42 42 42 38.3 38.3 38.3 46.4 46.4 46.4 099117156 45 201111454 Each of the color filters was evaluated using a thermosetting inkjet ink. For the chromaticity, NMP resistance, yttrium resistance, and surface hardness, a resin cured film was formed and evaluated as follows. Sergeant △ 〆 1 n,, mouth and mouth as shown in Table 6. (Formation of Coating Film) The coating of each of the above inkjet inks was carried out by a spin coater on a 0.7 mm thick glass substrate (manufactured by Corning Corporation, 1737). Then, pre-bake at 90 Ϊ: hot plate for 1 〇, then, within the dust-free baking phase, follow 2 〇〇. The crucible is heated for 30 minutes and then post-baked, and then baked according to 24 〇t: heating for 30 minutes to form a colored layer. [Evaluation method] (1) Preservation stability 5 Gg of each inkjet ink thus obtained was dispensed into a face towel, and placed in a sealed state at 60 C for one week. The viscosity of the inkjet ink after standing was measured. [Evaluation Criteria] The difference between the 〇 and viscosity measurement values is less than 5% before and after placement. △: The difference in viscosity measurement value was 5% or more and less than 1% by weight before and after the placement. X: The difference in viscosity measurement value is more than 10% before and after placement. (2) Chromaticity The chromaticity (γ, χ, y) under a C light source was measured using a microscopic spectrophotometer ("OPS-SP200" manufactured by Olympus Optics Co., Ltd.). (3) NMP resistance The substrate on which the colored layer was formed was immersed in the NMP solution for 30 minutes, and the chromatic aberration before and after the immersion was measured again at 099117156 46 201111454. [Evaluation Criteria] 〇: The color difference before and after NMP immersion is 2 or less. △ : The color difference before and after NMP immersion exceeds 2 and is 5 or less. X : The color difference before and after NMP immersion exceeds 5. (4) Resistance to NaOH The substrate on which the colored layer had been formed was immersed in a 10% NaOHaq solution for 15 minutes, and the chromatic aberration before and after the immersion was measured. [Evaluation Criteria] 〇: The color difference before and after immersion in a 10% NaOHaq solution was 2 or less. △: The color difference before and after immersion in a 10% NaOHaq solution exceeded 2 and was 5 or less. X. The color difference before and after impregnation in a 10% NaOHaq solution exceeds 5. (5) Surface hardness (pencil hardness) The erroneous pen hardness of the surface of the color filter layer was evaluated by the "pencil scratch test" in accordance with JIS κ 5400-1990 8.4.1. 099117156 47 201111454 [Table 6]
墨水保存 安定性 色度[C光源] 耐NMP性 耐NaOH性 表面硬度 X y Y 實施例A1 〇 0.651 0.339 21.55 〇 〇 2H 實施例A2 〇 0.651 0.339 21.57 〇 〇 3H 實施例A3 〇 0.651 0.339 21.47 〇 〇 2H 實施例A4 〇 0.291 0.600 58.13 〇 〇 2H Ϊ施例A5 〇 0.291 0.600 58.09 〇 〇 3H 實施例A6 〇 0.291 0.600 58.12 〇 〇 2H 實施例A7 〇 0.139 0.124 15.54 〇 〇 2H 實施例A8 〇 0.139 0.124 15.51 〇 〇 3H 實施例A9 〇 0.139 0.124 15.57 〇 〇 4H 較歹A1 Δ 0.651 0.339 21.13 Δ Δ B 比i交你丨A2 △ 0.651 0.339 21.03 Δ Δ HB 比較例A3 X 0.651 0.339 21.20 X X 2B 比較例A4 Δ 0.291 0.600 57.69 Δ Δ B 比i交你丨A 5 △ 0.291 0.600 57.55 Δ Δ HB 比ί交令丨A 6 X 0.291 0.600 57.72 X X 2B 比ΐ交你丨A 7 Δ 0.139 0.124 15.37 Δ Δ HB 比ΐ交你j A8 Δ 0.139 0.124 15.54 Δ Δ F 比較W A9 Δ 0.139 0.124 15.60 X X 2B 由表6的結果可確認第1發明的喷墨墨水係保存安定性優 異、硬化性優異、熱硬化後的耐藥性優異、輝度高且色域重 現性良好。 <實施例B系列> 依照以下的順序施行實施例B1〜B14、及比較例B1〜B6。 1.顏料分散液之調製 將顏料、顏料分散劑及溶劑依下述比例進行混合，並添加 直徑0.5mm的二氧化锆球珠200重量份，使用塗料攪拌器 (淺田鐵工公司製)施行3小時分散，調製顏料分散液。 (1)紅色顏料分散液之調製 [顏料分散液之組成] •顏料(C.I.色素紅254) : 4.5重量份 •顏料(C.I.色素紅177) : 7.5重量份 48 099117156 201111454 •顏料(C.L色素黃150) : 3.0重量份 •顏料分散劑（商品名：Disperbykl61 ，BYK-Chemie · Japan 製’溶劑中的固形份30重量: 3〇 〇重量份 • BDGAC(二乙二醇單丁醚醋酸酯）：55 〇重量份 (2) 綠色顏料分散液之調製 [顏料分散液之組成] •顏料(C.I.色素綠36) : 7.1重量份 •顏料(C.I.色素黃15〇) : 7.9重量份 •顏料为散劑（商品名：Disperbykl61，BYK-Chemie · Japan 製’溶劑中的固形份30重量％) : 30.0重量份 • BDGAC(二乙二醇單丁醚醋酸酯）：55.0重量份 (3) 藍色顏料分散液之調製 [顏料分散液之組成] •顏料(C.I.色素藍15 : 6) : 14.1重量份 •顏料(C.I.色素紫23) : 0.9重量份 •顏料分散劑（商品名：Disperbykl61，BYK-Chemie · Japan 製，溶劑中的固形份30重量％) : 30·0重量份 • BDGAC(二乙二醇單丁醚醋酸酯）：55,0重量份 2.丙烯酸系共聚物之合成 (1)丙烯酸系共聚物之聚合 在具備氣體導入管、溫度計、冷凝器及攪拌機的反應容器 中’裝填入二乙一醇單丁鍵醋酸醋(BDGAC) 150重量份，並 099117156 49 201111454 利用氮氣進行置換’加熱至ioo°c。在其中將甲基丙烯酸環 氧丙酯（GMA)50重量份、曱基丙烯酸二環戊酯（DCPMA)50 重量份、己酸過氧化第三丁基-2-乙酯1〇重量份的混合液， 歷時2小時滴下。 待滴下結束後’藉由在100°C下進行3小時反應，獲得 GMA/DCPMA共聚物（主鏈）溶液。 同樣地，將曱基丙烯酸1-金剛烷酯（ADAMA)、曱基丙烯 酸環己酯（CHMA)、曱基丙烯酸異祸酯（IBMa)、曱基丙烯酸 二環戊烯酯（DCPEMA)、曱基丙烯酸2_曱基-2-金剛烧酯 (MADAMA)、曱基丙烯酸2-乙基-2-金剛烧醋(EADAMA)， 依下表7所示比例聚合成丙烯酸系共聚物。 關於比較例用之丙烯酸系共聚物扮丨，依如表7所示，再 使用含芳香環之單體（曱基丙烯酸苄酯，BzMA)及含曱基單 體（曱基丙烯酸曱酯，MMA)，同樣地施行聚合。 另外’表7中的數值係表示「重量％」。 (2)乙婦性不飽和鍵之導入 在依上述方法所獲得之丙烯酸系共聚物中，添加表7所示 I的丙烯^(AA)，以及相對於丙烯酸系共聚物中的含有單 體之合計(含環氧基單體、含脂環歧的單體、及丙烯酸)i 莫耳份，添加對甲氧基酚〇 〇〇〇4莫耳份、及n，n-二甲基苄 耳份’取代氮導入管改為連接於空氣導入管，藉 下進行反應1〇小時，獲得環氧基與含叛基單體 099117156 50 201111454 進行了反應之於側鏈具有乙烯性不飽和鍵的丙烯酸系共聚 物d〜i。 099117156 51 201111454 1:¾ 重量平均 分子量 10000 8000 12000 12000 I I 6000 I I 15000 I I 20000 I 8000 I 12000 I 11000 11000 11000 後添加的含 羧基單體 (*1) CN 〇 cs § 含甲基的 單體 (重量％) 1 ^ ^ BzMA 含脂環式烴的單體(重量％) EADAMA MADAMA m DCPEMA 〇 BMA CHMA ADAMA in (N DCPMA 〇 含環縫單體 (重量％) GMA yr) v〇 ft ΐ K & 4 t ζ ^ 9-卜 II660 201111454 3.彩色濾光片用熱硬化性喷墨墨水之調製 將依上述所獲得之丙烯酸系共聚物（a〜1)、環氧樹脂、多 吕月b基性單體、熱聚合起始劑、及溶劑(BdGAC) ’依下表8 所示進行調配，而調製樹脂組成物。 接著’將上述顏料分散液與上述樹脂組成物充分混合，並 依顏料(P)與除了顏料以外的固形份(V)之調配重量比（P/V) 為0.6、以及混合液中的固形份為2〇重量％之方式，添加 BDGAC，而調製彩色濾光片用熱硬化性喷墨墨水^ 環氧樹脂係使用1分子中具有2個以上之環氧基的脂環式 環氧樹脂[產品名：EHPE-3150(表8中表示為「EHPE」）， Daicel化學工業(股)製]、及雙酚A型酚醛清漆系環氧樹脂 [產品名：ΕΠΚΟΤΕ 157S7〇(表8中表示為「EPIKOTE」），Ink retention stability chromaticity [C light source] NMP resistance NaOH resistance surface hardness X y Y Example A1 〇0.651 0.339 21.55 〇〇2H Example A2 〇0.651 0.339 21.57 〇〇3H Example A3 〇0.651 0.339 21.47 〇〇 2H Example A4 〇0.291 0.600 58.13 〇〇2H ΪExample A5 〇0.291 0.600 58.09 〇〇3H Example A6 〇0.291 0.600 58.12 〇〇2H Example A7 〇0.139 0.124 15.54 〇〇2H Example A8 〇0.139 0.124 15.51 〇 〇3H Example A9 〇0.139 0.124 15.57 〇〇4H 歹A1 Δ 0.651 0.339 21.13 Δ Δ B ratio i 丨A2 △ 0.651 0.339 21.03 Δ Δ HB Comparative Example A3 X 0.651 0.339 21.20 XX 2B Comparative Example A4 Δ 0.291 0.600 57.69 Δ Δ B ratio i pay you 丨 A 5 △ 0.291 0.600 57.55 Δ Δ HB than 交 丨 A 6 X 0.291 0.600 57.72 XX 2B than you 丨 A 7 Δ 0.139 0.124 15.37 Δ Δ HB than you A8 Δ 0.139 0.124 15.54 Δ Δ F Comparison W A9 Δ 0.139 0.124 15.60 XX 2B From the results of Table 6, it was confirmed that the inkjet ink of the first invention is excellent in storage stability, excellent in curability, and after heat curing. Excellent resistance, high brightness and good color gamut reproducibility. <Example B series> Examples B1 to B14 and Comparative Examples B1 to B6 were carried out in the following order. 1. Preparation of pigment dispersion The pigment, the pigment dispersant and the solvent were mixed in the following ratio, and 200 parts by weight of a zirconia ball having a diameter of 0.5 mm was added, and a paint agitator (manufactured by Asada Iron Works Co., Ltd.) was used. Disperse in hours to prepare a pigment dispersion. (1) Preparation of red pigment dispersion [Composition of pigment dispersion] • Pigment (CI Pigment Red 254): 4.5 parts by weight • Pigment (CI Pigment Red 177): 7.5 parts by weight 48 099117156 201111454 • Pigment (CL Pigment Yellow 150 ) : 3.0 parts by weight • Pigment Dispersant (trade name: Disperbykl61, BYK-Chemie · Japan's solid content in solvent 30 weight: 3 parts by weight • BDGAC (diethylene glycol monobutyl ether acetate): 55 〇 Parts by weight (2) Preparation of green pigment dispersion [Composition of pigment dispersion] • Pigment (CI Pigment Green 36) : 7.1 parts by weight • Pigment (CI Pigment Yellow 15〇) : 7.9 parts by weight • Pigment is a powder (product Name: Disperbykl61, BYK-Chemie · Japan's '30% by weight solids in solvent>: 30.0 parts by weight • BDGAC (diethylene glycol monobutyl ether acetate): 55.0 parts by weight (3) Blue pigment dispersion Preparation [Composition of Pigment Dispersion] • Pigment (CI Pigment Blue 15 : 6) : 14.1 parts by weight • Pigment (CI Pigment Violet 23): 0.9 parts by weight • Pigment Dispersant (trade name: Disperbykl61, BYK-Chemie Japan) , solid content in the solvent 30% by weight): 30·0 weight Ingredients • BDGAC (diethylene glycol monobutyl ether acetate): 55,0 parts by weight 2. Synthesis of acrylic copolymer (1) Polymerization of acrylic copolymer with gas introduction tube, thermometer, condenser and mixer In the reaction vessel, 'filled with 150 parts by weight of diacetyl alcohol monobutyl acetate (BDGAC), and 099117156 49 201111454 replaced with nitrogen 'heated to ioo ° ° C. In which glycyl methacrylate (GMA) 50 parts by weight of a mixture of 50 parts by weight of dicyclopentanyl methacrylate (DCPMA) and 1 part by weight of dibutyl-2-ethyl hexanoate, which was dropped over 2 hours. A GMA/DCPMA copolymer (backbone) solution was obtained by performing a reaction at 100 ° C for 3 hours. Similarly, 1-adamantyl methacrylate (ADAMA), cyclohexyl methacrylate (CHMA), Mercaptoacrylic acid isoester (IBMa), dicyclopentenyl decyl acrylate (DCPEMA), methacrylic acid 2_mercapto-2-imumaryl ester (MADAMA), 2-ethyl-2-gold thioglycolate The vinegar (EADAMA) was polymerized into an acrylic copolymer in the proportions shown in Table 7 below. The acrylic copolymer was used for dressing, and as shown in Table 7, the aromatic ring-containing monomer (benzyl benzyl acrylate, BzMA) and the fluorenyl-containing monomer (mercapto methacrylate, MMA) were used. Polymerization is carried out. Further, the numerical values in Table 7 indicate "% by weight". (2) Introduction of ethyl sulphate unsaturated bond In the acrylic copolymer obtained by the above method, propylene (AA) of I shown in Table 7 is added, and monomer containing in the acrylic copolymer is added. Total (containing epoxy-based monomer, alicyclic-containing monomer, and acrylic acid) i moles, adding p-methoxyphenol oxime 4 moles, and n, n-dimethylbenzyl The 'substituted nitrogen introduction tube is changed to be connected to the air introduction tube, and the reaction is carried out for 1 hour to obtain an epoxy group having an epoxy group and an alkyl group having an ethylenically unsaturated bond. Copolymer d~i. 099117156 51 201111454 1:3⁄4 Weight average molecular weight 10000 8000 12000 12000 II 6000 II 15000 II 20000 I 8000 I 12000 I 11000 11000 11000 Post-added carboxyl group-containing monomer (*1) CN 〇cs § Methyl-containing monomer (weight %) 1 ^ ^ BzMA alicyclic hydrocarbon-containing monomer (% by weight) EADAMA MADAMA m DCPEMA 〇BMA CHMA ADAMA in (N DCPMA 环 containing ring-stitching monomer (% by weight) GMA yr) v〇ft ΐ K & 4 t ζ ^ 9-b II660 201111454 3. Preparation of color filter for thermosetting inkjet ink The acrylic copolymer (a~1), epoxy resin, and Dollywood b basicity obtained according to the above The monomer, the thermal polymerization initiator, and the solvent (BdGAC) ' were formulated as shown in Table 8 below to prepare a resin composition. Next, 'the above pigment dispersion liquid is sufficiently mixed with the above resin composition, and the weight ratio (P/V) of the pigment (P) to the solid content (V) other than the pigment is 0.6, and the solid content in the mixed liquid BDGAC is added in an amount of 2% by weight, and a thermosetting inkjet ink for modulating a color filter is used. Epoxy resin is an alicyclic epoxy resin having two or more epoxy groups in one molecule. Name: EHPE-3150 (denoted as "EHPE" in Table 8), Daicel Chemical Industry Co., Ltd., and bisphenol A novolac epoxy resin [product name: 157 157S7〇 (Expressed in Table 8 as " EPIKOTE"),
Japan Epoxy Resins 公司製]。 夕&忐基性單體係使用二季戊四醇六及五丙烯酸酯混合 物[產品名：Aronix M403，五丙烯酸酯5〇〜6〇%，東亞合成 製]、一季戊四醇六及五丙烯酸酯混合物（產品名： M405，五丙浠酸g旨〜，東亞合成製）。 熱聚合起始劑係使用甘油雙（去㈣苯三動旨）單醋酸醋 與脂環式二麟Sf的混合物(新日本理化製）。 針、子所彳1得之各彩色濾光片用熱硬化性喷墨墨水，如下述 形成樹脂硬倾’針對表面硬度、密祕及耐ιτ◦形成性 施行評n _ 切絲色層而評估平坦性。評 099117156 53 201111454 估結果合併記於表8中。 (樹脂硬化膜之形成） 在厚0.7mm玻璃基板(Corning公司製，1737)上，利用旋 塗機施行上述各喷墨墨水的塗佈。 然後，在90°C加熱板上施行10分鐘預烤。其後，在無塵 烤箱内，依200°C施行30分鐘加熱而施行後烘烤，再依240°C 施行30分鐘加熱而施行後烘烤，形成著色層。 [評估方法] (1) 表面硬度(錯筆硬度） 針對上述彩色濾光片層表面的鉛筆硬度，根據JIS κ 5400-1990 8.4.1 ’利用「鉛筆刮痕試驗」施行評估。 (2) 密接性 針對上述著色層與基板間之密接性，根據JJS K 5400-1990 8.5.3，依照「附著性棋盤格勝帶法」施行評估。另外，表8 中δ己載棋盤格100個中，彩色濾光片層未被剝落而殘留的棋 盤格數。 (3)平坦性 (依喷墨方式進行的著色層形成) 在厚OJmm且l〇cmxl〇cm的玻璃基板(c〇rning公司製， Π37)上，使用黑轉用硬化性樹脂組成物，湘光學微影 法形成線寬20Mm、膜厚2.2/|111的黑矩陣圖案。 在上述基板利用黑矩陣區分的像素形成部中’利用喷墨方 099117156 54 2〇1111454 式使上述喷墨墨水附著。 然後，依120秒鐘、i〇Torr施行減壓乾燥，再在9〇。〇加 熱板上施行10分鐘預烤。然後，在無塵烤箱内，依2〇(Tc 加熱30分鐘而施行後烘烤’再依24(TC加熱30分鐘而施行 - 後烘烤，而在基板上形成著色層的圖案。 . (表面形狀測定） 針對依如上述利用喷墨方式所獲得之著色層，使用非接觸 式表面形狀測定裝置NewView 6K(Zygo公司製）施行測定， 並计异出表面形狀的分佈。將著色層的表面形狀分佈中的最 低部分設為A、最高部分設為β，利用高低差(Β-Α)依照以 下δ子估基準施行平坦性評估。 [評估基準] Ο : Β-Α < 0.5μηι Δ ： 0.5μιη^Β-Α< Ι.Ομιη X : 1.0μηι^Β-Α (4)耐ΙΤΟ形成性 1 將依如上述已形成樹脂硬化膜的基板，在異丙醇中浸潰5 为鐘，接著利用異丙醇蒸氣施行乾燥，經洗淨後，在基板設 定溫度200°C、6xl(T3Torr真空下，形成i20nm厚的ITO(氧 化銦錫）電極，並依下述基準施行評估。又，利用AFM測定 所形成的ITO膜之表面粗度(Ra)。AFM係使用曰本％比〇 股份有限公司的NanoScopellla。 099117156 55 201111454 [耐ITO形成性之評估基準] 〇：ΙΤΟ電極未觀測到皺折、龜裂等異常。 △ : ΙΤΟ電極觀測到數點皺折、龜裂等異常。 X : ΙΤΟ電極整面均觀測到皺折、龜裂等異常。 099117156 56 201111454 50磷〕 aJ PQ ON 们 CN 00 rn r-^ 5 Ο Qj K § ο < m 〇\ in CN CN oo cn t-H 卜 ο ο Oj X ο <1 < 寸 PQ ON ΙΟ <N cs 00 ro w-| g ο CQ ο X CO PQ 〇 (N 寸 1-Η ο m ffi 0 X (N m s tn Os o ffi § <] <] s t-H 寸 ro — δ ο CQ ο X X 对 PQ 〇 1〇 rn CO CS CS CN ffi m ο 〇 〇 PQ cs T-H uS ΓΛ V-J (N m o ffi CN ο r·^ 〇 〇 cs CQ ON 寸· A (N VO On 〇 S ο CN Ο ο yH 〇 〇 m 〇 00 in — 00 m CN On 〇 S ο Oj ffi CN ο ο τ—< 〇 〇 O 1-H CQ ON yn CN CN OO rn r-H »-H ο ffi (N ο r—^ 〇 〇 as PQ ο \T) r"H CN σ\ 寸 ON c5 ο OJ K (N Ο ο 〇 〇 00 W 〇 寸 rn 00 OS cn CO d <5 CN 寸 w (N ο ι^Η < 0 PQ 00 oi o 寸’ K ΓΟ ο r-H 〇 0 v〇 CQ 〇\ O) ^t* ffi CO Ο 〇 0 CQ γ-Η rn 00 On cn m 〇 ι> <ζ> ο ffi CN ο ο 〇 0 寸 ffl 〇 W-) cs CN vd 〇 CN c> K m ο r*H 〇 <] m CQ 〇 r〇 00 σ\ ro m »/Ί 〇 ο w 寸 Ο ο 〇 <] CN PQ 〇 寸 r〇 CO 〇\ cn ΓΛ u^i ο ο ο QJ w m ο Γ·Η 〇 < s 寸 rn oo 〇\ cn m O ο qj K ο Γ·Ή 〇 〈 4 <e] 赍 EHPE ΕΡΙΚΟΤΕ d r〇 o Τ3 <υ t+H W] • wM M403 [Μ405 ΜΤΑ-15 BDGAC 表面硬度 /—* 學 5 平坦性 ★ 治 ο η 5 顏料分散液 環氧樹脂 丙烯酸系共聚物 多官能基性單體 <0 戚 蒜贺1?萆奘 IS, 9--1660 201111454 由表8的結果可確認第2發明的喷墨墨水可實現熱硬化後 的密接性、表面硬度、及平坦性均優異之著色層。 099117156 58Japan Epoxy Resins company].夕 & 忐-based single system using a mixture of dipentaerythritol hexa- and pentaacrylate [product name: Aronix M403, pentaacrylate 5 〇 ~ 6 〇 %, made by East Asian synthesis], pentaerythritol hexa and penta acrylate mixture (product Name: M405, penta-propionic acid g-~, East Asian synthetic system). The thermal polymerization initiator was a mixture of glycerol bis(de(tetra)benzene trimethyl) monoacetic acid vinegar and an alicyclic bisphenol Sf (manufactured by Nippon Chemical Co., Ltd.). Each of the color filters obtained by the needles and the sub-groups is evaluated by the use of a thermosetting inkjet ink as described below for the hard surface of the resin to evaluate the surface hardness, the secret and the resistance to the formation of the n-cut color layer. Flatness. Commentary 099117156 53 201111454 The results of the merger are summarized in Table 8. (Formation of Resin Cured Film) On each of 0.7 mm thick glass substrates (manufactured by Corning, Inc., 1737), the above respective inkjet inks were applied by a spin coater. Then, pre-bake for 10 minutes on a hot plate at 90 °C. Thereafter, the mixture was baked in a dust-free oven at 200 ° C for 30 minutes, and then baked at 240 ° C for 30 minutes to form a colored layer. [Evaluation method] (1) Surface hardness (staggered hardness) The pencil hardness of the surface of the above color filter layer was evaluated by the "pencil scratch test" in accordance with JIS κ 5400-1990 8.4.1. (2) Adhesiveness The adhesion between the colored layer and the substrate was evaluated in accordance with JJS K 5400-1990 8.5.3 in accordance with the "Adhesive Checkerboard Winning Method". In addition, in Table 8, among the 100 ‧ contained checkerboards, the number of pieces of the remaining color of the color filter layer is not peeled off. (3) Flatness (formation of coloring layer by inkjet method) On a glass substrate (manufactured by c〇rning Co., Ltd., Π37) having a thickness of OJmm and a thickness of 〇cmxl 〇cm, a black curable resin composition is used. The optical lithography method formed a black matrix pattern having a line width of 20 Mm and a film thickness of 2.2/|111. In the pixel formation portion in which the substrate is divided by the black matrix, the inkjet ink is adhered by the ink jet method 099117156 54 2 1111454. Then, it was dried under reduced pressure for 120 seconds, i Torr, and then at 9 Torr. Preheat the plate for 10 minutes on the hot plate. Then, in a clean oven, 2 〇 (Tc is heated for 30 minutes and then post-baked' and then 24 (TC is heated for 30 minutes to perform - post-baking, and a pattern of colored layers is formed on the substrate. Shape measurement) The coloring layer obtained by the inkjet method as described above was measured by a non-contact surface shape measuring apparatus NewView 6K (manufactured by Zygo Co., Ltd.), and the surface shape distribution was measured. The lowest part of the distribution is set to A, the highest part is set to β, and the flatness evaluation is performed using the height difference (Β-Α) according to the following δ sub-estimation criteria. [Evaluation Criteria] Ο : Β-Α < 0.5μηι Δ : 0.5 ι Ο Α Α Ι Ο Ο ι ι : 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 The isopropyl alcohol vapor was dried, and after washing, an ITO (indium tin oxide) electrode having an i20 nm thickness was formed at a substrate set temperature of 200 ° C and 6 x 1 (T3 Torr vacuum), and evaluation was performed according to the following criteria. The surface roughness (Ra) of the formed ITO film was measured. AFM system Used for NanoScopellla of 〇本比比股份有限公司. 099117156 55 201111454 [Evaluation criteria for ITO formation resistance] 〇: No abnormalities such as wrinkles and cracks were observed on the ΙΤΟ electrode. △ : Several wrinkles were observed on the ΙΤΟ electrode. Abnormalities such as cracks X: Abnormalities such as wrinkles and cracks were observed on the entire surface of the electrode. 099117156 56 201111454 50Phosphorus] aJ PQ ON USCN 00 rn r-^ 5 Ο Qj K § ο < m 〇\ in CN CN oo cn tH οο ο Oj X ο <1 < inch PQ ON ΙΟ <N cs 00 ro w-| g ο CQ ο X CO PQ 〇(N inch 1-Η ο m ffi 0 X (N Ms tn Os o ffi § <] <] s tH inch ro — δ ο CQ ο XX vs PQ 〇1〇rn CO CS CS CN ffi m ο 〇〇PQ cs TH uS ΓΛ VJ (N mo ffi CN ο r ·^ 〇〇cs CQ ON inch · A (N VO On 〇S ο CN Ο ο yH 〇〇m 〇00 in — 00 m CN On 〇S ο Oj ffi CN ο ο τ—< 〇〇O 1-H CQ O N yn CN CN OO rn rH »-H ο ffi (N ο r—^ 〇〇as PQ ο \T) r"H CN σ\ inch ON c5 ο OJ K (N Ο ο 〇〇00 W 〇 inch rn 00 OS cn CO d <5 CN inch w (N ο ι^Η < 0 PQ 00 oi o inch ' K ΓΟ ο rH 〇0 v〇CQ 〇\ O) ^t* ffi CO Ο 〇0 CQ γ-Η Rn 00 On cn m 〇ι><ζ> ο ffi CN ο ο 〇0 inch ffl 〇W-) cs CN vd 〇CN c> K m ο r*H 〇<] m CQ 〇r〇00 σ\ Ro m »/Ί 〇ο w inch inch ο 〇<] CN PQ 〇 inch r〇CO 〇\ cn ΓΛ u^i ο ο ο QJ wm ο Γ·Η 〇< s inch rn oo 〇\ cn m O ο qj K ο Γ·Ή 〇< 4 <e] 赍EHPE ΕΡΙΚΟΤΕ dr〇o Τ3 <υ t+HW] • wM M403 [Μ405 ΜΤΑ-15 BDGAC Surface Hardness/—* Learning 5 Flatness ★ 治ο η 5 Pigment Dispersion Epoxy Acrylic Copolymer Polyfunctional Monomer <0 戚蒜贺1?萆奘IS, 9--16 60 201111454 From the results of Table 8, it was confirmed that the inkjet ink of the second invention is excellent in adhesion, surface hardness, and flatness after heat curing. 099117156 58