TWI671363B - Photosensitive resin composition and uses thereof - Google Patents
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Abstract
本發明係有關一種感光性樹脂組成物，及使用該感光性樹脂組成物以製造彩色濾光片及液晶顯示元件。上述感光性樹脂組成物包含顏料(A)、染料(B)、鹼可溶性樹脂(C)、具有乙烯性不飽和基之化合物(D)、光起始劑(E)、化合物(F)及溶劑(G)。根據本發明之感光性樹脂組成物所製得之彩色濾光片具有耐UV黃變性之優點。The present invention relates to a photosensitive resin composition and the use of the photosensitive resin composition to produce a color filter and a liquid crystal display element. The photosensitive resin composition includes a pigment (A), a dye (B), an alkali-soluble resin (C), a compound (D) having an ethylenically unsaturated group, a photoinitiator (E), a compound (F), and a solvent. (G). The color filter prepared by the photosensitive resin composition of the present invention has the advantage of being resistant to UV yellowing.
Description
本發明係有關一種感光性樹脂組成物，及使用該感光性樹脂組成物以製造彩色濾光片及液晶顯示元件；特別是提供一種感光性樹脂組成物，該感光性樹脂組成物所製得之彩色濾光片具有耐UV黃變性之優點。 The present invention relates to a photosensitive resin composition and the use of the photosensitive resin composition to manufacture color filters and liquid crystal display elements; in particular, to provide a photosensitive resin composition made of the photosensitive resin composition. Color filters have the advantage of being resistant to UV yellowing.
目前，彩色濾光片已被廣泛地應用在彩色液晶顯示器、彩色傳真機、彩色攝影機等辦公器材之領域。隨著市場需求日漸擴大，彩色濾光片之製作技術亦趨向多樣化，目前已開發染色法、印刷法、電鍍法以及分散法等製造方法，其中以分散法為主流製程。 At present, color filters have been widely used in the field of office equipment such as color liquid crystal displays, color fax machines, and color cameras. With the increasing market demand, the manufacturing technology of color filters also tends to be diversified. At present, manufacturing methods such as dyeing, printing, plating, and dispersion methods have been developed. Among them, dispersion method is the mainstream process.
分散法之製程係先將著色顏料分散於感光性樹脂中，再將該感光性樹脂塗佈於玻璃基板上，經過曝光、顯像等步驟，即可製得特定圖案。經重複三次操作，即可製得紅色(R)，綠色(G)及藍色(B)之畫素著色層之圖案，之後視需要可於畫素著色層之圖案上施加保護膜。 The dispersion process involves first dispersing a colored pigment in a photosensitive resin, then coating the photosensitive resin on a glass substrate, and then exposing, developing, and other steps to obtain a specific pattern. After repeating the operation three times, the pattern of the pixel-colored layer of red (R), green (G) and blue (B) can be obtained, and then a protective film can be applied on the pattern of the pixel-colored layer if necessary.
日本特開2001-075273揭示一感光性樹脂組成物，其包含羧酸基之不飽和單體與含有環氧丙基之單體所聚合而得之聚合物作為感光性樹脂之鹼可溶性樹脂。然而，此習知技術之感光性樹脂組成物製得之畫素層卻具有UV黃變的問題。 Japanese Patent Application Laid-Open No. 2001-075273 discloses a photosensitive resin composition containing a polymer obtained by polymerizing an unsaturated monomer having a carboxylic acid group and a monomer containing an epoxy group as an alkali-soluble resin of the photosensitive resin. However, the pixel layer made of the photosensitive resin composition of this conventional technique has a problem of UV yellowing.
因此，如何克服UV黃變之問題以達到目前業界的要求，為 本發明所屬技術領域中努力研究之目標。 Therefore, how to overcome the problem of UV yellowing to meet the current industry requirements, The objective of hard research in the technical field to which the present invention belongs.
本發明之感光性樹脂組成物藉由使用具有特殊結構之光起始劑及特殊結構之化合物，因而能夠使所製得之彩色濾光片具有耐UV黃變性之優點。 The photosensitive resin composition of the present invention can use a light initiator having a special structure and a compound having a special structure, so that the prepared color filter has the advantage of being resistant to UV yellowing.
因此，本發明提供一種感光性樹脂組成物，包含：顏料(A)；染料(B)；鹼可溶性樹脂(C)；具有乙烯性不飽和基之化合物(D)；光起始劑(E)；具有式(1)所示結構之化合物(F)；及溶劑(G)，其中，該光起始劑(E)包含環戊二酮肟酯化合物(E-1)，且該環戊二酮肟酯化合物(E-1)包含至少一種選自由式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)及式(E-1-5)所組成之群的環戊二酮肟酯化合物：
式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)及式(E-1-5)中，Ar1為鄰亞芳基或鄰亞雜芳基，該鄰亞芳基或該鄰亞雜芳基是以相鄰的兩個原子與Y1和羰基相連構成並環結構，其餘原子上的取代基各自獨立地選自由氫原子，鹵素原子，C1-C12烷基，C5-C7環烷基，被C5-C7環烷基取代之C1-C4烷基，苯基，任意被一個或多個C1-C4烷基、羧基、C1-C12烷基醯基、芳基醯基、雜芳基醯基、JT17、苯基、鹵素原子或CN取代之苯基，C1-C4烷基苄氧基，被T1C(O)O取代之C1-C4烷氧基，C1-C3亞烷基二氧基，T1C(O)O，C1-C12烷基硫基，C1-C4烷基苯硫基，被T1C(O)O取代之C1-C4烷基硫基，CN，羧基，C1-C12烷氧基甲醯基，芳基醯基，雜芳基醯基及JT18所組成之群；或Ar1之上述取代基中相鄰的兩個取代基之間或者取代基與Ar1之間通過單鍵、碳原子或羰基相連構成環狀結構；其中，JT17及JT18中，J係選自由O、S及NT19所組成之群；
Y1係選自由O、S、NT20、BT20、CT15T16、SiT15T16、S=O及C=O所組成之群；
Ar2係選自由下列結構所組成之群： 及，其中J係選自由O、S及NT19所組成之群；U1係選自由下列所組成之群：單鍵、C1-C10直鏈亞烷基、C1-C10支鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C2-C10直鏈亞烷基或C2-C10支鏈亞烷基、被一個或多個氧原子或硫原子***的C2-C10直鏈亞烷基或C2-C10支鏈亞烷基、無取代基的亞芳香基及有取代基的亞芳香基；Y2係選自由下列所組成之群：單鍵、O、S、NT20、BT20、CT15T16、SiT15T16、C=O及Y3-U2-Y3；U2係選自由下列所組成之群：C1-C10直鏈亞烷基、C1-C10支鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C2-C10直鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C2-C10支鏈亞烷基、被一個或多個氧原子或硫原子***的C2-C10直鏈亞烷基、被一個或多個氧原子或硫原子***的C2-C10支鏈亞烷基、無取代基的亞芳香基及有取代基的亞芳香基；Y3係選自由下列所組成之群：O、S、NT20、BT20及O-C(O)；
T1係選自由下列所組成之群：氫原子，C1-C18烷基，C1-C18烷氧基，C2-C18烯基，任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基或芳醯氧基取代及/或被C5-C7環亞烷基、亞苯基、O、S或NT17***之C2-C18烯基，任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基或芳醯氧基取代及/或被C5-C7環亞烷基、亞苯基、O、S或NT17***之C2-C18烷基，C5-C7環烷基，任意被一個或多個C1-C4烷基、苯基、鹵素原子或CN取代之C5-C7環烷基，苯基，任意被一個或多個C1-C4烷基、C1-C4烷氧基、苯基、鹵素原子或CN取代之苯基，萘基，苯甲醯基及苯氧基羰基；其中苯甲醯基及苯氧基羰基的苯基可被一個或兩個以上鹵素原子、T17、C5環烷基、C6環烷基、CN、OH或JT17所取代；T11及T12各自獨立地選自由下列所組成之群：氫原子，鹵素原子，C1-C12烷基，C5-C7環烷基，被C5-C7環烷基取代之C1-C4烷基，C1-C12烷氧基，C1-C4烷基苄氧基，苯基，任意被一個或多個C1-C4烷基、羧基、C1-C12烷基醯基、C1-C12芳基醯基、雜芳基醯基、JT17、苯基、鹵素原子或CN取代之苯基，C1-C4烷基苄氧基，被一個或多個C1-C12烷氧基、C1-C4烷基苄氧基或T1C(O)O取代之C1-C4烷氧基，T1C(O)O，CN，羧基，C1-C12烷氧基羰基，芳基羰基，雜芳基羰基，JT18，被一個或多個C1-C4烷基取代之苯氧基，被一個C1-C8烷基醯基、C5-C6環烷基醯基、芳基醯基或雜芳基醯基取代之苯氧基，被C5-C6環烷基取代之C1-C4烷基醯基苯氧基，C1-C3亞烷基二氧基，C1-C12烷基硫基，被T1C(O)O取代之C1-C4烷基硫基，被T1C(O)O取代之C1-C4烷基苯硫基，被一個C1-C8烷基醯基、C5-C6環烷基醯基、芳基醯基或雜芳基醯
基取代之苯硫基，被C5-C6環烷基取代之C1-C4烷基醯基苯硫基，及環氧丙基；其中環氧基可任意地與C1-C4烷基醛或酮縮合；或T11和T12相連構成飽和或不飽和環狀結構；T15及T16各自獨立地選自由下列所組成之群：氫原子，C1-C18烷基，被羧基取代之C1-C5烷基，被C1-C4烷氧基醯基取代之C1-C5烷基，被T1C(O)O取代之C1-C4烷基，任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基或芳醯氧基取代之C2-C18烷基，被C5-C7環亞烷基、亞苯基、O、S或NT17***之C2-C18烷基，C5-C7環烷基，任意被一個或多個C1-C4烷基、苯基、鹵素原子或CN取代之C5-C7環烷基，苯基，及任意被一個或多個C1-C4烷基、C1-C4烷氧基、羧基、C1-C12烷基醯基、C5-C6環烷基甲醯基、被C5-C6環烷基取代之C2-C4烷基醯基、苯甲醯基、JT17、苯基、鹵素原子或CN取代之苯基；或T15、T16與其共同所連的碳原子或矽原子一起構成環狀且成環之原子數為4至7；或T15、T16分別與相鄰的取代基一起構成環狀且成環之原子數為4至7；T17為C1-C4烷基；T18係選自由下列所組成之群：氫原子，C1-C18烷基，被C1-C4烷氧基醯基取代之C1-C5烷基，被T1C(O)O取代的C1-C4烷基，任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基或芳醯氧基取代之C2-C18烷基，被C5-C7環亞烷基、亞苯基、O、S或NT17***之C2-C18烷基，C5-C7環烷基，任意被一個或多個C1-C4烷基、苯基、鹵素原子或CN取代之C5-C7環烷基，
苯基，任意被一個或多個C1-C12烷基、羧基、C1-C12烷基醯基、C5-C6環烷基甲醯基、芳基醯基、雜芳基醯基、JT17、苯基、鹵素原子、CN或NO2取代之苯基，任意被一個有C5-C6環烷基取代之C2-C4烷基醯基取代的苯基，任意被一個有亞苯基、O、S或NT17***之C2-C12烷基醯基取代之苯基，C1-C4烷基醯基，C1-C4共軛烯醯基，苯甲醯基及苯氧基羰基；其中該苯甲醯基或該苯氧基羰基中的苯基可任意被一個或兩個以上鹵素原子、T17、C5環烷基、C6環烷基、CN、OH或JT17取代；或T18通過單鍵、碳原子、羰基與Ar1或Ar2中的芳環相連構成新的環；T19及T20各自獨立地選自由下列所組成之群：氫原子，C1-C18烷基，被C1-C4烷氧基醯基取代之C1-C5烷基，被T1C(O)O取代之C1-C4烷基，任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基或芳醯氧基取代之C2-C18烷基，被C5-C7環亞烷基、亞苯基、O、S或NT17***之C2-C18烷基，C5-C7環烷基，任意被一個或多個C1-C4烷基、苯基、鹵素原子或CN取代之C5-C7環烷基，苯基，及任意被一個或多個C1-C4烷基、羧基、C1-C12烷基醯基、C5-C6環烷基甲醯基、被C5-C6環烷基取代之C2-C4烷基醯基、芳基醯基、JT17、苯基、鹵素原子或CN取代之苯基；或T19分別通過單鍵、碳原子、羰基與Ar1或Ar2中的芳環相連構成新的環；其中當Ar1為取代咔唑基團時，Y1不為C、O、S或NT20；
於式(1)中：A1表示五員環或六員環之烴環或雜環；R1f各自獨立表示鹵素原子、氰基、羥基、硝基、羧基、可具有取代基之碳數為1至40之烷基、碳數為6至20之芳基、碳數為7至20之芳烷基或碳數為2至20之含雜環之基；R2f各自獨立表示碳數為1至20之烷基、碳數為2至20之烯基、碳數為6至20之芳基、碳數為7至20之芳烷基、碳數為2至20之含雜環之基或三烷基矽烷基；其中，R1f及R2f所示之烷基或芳烷基中之亞甲基可被選自由碳-碳雙鍵、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR'-、-S-S-及-SO2-之基所組成之群或前述基在氧原子不相鄰條件下之組合所取代，R'表示氫原子或碳數為1至8之烷基；複數個R1f彼此可鍵結形成苯環或萘環；複數個R1f及R2f彼此可分別相同或不同；h表示1至10之整數；e表示1至4之整數；f表示1至3之整數；
D表示單鍵、氮原子、氧原子、硫原子、磷原子、下述式(2)所示之基、>C=O、>NR3f、-OR3f、-SR3f、-NR3fR4f或具有與h為相同價數之可具有取代基之碳數為1至120之脂肪族烴基、可具有取代基之碳數為6至35之含芳香環之烴基、可具有取代基之碳數為2至35之含雜環之基，其中R3f及R4f表示氫原子、可具有取代基之碳數為1至35之脂肪族烴基、可具有取代基之碳數為6至35之含芳香環之烴基或可具有取代基之碳數為2至35之含雜環之基，該脂肪族烴基、含芳香環之烴基及含雜環之基可被選自由碳-碳雙鍵、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR'-、-S-S-、-SO2-及氮原子之基所組成之群或前述基在氧原子不相鄰條件下之組合所間雜，上述芳香環或雜環可與其他環縮合；其中，當D為氮原子、磷原子或下述式(2)所示之基時，h為3；當D為氧原子或硫原子時，h為2；當D為>C=O、-NH-CO-、-CO-NH-或>NR3f時，h為2；當D為-OR3f、-SR3f或-NR3fR4f時，h為1；其中，D可與A1一起形成環；
本發明亦提供一種彩色濾光片之製造方法，其係使用前述之感光性樹脂組成物形成一畫素層。 The invention also provides a method for manufacturing a color filter, which uses the aforementioned photosensitive resin composition to form a pixel layer.
本發明又提供一種彩色濾光片，其係由前述之方法所製得。 The present invention also provides a color filter, which is prepared by the aforementioned method.
本發明再提供一種液晶顯示元件，係包含前述之彩色濾光。 The present invention further provides a liquid crystal display element, which includes the aforementioned color filter.
本發明提供一種感光性樹脂組成物，其包含：
顏料(A)；染料(B)；鹼可溶性樹脂(C)；具有乙烯性不飽和基之化合物(D)；光起始劑(E)；具有式(1)所示結構之化合物(F)；及溶劑(G)，其中，該光起始劑(E)包含環戊二酮肟酯化合物(E-1)，且該環戊二酮肟酯化合物(E-1)包含至少一種選自由式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)及式(E-1-5)所組成之群的環戊二酮肟酯化合物：
式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)及式(E-1-5)中，Ar1為鄰亞芳基或鄰亞雜芳基，該鄰亞芳基或該鄰亞雜芳基是以相鄰的兩個原子與Y1和羰基相連構成並環結構，其餘原子上的取代基各自獨立地選自由氫原子，鹵素原子，C1-C12烷基，C5-C7環烷基，被C5-C7環烷基取代之C1-C4烷基，苯基，任意被一個或多個C1-C4烷基、羧基、C1-C12烷基醯基、芳基醯基、雜芳基醯基、JT17、苯基、鹵素原子或CN取代之苯基，C1-C4烷基苄氧基，被T1C(O)O取代之C1-C4烷氧基，C1-C3亞烷基二氧基，T1C(O)O，C1-C12烷基硫基，C1-C4烷基苯硫基，被T1C(O)O取代之C1-C4烷基硫基，CN，羧基，C1-C12烷氧基甲醯基，芳基醯基，雜芳基醯基及JT18所組成之群；或Ar1之上述取代基中相鄰的兩個取代基之間或者取代基與Ar1之間通過單鍵、碳原子或羰基相連構成環狀結構；其中，JT17及JT18中，J係選自由O、S及NT19所組成之群；Y1係選自由O、S、NT20、BT20、CT15T16、SiT15T16、S=O及C=O所組成之群；
Ar2係選自由下列結構所組成之群： 及，其中J係選自由O、S及NT19所組成之群；U1係選自由下列所組成之群：單鍵、C1-C10直鏈亞烷基、C1-C10支鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C2-C10直鏈亞烷基或C2-C10支鏈亞烷基、被一個或多個氧原子或硫原子***的C2-C10直鏈亞烷基或C2-C10支鏈亞烷基、無取代基的亞芳香基及有取代基的亞芳香基；Y2係選自由下列所組成之群：單鍵、O、S、NT20、BT20、CT15T16、SiT15T16、C=O及Y3-U2-Y3；U2係選自由下列所組成之群：C1-C10直鏈亞烷基、C1-C10支鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C2-C10直鏈亞烷基、被一個或多個氧原子或硫原子連在端基的C2-C10支鏈亞烷基、被一個或多個氧原子或硫原子***的C2-C10直鏈亞烷基、被一個或多個氧原子或硫原子***的C2-C10支鏈亞烷基、無取代基的亞芳香基及有取代基的亞芳香基；Y3係選自由下列所組成之群：O、S、NT20、BT20及O-C(O)；T1係選自由下列所組成之群：氫原子，C1-C18烷基，C1-C18烷氧基，C2-C18烯基，任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基或芳醯氧基取代及/
或被C5-C7環亞烷基、亞苯基、O、S或NT17***之C2-C18烯基，任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基或芳醯氧基取代及/或被C5-C7環亞烷基、亞苯基、O、S或NT17***之C2-C18烷基，C5-C7環烷基，任意被一個或多個C1-C4烷基、苯基、鹵素原子或CN取代之C5-C7環烷基，苯基，任意被一個或多個C1-C4烷基、C1-C4烷氧基、苯基、鹵素原子或CN取代之苯基，萘基，苯甲醯基及苯氧基羰基；其中苯甲醯基及苯氧基羰基的苯基可被一個或兩個以上鹵素原子、T17、C5環烷基、C6環烷基、CN、OH或JT17所取代；T11及T12各自獨立地選自由下列所組成之群：氫原子，鹵素原子，C1-C12烷基，C5-C7環烷基，被C5-C7環烷基取代之C1-C4烷基，C1-C12烷氧基，C1-C4烷基苄氧基，苯基，任意被一個或多個C1-C4烷基、羧基、C1-C12烷基醯基、C1-C12芳基醯基、雜芳基醯基、JT17、苯基、鹵素原子或CN取代之苯基，C1-C4烷基苄氧基，被一個或多個C1-C12烷氧基、C1-C4烷基苄氧基或T1C(O)O取代之C1-C4烷氧基，T1C(O)O，CN，羧基，C1-C12烷氧基羰基，芳基羰基，雜芳基羰基，JT18，被一個或多個C1-C4烷基取代之苯氧基，被一個C1-C8烷基醯基、C5-C6環烷基醯基、芳基醯基或雜芳基醯基取代之苯氧基，被C5-C6環烷基取代之C1-C4烷基醯基苯氧基，C1-C3亞烷基二氧基，C1-C12烷基硫基，被T1C(O)O取代之C1-C4烷基硫基，被T1C(O)O取代之C1-C4烷基苯硫基，被一個C1-C8烷基醯基、C5-C6環烷基醯基、芳基醯基或雜芳基醯基取代之苯硫基，被C5-C6環烷基取代之C1-C4烷基醯基苯硫基，及環氧丙基；其中環氧基可任意地與C1-C4烷基醛或酮縮合；或T11和T12相連構成飽和或不飽和環狀結構；
T15及T16各自獨立地選自由下列所組成之群：氫原子，C1-C18烷基，被羧基取代之C1-C5烷基，被C1-C4烷氧基醯基取代之C1-C5烷基，被T1C(O)O取代之C1-C4烷基，任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基或芳醯氧基取代之C2-C18烷基，被C5-C7環亞烷基、亞苯基、O、S或NT17***之C2-C18烷基，C5-C7環烷基，任意被一個或多個C1-C4烷基、苯基、鹵素原子或CN取代之C5-C7環烷基，苯基，及任意被一個或多個C1-C4烷基、C1-C4烷氧基、羧基、C1-C12烷基醯基、C5-C6環烷基甲醯基、被C5-C6環烷基取代之C2-C4烷基醯基、苯甲醯基、JT17、苯基、鹵素原子或CN取代之苯基；或T15、T16與其共同所連的碳原子或矽原子一起構成環狀且成環之原子數為4至7；或T15、T16分別與相鄰的取代基一起構成環狀且成環之原子數為4至7；T17為C1-C4烷基；T18係選自由下列所組成之群：氫原子，C1-C18烷基，被C1-C4烷氧基醯基取代之C1-C5烷基，被T1C(O)O取代的C1-C4烷基，任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基或芳醯氧基取代之C2-C18烷基，被C5-C7環亞烷基、亞苯基、O、S或NT17***之C2-C18烷基，C5-C7環烷基，任意被一個或多個C1-C4烷基、苯基、鹵素原子或CN取代之C5-C7環烷基，苯基，任意被一個或多個C1-C12烷基、羧基、C1-C12烷基醯基、C5-C6環烷基甲醯基、芳基醯基、雜芳基醯基、JT17、苯基、鹵素原子、CN或NO2取代之苯基，任意被一個有C5-C6環烷基取代之C2-C4烷基醯基
取代的苯基，任意被一個有亞苯基、O、S或NT17***之C2-C12烷基醯基取代之苯基，C1-C4烷基醯基，C1-C4共軛烯醯基，苯甲醯基及苯氧基羰基；其中該苯甲醯基或該苯氧基羰基中的苯基可任意被一個或兩個以上鹵素原子、T17、C5環烷基、C6環烷基、CN、OH或JT17取代；或T18通過單鍵、碳原子、羰基與Ar1或Ar2中的芳環相連構成新的環；T19及T20各自獨立地選自由下列所組成之群：氫原子，C1-C18烷基，被C1-C4烷氧基醯基取代之C1-C5烷基，被T1C(O)O取代之C1-C4烷基，任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基或芳醯氧基取代之C2-C18烷基，被C5-C7環亞烷基、亞苯基、O、S或NT17***之C2-C18烷基，C5-C7環烷基，任意被一個或多個C1-C4烷基、苯基、鹵素原子或CN取代之C5-C7環烷基，苯基，及任意被一個或多個C1-C4烷基、羧基、C1-C12烷基醯基、C5-C6環烷基甲醯基、被C5-C6環烷基取代之C2-C4烷基醯基、芳基醯基、JT17、苯基、鹵素原子或CN取代之苯基；或T19分別通過單鍵、碳原子、羰基與Ar1或Ar2中的芳環相連構成新的環；其中當Ar1為取代咔唑基團時，Y1不為C、O、S或NT20；
於式(1)中：
A1表示五員環或六員環之烴環或雜環；R1f各自獨立表示鹵素原子、氰基、羥基、硝基、羧基、可具有取代基之碳數為1至40之烷基、碳數為6至20之芳基、碳數為7至20之芳烷基或碳數為2至20之含雜環之基；R2f各自獨立表示碳數為1至20之烷基、碳數為2至20之烯基、碳數為6至20之芳基、碳數為7至20之芳烷基、碳數為2至20之含雜環之基或三烷基矽烷基；其中，R1f及R2f所示之烷基或芳烷基中之亞甲基可被選自由碳-碳雙鍵、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR'-、-S-S-及-SO2-之基所組成之群或前述基在氧原子不相鄰條件下之組合所取代，R'表示氫原子或碳數為1至8之烷基；複數個R1f彼此可鍵結形成苯環或萘環；複數個R1f及R2f彼此可分別相同或不同；h表示1至10之整數；e表示1至4之整數；f表示1至3之整數；D表示單鍵、氮原子、氧原子、硫原子、磷原子、下述式(2)所示之基、>C=O、>NR3f、-OR3f、-SR3f、-NR3fR4f或具有與h為相同價數之可具有取代基之碳數為1至120之脂肪族烴基、可具有取代基之碳數為6至35之含芳香環之烴基、可具有取代基之碳數為2至35之含雜環之基，其中R3f及R4f表示氫原子、可具有取代基之碳數為1至35之脂肪族烴基、可具有取代基之碳數為6至35之含芳香環之烴基或可具有取代基之碳數為2至35之含雜環之基，該脂肪族烴基、含芳香環之烴基及
含雜環之基可被選自由碳-碳雙鍵、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR'-、-S-S-、-SO2-及氮原子之基所組成之群或前述基在氧原子不相鄰條件下之組合所間雜，上述芳香環或雜環可與其他環縮合；其中，當D為氮原子、磷原子或下述式(2)所示之基時，h為3；當D為氧原子或硫原子時，h為2；當D為>C=O、-NH-CO-、-CO-NH-或>NR3f時，h為2；當D為-OR3f、-SR3f或-NR3fR4f時，h為1；其中，D可與A1一起形成環；
根據本發明之顏料(A)可為無機顏料、有機顏料或上述之組合。 The pigment (A) according to the present invention may be an inorganic pigment, an organic pigment, or a combination thereof.
該無機顏料可為金屬氧化物、金屬錯鹽等金屬化合物，其可選自於鐵、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、亞鉛、銻等金屬的氧化物、前述金屬的複合氧化物以及金屬錯鹽。 The inorganic pigment may be a metal compound such as a metal oxide or a metal salt, and may be selected from oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, lead, antimony, and the like. Metal complex oxides and metal complex salts.
該有機顏料可選自於C.1.顏料黃1、3、11、12、13、14、15、16、17、20、24、31、53、55、60、61、65、71、73、74、81、83、93、95、97、98、99、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、167、168、175；C.I.顏料橙1、5、13、14、16、17、24、34、36、38、40、43、46、49、51、61、63、64、71、73；C.I.顏料紅1、2、3、4、5、6、7、8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、31、32、37、38、40、41、42、48：1、48：2、48：3、 48：4、49：1、49：2、50：1、52：1、53：1、57、57：1、57：2、58：2、58：4、60：1、63：1、63：2、64：1、81：1、83、88、90：1、97、101、102、104、105、106、108、112、113、114、122、123、144、146、149、150、151、155、166、168、170、171、172、174、175、176、177、178、179、180、185、187、188、190、193、194、202、206、207、208、209、215、216、220、224、226、242、243、245、254、255、264、265；C.I.顏料紫1、14、19、23、29、32、33、36、37、38、39、40、50；C.I.顏料藍1、2、15、15：1、15：2、15：3、15：4、15：5、15：6、16、21、22、60、61、64、66；C.I.顏料綠7、36、37、42、58；C.I.顏料棕23、25、28；以及C.I.顏料黑1、7。上述之有機顏料可單獨一種或混合複數種使用。 The organic pigment can be selected from C.1. Pigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73 , 74, 81, 83, 93, 95, 97, 98, 99, 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, 167, 168, 175; CI pigment orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15 , 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265; CI Pigment Violet 1, 14, 19, 23, 29, 32, 33, 36, 37, 38, 39 , 40, 50; CI Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 21, 22, 60, 61, 64, 66; CI Pigment Green 7, 36, 37, 42, 58; CI Pigment Brown 23, 25, 28; and CI Pigment Black 1, 7. These organic pigments may be used alone or in combination.
該顏料(A)之平均粒子徑較佳為10nm至200nm；更佳為20nm至150nm；最佳為30nm至130nm。 The average particle diameter of the pigment (A) is preferably 10 nm to 200 nm; more preferably 20 nm to 150 nm; and most preferably 30 nm to 130 nm.
基於該鹼可溶性樹脂(C)之使用量為100重量份，該顏料(A)之使用量為5至300重量份；較佳為10至250重量份；更佳為15至200重量份。 Based on the use amount of the alkali-soluble resin (C) being 100 parts by weight, the use amount of the pigment (A) is 5 to 300 parts by weight; preferably 10 to 250 parts by weight; more preferably 15 to 200 parts by weight.
必要時，該顏料(A)也能選擇性地使用分散劑，例如：陽離子系、陰離子系、非離子系、兩性、聚矽氧烷系、氟系等之界面活性劑。 If necessary, the pigment (A) can also selectively use a dispersant, for example, a cationic, anionic, nonionic, amphoteric, polysiloxane, and fluorine-based surfactant.
前述之界面活性劑可包含但不限於聚環氧乙烷十二烷基醚、聚環氧乙烷硬脂醯醚、聚環氧乙烷油醚等之聚環氧乙烷烷基醚類；聚環氧乙烷辛基苯醚、聚環氧乙烷壬基苯醚等之聚環氧乙烷烷基苯醚類界面活性劑；聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯等之聚乙二醇二酯類界面活性劑；山梨糖醇酐脂肪酸酯類界面活性劑；脂肪酸改質的聚酯類界面活性劑；三級胺改質的聚胺基甲酸酯類界面活性劑；信越化學工業製造，型號為KP之商品、Toray Dow Corning Silicon製造，型號為SF-8427之商品、共榮社油脂化學工業製造，型號為Polyflow之商品、得克姆公司 (Tochem Products Co.，Ltd.)製造，型號為F-Top之商品、大日本印墨化學工業製造，型號為Megafac之產品、住友3M製造，型號為Fluorad之產品、旭硝子製造，型號為Asahi Guard及Surflon之商品。界面活性劑可單獨一種或混合複數種使用。 The aforementioned surfactant may include but is not limited to polyethylene oxide alkyl ethers such as polyethylene oxide dodecyl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether, etc .; Polyethylene oxide octyl phenyl ether, polyethylene oxide nonyl phenyl ether and other polyethylene oxide alkyl phenyl ether surfactants; polyethylene glycol dilaurate, polyethylene glycol dihard Polyethylene glycol diester surfactants such as fatty acid esters; sorbitan fatty acid ester surfactants; fatty acid modified polyester surfactants; tertiary amine modified polyurethanes Surfactant; manufactured by Shin-Etsu Chemical Co., Ltd., a product of KP, manufactured by Toray Dow Corning Silicon, manufactured by SF-8427, manufactured by Kyoeisha Oil Chemical Industry, manufactured by Polyflow Corporation, Deckerme (Tochem Products Co., Ltd.), model F-Top, Dainippon Ink Chemical Industry, model Megafac, Sumitomo 3M, model Fluorad, Asahi Glass, model Asahi Guard And Surflon products. The surfactant can be used singly or in combination.
根據本發明之染料(B)包含具有如式(II)所示之染料(B-1)：
式(II)中，L1至L4分別獨立表示氫原子、-L6、碳數為6至10之芳香烴基、或經鹵素原子、-L6、-OH、-OL6、-SO3 -、-SO3H、-SO3M、-COOH、-COOL6、-SO3L6、-SO2NHL8或-SO2NL8L9取代之碳數為6至10之芳香烴基；L5表示-SO3 -、-SO3H、-SO3M、-COOH、-COOL6、-SO3L6、-SO2NHL8或-SO2NL8L9；u表示0至5之整數；當u表示2至5時，複數個L5為相同或不同；Xb表示鹵素原子；a表示0或1；L6表示碳數為1至10之烷基或經鹵素原子取代且碳數為1至10之烷基，其中碳數為1至10之烷基或經鹵素原子取代且碳數為1至10之烷基中之-CH2-係未經置換或經置換為-O-、羰基或-NL7-；L7表示碳數為1至10之烷基或經鹵素原子取代且碳數為1至10之烷基；L8及L9各自獨立表示碳數為1至10之直鏈烷基、碳數為3至10之支鏈烷基、碳數為3至30之環烷基、或-Q；其中，碳數為1至10之直鏈烷基、碳數 為3至10之支鏈烷基或碳數為3至30之環烷基中之氫原子係未經取代或經一取代基所取代，該取代基係選自由羥基、鹵素原子、-Q、-CH=CH2及-CH=CH-L6所組成之群；碳數為1至10之直鏈烷基、碳數為3至10之支鏈烷基或碳數為3至30之環烷基中之-CH2-係未經置換或經置換為-O-、羰基或-NL7-；或L8和L9結合形成碳數為1至10之雜環基，其中碳數為1至10之雜環基中之氫原子係未經取代或經L6、-OH、或-Q所取代；Q表示碳數為6至10之芳香烴基、碳數為5至10之雜芳香基、經鹵素原子、-L6、-OH、-OL6、-NO2、-CH=CH2或-CH=CH-L6取代之碳數為6至10之芳香烴基、或經鹵素原子、-L6、-OH、-OL6、-NO2、-CH=CH2及-CH=CH-L6取代之碳數為5至10之雜芳香基；及M表示鉀或鈉。 In formula (II), L 1 to L 4 each independently represent a hydrogen atom, -L 6 , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, -L 6 , -OH, -OL 6 , -SO 3 - , -SO 3 H, -SO 3 M, -COOH, -COOL 6 , -SO 3 L 6 , -SO 2 NHL 8 or -SO 2 NL 8 L 9 substituted aromatic hydrocarbon groups having 6 to 10 carbon atoms; L 5 represents -SO 3 -, -SO 3 H, -SO 3 M, -COOH, -COOL 6, -SO 3 L 6, -SO 2 NHL 8 or -SO 2 NL 8 L 9; u represents 0 to 5 An integer; when u represents 2 to 5, a plurality of L 5 are the same or different; X b represents a halogen atom; a represents 0 or 1; L 6 represents an alkyl group having 1 to 10 carbon atoms or substituted with a halogen atom and An alkyl group having 1 to 10 carbon atoms, in which an alkyl group having 1 to 10 carbon atoms or an alkyl group substituted with a halogen atom and having 1 to 10 carbon atoms is -CH 2 -is unsubstituted or substituted with- O-, carbonyl or -NL 7- ; L 7 represents an alkyl group having 1 to 10 carbon atoms or an alkyl group substituted with a halogen atom and having 1 to 10 carbon atoms; L 8 and L 9 each independently represent a carbon number of 1 A straight-chain alkyl group having 10 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q; wherein the straight-chain alkyl group having 1 to 10 carbon atoms, carbon The number is 3 to The hydrogen atom in a branched alkyl group of 10 or a cycloalkyl group having 3 to 30 carbon atoms is unsubstituted or substituted with a substituent selected from the group consisting of a hydroxyl group, a halogen atom, -Q, -CH = A group consisting of CH 2 and -CH = CH-L 6 ; among linear alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms or cycloalkyl groups having 3 to 30 carbon atoms -CH 2 -is unsubstituted or substituted with -O-, carbonyl, or -NL 7- ; or L 8 and L 9 combine to form a heterocyclic group having 1 to 10 carbon atoms, in which the carbon number is 1 to 10 The hydrogen atom in the heterocyclic group is unsubstituted or substituted with L 6 , -OH, or -Q; Q represents an aromatic hydrocarbon group having 6 to 10 carbon atoms, a heteroaromatic group having 5 to 10 carbon atoms, Halogen atom, -L 6 , -OH, -OL 6 , -NO 2 , -CH = CH 2 or -CH = CH-L 6 substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, or halogen atom, -L 6, -OH, -OL 6, -NO 2, -CH = CH 2 and -CH = CH-L 6 carbon atoms substituted with the heteroaryl group of 5 to 10; and M represents sodium or potassium.
較佳地，L6包含但不限於甲基、乙基、丙基、異丙基、丁基、異丁基、戊基、異戊基、新戊基(neopentyl)、環戊基、己基、環己基、庚基、環庚烷、辛基、環辛基、2-乙基己基、壬基、癸基、三環[5.3.0.03,10]癸基[tricycle(5.3.0.03,10)decanyl]、甲氧基丙基、己氧基丙基、2-乙基己氧基丙基、甲氧基己基、或環氧基丙基。 Preferably, L 6 includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, Cyclohexyl, heptyl, cycloheptane, octyl, cyclooctyl, 2-ethylhexyl, nonyl, decyl, tricyclo [5.3.0.0 3,10 ] decyl [tricycle (5.3.0.0 3,10 ) decanyl], methoxypropyl, hexyloxypropyl, 2-ethylhexyloxypropyl, methoxyhexyl, or epoxypropyl.
較佳地，碳數為6至10之芳香烴基包含但不限於苯基或萘基等。 Preferably, the aromatic hydrocarbon group having 6 to 10 carbon atoms includes, but is not limited to, phenyl, naphthyl, and the like.
較佳地，-SO3L6包含但不限於甲基磺醯基(methanesulfonyl)、乙基磺醯基(ethanesulfonyl)、己基磺醯基(hexanesulfonyl)、或癸基磺醯基(decanesulfonyl)。 Preferably, -SO 3 L 6 includes, but is not limited to, methanesulfonyl, ethanesulfonyl, hexanesulfonyl, or decanesulfonyl.
較佳地，-COOL6包含但不限於甲氧基羰基(methyloxycarbonyl)、乙氧基羰基(ethyloxycarbonyl)、丙氧基羰基、異丙氧基羰基、丁氧基羰基、異丁氧基羰基、戊氧基羰基、異戊氧基羰基、新 戊氧基羰基、環戊氧基羰基、己氧基羰基、環己氧基羰基、庚氧基羰基、環庚氧基羰基、辛氧基羰基、環辛氧基羰基、2-乙基己氧基羰基、壬氧基羰基、癸氧基羰基、三環[5.3.0.03,10]癸基羰基、甲氧基丙氧基羰基、己氧基丙氧基羰基、2-乙基己氧基丙氧基羰基、或甲氧基己氧基羰基。 Preferably, -COOL 6 includes but is not limited to methyloxycarbonyl, ethyloxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, pentyl Oxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, ring Octyloxycarbonyl, 2-ethylhexyloxycarbonyl, nonoxycarbonyl, decyloxycarbonyl, tricyclic [5.3.0.0 3,10 ] decylcarbonyl, methoxypropoxycarbonyl, hexyloxypropyl Oxycarbonyl, 2-ethylhexyloxypropoxycarbonyl, or methoxyhexyloxycarbonyl.
較佳地，-SO2NHL8包含但不限於胺磺醯基(sulfamoyl)、甲基胺磺醯基、乙基胺磺醯基、丙基胺磺醯基、異丙基胺磺醯基、丁基胺磺醯基、異丁基胺磺醯基、戊基胺磺醯基、異戊基胺磺醯基、新戊基胺磺醯基、環戊基胺磺醯基、己基胺磺醯基、環己基胺磺醯基、庚基胺磺醯基、環庚烷胺磺醯基、辛基胺磺醯基、環辛基胺磺醯基、2-乙基己基胺磺醯基、壬基胺磺醯基、癸基胺磺醯基、三環[5.3.0.03,10]癸基胺磺醯基、甲氧基丙基胺磺醯基、己氧基丙基胺磺醯基、2-乙基己氧基丙基胺磺醯基、甲氧基己基胺磺醯基、環氧基丙基胺磺醯基、1,5-二甲基己基胺磺醯基、丙氧基丙基胺磺醯基、異丙氧基丙基胺磺醯基、3-苯基-1-甲基丙基胺磺醯基、
較佳地，該染料(B-1)包括具有如式(II-1)所示之染料：
於式(II-1)中：L11至L14各自獨立表示氫、-L6、碳數為6至10之芳香烴基、或經鹵素原子、-L6、-OH、-OL6、-SO3 -、-SO3H、-SO3Na、-COOH、-COOL6、-SO3L6、-SO2NHL8或-SO2NL8L9取代之碳數為6至10之芳香烴基；L15表示氫、-SO3 -、-SO3H、-SO2NHL8或-SO2NL8L9；L16表示-SO3 -、-SO3H、-SO2NHL8或-SO2NL8L9；X1b表示鹵素原子；a1表示0或1。 In the formula (II-1): L 11 to L 14 each independently represent hydrogen, -L 6 , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, -L 6 , -OH, -OL 6 ,- SO 3 -, -SO 3 H, -SO 3 Na, -COOH, -COOL 6, -SO 3 L 6, -SO 2 NHL 8 or -SO 2 NL 8 L 9 carbon atoms substituted with an aromatic of 6 to 10 of hydrocarbon group; L 15 represents hydrogen, -SO 3 -, -SO 3 H , -SO 2 NHL 8 or -SO 2 NL 8 L 9; L 16 represents -SO 3 -, -SO 3 H, -SO 2 NHL 8 or -SO 2 NL 8 L 9 ; X 1b represents a halogen atom; a 1 represents 0 or 1.
較佳地，該染料(B-1)包括具有如式(II-2)所示之染料：
於式(II-2)中：L21至L24各自獨立表示氫、-L26、碳數為6至10之芳香烴基、或經鹵素原子、-L26、-OH、-OL26、-SO3 -、-SO3H、-SO3Na、-COOH、-COOL26、-SO3L26、或-SO2NHL28取代之碳數為6至10之芳香烴基； L25表示-SO3 -、-SO3Na、-COOH、-COOL26、-SO3H、或-SO2NHL28；u1表示0至5之整數；當u1表示2至5時，複數個L25為相同或不同；X2b表示鹵素原子；a2表示0或1；L26表示碳數為1至10之烷基、或經鹵素原子或-OL27取代之碳數為1至10之烷基；L27表示碳數為1至10之烷基；及L28表示氫、-L26、-COOL26、碳數為6至10之芳香烴基、或經-L26或-OL26取代之碳數為6至10之芳香烴基。 In the formula (II-2): L 21 to L 24 each independently represent hydrogen, -L 26 , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, -L 26 , -OH, -OL 26 ,- SO 3 -, -SO 3 H, -SO 3 Na, -COOH, -COOL 26, -SO 3 L 26, or -SO 2 NHL 28 carbon atoms of the substituted aromatic hydrocarbon group of 6 to 10; L 25 represents -SO 3 -, -SO 3 Na, -COOH , -COOL 26, -SO 3 H, or -SO 2 NHL 28; u 1 represents an integer of 0-5; when u 1 represents 2 to 5, a plurality of L 25 The same or different; X 2b represents a halogen atom; a 2 represents 0 or 1; L 26 represents an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom or -OL 27 ; L 27 represents an alkyl group having a carbon number of 1 to 10; and L 28 represents hydrogen, -L 26 , -COOL 26 , an aromatic hydrocarbon group having a carbon number of 6 to 10, or a carbon number substituted with -L 26 or -OL 26 It is an aromatic hydrocarbon group of 6 to 10.
較佳地，該染料(B-1)包括具有如式(II-3)所示之染料：
於式(II-3)中：L31及L32各自獨立表示苯基、或經鹵素原子、-L26、-OL26、-COOL26、-SO3L26、或-SO2NHL28取代之苯基；L33表示-SO3 -、或-SO2NHL28；L34表示氫、-SO3 -、或-SO2NHL28；X3b表示鹵素原子；a3表示0或1； L26表示碳數為1至10之烷基、或經鹵素原子或-OL27取代之碳數為1至10之烷基；L27表示碳數為1至10之烷基；及L28表示氫、-L26、-COOL26、碳數為6至10之芳香烴基、或經-L26或-OL26取代之碳數為6至10之芳香烴基。 In formula (II-3): L 31 and L 32 each independently represent a phenyl group, or are substituted with a halogen atom, -L 26 , -OL 26 , -COOL 26 , -SO 3 L 26 , or -SO 2 NHL 28 the phenyl group; L 33 represents -SO 3 -, or -SO 2 NHL 28; L 34 represents hydrogen, -SO 3 -, or -SO 2 NHL 28; X 3b represents a halogen atom; a 3 represents 0 or 1; L 26 represents an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom or -OL 27 ; L 27 represents an alkyl group having 1 to 10 carbon atoms; and L 28 represents hydrogen , -L 26 , -COOL 26 , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms substituted with -L 26 or -OL 26 .
較佳地，該染料(B-1)包括具有如式(II-4)所示之染料：
於式(II-4)中：L41及L42各自獨立表示苯基、或經-L26或-SO2NHL28取代之苯基；L43表示-SO3 -、或-SO2NHL28；X4b表示鹵素原子；a4表示0或1；L26表示碳數為1至10之烷基、或經鹵素原子或-OL27取代之碳數為1至10之烷基；L27表示碳數為1至10之烷基；及L28表示氫、-L26、-COOL26、碳數為6至10之芳香烴基、或經-L26或-OL26取代之碳數為6至10之芳香烴基。 In the formula (II-4): L 41 and L 42 each independently represents a phenyl group, or by -L 26 or -SO 2 NHL 28 of the substituted phenyl group; L 43 represents -SO 3 -, or -SO 2 NHL 28 X 4b represents a halogen atom; a 4 represents 0 or 1; L 26 represents an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom or -OL 27 ; L 27 represents An alkyl group having 1 to 10 carbon atoms; and L 28 represents hydrogen, -L 26 , -COOL 26 , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or 6 to 10 carbon atoms substituted with -L 26 or -OL 26 Aromatic hydrocarbon group of 10.
於本發明之具體例中，該染料(B-1)包含但不限於如下式(i-1)至式(i-31)所示之化合物：
於式(i-1)中，Rc及Rd各自獨立表示氫、-SO3 -、-COOH或-SO2NHL81；L81表示2-乙基己基；Xb表示鹵素原子；a表示0或1。 In the formula (i-1) in a, R c and R d each independently represent hydrogen, -SO 3 -, -COOH, or -SO 2 NHL 81; L 81 represents a 2-ethylhexyl group; X b represents a halogen atom; A represents 0 or 1.
於式(i-2)中，Re表示氫、-SO3 -、-COOH或-SO2NHL81；L81表示2-乙基己基；Xb表示鹵素原子；a表示0或1。 In the formula (i-2) in, R e represents hydrogen, -SO 3 -, -COOH, or -SO 2 NHL 81; L 81 represents a 2-ethylhexyl group; X b represents a halogen atom; A represents 0 or 1.
於式(i-3)中，Re表示氫、-SO3 -、-COOH或-SO2NHL81；L81表示2-乙基己基；Xb表示鹵素原子；a表示0或1。 In the formula (i-3), R e represents hydrogen, -SO 3 -, -COOH, or -SO 2 NHL 81; L 81 represents a 2-ethylhexyl group; X b represents a halogen atom; A represents 0 or 1.
於式(i-4)中，Rf、Rg及Rh各自獨立表示-SO3 -、-SO3Na或-SO2NHL81；L81表示2-乙基己基。 In formula (i-4), R f , R g, and R h each independently represent —SO 3 — , —SO 3 Na, or —SO 2 NHL 81 ; L 81 represents 2-ethylhexyl.
於式(i-5)中，Rf、Rg及Rh各自獨立表示-SO3 -、-SO3Na或-SO2NHL81；L81表示2-乙基己基。 In formula (i-5), R f , R g, and R h each independently represent —SO 3 — , —SO 3 Na, or —SO 2 NHL 81 ; L 81 represents 2-ethylhexyl.
於式(i-6)中，Ri、Rj及Rk各自獨立表示氫、-SO3 -、-SO3H或-SO2NHL81；L81表示2-乙基己基。 In the formula (i-6), R i , R j and R k each independently represent hydrogen, -SO 3 -, -SO 3 H or -SO 2 NHL 81; L 81 represents a 2-ethylhexyl group.
於式(i-7)中，Ri、Rj及Rk各自獨立表示氫、-SO3 -、-SO3H或-SO2NHL81；L81表示2-乙基己基。 In the formula (i-7), R i , R j and R k each independently represent hydrogen, -SO 3 -, -SO 3 H or -SO 2 NHL 81; L 81 represents a 2-ethylhexyl group.
於式(i-8)中，Rl、Rm及Rn各自獨立表示-SO3 -、-SO3Na或-SO2NHL81；L81表示2-乙基己基。 In the formula (i-8), R l , R m and R n each independently represent -SO 3 -, -SO 3 Na or -SO 2 NHL 81; L 81 represents a 2-ethylhexyl group.
於式(i-9)中，Rl、Rm及Rn各自獨立表示-SO3 -、-SO3Na或-SO2NHL81； L81表示2-乙基己基。 In the formula (i-9), R l , R m and R n each independently represent -SO 3 -, -SO 3 Na or -SO 2 NHL 81; L 81 represents a 2-ethylhexyl group.
於式(i-10)中，Rp、Rq及Rr各自獨立表示氫、-SO3 -、-SO3H或-SO2NHL81；L81表示2-乙基己基。 In formula (i-10), R p , R q and R r each independently represent hydrogen, —SO 3 — , —SO 3 H, or —SO 2 NHL 81 ; L 81 represents 2-ethylhexyl.
於式(i-11)中，Rp、Rq及Rr各自獨立表示氫、-SO3 -、-SO3H或-SO2NHL81；L81表示2-乙基己基。 In formula (i-11), R p , R q and R r each independently represent hydrogen, —SO 3 — , —SO 3 H, or —SO 2 NHL 81 ; L 81 represents 2-ethylhexyl.
本發明之染料(B-1)之較佳具體例為式(i-1)(Rc與Rd為-SO3 -，a為0)〔C.I.酸性紅色染料52〕、式(i-22)〔C.I.酸性紅色染料289〕、式(i-28)之染料、式(i-31)之染料、或上述之任意組合。 Dye (B-1) of the present invention particularly preferred embodiment of formula (i-1) (R c and R d is -SO 3 -, a is 0) CI Acid red dye [52], of formula (i-22 ) [CI acid red dye 289], a dye of the formula (i-28), a dye of the formula (i-31), or any combination thereof.
於本發明之具體例中，基於該鹼可溶性樹脂(C)之使用量為100重量份，該染料(B-1)之使用量為3至50重量份；較佳為5至45重量份；更佳為10至40重量份。當使用該染料(B-1)時，該感光性樹脂組成物所形成之彩色濾光片具有更佳之耐UV黃變性。 In a specific example of the present invention, based on the used amount of the alkali-soluble resin (C) being 100 parts by weight, the used amount of the dye (B-1) is 3 to 50 parts by weight; preferably 5 to 45 parts by weight; More preferably, it is 10 to 40 parts by weight. When the dye (B-1) is used, the color filter formed by the photosensitive resin composition has better resistance to UV yellowing.
於本發明之較佳具體例中，染料(B)可進一步包含其它染料(B-2)。 In a preferred embodiment of the present invention, the dye (B) may further include other dyes (B-2).
較佳地，該其它染料(B-2)包含但不限於偶氮系染料、蒽醌系染料、酞菁系染料、醌亞胺系染料、喹啉系染料或硝基系染料。偶氮系染料包含但不限於C.I.酸性黃11、酸性橙7、酸性紅37、酸性紅180、酸性藍29、直接紅28、直接紅83、直接黃12、直接橙26、直接綠28、直接綠59、活性黃2、活性紅17、活性紅120、活性黑5、分散橙5、分散紅58、分散藍165、鹼性藍41、鹼性紅18、媒介紅7、媒介黃5、媒介黑7等；蒽醌系染料包含但不限於C.I.巴德藍4(Batblue 4)、酸性藍40、酸性綠25、活性藍19、活性藍49、分散紅60、分散藍56、分散藍60等；酞菁系染料包含但不限於C.I.鹼性藍5等；醌亞胺系染料包含但不限於C.I.鹼性藍3、鹼性藍9等；喹啉系染料C.I.溶劑黃33、酸性黃3、分散黃64等；硝基系染料包含但不限於 C.I.酸性黃1、酸性橙3、分散黃42等。上述其它染料一般可單獨或混合多種使用。 Preferably, the other dye (B-2) includes, but is not limited to, an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinimine dye, a quinoline dye, or a nitro dye. Azo dyes include but are not limited to CI Acid Yellow 11, Acid Orange 7, Acid Red 37, Acid Red 180, Acid Blue 29, Direct Red 28, Direct Red 83, Direct Yellow 12, Direct Orange 26, Direct Green 28, Direct Green 59, Reactive Yellow 2, Reactive Red 17, Reactive Red 120, Reactive Black 5, Disperse Orange 5, Disperse Red 58, Disperse Blue 165, Basic Blue 41, Basic Red 18, Medium Red 7, Medium Yellow 5, Medium Black 7 and others; anthraquinone-based dyes include but are not limited to CI Batblue 4, Acid Blue 40, Acid Green 25, Reactive Blue 19, Reactive Blue 49, Disperse Red 60, Disperse Blue 56, Disperse Blue 60, etc. ; Phthalocyanine dyes include, but are not limited to, CI Basic Blue 5, etc .; quinone imine dyes include, but are not limited to, CI Basic Blue 3, Basic Blue 9, etc .; quinoline dyes CI Solvent Yellow 33, Acid Yellow 3, Disperse Yellow 64, etc .; nitro dyes include but are not limited to C.I. Acid Yellow 1, Acid Orange 3, Disperse Yellow 42 and the like. The above-mentioned other dyes can be used singly or in combination.
於本發明之具體例中，基於該鹼可溶性樹脂(C)之使用量為100重量份，該其它染料(B-2)之使用量為0重量份至47重量份；較佳為0重量份至40重量份；更佳為0重量份至30重量份。 In a specific example of the present invention, based on the used amount of the alkali-soluble resin (C) is 100 parts by weight, the used amount of the other dye (B-2) is 0 to 47 parts by weight; preferably 0 parts by weight To 40 parts by weight; more preferably 0 to 30 parts by weight.
基於該鹼可溶性樹脂(C)之使用量為100重量份，該染料(B)之使用量為5重量份至50重量份；較佳為10重量份至45重量份；更佳為15重量份至40重量份。 Based on the use amount of the alkali-soluble resin (C) being 100 parts by weight, the use amount of the dye (B) is 5 parts by weight to 50 parts by weight; preferably 10 parts by weight to 45 parts by weight; more preferably 15 parts by weight To 40 parts by weight.
根據本發明之鹼可溶性樹脂(C)包含一第一鹼可溶性樹脂(C-1)，該第一鹼可溶性樹脂(C-1)係由一混合物進行聚合反應所製得，且該混合物包含一具有至少二個環氧基之環氧化合物(c-1-1)及一具有至少一個羧酸基及至少一個乙烯性不飽和基之化合物(c-1-2)。除此之外，上述混合物更可選擇性地包含羧酸酐化合物(c-1-3)及/或含環氧基的化合物(c-1-4)。 The alkali-soluble resin (C) according to the present invention includes a first alkali-soluble resin (C-1). The first alkali-soluble resin (C-1) is prepared by polymerizing a mixture, and the mixture includes a An epoxy compound (c-1-1) having at least two epoxy groups and a compound (c-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group. In addition, the mixture may further optionally include a carboxylic anhydride compound (c-1-3) and / or an epoxy group-containing compound (c-1-4).
該具有至少二個環氧基的環氧化合物(c-1-1)可具有如下式(III-1)或下式(III-2)所示之結構。在此處，「環氧化合物(c-1-1)可具有如下式(III-1)或下式(III-2)所示之結構」的敘述亦涵蓋了具有如下式(III-1)所示之結構的化合物及具有如下式(III-2)所示之結構的化合物同時存在而作為環氧化合物(c-1-1)的情形。具體而言，前述具有至少二個環氧基的環氧化合物(c-1-1)例如是具有如下式(III-1)所示之結構：
於式(III-1)中，R1c、R2c、R3c以及R4c分別為相同或不同，且表示氫原子、鹵素原子、碳數為1至5之烷基、碳數為1至5之烷氧基、碳數為6至12之芳香基或碳數為6至12之芳烷基。 In formula (III-1), R 1c , R 2c , R 3c and R 4c are the same or different, and represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and a carbon number of 1 to 5 An alkoxy group, an aromatic group having 6 to 12 carbons, or an aralkyl group having 6 to 12 carbons.
前述式(III-1)之具有至少二個環氧基的環氧化合物(c-1-1)可包括由雙酚芴型化合物(bisphenol fluorene)與鹵化環氧丙烷(epihalohydrin)反應而得之含環氧基之雙酚芴型化合物，但並不限於此。 The epoxy compound (c-1-1) of the aforementioned formula (III-1) having at least two epoxy groups may include a compound obtained by reacting a bisphenol fluorene compound with an epihalohydrin The epoxy-containing bisphenol amidine type compound is not limited thereto.
作為上述雙酚芴型化合物的具體例，可列舉但不限於：9,9-雙(4-羥基苯基)芴〔9,9-bis(4-hydroxy phenyl)fluorene〕、9,9-雙(4-羥基-3-甲基苯基)芴〔9,9-bis(4-hydroxy-3-methylphenyl)fluorene〕、9,9-雙(4-羥基-3-氯苯基)芴〔9,9-bis(4-hydroxy-3-chlorophenyl)fluorene〕、9,9-雙(4-羥基-3-溴苯基)芴〔9,9-bis(4-hydroxy-3-bromophenyl)fluorene〕、9,9-雙(4-羥基-3-氟苯基)芴〔9,9-bis(4-hydroxy-3-fluorophenyl)fluorene〕、9,9-雙(4-羥基-3-甲氧基苯基)芴〔9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene〕、9,9-雙(4-羥基-3,5-二甲基苯基)芴〔9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene〕、9,9-雙(4-羥基-3,5-二氯苯基)芴〔9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene〕、9,9-雙(4-羥基-3,5-二溴苯基)芴〔9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene〕等化合物。 Specific examples of the bisphenol fluorene type compound include, but are not limited to, 9,9-bis (4-hydroxyphenyl) fluorene [9,9-bis (4-hydroxyphenyl) fluorene], 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (9,9-bis (4-hydroxy-3-methylphenyl) fluorene), 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene (9 , 9-bis (4-hydroxy-3-chlorophenyl) fluorene], 9,9-bis (4-hydroxy-3-bromophenyl) fluorene [9,9-bis (4-hydroxy-3-bromophenyl) fluorene] , 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene [9,9-bis (4-hydroxy-3-fluorophenyl) fluorene], 9,9-bis (4-hydroxy-3-methoxy) Phenyl) fluorene [9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene], 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene [9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene], 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene (9,9-bis (4-hydroxy-3,5-dichlorophenyl) ) fluorene], 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene [9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene] and other compounds.
上述鹵化環氧丙烷(epihalohydrin)可包括但不限於3-氯-1,2-環氧丙烷(epichlorohydrin)或3-溴-1,2-環氧丙烷(epibromohydrin)等。 The above-mentioned halogenated propylene oxide (epihalohydrin) may include, but is not limited to, 3-chloro-1,2-epoxypropane (epichlorohydrin) or 3-bromo-1,2-epoxypropane (epibromohydrin) and the like.
上述由雙酚芴型化合物與鹵化環氧丙烷反應所得之含環氧基之雙酚芴型化合物包含但不限於：(1)新日鐵化學(Nippon Steel Chemical Co.,Ltd)所製造之商品：例如ESF-300等；(2)大阪瓦斯(Osaka Gas Co.,Ltd)所製造之商品：例如PG-100、EG-210等；(3)短信科技(S.M.S Technology Co.,Ltd)所製造之商品：例如SMS-F9PhPG、SMS-F9CrG、SMS-F914PG等。 The epoxy-containing bisphenol fluorene type compound obtained by reacting the bisphenol fluorene type compound with halogenated propylene oxide includes, but is not limited to: (1) products manufactured by Nippon Steel Chemical Co., Ltd. : For example ESF-300, etc .; (2) Goods made by Osaka Gas Co., Ltd: For example, PG-100, EG-210, etc .; (3) SMS Technology Co., Ltd): For example, SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, etc.
其次，該具有至少二個環氧基的環氧化合物(c-1-1)亦可具有如下式(III-2)所示之結構：
於式(III-2)中，R5c至R18c分別為相同或不同，且可各自獨立表示氫原子、鹵素原子、碳數為1至8之烷基或碳數為6至15之芳香基；及g表示0至10的整數。 In formula (III-2), R 5c to R 18c are respectively the same or different, and each may independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aromatic group having 6 to 15 carbon atoms ; And g represents an integer from 0 to 10.
前述式(III-2)之具有至少二個環氧基的環氧化合物(c-1-1)例如是藉由在鹼金屬氫氧化物存在下，使具有下式(III-2-1)結構之化合物與鹵化環氧丙烷進行反應而得。 The epoxy compound (c-1-1) having at least two epoxy groups in the aforementioned formula (III-2) has, for example, the following formula (III-2-1) in the presence of an alkali metal hydroxide The structured compound is obtained by reacting a halogenated propylene oxide.
在式(III-2-1)中，R5c至R18c以及g之定義係分別與式(III-2)中之R5c至R18c以及g之定義相同，在此不另贅述。 In the formula (III-2-1), R 5c 5c to R 18c and R 18c is defined the same as the g line and respectively to the formula R (III-2) in the definition of g's, which is not repeated herein.
再者，前述式(III-2)之具有至少二個環氧基的環氧化合物(c-1-1)例如是在酸觸媒存在下，使用具有下式(III-2-2)結構之化合物與酚(phenol)類進行縮合反應後，形成具有式(III-2-1)結構之化合物。接著，藉由加入過量的鹵化環氧丙烷進行脫鹵化氫反應(dehydrohalogenation)，而獲得如式(III-2)所示之具有至少二個環氧基的環氧化合物(c-1-1)。 The epoxy compound (c-1-1) having at least two epoxy groups in the formula (III-2) is, for example, a compound having the following formula (III-2-2) in the presence of an acid catalyst. The compound is subjected to a condensation reaction with phenols to form a compound having a structure of formula (III-2-1). Next, an excess of halogenated propylene oxide is added to perform a dehydrohalogenation reaction to obtain an epoxy compound (c-1-1) having at least two epoxy groups as shown in formula (III-2) .
在上式(III-2-2)中，R19c與R20c分別為相同或不同之氫原子、鹵素原子、碳數為1至8之烷基或碳數為6至15之芳香基；T1及T2分別為相同或不同之鹵素原子、碳數為1至6之烷基或碳數為1至6之烷氧基。較佳地，前述之鹵素原子可例如氯或溴，前述之烷基可例如甲基、乙基或第三丁基，前述之烷氧基可例如甲氧基或乙氧基。 In the above formula (III-2-2), R 19c and R 20c are respectively the same or different hydrogen atom, halogen atom, alkyl group having 1 to 8 carbons, or aromatic group having 6 to 15 carbons; T 1 and T 2 are respectively the same or different halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. Preferably, the aforementioned halogen atom may be, for example, chlorine or bromine, the aforementioned alkyl group may be, for example, methyl, ethyl, or third butyl, and the aforementioned alkoxy group may be, for example, methoxy or ethoxy.
作為上述酚類的具體例，可列舉但不限於如：酚(phenol)、甲酚(cresol)、乙酚(ethylphenol)、n-丙酚(n-propylphenol)、異丁酚(isobutylphenol)、t-丁酚(t-butylphenol)、辛酚(octylphenol)、壬基苯酚(nonylphenol)、茬酚(xylenol)、甲基丁基苯酚(methylbutylphenol)、二第三丁基酚(di-t-butylphenol)、乙烯苯酚(vinylphenol)、丙烯苯酚(propenylphenol)、乙炔苯酚(ethinylphenol)、環戊苯酚(cyclopentylphenol)、環己基酚(cyclohexylphenol)或環己基甲酚(cyclohexylcresol)等。上述酚類一般可單獨或混合多種使用。 Specific examples of the above phenols include, but are not limited to, phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t -T-butylphenol, octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol , Vinylphenol, propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol or cyclohexylcresol, etc. These phenols can be used singly or in combination.
基於上述具有式(III-2-2)結構之化合物的使用量為1莫耳，酚類的使用量為0.5莫耳至20莫耳，其中以2莫耳至15莫耳較佳。 Based on the above-mentioned compound having the formula (III-2-2), the usage amount is 1 mol, and the usage amount of phenols is 0.5 mol to 20 mol, with 2 mol to 15 mol being preferred.
作為上述酸觸媒的具體例，可列舉但不限於如：鹽酸、硫酸、對甲苯磺酸(p-toluenesulfonic acid)、草酸(oxalic acid)、三氟化硼(boron trifluoride)、無水氯化鋁(anhydrous aluminium chloride)、氯化鋅(zinc chloride)等，其中以對甲苯磺酸、硫酸或鹽酸較佳。上述酸觸媒可單獨或混合多種使用。 Specific examples of the acid catalyst include, but are not limited to, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, and anhydrous aluminum chloride. (anhydrous aluminium chloride), zinc chloride (zinc chloride), etc. Among them, p-toluenesulfonic acid, sulfuric acid, or hydrochloric acid is preferred. These acid catalysts can be used alone or in combination.
另外，上述酸觸媒之使用量雖無特別之限制，但基於上述具 有式(III-2-2)結構之化合物的使用量為100重量百分比(wt%)，酸觸媒的使用量較佳為0.1wt%至30wt%。 In addition, although the amount of the acid catalyst used is not particularly limited, The use amount of the compound having the formula (III-2-2) is 100% by weight (wt%), and the use amount of the acid catalyst is preferably 0.1% to 30% by weight.
上述縮合反應可在無溶劑或是在有機溶劑存在下進行。其次，上述有機溶劑的具體例可列舉但不限於如：甲苯(toluene)、二甲苯(xylene)或甲基異丁基酮(methyl isobutyl ketone)等。上述有機溶劑可單獨或混合多種使用。 The above-mentioned condensation reaction can be performed without a solvent or in the presence of an organic solvent. Secondly, specific examples of the organic solvents mentioned above include, but are not limited to, toluene, xylene, methyl isobutyl ketone, and the like. These organic solvents can be used alone or in combination.
基於具有式(III-2-2)結構之化合物及酚類的使用量總和為100wt%，上述有機溶劑的使用量為50wt%至300wt%，其中以100wt%至250wt%較佳。另外，上述縮合反應的操作溫度為40℃至180℃，且縮合反應的操作時間為1小時至8小時。 Based on the total amount of the compound and the phenols having the structure of the formula (III-2-2) being 100% by weight, the amount of the organic solvent used is 50% to 300% by weight, and 100% to 250% by weight is preferred. In addition, the operation temperature of the condensation reaction is 40 ° C to 180 ° C, and the operation time of the condensation reaction is 1 hour to 8 hours.
在完成上述縮合反應後，可進行中和處理或水洗處理。上述中和處理是將反應後的溶液之pH值調整為pH 3至pH 7，其中以pH 5至pH 7較佳。上述水洗處理可使用中和劑來進行，此中和劑為鹼性物質，且其具體例可列舉：氫氧化鈉(sodium hydroxide)、氫氧化鉀(potassium hydroxide)等鹼金屬氫氧化物；氫氧化鈣(calcium hydroxide)、氫氧化鎂(magnesium hydroxide)等鹼土類金屬氫氧化物；二伸乙三胺(diethylene triamine)、三伸乙四胺(triethylene tetramine)、苯胺(aniline)、苯二胺(phenylene diamine)等有機胺；以及氨(ammonia)、磷酸二氫鈉(sodium dihydrogen phosphate)等。上述水洗處理可採用習知方法進行，例如，在反應後的溶液中，加入含中和劑的水溶液，反覆進行萃取即可。經中和處理或水洗處理後，經減壓加熱處理，將未反應的酚類及溶劑予以餾除，並進行濃縮，即可獲得具有式(III-2-1)結構之化合物。 After the above condensation reaction is completed, a neutralization treatment or a water washing treatment may be performed. In the above neutralization treatment, the pH value of the solution after the reaction is adjusted to pH 3 to pH 7, and pH 5 to pH 7 is preferred. The above-mentioned water washing treatment can be performed using a neutralizing agent, and the neutralizing agent is an alkaline substance, and specific examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; hydrogen Alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; diethylene triamine, triethylene tetramine, aniline, and phenylenediamine (phenylene diamine) and other organic amines; and ammonia (ammonia), sodium dihydrogen phosphate (sodium dihydrogen phosphate), and so on. The above-mentioned water washing treatment can be performed by a conventional method. For example, an aqueous solution containing a neutralizing agent is added to the solution after the reaction, and extraction can be performed repeatedly. After the neutralization treatment or the water washing treatment, the unreacted phenols and the solvent are distilled off under reduced pressure and heat treatment, and then concentrated to obtain a compound having the structure of formula (III-2-1).
作為上述鹵化環氧丙烷的具體例，可例舉但不限於如：3-氯-1,2-環氧丙烷(3-chloro-1,2-epoxypropane)、3-溴-1,2-環氧丙烷 (3-bromo-1,2-epoxypropane)或上述任意組合。在進行上述脫鹵化氫反應之前，可預先添加或於反應過程中添加氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物。上述脫鹵化氫反應的操作溫度為20℃至120℃，其操作時間範圍為1小時至10小時。 Specific examples of the halogenated propylene oxide include, but are not limited to, 3-chloro-1,2-epoxypropane, 3-bromo-1,2-cyclo Propane (3-bromo-1,2-epoxypropane) or any combination thereof. Before carrying out the dehydrohalogenation reaction, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or during the reaction. The operation temperature of the above dehalogenation reaction is 20 ° C to 120 ° C, and the operation time range is 1 hour to 10 hours.
於本發明之具體例中，上述脫鹵化氫反應中所添加之鹼金屬氫氧化物亦可使用其水溶液。在此具體例中，將上述鹼金屬氫氧化物水溶液連續添加至脫鹵化氫反應系統內的同時，可於減壓或常壓下，連續蒸餾出水及鹵化環氧丙烷，藉此分離並除去水，同時可將鹵化環氧丙烷連續地回流至反應系統內。 In a specific example of the present invention, an aqueous solution of the alkali metal hydroxide added in the dehydrohalogenation reaction may be used. In this specific example, while the above-mentioned alkali metal hydroxide aqueous solution is continuously added to the dehydrohalogenation reaction system, water and halogenated propylene oxide can be continuously distilled under reduced or normal pressure, thereby separating and removing water. At the same time, the halogenated propylene oxide can be continuously refluxed into the reaction system.
上述脫鹵化氫反應進行前，亦可添加氯化四甲銨(tetramethyl ammonium chloride)、溴化四甲銨(tetramethyl ammonium bromide)、三甲基苄基氯化銨(trimethyl benzyl ammonium chloride)等的四級銨鹽作為觸媒，並在50℃至150℃下，反應1小時至5小時，再加入鹼金屬氫氧化物或其水溶液，於20℃至120℃的溫度下，使其反應1小時至10小時，以進行脫鹵化氫反應。 Before the above dehydrohalogenation reaction proceeds, tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethyl benzyl ammonium chloride, etc. may be added. Grade ammonium salt as a catalyst, and react at 50 ° C to 150 ° C for 1 hour to 5 hours, and then add an alkali metal hydroxide or an aqueous solution thereof, and react it at a temperature of 20 ° C to 120 ° C for 1 hour to 10 hours for dehydrohalogenation reaction.
基於上述具有式(III-2-1)結構之化合物中的羥基總當量為1當量，上述鹵化環氧丙烷的使用量可為1當量至20當量，其中以2當量至10當量較佳。基於上述具有式(III-2-1)結構之化合物中的羥基總當量為1當量，上述脫鹵化氫反應中添加的鹼金屬氫氧化物的使用量可為0.8當量至15當量，其中以0.9當量至11當量較佳。 Based on the total equivalents of the hydroxyl groups in the compound having the formula (III-2-1) is 1 equivalent, the amount of the halogenated propylene oxide used may be 1 to 20 equivalents, with 2 to 10 equivalents being preferred. Based on the total equivalents of the hydroxyl groups in the compound having the formula (III-2-1) is 1 equivalent, the amount of the alkali metal hydroxide added in the above-mentioned dehydrohalogenation reaction may be 0.8 equivalent to 15 equivalents, of which 0.9 Equivalents to 11 equivalents are preferred.
此外，為了使上述脫鹵化氫反應順利進行，除了可添加甲醇、乙醇等醇類之外，亦可添加二甲碸(dimethyl sulfone)、二甲亞碸(dimethyl sulfoxide)等非質子性(aprotic)的極性溶媒等來進行反應。在使用醇類的情況下，基於上述鹵化環氧丙烷的總量為100wt%，醇類的使用 量可為2wt%至20wt%，較佳為4wt%至15wt%。在使用非質子性的極性溶媒的例子中，基於鹵化環氧丙烷的總量為100wt%，非質子性的極性溶媒的使用量可為5wt%至100wt%，其中，以10wt%至90wt%較佳。 In addition, in order to make the dehydrohalogenation reaction proceed smoothly, in addition to alcohols such as methanol and ethanol, aprotic such as dimethyl sulfone and dimethyl sulfoxide may be added. Polar solvents and the like to carry out the reaction. In the case of alcohols, based on the total amount of the halogenated propylene oxide is 100% by weight, the use of alcohols The amount may be 2 wt% to 20 wt%, preferably 4 wt% to 15 wt%. In the case of using an aprotic polar solvent, based on the total amount of halogenated propylene oxide being 100 wt%, the amount of aprotic polar solvent used may be 5 wt% to 100 wt%, wherein 10 wt% to 90 wt% good.
在完成脫鹵化氫反應後，可選擇性地進行水洗處理。之後，利用加熱減壓的方式除去鹵化環氧丙烷、醇類及非質子性的極性溶媒等。上述加熱減壓例如是於溫度為110℃至250℃，且壓力為1.3kPa(10mmHg)以下的環境下進行。 After the dehydrohalogenation reaction is completed, a water washing treatment may be optionally performed. After that, halogenated propylene oxide, alcohols, aprotic polar solvents, and the like are removed by heating and decompression. The heating and decompression are performed, for example, in an environment having a temperature of 110 ° C to 250 ° C and a pressure of 1.3 kPa (10 mmHg) or less.
為了避免形成之環氧樹脂含有加水分解性鹵素，可將脫鹵化氫反應後的溶液加入甲苯、甲基異丁基酮(methyl isobutyl ketone)等溶劑，並加入氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物水溶液，再次進行脫鹵化氫反應。在脫鹵化氫反應中，基於上述具有式(III-2-1)結構之化合物中的羥基總當量為1當量，鹼金屬氫氧化物的使用量為0.01莫耳至0.3莫耳，其中，以0.05莫耳至0.2莫耳較佳。另外，上述脫鹵化氫反應的操作溫度範圍為50℃至120℃，且其操作時間範圍為0.5小時至2小時。 In order to avoid the formation of epoxy resins containing hydrolyzable halogens, the solution after the dehydrohalogenation reaction can be added to solvents such as toluene and methyl isobutyl ketone, and alkalis such as sodium hydroxide and potassium hydroxide can be added. The metal hydroxide aqueous solution is dehydrohalogenated again. In the dehydrohalogenation reaction, based on the total equivalents of the hydroxyl groups in the compound having the structure of the formula (III-2-1) above, the equivalent amount of the alkali metal hydroxide is 0.01 mol to 0.3 mol. It is preferably from 0.05 mol to 0.2 mol. In addition, the operation temperature range of the above-mentioned dehydrohalogenation reaction is from 50 ° C to 120 ° C, and the operation time range is from 0.5 hours to 2 hours.
在完成脫鹵化氫反應後，藉由過濾及水洗等步驟去除鹽類。此外，亦可利用加熱減壓的方式，將甲苯、甲基異丁基酮等溶劑予以餾除，而可獲得如式(III-2)所示之具有至少二個環氧基的環氧化合物(c-1-1)。上述式(III-2)之具有至少二個環氧基的環氧化合物(c-1-1)可包含但不限於如商品名為NC-3000、NC-3000H、NC-3000S及NC-3000P等日本化藥(Nippon Kayaku Co.Ltd.)所製造之商品。 After the dehydrohalogenation reaction is completed, the salts are removed by steps such as filtration and water washing. In addition, solvents such as toluene and methyl isobutyl ketone can be distilled off by heating and decompression to obtain an epoxy compound having at least two epoxy groups as shown in formula (III-2). (c-1-1). The epoxy compound (c-1-1) of the above formula (III-2) having at least two epoxy groups may include, but is not limited to, such as the trade names NC-3000, NC-3000H, NC-3000S, and NC-3000P And other products manufactured by Nippon Kayaku Co. Ltd.
前述具有至少一個羧酸基及至少一個乙烯性不飽和基的化合物(c-1-2)例如是選自於由以下(1)至(3)所組成之群組：(1)丙烯酸、甲基丙烯酸、2-甲基丙烯醯氧乙基丁二酸(2-methacryloyloxyethylbutanedioic acid)、2-甲基丙烯醯氧丁基丁二酸、2-甲基丙烯醯氧乙基己二酸、2-甲基 丙烯醯氧丁基己二酸、2-甲基丙烯醯氧乙基六氫鄰苯二甲酸、2-甲基丙烯醯氧乙基馬來酸、2-甲基丙烯醯氧丙基馬來酸、2-甲基丙烯醯氧丁基馬來酸、2-甲基丙烯醯氧丙基丁二酸、2-甲基丙烯醯氧丙基己二酸、2-甲基丙烯醯氧丙基四氫鄰苯二甲酸、2-甲基丙烯醯氧丙基鄰苯二甲酸、2-甲基丙烯醯氧丁基鄰苯二甲酸、或2-甲基丙烯醯氧丁基氫鄰苯二甲酸；(2)由含羥基之(甲基)丙烯酸酯與二元羧酸化合物反應而得之化合物，其中二元羧酸化合物包含但不限於己二酸、丁二酸、馬來酸、鄰苯二甲酸；(3)由含羥基之(甲基)丙烯酸酯與羧酸酐化合物反應而得之半酯化合物，其中含羥基之(甲基)丙烯酸酯包含但不限於2-羥基乙基丙烯酸酯〔(2-hydroxyethyl)acrylate〕、2-羥基乙基甲基丙烯酸酯〔(2-hydroxyethyl)methacrylate〕、2-羥基丙基丙烯酸酯〔(2-hydroxypropyl)acrylate〕、2-羥基丙基甲基丙烯酸酯〔(2-hydroxypropyl)methacrylate〕、4-羥基丁基丙烯酸酯〔(4-hydroxybutyl)acrylate〕、4-羥基丁基甲基丙烯酸酯[(4-hydroxybutyl)methacrylate〕、或季戊四醇三甲基丙烯酸酯等。另外，此處所述之羧酸酐化合物可與下述第一鹼可溶性樹脂(C-1)之混合物所含的羧酸酐化合物(c-1-3)相同，故於此不再贅述。 The compound (c-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is selected from the group consisting of (1) to (3), for example: (1) acrylic acid, Acrylic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methacryloyloxyethylbutanedioic acid methyl Acrylic acid oxybutyl adipic acid, 2-methacrylic acid oxyethyl hexahydrophthalic acid, 2-methacrylic acid oxyethyl maleic acid, 2-methacrylic acid oxypropyl maleic acid , 2-methacrylic acid oxobutyl maleic acid, 2-methacrylic acid oxopropyl succinic acid, 2-methacrylic acid oxypropyl adipic acid, 2-methacrylic acid oxypropyl tetracarboxylic acid Hydrophthalic acid, 2-methacrylic acid oxypropyl phthalic acid, 2-methacrylic acid oxybutyl phthalic acid, or 2-methacrylic acid oxybutyl phthalic acid; (2) A compound obtained by reacting a hydroxyl-containing (meth) acrylate with a dicarboxylic acid compound, wherein the dicarboxylic acid compound includes, but is not limited to, adipic acid, succinic acid, maleic acid, orthophthalic acid Formic acid; (3) a half-ester compound obtained by reacting a hydroxyl-containing (meth) acrylate with a carboxylic anhydride compound, wherein the hydroxyl-containing (meth) acrylate includes, but is not limited to, 2-hydroxyethyl acrylate [( 2-hydroxyethyl) acrylate], 2-hydroxyethyl methacrylate [(2-hydroxyethyl) methacrylate], 2-hydroxypropyl acrylate [(2-hydroxypropyl) acrylate], 2-hydroxypropylmethyl Acrylate [(2-hydroxypropyl) methacrylate], 4-hydroxybutyl acrylate [(4-hydroxybutyl) acrylate], 4-hydroxybutyl methacrylate [(4-hydroxybutyl) methacrylate], or pentaerythritol trimethacrylate Wait. In addition, the carboxylic acid anhydride compound described herein may be the same as the carboxylic acid anhydride compound (c-1-3) contained in the mixture of the first alkali-soluble resin (C-1) described below, and will not be repeated here.
上述第一鹼可溶性樹脂(C-1)之混合物更可選擇性地包含羧酸酐化合物(c-1-3)及/或含環氧基的化合物(c-1-4)。上述羧酸酐化合物(c-1-3)可選自由以下(1)至(2)所組成之群組：(1)丁二酸酐(butanedioic anhydride)、順丁烯二酸酐(maleic anhydride)、衣康酸酐(Itaconic anhydride)、鄰苯二甲酸酐(phthalic anhydride)、四氫鄰苯二甲酸酐(tetrahydrophthalic anhydride)、六氫鄰苯二甲酸酐(hexahydrophthalic anhydride)、甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、甲基橋亞甲基四氫鄰苯二甲酸酐(methyl endo-methylene tetrahydro phthalic anhydride)、氯茵酸酐(chlorendic anhydride)、戊二酸酐或偏三苯甲酸酐(1,3-dioxoisobenzofuran-5-carboxylic anhydride)等二元羧酸酐化合物；以及(2)二苯甲酮四甲酸二酐(benzophenone tetracarboxylic dianhydride，簡稱BTDA)、雙苯四甲酸二酐或雙苯醚四甲酸二酐等四元羧酸酐化合物。 The mixture of the first alkali-soluble resin (C-1) may further optionally include a carboxylic anhydride compound (c-1-3) and / or an epoxy group-containing compound (c-1-4). The above carboxylic anhydride compound (c-1-3) can be selected from the group consisting of (1) to (2): (1) butanedioic anhydride, maleic anhydride, clothing Itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride , Methyl hexahydrophthalic anhydride, methyl endo-methylene tetrahydro phthalic anhydride anhydride), chlorendic anhydride, glutaric anhydride or 1,3-dioxoisobenzofuran-5-carboxylic anhydride; and (2) benzophenone tetracarboxylic acid di Tetracarboxylic acid anhydride compounds such as benzophenone tetracarboxylic dianhydride (BTDA), diphenyltetracarboxylic dianhydride or bisphenyl ether tetracarboxylic dianhydride.
上述含環氧基的化合物(c-1-4)例如是選自甲基丙烯酸環氧丙酯、3,4-環氧基環己基甲基丙烯酸酯、含不飽和基的縮水甘油醚化合物、含環氧基的不飽和化合物或上述之任意組合所組成的群組。前述含不飽和基的縮水甘油醚化合物包含但不限於商品名Denacol EX-111、EX-121 Denacol、Denacol EX-141、Denacol EX-145、Denacol EX-146、Denacol EX-171、Denacol EX-192等的化合物(以上為長瀨化成工業株式會社之商品)。 The epoxy-group-containing compound (c-1-4) is, for example, selected from glycidyl methacrylate, 3,4-epoxy cyclohexyl methacrylate, unsaturated glycidyl ether-containing compound, A group of epoxy-containing unsaturated compounds or any combination thereof. The aforementioned unsaturated group-containing glycidyl ether compound includes, but is not limited to, trade names Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192 And other compounds (the above are commercial products of Nagase Chemical Industries, Ltd.).
前述第一鹼可溶性樹脂(C-1)可由式(III-1)之具有至少二個環氧基的環氧化合物(c-1-1)與具有至少一個羧酸基及至少一個乙烯性不飽和基的化合物(c-1-2)進行聚合反應，形成含羥基的反應產物，接著，再添加羧酸酐化合物(c-1-3)進行反應所製得。基於上述含羥基的反應產物的羥基總當量為1當量，羧酸酐化合物(c-1-3)所含有的酸酐基的當量較佳為0.4當量至1當量，更佳為0.75當量至1當量。當使用多個羧酸酐化合物(c-1-3)時，可於反應中依序添加或同時添加。當使用二元羧酸酐化合物及四元羧酸酐化合物作為羧酸酐化合物(c-1-3)時，二元羧酸酐化合物及四元羧酸酐化合物的莫耳比例較佳為1/99至90/10，更佳為5/95至80/20。另外，上述反應的操作溫度範圍例如是在50℃至130℃的範圍。 The first alkali-soluble resin (C-1) may be an epoxy compound (c-1-1) having at least two epoxy groups and at least one carboxylic acid group and at least one ethylenic compound having the formula (III-1). The saturated compound (c-1-2) is polymerized to form a reaction product containing a hydroxyl group, and then a carboxylic anhydride compound (c-1-3) is added and reacted. Based on the total hydroxyl equivalent of the hydroxyl-containing reaction product, the equivalent of the acid anhydride group contained in the carboxylic anhydride compound (c-1-3) is preferably from 0.4 to 1 equivalent, and more preferably from 0.75 to 1 equivalent. When a plurality of carboxylic anhydride compounds (c-1-3) are used, they can be added sequentially or simultaneously during the reaction. When the dicarboxylic acid anhydride compound and the tetracarboxylic acid anhydride compound are used as the carboxylic acid anhydride compound (c-1-3), the molar ratio of the dicarboxylic acid anhydride compound and the tetracarboxylic acid anhydride compound is preferably 1/99 to 90 / 10, more preferably 5/95 to 80/20. The operating temperature range of the reaction is, for example, a range of 50 ° C to 130 ° C.
前述第一鹼可溶性樹脂(C-1)可由式(III-2)之具有至少二個環氧基的環氧化合物(c-1-1)與具有至少一個羧酸基及至少一個乙烯性不飽 和基的化合物(c-1-2)進行反應，形成含羥基的反應產物，接著，再藉由添加羧酸酐化合物(c-1-3)及/或含環氧基的化合物(c-1-4)進行聚合反應所製得。基於式(III-2)之具有至少二個環氧基的環氧化合物(c-1-1)上的環氧基總當量為1當量，上述具有至少一個羧酸基及至少一個乙烯性不飽和基的化合物(c-1-2)的酸價當量較佳為0.8當量至1.5當量，更佳為0.9當量至1.1當量。基於上述含羥基的反應產物的羥基總量為100莫耳百分比(莫耳%)，羧酸酐化合物(c-1-3)的使用量較佳為10莫耳%至100莫耳%，更佳為20莫耳%至100莫耳%，特佳為30莫耳%至100莫耳%。 The first alkali-soluble resin (C-1) may be an epoxy compound (c-1-1) having at least two epoxy groups and at least one carboxylic acid group and at least one ethylenic compound having the formula (III-2). full Reacts with the compound (c-1-2) to form a hydroxyl-containing reaction product, and then adds a carboxylic anhydride compound (c-1-3) and / or an epoxy-containing compound (c-1) -4) Obtained by polymerization. Based on the formula (III-2), the epoxy compound on the epoxy compound (c-1-1) having at least two epoxy groups has a total equivalent weight of 1 equivalent, and the above has at least one carboxylic acid group and at least one ethylenic compound. The acid value equivalent of the saturated compound (c-1-2) is preferably 0.8 to 1.5 equivalents, and more preferably 0.9 to 1.1 equivalents. Based on the total hydroxyl groups of the above-mentioned hydroxyl-containing reaction product, 100 mole% (mol%), and the usage amount of the carboxylic anhydride compound (c-1-3) is preferably 10 mole% to 100 mole%, more preferably It is 20 mol% to 100 mol%, and particularly preferred is 30 mol% to 100 mol%.
在製備上述第一鹼可溶性樹脂(C-1)時，為了加速反應，通常會於反應溶液中添加鹼性化合物作為反應觸媒。上述反應觸媒可單獨或混合使用，且上述反應觸媒包含但不限於：三苯基膦(triphenyl phosphine)、三苯基銻(triphenyl stibine)、三乙胺(triethylamine)、三乙醇胺(triethanolamine)、氯化四甲基銨(tetramethyl ammonium chloride)、氯化苄基三乙基銨(benzyltriethyl ammonium chloride)等。基於上述具有至少二個環氧基的環氧化合物(c-1-1)與具有至少一個羧酸基及至少一個乙烯性不飽和基的化合物(c-1-2)的使用量總和為100重量份，反應觸媒的使用量較佳為0.01至10重量份，更佳為0.3至5重量份。 When the first alkali-soluble resin (C-1) is prepared, in order to accelerate the reaction, a basic compound is usually added to the reaction solution as a reaction catalyst. The above reaction catalysts can be used alone or in combination, and the above reaction catalysts include but are not limited to: triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine , Tetramethyl ammonium chloride, benzyltriethyl ammonium chloride, and the like. The total amount of the epoxy compound (c-1-1) having at least two epoxy groups and the compound (c-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100. The use amount of the reaction catalyst is preferably 0.01 to 10 parts by weight, and more preferably 0.3 to 5 parts by weight.
此外，為了控制聚合度，通常還會於反應溶液中添加聚合抑制劑(polymerization inhibitor)。上述聚合抑制劑可包含但不限於：甲氧基酚(methoxyphenol)、甲基氫醌(methylhydroquinone)、氫醌(hydroquinone)、2,6-二第三丁基對甲酚(2,6-di-t-butyl-p-cresol)或吩噻嗪(phenothiazine)等。一般而言，上述聚合抑制劑可單獨或混合多種使用。基於上述具有至少二個環氧基的環氧化合物(c-1-1)與具有至少一個羧酸基及至少一個乙烯性不飽和基的化合物(c-1-2)的使用量總和為100重量份， 聚合抑制劑的使用量較佳為0.01至10重量份，更佳為0.1至5重量份。 In addition, in order to control the degree of polymerization, a polymerization inhibitor is usually added to the reaction solution. The above polymerization inhibitor may include, but is not limited to: methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol (2,6-di -t-butyl-p-cresol) or phenothiazine. In general, the above-mentioned polymerization inhibitors can be used alone or in combination. The total amount of the epoxy compound (c-1-1) having at least two epoxy groups and the compound (c-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100. Parts by weight The amount of the polymerization inhibitor used is preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight.
在製備該第一鹼可溶性樹脂(C-1)時，必要時可使用聚合反應溶劑。作為上述聚合反應溶劑的具體例，可列舉如：乙醇、丙醇、異丙醇、丁醇、異丁醇、2-丁醇、己醇或乙二醇等醇類化合物；甲乙酮或環己酮等酮類化合物；甲苯或二甲苯等芳香族烴類化合物；賽珞素(cellosolve)或丁基賽珞素(butyl cellosolve)等賽珞素類化合物；卡必妥(carbitol)或丁基卡必妥(butyl carbitol)等卡必妥類化合物；丙二醇單甲醚(propylene glycol monomethyl ether)等丙二醇烷基醚類化合物；二丙二醇單甲醚〔di(propylene glycol)methyl ether〕等多丙二醇烷基醚〔poly(propylene glycol)alkyl ether〕類化合物；醋酸乙酯、醋酸丁酯、乙二醇***醋酸酯(ethylene glycol monoethyl ether acetate)或丙二醇甲醚醋酸酯(propylene glycol methyl ether acetate)等醋酸酯類化合物；乳酸乙酯(ethyl lactate)或乳酸丁酯(butyl lactate)等乳酸烷酯(alkyl lactate)類化合物；或二烷基二醇醚類；或3-乙氧基丙酸乙酯。上述聚合反應溶劑一般可單獨或混合多種使用。另外，上述第一鹼可溶性樹脂(C-1)的酸價較佳為50mgKOH/g至200mgKOH/g，更佳為60mgKOH/g至150mgKOH/g。 When preparing the first alkali-soluble resin (C-1), a polymerization reaction solvent may be used if necessary. Specific examples of the polymerization reaction solvent include alcohol compounds such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, or ethylene glycol; methyl ethyl ketone or cyclohexanone Other ketones; aromatic hydrocarbons such as toluene or xylene; cellosolve or butyl cellosolve; carbitol or butyl carbohydrate Carbitol compounds such as butyl carbitol; propylene glycol alkyl ether compounds such as propylene glycol monomethyl ether; polypropylene glycol alkyl ethers such as di (propylene glycol) methyl ether [Poly (propylene glycol) alkyl ether] compounds; acetates such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, or propylene glycol methyl ether acetate Compounds; alkyl lactate compounds such as ethyl lactate or butyl lactate; or dialkyl glycol ethers; or ethyl 3-ethoxypropionate. The above-mentioned polymerization reaction solvents can be used singly or in combination. The acid value of the first alkali-soluble resin (C-1) is preferably 50 mgKOH / g to 200 mgKOH / g, and more preferably 60 mgKOH / g to 150 mgKOH / g.
另外，上述第一鹼可溶性樹脂(C-1)藉由膠體滲透層析儀(Gel Permeation Chromatography,GPC)測定之聚苯乙烯換算的數目平均分子量一般為500至10,000，較佳為800至8,000，更佳為1,000至6,000。 In addition, the above-mentioned first alkali-soluble resin (C-1) has a polystyrene-equivalent number average molecular weight measured by a gel permeation chromatography (GPC) of generally 500 to 10,000, preferably 800 to 8,000, More preferably, it is 1,000 to 6,000.
於本發明之具體例中，基於該鹼可溶性樹脂(C)之使用量為100重量份，該第一鹼可溶性樹脂(C-1)之使用量為0至90重量份；較佳為10至80重量份；更佳為20至70重量份。當使用該第一鹼可溶性樹脂(C-1)時，該感光性樹脂組成物所形成之彩色濾光片具有更佳之耐UV黃變性。 In a specific example of the present invention, based on the used amount of the alkali-soluble resin (C) being 100 parts by weight, the used amount of the first alkali-soluble resin (C-1) is 0 to 90 parts by weight; preferably 10 to 80 parts by weight; more preferably 20 to 70 parts by weight. When the first alkali-soluble resin (C-1) is used, the color filter formed by the photosensitive resin composition has better resistance to UV yellowing.
根據本發明之鹼可溶性樹脂(C)可更包含第二鹼可溶性樹脂 (C-2)，其係由具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)以及其他可共聚合之乙烯性不飽和單體(c-2-2)共聚合後，與具有環氧基之乙烯性不飽和單體(c-2-3)反應而得。 The alkali-soluble resin (C) according to the present invention may further include a second alkali-soluble resin (C-2), which is composed of ethylenically unsaturated monomer (c-2-1) with one or more carboxylic acid or carboxylic anhydride and other copolymerizable ethylenically unsaturated monomer (c-2- 2) Obtained after copolymerization with an ethylenically unsaturated monomer (c-2-3) having an epoxy group.
在一實施例中，該第二鹼可溶性樹脂(C-2)係先將具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)與其他可共聚合之乙烯性不飽和單體(c-2-2)進行雙鍵共聚合反應，以形成一聚合物，其中此聚合物之側鏈具有羧酸基。然後，此聚合物之側鏈中的羧酸基與具有環氧基之乙烯性不飽和單體(c-2-3)進行加成反應，而製得第二鹼可溶性樹脂(C-2)。 In one embodiment, the second alkali-soluble resin (C-2) is an ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acid or carboxylic anhydride and other copolymerizable resins. The ethylenically unsaturated monomer (c-2-2) undergoes a double bond copolymerization reaction to form a polymer, wherein the side chain of the polymer has a carboxylic acid group. Then, the carboxylic acid group in the side chain of the polymer is subjected to an addition reaction with an ethylenically unsaturated monomer (c-2-3) having an epoxy group to obtain a second alkali-soluble resin (C-2) .
在另一實施例中，該第二鹼可溶性樹脂(C-2)係先將其他可共聚合之乙烯性不飽和單體(c-2-2)與具有環氧基之乙烯性不飽和單體(c-2-3)進行雙鍵共聚合反應，以形成一聚合物，其中此聚合物之側鏈具有環氧基。然後，此聚合物之側鏈中的環氧基與具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)進行加成反應，而製得該第二鹼可溶性樹脂(C-2)。 In another embodiment, the second alkali-soluble resin (C-2) is obtained by firstly copolymerizing other copolymerizable ethylenically unsaturated monomers (c-2-2) and ethylenically unsaturated monomers having epoxy groups. The body (c-2-3) undergoes a double bond copolymerization reaction to form a polymer, wherein the side chain of the polymer has an epoxy group. Then, the epoxy group in the side chain of the polymer is subjected to an addition reaction with an ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acids or carboxylic anhydrides to prepare the second base. Soluble resin (C-2).
在又一實施例中，該第二鹼可溶性樹脂(C-2)係先將其他可共聚合之乙烯性不飽和單體(c-2-2)與具有環氧基之乙烯性不飽和單體(c-2-3)進行雙鍵共聚合反應，以形成一聚合物，其中此聚合物之側鏈具有環氧基。然後，此聚合物之側鏈中的環氧基與具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)進行加成反應後，進一步與酸酐類化合物進行半酯化反應而製得該第二鹼可溶性樹脂(C-2)。 In yet another embodiment, the second alkali-soluble resin (C-2) is firstly other copolymerizable ethylenically unsaturated monomer (c-2-2) and an ethylenically unsaturated monomer having an epoxy group. The body (c-2-3) undergoes a double bond copolymerization reaction to form a polymer, wherein the side chain of the polymer has an epoxy group. Then, the epoxy group in the side chain of the polymer is subjected to addition reaction with an ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acid or carboxylic anhydride, and then further carried out with an acid anhydride compound. The second ester-soluble resin (C-2) was obtained by a half-esterification reaction.
前述之具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)，其中，該具有一個或一個以上羧酸之乙烯性不飽和單體可包含但不限於不飽和單羧酸化合物、不飽和多羧酸化合物、具有不飽和基及 一個羧酸基之多環化合物，或具有不飽和基及多個羧酸基之多環化合物。 The aforementioned ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acids or carboxylic anhydrides, wherein the ethylenically unsaturated monomer having one or more carboxylic acids may include but is not limited to Saturated monocarboxylic acid compounds, unsaturated polycarboxylic acid compounds, A polycyclic compound with one carboxylic acid group, or a polycyclic compound with unsaturated groups and multiple carboxylic acid groups.
前述不飽和單羧酸化合物可包含但不限於(甲基)丙烯酸、丁烯酸、α-氯丙烯酸、乙基丙烯酸、肉桂酸、2-(甲基)丙烯醯乙氧基丁二酸酯(2-(meth)acryloyloxy ethyl succinate monoester)、2-(甲基)丙烯醯乙氧基六氫化苯二甲酸酯、2-(甲基)丙烯醯乙氧基苯二甲酸酯或omega-羧酸基聚己內酯多元醇單丙烯酸酯等。該omega-羧酸基聚己內酯多元醇單丙烯酸酯可為東亞合成製造，型號為ARONIX M-5300之商品。 The aforementioned unsaturated monocarboxylic acid compound may include, but is not limited to, (meth) acrylic acid, butenoic acid, α -chloroacrylic acid, ethacrylic acid, cinnamic acid, 2- (meth) acrylic acid ethoxysuccinate ( 2- (meth) acryloyloxy ethyl succinate monoester), 2- (meth) acryl ethoxy hexahydrophthalate, 2- (meth) acryl ethoxy hexahydrophthalate, or omega-carboxyl Acid-based polycaprolactone polyol monoacrylate and the like. The omega-carboxylic acid polycaprolactone polyol monoacrylate can be manufactured by East Asia Synthetic, and the product is model ARONIX M-5300.
前述不飽和多羧酸化合物可包含但不限於馬來酸、富馬酸、甲基富馬酸、衣康酸或檸康酸等。 The aforementioned unsaturated polycarboxylic acid compound may include, but is not limited to, maleic acid, fumaric acid, methyl fumaric acid, itaconic acid, citraconic acid, and the like.
前述具有不飽和基及一個羧酸基之多環化合物可包含但不限於5-羧酸基雙環[2.2.1]庚-2-烯、5-羧酸基-5-甲基雙環[2.2.1]庚-2-烯、5-羧酸基-5-乙基雙環[2.2.1]庚-2-烯、5-羧酸基-6-甲基雙環[2.2.1]庚-2-烯或5-羧酸基-6-乙基雙環[2.2.1]庚-2-烯等。 The aforementioned polycyclic compound having an unsaturated group and one carboxylic acid group may include, but is not limited to, 5-carboxylic acid bicyclo [2.2.1] hept-2-ene, 5-carboxylic acid-5-methylbicyclo [2.2. 1] hept-2-ene, 5-carboxylic acid-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxylic acid-6-methylbicyclo [2.2.1] hept-2-ene Ene or 5-carboxylic acid-6-ethylbicyclo [2.2.1] hept-2-ene and the like.
前述具有不飽和基及多個羧酸基的多環化合物可例如5,6-二羧酸基二環[2.2.1]庚-2-烯等。 Examples of the polycyclic compound having an unsaturated group and a plurality of carboxylic acid groups include 5,6-dicarboxylic acid bicyclo [2.2.1] hept-2-ene and the like.
較佳地，前述具有一個或一個以上羧酸之乙烯性不飽和單體是選自於丙烯酸、甲基丙烯酸、2-甲基丙烯醯乙氧基丁二酸酯、2-甲基丙烯醯基乙氧基六氫化苯二甲酸酯，或上述化合物之任意組合。 Preferably, the aforementioned ethylenically unsaturated monomer having one or more carboxylic acids is selected from the group consisting of acrylic acid, methacrylic acid, 2-methacrylic acid, ethoxysuccinate, and 2-methacrylic acid. Ethoxyhexahydrophthalate, or any combination of the above.
前述具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)，其中，前述具有一個或一個以上羧酸酐之乙烯性不飽和單體可包含但不限於不飽和羧酸酐化合物或具有不飽和基與羧酸酐的多環化合物。 The aforementioned ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acid or carboxylic anhydride, wherein the aforementioned ethylenically unsaturated monomer having one or more carboxylic anhydride may include, but is not limited to, unsaturated A carboxylic anhydride compound or a polycyclic compound having an unsaturated group and a carboxylic anhydride.
前述不飽和羧酸酐化合物可包含但不限於馬來酸酐、富馬酸酐、甲基富馬酸酐、衣康酸酐或檸康酸酐等。前述具有不飽和基及羧酸酐 的多環化合物可包含但不限於5,6-二羧酸酐二環[2.2.1]庚-2-烯等。 The aforementioned unsaturated carboxylic anhydride compound may include, but is not limited to, maleic anhydride, fumaric anhydride, methyl fumaric anhydride, itaconic anhydride, citraconic anhydride, and the like. The aforementioned has an unsaturated group and a carboxylic anhydride The polycyclic compound may include, but is not limited to, 5,6-dicarboxylic anhydride bicyclo [2.2.1] hept-2-ene and the like.
較佳地，前述具有一個或一個以上羧酸酐之乙烯性不飽和單體為馬來酸酐。 Preferably, the aforementioned ethylenically unsaturated monomer having one or more carboxylic anhydrides is maleic anhydride.
上述之具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)可單獨一種或混合複數種使用。 The aforementioned ethylenically unsaturated monomers (c-2-1) having one or more carboxylic acids or carboxylic anhydrides may be used alone or in combination.
於本發明之具體例中，基於該第二鹼可溶性樹脂(C-2)之該具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)及該其他可共聚合之乙烯性不飽和單體(c-2-2)共聚合用單體之使用量為100重量份，該具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)之使用量為10至90重量份；較佳為15至85重量份；更佳為20至80重量份。 In a specific example of the present invention, based on the second alkali-soluble resin (C-2), the ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acid or carboxylic anhydride and the other The amount of the copolymerized ethylenically unsaturated monomer (c-2-2) is 100 parts by weight, and the ethylenically unsaturated monomer (c- 2-1) is used in an amount of 10 to 90 parts by weight; preferably 15 to 85 parts by weight; more preferably 20 to 80 parts by weight.
前述其他可共聚合之乙烯性不飽和單體(c-2-2)可包含但不限於(甲基)丙烯酸烷基酯、(甲基)丙烯酸脂環族酯、(甲基)丙烯酸芳基酯、不飽和二羧酸酯、(甲基)丙烯酸羥烷酯、具有(甲基)丙烯酸酯基的聚醚、苯乙烯化合物或上述化合物以外的不飽和化合物。 The aforementioned other copolymerizable ethylenically unsaturated monomer (c-2-2) may include, but is not limited to, alkyl (meth) acrylate, cycloaliphatic (meth) acrylate, and aryl (meth) acrylate Esters, unsaturated dicarboxylic acid esters, hydroxyalkyl (meth) acrylates, polyethers having a (meth) acrylate group, styrene compounds, or unsaturated compounds other than the above compounds.
上述之(甲基)丙烯酸烷基酯可包含但不限於(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁基酯或(甲基)丙烯酸第三丁基酯等。 The aforementioned alkyl (meth) acrylate may include, but is not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ( N-butyl methacrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, and the like.
上述之(甲基)丙烯酸脂環族酯可包含但不限於(甲基)丙烯酸環己酯、(甲基)丙烯酸-2-甲基環己酯、(甲基)丙烯酸雙環戊酯{或稱三環[5.2.1.02,6]癸-8-基(甲基)丙烯酸酯}、(甲基)丙烯酸二環戊氧基乙酯、(甲基)丙烯酸異冰片酯或(甲基)丙烯酸四氫呋喃酯等。 The aforementioned (meth) acrylic cycloaliphatic ester may include, but is not limited to, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and dicyclopentyl (meth) acrylate {or, Tricyclo [5.2.1.0 2,6 ] dec-8-yl (meth) acrylate}, dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate or (meth) acrylic acid Tetrahydrofuran ester.
上述(甲基)丙烯酸芳基酯可包含但不限於(甲基)丙烯酸苯基酯或甲基丙烯酸苯甲酯等。 The aryl (meth) acrylate may include, but is not limited to, phenyl (meth) acrylate, benzyl methacrylate, and the like.
前述不飽和二羧酸酯可包含但不限於馬來酸二乙酯、富馬酸二乙酯或衣康酸二乙酯等。 The aforementioned unsaturated dicarboxylic acid ester may include, but is not limited to, diethyl maleate, diethyl fumarate, diethyl itaconic acid, and the like.
前述(甲基)丙烯酸羥烷酯可包含但不限於(甲基)丙烯酸-2-羥基乙酯或(甲基)丙烯酸-2-羥基丙酯等。 The aforementioned hydroxyalkyl (meth) acrylate may include, but is not limited to, 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate, and the like.
前述具有(甲基)丙烯酸酯基的聚醚可包含但不限於聚乙二醇單(甲基)丙烯酸酯或聚丙二醇單(甲基)丙烯酸酯等。 The aforementioned polyether having a (meth) acrylate group may include, but is not limited to, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like.
前述苯乙烯系化合物可包含但不限於苯乙烯、α-甲基苯乙烯、間-甲基苯乙烯，對-甲基苯乙烯或對-甲氧基苯乙烯等。 The aforementioned styrene-based compound may include, but is not limited to, styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, or p-methoxystyrene, and the like.
上述化合物以外之不飽和化合物可包含但不限於丙烯腈、甲基丙烯腈、氯乙烯、偏二氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙烯乙酯、1,3-丁二烯、異戊二烯、2,3-二甲基1,3-丁二烯、N-丁二醯亞胺基-3-馬來醯亞胺苯甲酸酯、N-丁二醯亞胺基-4-馬來醯亞胺丁酸酯、N-丁二醯亞胺基-6-馬來醯亞胺己酸酯、N-丁二醯亞胺基-3-馬來醯亞胺丙酸酯、N-(9-吖啶基)馬來醯亞胺、N-辛基馬來醯亞胺(N-octylmaleimide)、N-環己基馬來醯亞胺(N-cyclohexylmaleimide)或N-苯基馬來醯亞胺(N-phenylmaleimide)等。 Unsaturated compounds other than the above compounds may include, but are not limited to, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl ethyl ester, 1,3-butadiene, Isoprene, 2,3-dimethyl 1,3-butadiene, N-butanediimino-3-maleimide benzoate, N-butadiene imino- 4-maleimide iminobutyrate, N-butanediimide imino-6-maleimide iminohexanoate, N-butamidine imino-3-maleimide propionate , N- (9-acridyl) maleimide, N-octylmaleimide, N-cyclohexylmaleimide, or N-phenyl Maleimide (N-phenylmaleimide) and the like.
前述其他可共聚合之乙烯性不飽和單體(c-2-2)可單獨一種或混合複數種使用。 The aforementioned other copolymerizable ethylenically unsaturated monomers (c-2-2) may be used alone or in combination.
較佳地，前述其他可共聚合之乙烯性不飽和單體(c-2-2)是選自於(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸第三丁基酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸雙環戊酯、甲基丙烯酸異冰片酯、(甲基)丙烯酸二環戊氧基乙酯、苯乙烯、對-甲氧基苯乙烯或上述化合物之任意組合。 Preferably, the aforementioned other copolymerizable ethylenically unsaturated monomer (c-2-2) is selected from methyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid 2- Hydroxyethyl ester, third butyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentyl (meth) acrylate, isobornyl methacrylate, dicyclopentyloxy (meth) acrylate Ethyl ester, styrene, p-methoxystyrene, or any combination thereof.
於本發明之具體例中，基於該第二鹼可溶性樹脂(C-2)之該 具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)及該其他可共聚合之乙烯性不飽和單體(c-2-2)共聚合用單體之使用量總和為100重量份，該其他可共聚合之乙烯性不飽和單體(c-2-2)之使用量為10至90重量份；較佳為15至85重量份；更佳為20至80重量份。 In a specific example of the present invention, based on the second alkali-soluble resin (C-2), the Ethylene unsaturated monomer (c-2-1) having one or more carboxylic acid or carboxylic anhydride and the other copolymerizable ethylenically unsaturated monomer (c-2-2) The total amount used is 100 parts by weight, and the other copolymerizable ethylenically unsaturated monomer (c-2-2) is used in an amount of 10 to 90 parts by weight; preferably 15 to 85 parts by weight; more preferably 20 To 80 parts by weight.
該具有環氧基之乙烯性不飽和單體(c-2-3)可包含但不限於具有環氧基的(甲基)丙烯酸酯化合物、具有環氧基的α-烷基丙烯酸酯化合物或環氧丙醚化合物等。 The ethylenically unsaturated monomer (c-2-3) having an epoxy group may include, but is not limited to, a (meth) acrylate compound having an epoxy group, an α -alkylacrylate compound having an epoxy group, or Glycidyl ether compounds and the like.
前述具有環氧基的(甲基)丙烯酸酯化合物可包含但不限於(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸2-甲基環氧丙酯、(甲基)丙烯酸3,4-環氧丁酯、(甲基)丙烯酸6,7-環氧庚酯、(甲基)丙烯酸3,4-環氧環己酯或(甲基)丙烯酸3,4-環氧環己基甲酯等。 The aforementioned (meth) acrylate compound having an epoxy group may include, but is not limited to, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and (meth) acrylic acid 3,4 -Butylene oxide, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate or 3,4-epoxycyclohexyl methyl (meth) acrylate Wait.
前述具有環氧基的α-烷基丙烯酸酯化合物可包含但不限於α-乙基丙烯酸環氧丙酯、α-正丙基丙烯酸環氧丙酯、α-正丁基丙烯酸環氧丙酯或α-乙基丙烯酸-6,7-環氧庚酯等。 The aforementioned α -alkyl acrylate compound having an epoxy group may include, but is not limited to, α -ethyl acrylate, α -n-propyl acrylate, α -n-butyl acrylate, or α -ethylacrylic acid-6,7-epoxyheptyl ester and the like.
前述環氧丙醚化合物可包含但不限於鄰-乙烯基苯甲基環氧丙醚(o-vinylbenzylglycidylether)、間-乙烯基苯甲基環氧丙醚(m-vinylbenzylglycidylether)或對-乙烯基苯甲基環氧丙醚(p-vinylbenzylglycidylether)等。 The foregoing glycidyl ether compound may include, but is not limited to, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, or p-vinylbenzene Methyl glycidyl ether (p-vinylbenzylglycidylether) and the like.
該具有環氧基之乙烯性不飽和單體(c-2-3)可單獨一種或混合複數種使用。 The ethylenically unsaturated monomer (c-2-3) having an epoxy group may be used alone or in combination.
較佳地，前述具有環氧基之乙烯性不飽和單體(c-2-3)是選自於甲基丙烯酸環氧丙酯、甲基丙烯酸2-甲基環氧丙酯、甲基丙烯酸3,4-環氧環己基甲酯、甲基丙烯酸6,7-環氧庚酯、鄰-乙烯基苯甲基環氧丙醚、間-乙烯基苯甲基環氧丙醚、對-乙烯基苯甲基環氧丙醚或上述化合物之任意組 合。 Preferably, the aforementioned ethylenically unsaturated monomer (c-2-3) having an epoxy group is selected from the group consisting of glycidyl methacrylate, 2-methylglycidyl methacrylate, and methacrylic acid 3,4-epoxycyclohexyl methyl ester, 6,7-epoxyheptyl methacrylate, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-ethylene Phenylbenzyl glycidyl ether or any group of the above compounds Together.
於製備第二鹼可溶性樹脂(C-2)時，可使用溶劑，溶劑可單獨或混合使用，且溶劑包含但不限於乙二醇甲醚、乙二醇***、二乙二醇甲醚、二乙二醇***、二乙二醇正丙醚、二乙二醇正丁醚、三乙二醇甲醚、三乙二醇***、丙二醇甲醚、丙二醇***、一縮二丙二醇甲醚、一縮二丙二醇***、一縮二丙二醇正丙醚、一縮二丙二醇正丁醚、二縮三丙二醇甲醚、二縮三丙二醇***等之(聚)亞烷基二醇單烷醚類；乙二醇甲醚醋酸酯、乙二醇***醋酸酯、丙二醇甲醚醋酸酯(propylene glycol methyl ether acetate，簡稱PGMEA)、丙二醇***醋酸酯等之(聚)亞烷基二醇單烷醚醋酸酯類；二乙二醇二甲醚、二乙二醇甲***、二乙二醇二***、四氫呋喃等之其他醚類；甲乙烷酮、環己酮、2-庚酮、3-庚酮等之酮類；2-羥基丙酸甲酯、2-羥基丙酸乙酯等之乳酸烷酯類；2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯(ethyl 3-ethoxypropionate，簡稱EEP)、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、乙酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-甲氧基丁酸乙酯等之其他酯類；甲苯、二甲苯等之芳香族碳氫化合物類；氮-甲基吡咯烷酮(NMP)、氮，氮-二甲基甲醯胺(DMF)、或氮，氮-二甲基乙醯胺(DMAC)等醯胺類等。較佳地，溶劑是選自丙二醇甲醚醋酸酯、3-乙氧基丙酸乙酯、或此等組合。(聚)亞烷基二醇單烷醚類是指亞烷基二醇單烷醚類或聚亞烷基二醇單烷醚類。(聚)亞烷基二醇單烷醚醋酸酯類是指亞烷基二醇單烷醚醋 酸酯類或聚亞烷基二醇單烷醚醋酸酯類。 When preparing the second alkali-soluble resin (C-2), a solvent may be used, and the solvents may be used alone or in combination. The solvent includes, but is not limited to, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, Glycol ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ether, propylene glycol methyl ether, propylene glycol ether, dipropylene glycol methyl ether, dipropylene glycol (Poly) alkylene glycol monoalkane ethers such as diethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ether, etc .; ethylene glycol methyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate, ethylene glycol ether acetate, propylene glycol methyl ether acetate (PGMEA), propylene glycol ether acetate, and the like; diethylene glycol Other ethers such as dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; 2 -Alkyl lactates such as methyl hydroxypropionate and ethyl 2-hydroxypropionate; methyl 2-hydroxy-2-methylpropionate , Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate Ethyl 3-ethoxypropionate (EEP), ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl Acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, acetic acid Isoamyl, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, ethyl酯 Methyl acetate, ethyl acetate, ethyl 2-methoxybutyrate and other esters; aromatic hydrocarbons such as toluene and xylene; nitrogen-methylpyrrolidone (NMP), nitrogen, N-dimethylformamide (DMF), or amines such as nitrogen, nitrogen-dimethylacetamide (DMAC), and the like. Preferably, the solvent is selected from propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, or a combination thereof. The (poly) alkylene glycol monoalkyl ethers refer to alkylene glycol monoalkyl ethers or polyalkylene glycol monoalkyl ethers. (Poly) alkylene glycol monoalkyl ether acetates refer to alkylene glycol monoalkyl ether vinegar Acid esters or polyalkylene glycol monoalkyl ether acetates.
第二鹼可溶性樹脂(C-2)製備時所使用之起始劑一般為自由基型聚合起始劑，具體例可包含但不限於：2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、2,2'-偶氮雙-2-甲基丁腈(2,2'-azobis-2-methyl butyronitrile，簡稱AMBN)等之偶氮(azo)化合物；異丙苯過氧化氫、二異丙基苯氫過氧化物、2-第三丁基過氧化物、過氧化月桂醯、過氧化苯甲醯、第三丁基過氧化異丙基碳酸酯、第三丁基過氧化-2-己酸乙酯等之過氧化合物。上述之自由基型聚合起始劑可單獨一種或混合複數種使用。同時，該自由基型聚合起始劑可與過度金屬鹽類或胺類一起併用。 The initiator used in the preparation of the second alkali-soluble resin (C-2) is generally a radical polymerization initiator, and specific examples may include, but are not limited to, 2,2'-azobisisobutyronitrile, 2, 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-couple Azo compounds such as 2,2'-azobis-2-methyl butyronitrile (AMBN); cumene hydrogen peroxide, diisopropylbenzene hydroperoxide , 2-third butyl peroxide, lauryl peroxide, benzamidine peroxide, third butyl peroxide isopropyl carbonate, third butyl peroxy-2-hexanoate, etc. Oxygen compound. The above-mentioned radical polymerization initiators can be used singly or in combination. At the same time, the radical polymerization initiator can be used in combination with a transition metal salt or an amine.
於本發明之具體例中，基於該第二鹼可溶性樹脂(C-2)之該具有一個或一個以上羧酸或羧酸酐之乙烯性不飽和單體(c-2-1)及該其他可共聚合之乙烯性不飽和單體(c-2-2)共聚合用單體之使用量總和為100重量份，該具有環氧基之乙烯性不飽和單體(c-2-3)之使用量範圍為1至35重量份；較佳為3至30重量份；更佳為5至25重量份。 In a specific example of the present invention, based on the second alkali-soluble resin (C-2), the ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acid or carboxylic anhydride and the other The total amount of the copolymerized ethylenically unsaturated monomer (c-2-2) used for the copolymerization monomer is 100 parts by weight, and the amount of the ethylenically unsaturated monomer (c-2-3) having an epoxy group is The amount used ranges from 1 to 35 parts by weight; preferably 3 to 30 parts by weight; more preferably 5 to 25 parts by weight.
另外，上述第二鹼可溶性樹脂(C-2)藉由膠體滲透層析儀(Gel Permeation Chromatography,GPC)測定之聚苯乙烯換算的數目平均分子量一般為1000至35,000，較佳為3,000至30,000，更佳為5,000至25,000。 In addition, the above-mentioned second alkali-soluble resin (C-2) has a polystyrene-equivalent number average molecular weight measured by a gel permeation chromatography (GPC) of generally 1,000 to 35,000, preferably 3,000 to 30,000, More preferably, it is 5,000 to 25,000.
於本發明之具體例中，基於該鹼可溶性樹脂(C)之使用量為100重量份，該第二鹼可溶性樹脂(C-2)之使用量為10至100重量份；較佳為20至90重量份；更佳為30至80重量份。 In a specific example of the present invention, based on the used amount of the alkali-soluble resin (C) being 100 parts by weight, the used amount of the second alkali-soluble resin (C-2) is 10 to 100 parts by weight; preferably 20 to 90 parts by weight; more preferably 30 to 80 parts by weight.
根據本發明之具有乙烯性不飽和基之化合物(D)可包含具有至少一個乙烯性不飽和基之不飽和化合物及具有至少二個乙烯性不飽和基 之不飽和化合物。 The compound (D) having an ethylenically unsaturated group according to the present invention may include an unsaturated compound having at least one ethylenically unsaturated group and at least two ethylenically unsaturated groups Of unsaturated compounds.
上述具有至少一個乙烯性不飽和基之不飽和化合物的具體例可包含但不限於丙烯醯胺、丙烯醯嗎啉、甲基丙烯醯嗎啉、丙烯酸-7-胺基-3,7-二甲基辛酯、甲基丙烯酸-7-胺基-3,7-二甲基辛酯、異丁氧基甲基丙烯醯胺、異丁氧基甲基甲基丙烯醯胺、丙烯酸異冰片基氧乙酯、甲基丙烯酸異冰片基氧乙酯、丙烯酸異冰片酯、甲基丙烯酸異冰片酯、丙烯酸-2-乙基己酯、甲基丙烯酸-2-乙基己酯、乙基二甘醇丙烯酸酯、乙基二甘醇甲基丙烯酸酯、第三辛基丙烯醯胺、第三辛基甲基丙烯醯胺、二丙酮丙烯醯胺、二丙酮甲基丙烯醯胺、丙烯酸二甲胺基酯、甲基丙烯酸二甲胺基酯、丙烯酸十二烷基酯、甲基丙烯酸十二烷基酯、丙烯酸二環戊烯氧乙酯、甲基丙烯酸二環戊烯氧乙酯、丙烯酸二環戊烯酯、甲基丙烯酸二環戊烯酯、氮，氮-二甲基丙烯醯胺、氮，氮-二甲基甲基丙烯醯胺、丙烯酸四氯苯酯、甲基丙烯酸四氯苯酯、丙烯酸-2-四氯苯氧基乙酯、甲基丙烯酸-2-四氯苯氧基乙酯、丙烯酸四氫糠酯、甲基丙烯酸四氫糠酯、丙烯酸四溴苯酯、甲基丙烯酸四溴苯酯、丙烯酸-2-四溴苯氧基乙酯、甲基丙烯酸-2-四溴苯氧基乙酯、丙烯酸-2-三氯苯氧基乙酯、甲基丙烯酸-2-三氯苯氧基乙酯、丙烯酸三溴苯酯、甲基丙烯酸三溴苯酯、丙烯酸-2-三溴苯氧基乙酯、甲基丙烯酸-2-三溴苯氧基乙酯、丙烯酸-2-羥乙酯、甲基丙烯酸-2-羥乙酯、丙烯酸-2-羥丙酯、甲基丙烯酸-2-羥丙酯、乙烯基己內醯胺、氮-乙烯基皮酪烷酮、丙烯酸苯氧基乙酯、甲基丙烯酸苯氧基乙酯、丙烯酸五氯苯酯、甲基丙烯酸五氯苯酯、丙烯酸五溴苯酯、甲基丙烯酸五溴苯酯、聚單丙烯酸乙二醇酯、聚單甲基丙烯酸乙二醇酯、聚單丙烯酸丙二醇酯、聚單甲基丙烯酸丙二醇酯、丙烯酸冰片酯，或甲基丙烯酸冰片酯等。其中，該具有至少一個乙烯性不飽和基之不飽和化合物可單獨一種使用或混合複數種使用。 Specific examples of the aforementioned unsaturated compound having at least one ethylenically unsaturated group may include, but are not limited to, acrylamide, acrylamidomorpholine, methacrylamidomorpholine, acrylic acid-7-amino-3,7-dimethyl Octyl ester, methacrylic acid 7-amino-3,7-dimethyloctyl ester, isobutoxymethacrylamide, isobutoxymethylmethacrylamide, isobornyl acrylate Ethyl ester, isobornyloxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, ethyldiethylene glycol Acrylate, Ethyl Diethylene Glycol Methacrylate, Third Octyl Acrylamidoxamine, Third Octyl Methacrylamidine, Diacetone Acrylamidine, Diacetone Methacrylamidine, Dimethyamine Acrylate Ester, dimethylamino methacrylate, dodecyl acrylate, dodecyl methacrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyl ethyl methacrylate, dicyclopentyl acrylate Pentenyl, dicyclopentenyl methacrylate, nitrogen, nitrogen-dimethylacrylamide, nitrogen, nitrogen-dimethylmethacryl Amine, tetrachlorophenyl acrylate, tetrachlorophenyl methacrylate, 2-tetrachlorophenoxyethyl acrylate, 2-tetrachlorophenoxyethyl methacrylate, tetrahydrofurfuryl acrylate, methyl Tetrahydrofurfuryl acrylate, tetrabromophenyl acrylate, tetrabromophenyl methacrylate, 2-tetrabromophenoxyethyl acrylate, 2-tetrabromophenoxyethyl methacrylate, 2-acrylate Trichlorophenoxyethyl, 2-trichlorophenoxyethyl methacrylate, tribromophenyl acrylate, tribromophenyl methacrylate, 2-tribromophenoxyethyl acrylate, methyl Tribromophenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, vinyl Caprolactam, nitrogen-vinyl butyrone, phenoxyethyl acrylate, phenoxyethyl methacrylate, pentachlorophenyl acrylate, pentachlorophenyl methacrylate, pentabromophenyl acrylate, Pentabromophenyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, acrylic acid Acid, bornyl, isobornyl acrylate or methacrylate and the like. The unsaturated compound having at least one ethylenically unsaturated group may be used alone or in combination.
上述具有至少二個乙烯性不飽和基之不飽和化合物的具體例可包含但不限於乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、二丙烯酸二環戊烯酯、二甲基丙烯酸二環戊烯酯、三甘醇二丙烯酸酯、四甘醇二丙烯酸酯、四甘醇二甲基丙烯酸酯、三(2-羥乙基)異氰酸酯二丙烯酸酯、三(2-羥乙基)異氰酸酯二甲基丙烯酸酯、三(2-羥乙基)異氰酸酯三丙烯酸酯、三(2-羥乙基)異氰酸酯三甲基丙烯酸酯、己內酯改質之三(2-羥乙基)異氰酸酯三丙烯酸酯、己內酯改質之三(2-羥乙基)異氰酸酯三甲基丙烯酸酯、三丙烯酸三羥甲基丙酯、三甲基丙烯酸三羥甲基丙酯、環氧乙烷(以下簡稱EO)改質之三丙烯酸三羥甲基丙酯、EO改質之三甲基丙烯酸三羥甲基丙酯、環氧丙烷(以下簡稱PO)改質之三丙烯酸三羥甲基丙酯、PO改質之三甲基丙烯酸三羥甲基丙酯、三甘醇二丙烯酸酯、三甘醇二甲基丙烯酸酯、新戊二醇二丙烯酸酯、新戊二醇二甲基丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、1,6-己二醇二丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、聚酯二丙烯酸酯、聚酯二甲基丙烯酸酯、聚乙二醇二丙烯酸酯、聚乙二醇二甲基丙烯酸酯、二季戊四醇六丙烯酸酯(dipentaerythritol hexaacrylate；DPHA)、二季戊四醇六甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇五甲基丙烯酸酯、二季戊四醇四丙烯酸酯、二季戊四醇四甲基丙烯酸酯、己內酯改質之二季戊四醇六丙烯酸酯、己內酯改質之二季戊四醇六甲基丙烯酸酯、己內酯改質之二季戊四醇五丙烯酸酯、己內酯改質之二季戊四醇五甲基丙烯酸酯、四丙烯酸二三羥甲基丙酯、四甲基丙烯酸二三羥甲基丙酯、EO改質之雙酚A二丙烯酸酯、EO改質之雙酚A二甲基丙烯酸酯、PO改質之雙酚A二丙烯酸酯、PO改質之雙酚A二甲基丙烯酸酯、EO改質之氫化雙酚A二丙烯酸酯、EO改質之氫化雙酚 A二甲基丙烯酸酯、PO改質之氫化雙酚A二丙烯酸酯、PO改質之氫化雙酚A二甲基丙烯酸酯、PO改質之甘油三丙酸酯、EO改質之雙酚F二丙烯酸酯、EO改質之雙酚F二甲基丙烯酸酯、酚醛聚縮水甘油醚丙烯酸酯、酚醛聚縮水甘油醚甲基丙烯酸酯、日本東亞合成株式會社製造且型號為TO-1382之商品，或者由日本化藥股份有限公司製造且其型號為KAYARAD DPCA-12、KAYARAD DPCA-20、KAYARAD DPCA-30、KAYARAD DPCA-60或KAYARAD DPCA-120之商品等。其中，該具有至少二個乙烯性不飽和基之不飽和化合物可單獨一種使用或混合複數種使用。 Specific examples of the aforementioned unsaturated compound having at least two ethylenically unsaturated groups may include, but are not limited to, ethylene glycol diacrylate, ethylene glycol dimethacrylate, dicyclopentenyl diacrylate, and dimethacrylic acid. Dicyclopentenyl ester, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tris (2-hydroxyethyl) isocyanate diacrylate, tris (2-hydroxyethyl) Isocyanate dimethacrylate, tris (2-hydroxyethyl) isocyanate triacrylate, tris (2-hydroxyethyl) isocyanate trimethacrylate, caprolactone modified tris (2-hydroxyethyl) isocyanate Triacrylate, caprolactone modified tris (2-hydroxyethyl) isocyanate trimethacrylate, trimethylol propyl triacrylate, trimethylol propyl trimethacrylate, ethylene oxide ( (Hereinafter referred to as EO) modified trimethylol propyl triacrylate, EO modified trimethylol propyl trimethacrylate, propylene oxide (hereinafter referred to as PO) modified trimethylol propyl triacrylate , PO modified trimethylol propyl trimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethyl Enoate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6- Hexanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, polyester diacrylate, Polyester dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate Ester, dipentaerythritol pentamethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, caprolactone modified dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexamethacrylate, Caprolactone modified pentaerythritol pentaacrylate, caprolactone modified pentaerythritol pentamethacrylate, ditrimethylol tetraacrylate, ditrimethyl methacrylate Methylpropyl ester, EO modified bisphenol A diacrylate, EO modified bisphenol A dimethacrylate, PO modified bisphenol A diacrylate, PO modified bisphenol A dimethyl Acrylate, EO modified hydrogenated bisphenol A diacrylate, EO modified hydrogenated bisphenol A dimethacrylate, PO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A dimethacrylate, PO modified glycerol tripropionate, EO modified bisphenol F Diacrylate, EO modified bisphenol F dimethacrylate, phenolic polyglycidyl ether acrylate, phenolic polyglycidyl ether methacrylate, a product manufactured by Japan Toa Synthesis Co., Ltd. and model number TO-1382, Or products manufactured by Nippon Kayaku Co., Ltd. and whose models are KAYARAD DPCA-12, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, or KAYARAD DPCA-120. The unsaturated compound having at least two ethylenically unsaturated groups may be used alone or in combination.
較佳地，該具有乙烯性不飽和基之化合物(D)是選自於三丙烯酸三羥甲基丙酯、EO改質之三丙烯酸三羥甲基丙酯、PO改質之三丙烯酸三羥甲基丙酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇四丙烯酸酯、己內酯改質之二季戊四醇六丙烯酸酯、四丙烯酸二三羥甲基丙酯、PO改質之甘油三丙酸酯、KAYARAD DPCA-12、KAYARAD DPCA-20、KAYARAD DPCA-30、KAYARAD DPCA-60或KAYARAD DPCA-120或上述化合物之任意組合。 Preferably, the compound (D) having an ethylenically unsaturated group is selected from the group consisting of trimethylolpropyl triacrylate, trimethylolpropyl triacrylate modified by EO, and trihydroxymethyltriacrylate modified by PO. Methylpropyl ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate, tetraacrylate ditrihydroxyol Methylpropyl ester, PO modified glycerol tripropionate, KAYARAD DPCA-12, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 or KAYARAD DPCA-120 or any combination of the above compounds.
上述具有乙烯性不飽和基之化合物(D)可單獨一種使用或混合複數種使用。 The compound (D) having an ethylenically unsaturated group may be used alone or in combination.
基於該鹼可溶性樹脂(C)之使用量為100重量份，該具有乙烯性不飽和基之化合物(D)之使用量為20至200重量份；較佳為30至180重量份；更佳為50至150重量份。 Based on the use amount of the alkali-soluble resin (C) being 100 parts by weight, the use amount of the compound (D) having an ethylenically unsaturated group is 20 to 200 parts by weight; preferably 30 to 180 parts by weight; more preferably 50 to 150 parts by weight.
該光起始劑(E)包含環戊二酮肟酯化合物(E-1)，且環戊二酮肟酯化合物(E-1)包含至少一種由式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)及式(E-1-5)所組成之群的環戊二酮肟酯化合物。 The photoinitiator (E) contains a cyclopentadione oxime ester compound (E-1), and the cyclopentadione oxime ester compound (E-1) contains at least one of formula (E-1-1), formula ( E-1-2), cyclopentadione oxime ester compounds of the group consisting of formula (E-1-3), formula (E-1-4) and formula (E-1-5).
系列1：由式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)及式(E-1-5)所示之環戊二酮肟酯化合物，其中Ar1為鄰亞芳基或鄰亞雜芳基，上述鄰亞芳基或上述鄰亞雜芳基是以相鄰的兩個原子與Y1和羰基相連構成並環結構，其餘原子上的取代基各自選自由氫原子；鹵素原子；C1-C12烷基；C5-C7環烷基；被C5-C7環烷基取代之C1-C4烷基；苯基；任意被一個或多個C1-C4烷基、羧基、C1-C12烷基醯基、C1-C12芳基醯基、雜芳基醯基、JT17、苯基、鹵素原子或CN取代之苯基；C1-C4烷基苄氧基；被T1C(O)O 取代之C1-C4烷氧基；C1-C3亞烷基二氧基；T1C(O)O；C1-C12烷基硫基；C1-C4烷基苯硫基；被T1C(O)O取代之C1-C4烷基硫基；CN；羧基；C1-C12烷氧基甲醯基；芳基醯基；雜芳基醯基及JT18所組成之群；或Ar1之上述取代基中相鄰的兩個取代基之間或者取代基與Ar1之間通過單鍵、碳原子、羰基相連構成環狀結構；其中，JT17及JT18中，J係選自由O、S及NT19所組成之群；Y1係選自由O、S、NT20、BT20、CT15T16、SiT15T16、S=O及C=O所組成之群； Ar2係選自由下列結構所組成之群：及，其中J係選自由O、S及NT19所組成之群；U1為單鍵、C1-C10直鏈亞烷基、C1-C10支鏈亞烷基；或U1為被一個或多個氧原子或硫原子連在端基的C2-C10直鏈亞烷基或C2-C10支鏈亞烷基；或U1為被一個或多個氧原子或硫原子***的C2-C10直鏈亞烷基或C2-C10支鏈亞烷基；或U1為無取代基的亞芳香基或有取代基的亞芳香基；Y2為單鍵、O、S、NT20、BT20、CT15T16、SiT15T16、C=O、或Y3-U2-Y3；U2為C1-C10直鏈亞烷基或C1-C10支鏈亞烷基；或U2為被一個或多個氧原子或硫原子連在端基的C2-C10直鏈亞烷基或被一個或多個氧原子或硫原子連在端基的C2-C10支鏈亞烷基； 或U2被一個或多個氧原子或硫原子***的C2-C10直鏈亞烷基或被一個或多個氧原子或硫原子***的C2-C10支鏈亞烷基；或U2為無取代基的亞芳香基或有取代基的亞芳香基；Y3為O、S、NT20、BT20或O-C(O)；T1為氫原子、C1-C18烷基、C1-C18烷氧基；或T1為任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基或芳醯氧基取代及/或被C5-C7環亞烷基、亞苯基、O、S或NT17***的C2-C18烷基；C2-C18烯基；任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基或芳醯氧基取代及/或被C5-C7環亞烷基、亞苯基、O、S或NT17***的C2-C18烯基，或上述兩者情況同時存在；或T1為C5-C7環烷基，或任意被一個或多個C1-C4烷基、苯基、鹵素原子、CN取代的C5-C7環烷基；或T1為苯基，或任意被一個或多個C1-C4烷基、C1-C4烷氧基、苯基、鹵素原子或CN取代的苯基；或T1為萘基、苯甲醯基、苯氧基羰基，其中苯甲醯基及苯氧基羰基的苯基任意被一個或兩個以上鹵素原子、T17、C5或C6環烷基、CN、OH或上述JT17所取代；T11及T12各自分別為氫原子、鹵素原子、C1-C12烷基、C5-C7環烷基，C5-C7環烷基取代的C1-C4烷基、C1-C12烷氧基；或T11及T12各自分別為苯基，或任意被一個或多個C1-C4烷基、羧基、C1-C12烷基醯基、C1-C12芳基醯基、雜芳基醯基、上述JT17、苯基、鹵素原子、CN取代的苯基； 或T11及T12各自分別為C1-C4烷基苄氧基；被一個或多個C1-C12烷氧基、C1-C4烷基苄氧基、T1C(O)O取代的C1-C4烷氧基；或T11及T12各自分別為T1C(O)O、CN、羧基、C1-C12烷氧基羰基、芳基羰基、雜芳基羰基、上述JT18；或T11及T12各自分別為被一個或多個C1-C4烷基取代的苯氧基；被一個C1-C8烷基醯基、C5-C6環烷基醯基、芳基醯基、雜芳基醯基取代的苯氧基；被C5-C6環烷基取代的C1-C4烷基醯基苯氧基；C1-C3亞烷基二氧基；C1-C12烷基硫基；被T1C(O)O取代的C1-C4烷基硫基；被T1C(O)O取代的C1-C4烷基苯硫基；被一個C1-C8烷基醯基、C5-C6環烷基醯基、芳基醯基、雜芳基醯基取代的苯硫基；或T11及T12各自分別為被C5-C6環烷基取代的C1-C4烷基醯基苯硫基；或T11及T12各自分別為環氧丙基，其中上述環氧基可任意地與C1-C4烷基醛、酮縮合；或上述T11及T12相連構成飽和或不飽和環狀結構；T15及T16各自分別為氫原子、C1-C18烷基、被羧基取代的C1-C5烷基、被C1-C4烷氧基醯基取代的C1-C5烷基、被T1C(O)O取代的C1-C4烷基；或T15及T16各自分別為任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基、芳醯氧基取代的C2-C18烷基，或是被C5-C7環亞烷基、亞苯基、O、S或NT17***的C2-C18烷基，或是上述兩種情況同時存在；或T15及T16各自分別為C5-C7環烷基，或任意被一個或多個C1-C4烷基、苯基、鹵素原子、CN取代的C5-C7環烷基； 或T15及T16各自分別為苯基，或任意被一個或多個C1-C4烷基、C1-C4烷氧基、羧基、C1-C12烷基醯基、C5-C6環烷基甲醯基、C5-C6環烷基取代的C2-C4烷基醯基、芳基醯基、上述JT17、苯基、鹵素原子或CN取代的苯基；或上述T15及T16與其共同所連的碳原子或矽原子一起構成環狀且成環之原子數為4至7；或上述T15及T16分別與相鄰的取代基一起構成環狀且成環之原子數為4至7；T17為C1-C4烷基；T18為氫原子、C1-C18烷基、被C1-C4烷氧基醯基取代的C1-C5烷基、被T1C(O)O取代的C1-C4烷基；或T18為任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基或芳醯氧基取代的C2-C18烷基，或是被C5-C7環亞烷基、亞苯基、O、S或NT17***的C2-C18烷基，或是上述兩種情況同時存在；或T18為C5-C7環烷基，或任意被一個或多個C1-C4烷基、苯基、鹵素原子或CN取代的C5-C7環烷基；或T18為苯基，或任意被一個或多個C1-C12烷基、羧基、C1-C12烷基醯基、被亞苯基、O、S或NT17***的C2-C12烷基醯基、C5-C6環烷基甲醯基、C5-C6環烷基取代的C2-C4烷基醯基、芳基醯基、雜芳基醯基、上述JT17、苯基、鹵素原子、CN或NO2取代的苯基，其中具體的芳基醯基有苯甲醯基、被一個或多個鹵素原子、C1-C4烷基、C1-C4烷氧基取代的苯甲醯基；或T18為C1-C4烷基醯基、C1-C4共軛烯醯基、苯甲醯基、苯氧基羰基，其中上述苯甲醯基及上述苯氧基羰基中的苯基可任意被一個或兩個以上鹵素 原子、上述T17、C5環烷基、C6環烷基、CN、OH或上述JT17取代；或T18通過單鍵、碳原子、羰基與Ar1或Ar2中的芳環相連構成新的環；T19及T20各自分別為氫原子、C1-C18烷基、被C1-C4烷氧基醯基取代的C1-C5烷基、被T1C(O)O取代的C1-C4烷基；或T19及T20各自分別為任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基或芳醯氧基取代的C2-C18烷基，被C5-C7環亞烷基、亞苯基、O、S或NT17***的C2-C18烷基，或是上述兩種情況同時存在；或T19及T20各自分別為C5-C7環烷基，或任意被一個或多個C1-C4烷基、苯基、鹵素原子或CN取代的C5-C7環烷基；或T19及T20各自分別為苯基，或任意被一個或多個C1-C4烷基、羧基、C1-C12烷基醯基、C5-C6環烷基甲醯基、C5-C6環烷基取代的C2-C4烷基醯基、芳基醯基、上述JT17、苯基、鹵素原子或CN取代的苯基；或T19分別透過單鍵、碳原子、羰基與Ar1或Ar2中的芳環相連構成新的環；其中當Ar1為取代咔唑基團時，Y1不是C、O、S、NT20。 Series 1: shown by formula (E-1-1), formula (E-1-2), formula (E-1-3), formula (E-1-4), and formula (E-1-5) Cyclopentadione oxime ester compound, wherein Ar 1 is an o-arylene or an o-arylene, and the above-mentioned o-arylene or the o-heteroarylene is connected to Y 1 and a carbonyl group by two adjacent atoms Constitute a ring structure, the substituents on the remaining atoms are each selected from the group consisting of a hydrogen atom; a halogen atom; a C 1 -C 12 alkyl group; a C 5 -C 7 cycloalkyl group; a C 1 substituted by a C 5 -C 7 cycloalkyl group -C 4 alkyl; phenyl; any one or more C 1 -C 4 alkyl, carboxyl, C 1 -C 12 alkylfluorenyl, C 1 -C 12 arylfluorenyl, heteroarylfluorenyl , JT 17, a phenyl group, a halogen atom or the phenyl group substituted with CN; C 1 -C 4 alkylbenzyl group; the substituted T 1 C (O) O C 1 -C 4 alkoxy; C 1 -C 3 alkylene dioxy; T 1 C (O) O; C 1 -C 12 alkylthio; C 1 -C 4 alkylphenylthio; C 1 -substituted by T 1 C (O) O C 4 alkylthio; CN; carboxyl; C 1 -C 12 alkoxymethylfluorenyl; arylfluorenyl; heteroarylfluorenyl and JT 18 ; or the middle phase of the above substituents of Ar 1 Between two adjacent substituents or between substituents and Ar 1 Bonds, carbon atoms, and carbonyl groups are connected to form a cyclic structure; of JT 17 and JT 18 , J is selected from the group consisting of O, S, and NT 19 ; Y 1 is selected from the group consisting of O, S, NT 20 , and BT 20 , CT 15 T 16 , SiT 15 T 16 , S = O and C = O; Ar 2 is selected from the group consisting of: and Where J is selected from the group consisting of O, S and NT 19 ; U 1 is a single bond, C 1 -C 10 straight chain alkylene, C 1 -C 10 branched alkylene; or U 1 is A C 2 -C 10 straight chain alkylene group or a C 2 -C 10 branched alkylene group with one or more oxygen or sulfur atoms attached to the end group; or U 1 is represented by one or more oxygen or sulfur atoms Inserted C 2 -C 10 straight chain alkylene or C 2 -C 10 branched alkylene; or U 1 is unsubstituted or substituted arylene; Y 2 is a single bond, O, S, NT 20 , BT 20 , CT 15 T 16 , SiT 15 T 16 , C = O, or Y 3 -U 2 -Y 3 ; U 2 is a C 1 -C 10 linear alkylene group or C 1 -C 10 branched alkylene group; or U 2 is a C 2 -C 10 straight chain alkylene group connected to one end by one or more oxygen atoms or sulfur atoms or connected by one or more oxygen atoms or sulfur atoms C 2 -C 10 branched alkylene groups at the end groups; or C 2 -C 10 straight chain alkylene groups with U 2 inserted by one or more oxygen or sulfur atoms or by one or more oxygen atoms or sulfur A C 2 -C 10 branched alkylene group with an atom inserted; or U 2 is an unsubstituted arylene group or a substituted arylene group; Y 3 is O, S, NT 20 , BT 20 Or OC (O); T 1 is a hydrogen atom, C 1 -C 18 alkyl, C 1 -C 18 alkoxy; or T 1 is optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkylfluorenyl or arylfluorenyloxy and / or substituted by C 5 -C 7 cycloalkylene , phenylene, O, S, or NT 17 inserted C 2 -C 18 alkyl; C 2 -C 18 alkenyl; optionally substituted with one or more halogen atoms, C 1 -C 4 alkyl, C 5 - C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkylfluorenyl or arylfluorenyloxy and / or substituted by C 5 -C 7 cycloalkylene, C 2 -C 18 alkenyl with phenyl, O, S or NT 17 inserted, or both; or T 1 is C 5 -C 7 cycloalkyl, or any one or more C 1- C 4 alkyl, phenyl, halogen atom, CN substituted C 5 -C 7 cycloalkyl; or T 1 is phenyl, or any one or more C 1 -C 4 alkyl, C 1 -C 4 An alkoxy group, a phenyl group, a halogen atom, or a CN-substituted phenyl group; or T 1 is a naphthyl group, a benzamyl group, or a phenoxycarbonyl group, in which the phenyl group of the benzamyl group and the phenoxycarbonyl group is optionally one or More than two halogens Element atom, T 17 , C 5 or C 6 cycloalkyl, CN, OH or the above JT 17 ; T 11 and T 12 are each a hydrogen atom, a halogen atom, a C 1 -C 12 alkyl group, or C 5- C 7 cycloalkyl, C 5 -C 7 cycloalkyl substituted C 1 -C 4 alkyl, C 1 -C 12 alkoxy; or T 11 and T 12 are each phenyl, or any one or Multiple C 1 -C 4 alkyl, carboxyl, C 1 -C 12 alkylfluorenyl, C 1 -C 12 arylfluorenyl, heteroarylfluorenyl, JT 17 above, phenyl, halogen atom, CN substitution Phenyl; or T 11 and T 12 are each C 1 -C 4 alkylbenzyloxy; each is substituted by one or more C 1 -C 12 alkoxy, C 1 -C 4 alkylbenzyloxy, T 1 C (O) O substituted C 1 -C 4 alkoxy; or T 11 and T 12 are each T 1 C (O) O, CN, carboxyl, C 1 -C 12 alkoxycarbonyl, aryl Carbonyl, heteroarylcarbonyl, JT 18 above; or T 11 and T 12 are each a phenoxy group substituted with one or more C 1 -C 4 alkyl groups; a C 1 -C 8 alkylfluorenyl group, C 5 -C 6 cycloalkylfluorenyl, arylfluorenyl, heteroarylfluorenyl substituted phenoxy; C 1 -C 4 alkylfluorenylphenoxy substituted with C 5 -C 6 cycloalkyl ; C 1 -C 3 alkylene Dioxy group; C 1 -C 12 alkylthio; is T 1 C (O) O-substituted C 1 -C 4 alkylthio; substituted with T 1 C (O) O C 1 -C 4 Alkylphenylthio; phenylthio substituted with one C 1 -C 8 alkylfluorenyl, C 5 -C 6 cycloalkylfluorenyl, arylfluorenyl, heteroarylfluorenyl; or T 11 and T 12 are each a C 1 -C 4 alkylfluorenylphenylthio group substituted with a C 5 -C 6 cycloalkyl group; or T 11 and T 12 are each an epoxy propyl group, wherein the epoxy group may be optionally Condensed with C 1 -C 4 alkyl aldehydes and ketones; or connected to the above T 11 and T 12 to form a saturated or unsaturated cyclic structure; T 15 and T 16 are each a hydrogen atom, a C 1 -C 18 alkyl group, carboxy-substituted C 1 -C 5 alkyl, substituted C 1 -C 4 alkoxy C 1 -C 5 acyl group, substituted T 1 C (O) O C 1 -C 4 alkyl; Or T 15 and T 16 are each optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1- C 4 alkylfluorenyloxy, arylfluorenyloxy substituted C 2 -C 18 alkyl, or C 2 inserted by C 5 -C 7 cycloalkylene, phenylene, O, S or NT 17 -C 18 alkyl, or both Conditions exist; or T 15 and T 16 each independently is C 5 -C 7 cycloalkyl, or optionally substituted with one or more C 1 -C 4 alkyl group, a phenyl group, a halogen atom, CN substituted C 5 -C 7 cycloalkyl; or T 15 and T 16 are each phenyl, or any one or more of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxyl, C 1 -C 12 alkyl Fluorenyl, C 5 -C 6 cycloalkylmethylfluorenyl, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkylfluorenyl, arylfluorenyl, JT 17 above, phenyl, halogen atom or CN-substituted phenyl; or the above-mentioned T 15 and T 16 together with the carbon or silicon atom to which they are connected form a ring and the number of ring-forming atoms is 4 to 7; or the above-mentioned T 15 and T 16 are respectively adjacent to The substituents together form a ring and the number of ring atoms is 4 to 7; T 17 is a C 1 -C 4 alkyl group; T 18 is a hydrogen atom, C 1 -C 18 alkyl group, and C 1 -C 4 alkoxy group substituted acyl group C 1 -C 5 alkyl, substituted with T 1 C (O) O C 1 -C 4 alkyl; T 18 with one or more halogen atoms or arbitrary, C 1 -C 4 alkoxy , C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkylfluorenyl or arylfluorenyl substituted C 2 -C 18 alkyl , Or a C 2 -C 18 alkyl group inserted by a C 5 -C 7 cycloalkylene group, a phenylene group, O, S, or NT 17 or both of the above; or T 18 is C 5- C 7 cycloalkyl, or any C 5 -C 7 cycloalkyl substituted with one or more C 1 -C 4 alkyl, phenyl, halogen atoms, or CN; or T 18 is phenyl, or any Or more C 1 -C 12 alkyl, carboxyl, C 1 -C 12 alkylfluorenyl, C 2 -C 12 alkylfluorenyl inserted by phenylene, O, S or NT 17 , C 5 -C 6 -cycloalkylformamyl, C 5 -C 6 -cycloalkyl substituted C 2 -C 4 alkylfluorenyl, arylfluorenyl, heteroarylfluorenyl, JT 17 described above, phenyl, halogen atom, CN Or NO 2 substituted phenyl, wherein specific arylfluorenyl groups are benzamidine, benzamidine substituted with one or more halogen atoms, C 1 -C 4 alkyl, C 1 -C 4 alkoxy Or T 18 is a C 1 -C 4 alkylfluorenyl group, a C 1 -C 4 conjugated alkenylfluorenyl group, a benzamidine group, a phenoxycarbonyl group, wherein the above benzamidine group and the above phenoxycarbonyl group Phenyl may be optionally substituted with one or more halogen atoms, the above-mentioned T 17 , C 5 cycloalkyl, C 6 cycloalkyl, CN, OH, or the above-mentioned JT 17 ; Or T 18 is connected to the aromatic ring in Ar 1 or Ar 2 through a single bond, carbon atom, carbonyl group to form a new ring; T 19 and T 20 are each a hydrogen atom, a C 1 -C 18 alkyl group, and a C 1- C 4 alkoxyfluorenyl substituted C 1 -C 5 alkyl, T 1 C (O) O substituted C 1 -C 4 alkyl; or T 19 and T 20 are each optionally substituted by one or more Halogen atom, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkoxy or aryloxy C 2 -C 18 alkyl, C 5 -C 7 cycloalkylene, phenylene, O, S, or NT 17 inserted C 2 -C 18 alkyl, or where both exist; or T 19 and T 20 each independently is C 5 -C 7 cycloalkyl, or optionally substituted with one or more C 1 -C 4 alkyl group, a phenyl group, a halogen atom or CN substituted C 5 -C 7 cycloalkyl; or T 19 and T 20 are each a phenyl group, or any one or more of C 1 -C 4 alkyl, carboxyl, C 1 -C 12 alkylfluorenyl, C 5 -C 6 cycloalkylmethylfluorenyl, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkyl acyl, aryl acyl, above JT 17, a phenyl group, a halogen atom or CN substituted phenyl; or T 19, respectively, through a single , A carbon atom, a carbonyl group or Ar 1 and Ar 2 are aromatic ring attached to form a new ring; wherein when Ar 1 is a substituted carbazolyl group, Y 1 is not a C, O, S, NT 20 .
系列2：由式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)及式(E-1-5)所示之環戊二酮肟酯化合物，其中Ar1為鄰亞芳基或鄰亞雜芳基，但不是由芳香環及雜環中的2個以上而形成稠環的鄰亞芳基或鄰亞雜芳基，上述鄰亞芳基或鄰亞雜芳基是以相鄰的兩個原子與Y1和羰基相連構成並環結構，其餘原子上的取代基各自為：氫原子；鹵素原子；C1-C12烷基；C5-C7環烷基；被C5-C7環烷基取代的C1-C4烷基；或是苯基；或任意被一個或多個C1-C4烷基、羧基、C1-C12烷基醯基或芳基醯基、雜芳基醯基、JT17、苯基、鹵素原子或CN取代的苯基；或是C1-C4烷基苄氧基；被T1C(O)O取代的C1-C4烷氧基；C1-C3亞烷基二氧基；T1C(O)O；C1-C12烷基硫基；C1-C4 烷基苯硫基；被T1C(O)O取代的C1-C4烷基硫基；CN；羧基；C1-C12烷氧基甲醯基；芳基醯基；雜芳基醯基及JT18。 Series 2: shown by formula (E-1-1), formula (E-1-2), formula (E-1-3), formula (E-1-4), and formula (E-1-5) Cyclopentadione oxime ester compound, wherein Ar 1 is an o-arylene or o-arylene, but it is not an o-arylene or o-arylene which is a fused ring formed by two or more of aromatic rings and heterocyclic rings. Aryl, the above-mentioned adjacent arylene or adjacent heteroarylene is a ring structure formed by connecting two adjacent atoms to Y 1 and a carbonyl group, and the substituents on the remaining atoms are each: hydrogen atom; halogen atom; C 1 -C 12 alkyl; C 5 -C 7 cycloalkyl; C 1 -C 4 alkyl substituted with C 5 -C 7 cycloalkyl; or phenyl; or any one or more C 1 -C 4- alkyl, carboxyl, C 1 -C 12 alkylfluorenyl or arylfluorenyl, heteroarylfluorenyl, JT 17 , phenyl, halogen atom or CN-substituted phenyl; or C 1 -C 4 alkyl Benzyloxy; C 1 -C 4 alkoxy substituted with T 1 C (O) O; C 1 -C 3 alkylene dioxy; T 1 C (O) O; C 1 -C 12 alkane thio group; C 1 -C 4 alkyl group; a T 1 C (O) O-substituted C 1 -C 4 alkylthio; the CN; a carboxyl group; C 1 -C 12 acyl alkoxysilyl ; Arylfluorenyl; heteroarylfluorenyl and JT 18 .
此外，當鄰亞芳基或者鄰亞雜芳基是單環結構時，其中相鄰的兩個取代基可以相連構成環狀結構，但不是稠環結構；當鄰亞芳基或者鄰亞雜芳基是兩個環以上的非稠環結構時，其中相鄰的兩個取代基可以相連構成環狀結構。 In addition, when the adjacent arylene or adjacent heteroarylene is a monocyclic structure, two adjacent substituents may be connected to form a cyclic structure, but not a fused ring structure; when the adjacent arylene or adjacent heteroarylene is When the group is a non-fused ring structure having more than two rings, two adjacent substituents may be connected to form a cyclic structure.
且，式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)、式(E-1-5)等結構式中其他基團定義同系列1中相應化合物的基團定義。 In addition, in the structural formulas such as formula (E-1-1), formula (E-1-2), formula (E-1-3), formula (E-1-4), formula (E-1-5), etc. Other group definitions are the same as those of the corresponding compounds in Series 1.
系列3：由式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)及式(E-1-5)所示之環戊二酮肟酯化合物，其中Ar1為以下鄰亞芳基或鄰亞雜芳基：
且，式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)、式(E-1-5)等結構式中其他基團定義同系列2中相應化合物的基團定義。 In addition, in the structural formulas such as formula (E-1-1), formula (E-1-2), formula (E-1-3), formula (E-1-4), formula (E-1-5), etc. The definition of other groups is the same as that of the corresponding compound in Series 2.
系列4：由式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)、 式(E-1-5)所示之環戊二酮肟酯化合物，其中Ar1為T11、T12、T13及T14各自為氫原子；或T11、T12、T13及T14各自為被一個或多個C1-C12烷氧基、C1-C4烷基苄氧基取代的C1-C4烷氧基、T1C(O)O取代的C1-C4烷氧基；或T11、T12、T13及T14各自為被一個或多個C1-C4烷基取代的苯氧基；被一個C1-C8烷基醯基、C5-C6環烷基醯基、芳基醯基、雜芳基醯基取代的苯氧基；C5-C6環烷基取代的C1-C4烷基醯基苯氧基；C1-C3亞烷基二氧基；T1C(O)O；C1-C12烷基硫基；T1C(O)O取代的C1-C4烷基硫基；C1-C4烷基苯硫基；T1C(O)O取代的C1-C4烷基苯硫基；或T11、T12、T13及T14各自為被一個C1-C8烷基醯基、C5-C6環烷基醯基、芳基醯基、雜芳基醯基取代的苯硫基，或C5-C6環烷基取代的C1-C4烷基醯基苯硫基；Y1為CH2、CHCH3或C(CH3)2； Ar2為或U1為單鍵或1,3-亞苯基； T1為甲基、乙基、苯基、2-甲基苯基、3-甲基苯基、2,4,6-三甲基苯基或2,6-二甲氧基苯基；T20為C1-C8烷基。 Series 4: shown by formula (E-1-1), formula (E-1-2), formula (E-1-3), formula (E-1-4), formula (E-1-5) Cyclopentanedione oxime ester compound, wherein Ar 1 is T 11 , T 12 , T 13, and T 14 are each a hydrogen atom; or T 11 , T 12 , T 13, and T 14 are each one by one or more C 1 -C 12 alkoxy, C 1 -C 4 alkane Benzyloxy-substituted C 1 -C 4 alkoxy, T 1 C (O) O substituted C 1 -C 4 alkoxy; or T 11 , T 12 , T 13 and T 14 are each substituted by one or Multiple C 1 -C 4 alkyl substituted phenoxy groups; substituted with one C 1 -C 8 alkylfluorenyl, C 5 -C 6 cycloalkylfluorenyl, arylfluorenyl, heteroarylfluorenyl Phenoxy; C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkylfluorenylphenoxy; C 1 -C 3 alkylenedioxy; T 1 C (O) O; C 1- C 12 alkylthio; T 1 C (O) O substituted C 1 -C 4 alkylthio; C 1 -C 4 alkylphenylthio; T 1 C (O) O substituted C 1 -C 4 alkylphenylthio; or T 11 , T 12 , T 13 and T 14 are each a C 1 -C 8 alkylfluorenyl, C 5 -C 6 cycloalkylfluorenyl, arylfluorenyl, hetero Arylsulfanyl substituted phenylthio, or C 5 -C 6 cycloalkyl substituted C 1- C 4 alkylfluorenylphenylthio; Y 1 is CH 2 , CHCH 3 or C (CH 3 ) 2 ; Ar 2 is or U 1 is a single bond or 1,3-phenylene; T 1 is methyl, ethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 2,4,6-trimethylbenzene Or 2,6-dimethoxyphenyl; T 20 is C 1 -C 8 alkyl.
且，上述式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)、式(E-1-5)等結構式中其他基團定義同系列3中相應化合物的基團定義。 In addition, the structural formulas such as the formula (E-1-1), the formula (E-1-2), the formula (E-1-3), the formula (E-1-4), and the formula (E-1-5) The definition of other groups in the same group as the corresponding compounds in Series 3.
系列5：由式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)、式(E-1-5)所示之環戊二酮肟酯化合物，其中Ar1的取代基中，其中至少一個取代基處於與Ar1相連羰基的對位；於Ar2中，O原子或N原子處於與苯環相連的羰基的對位。且，上述式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)、式(E-1-5)等結構式中其他基團定義同系列4中相應化合物的基團定義。 Series 5: shown by formula (E-1-1), formula (E-1-2), formula (E-1-3), formula (E-1-4), formula (E-1-5) the oxime ester compound cyclopentadione, wherein the substituents Ar 1, wherein at least one substituent in the para position with Ar 1 attached to the carbonyl group; in Ar 2, O atom or N atom in the carbonyl group attached to the benzene ring Alignment. In addition, the structural formulas such as the formula (E-1-1), the formula (E-1-2), the formula (E-1-3), the formula (E-1-4), and the formula (E-1-5) The definition of other groups in the same group as the corresponding compounds in Series 4.
系列6：由式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)、式(E-1-5)所示之環戊二酮肟酯化合物，其中Ar1為鄰亞芳基或鄰亞雜芳基，鄰亞芳基或鄰亞雜芳基以相鄰的兩個原子與Y1和羰基相連構成並環結構，其餘原子上的取代基各自為氫原子；鹵素原子；C1-C12烷基；C5-C7環烷基；C5-C7環烷基取代的C1-C4烷基；或是苯基；或任意被一個或多個C1-C4烷基、羧基、C1-C12烷基醯基或芳基醯基、JT17、苯基、鹵素原子、CN取代的苯基；C1-C4烷基苄氧基；T1C(O)O取代的C1-C4烷氧基；C1-C3亞烷基二氧基；T1C(O)O；C1-C12烷基硫基；C1-C4烷基苯硫基；T1C(O)O取代的C1-C4烷基硫基；CN；羧基；C1-C12烷氧基羰基；芳基羰基；雜芳基羰基；JT18；或上述相鄰的兩個取代基之間或取代基與Ar1之間可以通過單鍵、碳原子、羰基可以相連構成環狀結構；J為O、S或NT19；Y1為CT15T16。且，上述式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)、式(E-1-5)等結構式中其他基團定義同系列1中相應化合物的基團定義。 Series 6: shown by formula (E-1-1), formula (E-1-2), formula (E-1-3), formula (E-1-4), formula (E-1-5) Cyclopentanedione oxime ester compound, wherein Ar 1 is an o-arylene or o-arylene, and an o-arylene or o-arylene is connected to Y 1 and a carbonyl group by two adjacent atoms to form a ring Structure, the substituents on the remaining atoms are each a hydrogen atom; a halogen atom; C 1 -C 12 alkyl; C 5 -C 7 cycloalkyl; C 5 -C 7 cycloalkyl substituted C 1 -C 4 alkyl ; Or phenyl; or any substituted with one or more C 1 -C 4 alkyl, carboxyl, C 1 -C 12 alkylfluorenyl or arylfluorenyl, JT 17 , phenyl, halogen atom, CN Phenyl; C 1 -C 4 alkylbenzyloxy; T 1 C (O) O substituted C 1 -C 4 alkoxy; C 1 -C 3 alkylene dioxy; T 1 C (O) O; C 1 -C 12 alkylthio; C 1 -C 4 alkylphenylthio; T 1 C (O) O substituted C 1 -C 4 alkylthio; CN; carboxyl; C 1 -C 12 Alkoxycarbonyl; arylcarbonyl; heteroarylcarbonyl; JT 18 ; or between the two adjacent substituents or between the substituents and Ar 1 can be connected to form a ring through a single bond, a carbon atom, or a carbonyl group structure; J is O, S or NT 19; Y 1 CT 15 T 16. In addition, the structural formulas such as the formula (E-1-1), the formula (E-1-2), the formula (E-1-3), the formula (E-1-4), and the formula (E-1-5) The definition of other groups in the same group as the corresponding compounds in Series 1.
系列7：由式(E-1-1)所示之環戊二酮肟酯化合物，其中Ar1 為鄰亞芳基或鄰亞雜芳基，鄰亞芳基或鄰亞雜芳基以相鄰的兩個原子與Y1和羰基相連構成並環結構，其餘原子上的取代基各自為氫原子、C1-C12烷基、C5-C7環烷基、C5-C7環烷基取代的C1-C4烷基、JT18，或上述相鄰的兩個取代基之間或取代基與Ar1之間可以通過單鍵、碳原子、羰基相連構成環狀結構；但Ar1不是取代咔唑基團；J為O、S或NT19；Y1為O、S、CT15T16或C=O；T1為氫原子、C1-C18烷基或烷氧基、C2-C18烯基；或T1為任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基、芳醯氧基取代及/或被C5-C7環亞烷基、亞苯基、O、S、NT17***的C2-C18烷基，或是上述兩種情況同時存在；或T1為C2-C18烯基；任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基、芳醯氧基取代及/或被C5-C7環亞烷基、亞苯基、O、S、NT17***的C2-C18烯基，或是上述兩種情況同時存在；或T1為C5-C7環烷基，或任意被一個或多個C1-C4烷基、苯基、鹵素原子、CN取代的C5-C7環烷基；或T1為苯基，或任意被一個或多個C1-C4烷基、C1-C4烷氧基、苯基、鹵素原子、CN取代的苯基；或T1為萘基或苯甲醯基、苯氧基羰基，其中苯甲醯基或苯氧基羰基的苯基任意被一個或兩個以上鹵素原子、T17、C5環烷基、C6環烷基、CN、OH、JT17取代；T15、T16分別為氫原子、C1-C18烷基； 或T15、T16為任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基、芳醯氧基取代的C2-C18烷基，被C5-C7環亞烷基、亞苯基、O、S、NT17***的C2-C18烷基；或是上述兩種情況同時存在；或T15、T16為C5-C7環烷基；或T15、T16為分別為苯基，或任意被一個或多個C1-C4烷基、C1-C4烷氧基、苯基、鹵素原子、CN取代的苯基；或T15、T16與其共同所連的碳原子一起構成環狀且成環之原子數為4至7；T17為C1-C4烷基；T18為苯基，或任意被一個或多個C1-C12烷基、C1-C12烷基醯基、被亞苯基、O、S、NT17***的C2-C12烷基醯基、C5-C6環烷基甲醯基、C5-C6環烷基取代的C2-C4烷基醯基、芳基醯基、雜芳基醯基、上述JT17或NO2取代的苯基；其中具體的芳基醯基為未被取代的苯甲醯基、被一個或多個鹵素原子、C1-C8烷基、C1-C8烷氧基取代的苯甲醯基；或上述T18通過單鍵、碳原子、羰基與Ar1中的芳環相連構成新的環；T19為氫原子、C1-C18烷基、C1-C4烷氧基醯基取代的C1-C5烷基、T1C(O)O取代的C1-C4烷基；或T19為任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基、芳醯氧基取代的C2-C18烷基，或是被C5-C7環亞烷基、亞苯基、O、S、NT17***的C2-C18烷基；或T19為C5-C7環烷基，或是任意被一個或多個C1-C4烷基、苯基、鹵素原子、CN取代的C5-C7環烷基；或T19為苯基，或任意被一個或多個C1-C4烷基、羧基、C1-C12烷基醯基、C5-C6環烷基甲醯基、C5-C6環烷基取代的C2-C4烷基醯基、芳基醯基、上述 JT17、苯基、鹵素原子或CN取代的苯基；或上述T19分別通過單鍵、碳原子、羰基與Ar1中的芳環相連構成新的環。 Series 7: a cyclopentadione oxime ester compound represented by formula (E-1-1), wherein Ar 1 is an o-arylene or o-arylene, and the o-arylene or o-arylene is phase Two adjacent atoms are connected to Y 1 and a carbonyl group to form a ring structure. The substituents on the remaining atoms are each a hydrogen atom, a C 1 -C 12 alkyl group, a C 5 -C 7 cycloalkyl group, and a C 5 -C 7 ring. Alkyl-substituted C 1 -C 4 alkyl, JT 18 , or between the two adjacent substituents or between the substituent and Ar 1 may be connected by a single bond, a carbon atom, or a carbonyl group to form a cyclic structure; but Ar 1 is not a substituted carbazole group; J is O, S, or NT 19 ; Y 1 is O, S, CT 15 T 16 or C = O; T 1 is a hydrogen atom, C 1 -C 18 alkyl or alkoxy , C 2 -C 18 alkenyl; or T 1 is optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl group, CN, C 1 -C 4 alkanoyl group, an acyl group, a substituted aryloxy and / or C 5 -C 7 cycloalkylene, phenylene, O, S, NT 17 inserted into the C 2 -C 18 Alkyl, or both of the above; or T 1 is C 2 -C 18 alkenyl; any one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkylfluorenyloxy, arylfluorenyloxy and / or C 5 -C 7 cycloalkylene C 2 -C 18 alkenyl with phenylene, phenylene, O, S, NT 17 inserted, or both, or T 1 is C 5 -C 7 cycloalkyl, or any one or more C 1 -C 4 alkyl, phenyl, halogen atom, CN substituted C 5 -C 7 cycloalkyl; or T 1 is phenyl, or any one or more C 1 -C 4 alkyl, C 1- C 4 alkoxy, phenyl, halogen atom, CN substituted phenyl; or T 1 is naphthyl or benzamyl, phenoxycarbonyl, of which benzyl or phenoxycarbonyl is phenyl Arbitrarily substituted with one or two halogen atoms, T 17 , C 5 cycloalkyl, C 6 cycloalkyl, CN, OH, JT 17 ; T 15 and T 16 are hydrogen atom, C 1 -C 18 alkyl, respectively ; Or T 15 and T 16 are optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkoxyl, arylfluorenyl substituted C 2 -C 18 alkyl, C 2 -C 1 inserted by C 5 -C 7 cycloalkylene, phenylene, O, S, NT 17 8 alkyl groups; or both of the above conditions exist; or T 15 and T 16 are C 5 -C 7 cycloalkyl groups; or T 15 and T 16 are phenyl groups respectively, or any one or more of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, phenyl, halogen atom, CN substituted phenyl; or T 15 , T 16 together with the carbon atom to which they are attached form a cyclic and ring-forming number of atoms Is 4 to 7; T 17 is C 1 -C 4 alkyl; T 18 is phenyl, or any one or more C 1 -C 12 alkyl, C 1 -C 12 alkylfluorenyl, or phenylene C 2 -C 12 alkylfluorenyl, O, S, NT 17 inserted, C 5 -C 6 cycloalkylmethylfluorenyl, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkylfluorenyl , Arylfluorenyl, heteroarylfluorenyl, phenyl substituted with JT 17 or NO 2 above; where the specific arylfluorenyl is unsubstituted benzamidine, one or more halogen atoms, C 1- C 8 alkyl, C 1 -C 8 alkoxy substituted benzamidine; or the above T 18 is connected to the aromatic ring in Ar 1 through a single bond, carbon atom, carbonyl group to form a new ring; T 19 is a hydrogen atom, C 1 -C 18 alkyl, C 1 -C 4 alkoxy substituted with acyl C 1 -C 5 alkyl, T 1 C (O) O-substituted C 1 -C 4 alkoxy ; Or T 19 is optionally substituted with one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyl group, aryloxy group, acyl-substituted C 2 -C 18 alkyl, or is C 5 -C 7 cycloalkylene, phenylene, O, S, NT 17 inserted into the C 2 -C 18 alkyl group; or T 19 is a C 5 -C 7 cycloalkyl, or optionally substituted with one or more C 1 -C 4 alkyl group, a phenyl group, a halogen atom, CN substituted C 5 -C 7 cycloalkyl; or T 19 is phenyl, or any one or more C 1 -C 4 alkyl, carboxyl, C 1 -C 12 alkylfluorenyl, C 5 -C 6 cycloalkylmethylfluorenyl, C 5 -C 6 Cycloalkyl-substituted C 2 -C 4 alkylfluorenyl, arylfluorenyl, the above-mentioned JT 17 , phenyl, halogen atom, or CN-substituted phenyl; or the above T 19 through a single bond, carbon atom, carbonyl group, and The aromatic rings in Ar 1 are connected to form a new ring.
上述式(E-1-1)之結構式中其他基團定義同系列1中相應化合物的基團定義。 The definition of other groups in the structural formula of the above formula (E-1-1) is the same as that of the corresponding compounds in series 1.
上述式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)、式(E-1-5)之結構式中，T1C(O)還可以被(T1)2P或T1S(O2)代替生成對應的亞磷(膦)酸酯或磺酸酯，也具有光致自由基或光致陽離子引發作用。 In the above formulae (E-1-1), (E-1-2), (E-1-3), (E-1-4), (E-1-5), T 1 C (O) can also be replaced by (T 1 ) 2 P or T 1 S (O 2 ) to form the corresponding phosphorous (phosphonic) acid ester or sulfonic acid ester. It also has photo-induced free radical or photo-cation induced effect.
系列8：由式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)、式(E-1-5)所示之環戊二酮肟酯化合物之實例包括下列由式(I-1)至式(I-35)所表示的化合物：
此外，所述的系列1-8中的由式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)、式(E-1-5)所示之環戊二酮肟酯化合物的製造方法，包含以下步驟： In addition, the series 1-8 includes formula (E-1-1), formula (E-1-2), formula (E-1-3), formula (E-1-4), formula ( The method for producing a cyclopentadione oxime ester compound represented by E-1-5) includes the following steps:
步驟1：以由式(A)或式(B-1)、式(B-2)所示之化合物的其中之一(其中Ar1，Y1，Ar2的定義與已有的描述相同)的羰基鄰位亞甲基上進行選擇性肟化。上述選擇性肟化方法是以亞硝酸烷基酯在酸性醇溶液中 發生肟化反應，分别得到對應的中間體(分別由式(C)、式(D-1)、式(D-2)所示之化合物)。又，當肟基團具有順反立體手性時，得到單一手性之由式(C)、式(D-1)、式(D-2)所示的化合物或各自對映體的混合物。 Step 1: One of the compounds represented by formula (A), formula (B-1), and formula (B-2) (wherein the definitions of Ar 1 , Y 1 , and Ar 2 are the same as the existing description) The carbonyl group is ortho-methylene to undergo selective oximation. In the above selective oximation method, an alkyl nitrite is subjected to an oximation reaction in an acidic alcohol solution to obtain corresponding intermediates (respectively from formula (C), formula (D-1), formula (D-2) Compound shown). In addition, when the oxime group has a cis-trans stereo chirality, a compound represented by formula (C), formula (D-1), or formula (D-2) or a mixture of respective enantiomers of a single chirality is obtained.
步驟2：將上述由式(C)所式之化合物的中間體與下列醯化試 劑()或其等價醯化試劑發生酯化反應，得到與其對應之由式(E-1-1)、式(E-1-4)、式(E-1-5)所示的環戊二酮肟酯化合物；或將上述由式(D-1)以及式(D-2)所式之化合物的中間體之一與下列醯化試劑()或其等價醯化試劑發生酯化反應，得到與其對應之由式(E-1-2)、式(E-1-3)所示的環戊二酮肟酯化合物。 Step 2: The above intermediate of the compound represented by the formula (C) and the following chelating reagent ( ) Or its equivalent tritiated reagent, an esterification reaction is performed to obtain the corresponding cyclopentadiene represented by the formula (E-1-1), (E-1-4), and (E-1-5). A ketoxime ester compound; or one of the above-mentioned intermediates of the compound represented by the formula (D-1) and the formula (D-2) with the following hydrazone reagent ( ) Or its equivalent halogenating agent undergoes an esterification reaction to obtain a corresponding cyclopentanedionone oxime ester compound represented by formula (E-1-2) and formula (E-1-3).
當由式(C)、式(D-1)、式(D-2)所示之化合物的中間體具有立體手性時，可分別得到單一手性之由式(E-1-1)、式(E-1-2)、式(E-1-3)、式(E-1-4)、式(E-1-5)所示的環戊二酮肟酯化合物或各自異構體的混合物，其中T1和U1的定義與已有的描述相同。 When the intermediate of the compound represented by formula (C), formula (D-1), or formula (D-2) has stereo chirality, a single chirality can be obtained by formula (E-1-1), Cyclopentadione oxime ester compounds or their isomers represented by formula (E-1-2), formula (E-1-3), formula (E-1-4), and formula (E-1-5) A mixture in which the definitions of T 1 and U 1 are the same as those already described.
其中，於上述由式(E-1-1)所示之環戊二酮肟酯化合物的製造方法中，所述之由式(A)所式之化合物更可以為： 其中Ar1是鄰亞芳基或鄰亞雜芳基，鄰亞芳基或鄰亞雜芳基以相鄰的兩個原子與Y1和羰基相連構成並環結構，其餘原子上的取代基各自為氫原子、C1-C12烷基、C5-C7環烷基、C5-C7環烷基取代的C1-C4烷基、JT18；或其中上述Ar1上的取代基中相鄰的兩個取代基之間或取代基與Ar1之間可以通過單鍵、碳原子、羰基相連構成環狀結構；但Ar1不是取代咔唑基團；J為O、S或NT19；Y1為O、S、CT15T16或C=O；T15、T16分別為氫原子、C1-C18烷基；或T15、T16為任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基、芳醯氧基取代的C2-C18烷基，或被C5-C7環亞烷基、亞苯基、O、S、NT17***的C2-C18烷基；或T15、T16為C5-C7環烷基；或T15、T16分別為苯基或任意被一個或多個C1-C4烷基、C1-C4烷氧基、苯基、鹵素原子、CN取代的苯基；或T15、T16為與其共同所連的碳原子一起構成環狀且成環之原子數為4至7；T17為C1-C4烷基；T18為苯基或任意被一個或多個C1-C4烷基、C1-C12烷基醯基、被亞苯基、O、S、NT17***的C2-C12烷基醯基、C5-C6環烷基甲醯基、C5-C6環烷基取代的C2-C4烷基醯基、芳基醯基、雜芳基醯基、上述JT17、NO2取代的苯基；其中具體的芳基醯基為未被取代的苯甲醯基、被一个或多个多個鹵素原子、C1-C8烷基、C1-C8烷氧基取代的苯甲醯基；T19為氫原子、C1-C18烷基、C1-C4烷氧基醯基取代的C1-C5烷基、T1C(O)O取代的C1-C4烷基； 或T19為任意被一個或多個鹵素原子、C1-C4烷基、C5-C7環烷基、雜環烷基、苯基、雜芳基、CN、C1-C4烷醯氧基、芳醯氧基取代的C2-C18烷基，或是被C5-C7環亞烷基、亞苯基、O、S、NT17***的C2-C18烷基；或T19為C5-C7環烷基，或任意被一個或多個C1-C4烷基、苯基、鹵素原子、CN取代的C5-C7環烷基；或T19為苯基，或任意被一個或多個C1-C4烷基、羧基、C1-C12烷基醯基、C5-C6環烷基甲醯基、C5-C6環烷基取代的C2-C4烷基醯基、芳基醯基、上述JT17、苯基、鹵素原子、CN取代的苯基。 Wherein, in the method for producing a cyclopentadione oxime ester compound represented by the formula (E-1-1), the compound represented by the formula (A) may be: wherein Ar 1 is an adjacent An aryl group or an adjacent heteroarylene group, an adjacent arylene group, or an adjacent heteroarylene group is connected to Y 1 and a carbonyl group by two adjacent atoms to form a ring structure, and the substituents on the remaining atoms are each a hydrogen atom, C 1 -C 12 alkyl, C 5 -C 7 cycloalkyl, C 5 -C 7 cycloalkyl substituted C 1 -C 4 alkyl, JT 18 ; or two adjacent ones of the above-mentioned substituents on Ar 1 A single ring, carbon atom, or carbonyl group can be connected to form a cyclic structure between the substituents or between the substituents and Ar 1 ; but Ar 1 is not a substituted carbazole group; J is O, S, or NT 19 ; Y 1 is O, S, CT 15 T 16 or C = O; T 15 and T 16 are hydrogen atom, C 1 -C 18 alkyl group respectively; or T 15 and T 16 are optionally one or more halogen atoms, C 1- C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkylfluorenyloxy, arylfluorenyl substituted C 2 -C 18 alkyl Or a C 2 -C 18 alkyl group inserted by C 5 -C 7 cycloalkylene, phenylene, O, S, NT 17 ; or T 15 , T 16 is C 5 -C 7 cycloalkyl; or T 15 , T 16 are phenyl or any one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy, phenyl , A halogen atom, a CN-substituted phenyl group; or T 15 and T 16 are cyclic and ring-forming atoms that form a ring together with the carbon atom to which they are commonly connected; T 17 is a C 1 -C 4 alkyl group; T 18 is phenyl or any C 1 -C 4 alkyl, C 1 -C 12 alkylfluorenyl, C 2 -C 12 alkyl inserted by phenylene, O, S, NT 17 Fluorenyl, C 5 -C 6 cycloalkylmethylfluorenyl, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkylfluorenyl, arylfluorenyl, heteroarylfluorenyl, JT 17 above, NO 2 substituted phenyl; where the specific arylfluorenyl is unsubstituted benzamidine, one or more halogen atoms, C 1 -C 8 alkyl, C 1 -C 8 alkoxy Substituted benzamidine; T 19 is a hydrogen atom, C 1 -C 18 alkyl, C 1 -C 4 alkoxyfluorenyl substituted C 1 -C 5 alkyl, T 1 C (O) O substituted C 1 -C 4 alkyl; or T 19 is optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkane C 2 -C 18 alkyl substituted with fluorenyloxy, arylfluorenyloxy, or C 2 -C 18 alkyl inserted with C 5 -C 7 cycloalkylene, phenylene, O, S, NT 17 ; or T 19 is a C 5 -C 7 cycloalkyl, or optionally substituted with one or more C 1 -C 4 alkyl group, a phenyl group, a halogen atom, CN substituted C 5 -C 7 cycloalkyl; or T 19 Is phenyl, or any one or more C 1 -C 4 alkyl, carboxyl, C 1 -C 12 alkylfluorenyl, C 5 -C 6 cycloalkylmethylfluorenyl, C 5 -C 6 cycloalkane C 2 -C 4 alkylfluorenyl, arylfluorenyl, JT 17 described above, phenyl, halogen atom, CN substituted phenyl.
基於該鹼可溶性樹脂(C)之使用量為100重量份，該環戊二酮肟酯化合物(E-1)之使用量為5重量份至50重量份，較佳為7重量份至45重量份，更佳為9重量份至40重量份。 Based on the used amount of the alkali-soluble resin (C) being 100 parts by weight, the used amount of the cyclopentadione oxime ester compound (E-1) is 5 to 50 parts by weight, preferably 7 to 45 parts by weight Parts, more preferably 9 parts by weight to 40 parts by weight.
根據本發明之光起始劑(E)可進一步包含其它自由基型光起始劑(E-2)。 The photo-initiator (E) according to the present invention may further include other radical-type photo-initiators (E-2).
該其它自由基型光起始劑(E-2)可選自於苯乙酮系化合物(acetophenone)、二咪唑系化合物(biimidazole)、醯肟系化合物(acyl oxime)或此等之一組合。 The other free radical type photoinitiator (E-2) may be selected from acetophenone, biimidazole, acyl oxime, or a combination thereof.
上述的苯乙酮系化合物是選自於對二甲胺苯乙酮(p-dimethylamino-acetophenone)、α,α’-二甲氧基氧化偶氮苯乙酮(α,α’-dimethoxyazoxy-acetophenone)、2,2’-二甲基-2-苯基苯乙酮(2,2’-dimethyl-2-phenyl-acetophenone)、對甲氧基苯乙酮(p-methoxy-acetophenone)、2-甲基-1-(4-甲基硫代苯基)-2-嗎啉代-1-丙酮〔2-methyl-1-(4-methylthio phenyl)-2-morpholino-1-propanone〕、2-苄基-2-氮，氮-二甲胺-1-(4-嗎啉代苯基)-1-丁酮〔2-benzyl-2-N,N-di-methylamino-1-(4-morpholinophenyl)-1-butanone〕。 The acetophenone-based compound is selected from the group consisting of p-dimethylamino-acetophenone, α, α'-dimethoxyazoxy-acetophenone ), 2,2'-dimethyl-2-phenyl-acetophenone (2,2'-dimethyl-2-phenyl-acetophenone), p-methoxy-acetophenone, 2- Methyl-1- (4-methylthiophenyl) -2-morpholino-1-acetone [2-methyl-1- (4-methylthio phenyl) -2-morpholino-1-propanone], 2- Benzyl-2-nitro, nitro-dimethylamine-1- (4-morpholinophenyl) -1-butanone [2-benzyl-2-N, N-di-methylamino-1- (4-morpholinophenyl ) -1-butanone].
上述的二咪唑系化合物是選自於2,2’-雙(鄰-氯苯基)-4,4’,5,5’-四苯基二咪唑〔2,2’-bis(o-chlorophenyl)-4,4’,5,5’-tetraphenyl-biimidazole〕、2,2’-雙(鄰-氟苯基)-4,4,5,5’-四苯基二咪唑〔2,2’-bis(o-fluorophenyl)-4,4’,5,5’-tetraphenyl-biimidazole〕、2,2’-雙(鄰-甲基苯基)-4,4’,5,5’-四苯基二咪唑〔2,2’-bis(o-methylphenyl)-4,4’,5,5’-tetraphenyl-biimidazole〕、2,2’-雙(鄰-甲氧基苯基)-4,4’,5,5’-四苯基二咪唑〔2,2’-bis(o-methoxyphenyl)-4,4’,5,5’-tetraphenyl-biimidazole〕、2,2’-雙(鄰-乙基苯基)-4,4’,5,5’-四苯基二咪唑〔2,2’-bis(o-ethylphenyl)-4,4’，5,5’-tetraphenyl-biimidazole〕、2,2’-雙(對甲氧基苯基)-4,4’,5,5’-四苯基二咪唑〔2,2’-bis(p-methoxyphenyl)-4,4’,5,5’-tetraphenyl-biimidazole〕、2,2’-雙(2,2’,4,4’-四甲氧基苯基)-4,4’,5,5’-四苯基二咪唑〔2,2’-bis(2,2’,4,4’-tetramethoxyphenyl)-4,4’,5,5’-tetraphenyl-biimidazole〕、2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基二咪唑〔2,2’-bis(2-chlorophenyl)-4,4’,5,5’-tetraphenyl-biimidazole〕、2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基二咪唑〔2,2’-bis(2,4-dichlorophenyl)-4,4’,5,5’-tetraphenyl-biimidazole〕。 The above diimidazole-based compound is selected from 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyldiimidazole [2,2'-bis (o-chlorophenyl ) -4,4 ', 5,5'-tetraphenyl-biimidazole], 2,2'-bis (o-fluorophenyl) -4,4,5,5'-tetraphenyldiimidazole [2,2' -bis (o-fluorophenyl) -4,4 ', 5,5'-tetraphenyl-biimidazole], 2,2'-bis (o-methylphenyl) -4,4', 5,5'-tetraphenyl Diimidazole [2,2'-bis (o-methylphenyl) -4,4 ', 5,5'-tetraphenyl-biimidazole], 2,2'-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenyldiimidazole [2,2'-bis (o-methoxyphenyl) -4,4', 5,5'-tetraphenyl-biimidazole], 2,2'-bis (o-B Phenyl) -4,4 ', 5,5'-tetraphenyldiimidazole [2,2'-bis (o-ethylphenyl) -4,4', 5,5'-tetraphenyl-biimidazole], 2, 2'-bis (p-methoxyphenyl) -4,4 ', 5,5'-tetraphenyldiimidazole [2,2'-bis (p-methoxyphenyl) -4,4', 5,5 ' -tetraphenyl-biimidazole], 2,2'-bis (2,2 ', 4,4'-tetramethoxyphenyl) -4,4', 5,5'-tetraphenyldiimidazole [2,2 '-bis (2,2', 4,4'-tetramethoxyphenyl) -4,4 ', 5,5'-tetraphenyl-biim idazole], 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyldiimidazole [2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-biimidazole], 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyldiimidazole [2,2'-bis ( 2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-biimidazole].
上述的醯肟系化合物是選自於乙烷酮，1-[9-乙基-6-(2-甲基苯甲醯基)-9氫-咔唑-3-取代基]-,1-(氧-乙醯肟)〔Ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime)，例如Ciba Specialty Chemicals製之品名為CGI-242者，其結構如下式(E-2-1)所示〕、1-[4-(苯基硫代)苯基]-辛烷-1,2-二酮2-(O-苯醯基肟)〔1-[4-(benzoyl)phenyl]-heptane-1,2-dione 2-(O-benzoyloxime)，例如Ciba Specialty Chemicals製造之商品名為
CGI-124之商品，其結構如下式(E-2-2)所示〕、乙烷酮，1-[9-乙基-6-(2-氯-4-苯甲基-硫代-苯甲醯基)-9氫-咔唑-3-取代基]-,1-(氧-乙醯肟)〔Ethanone,1-[9-ethyl-6-(2-cholro-4-benzyl-thio-benzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime)，例如旭電化公司製，其結構如下式(E-2-3)所示〕：
較佳地，該其它自由基型光起始劑(E-2)為2-甲基-1-(4-甲基硫代苯基)-2-嗎啉代-1-丙酮、2-苄基-2-氮，氮-二甲胺-1-(4-嗎啉代苯基)-1-丁酮、2,2’-雙(鄰-氯苯基)-4,4’,5,5’-四苯基二咪唑、乙烷酮，1-[9-乙基-6-(2-甲基苯甲醯基)-9氫-咔唑-3-取代基]-,1-(氧-乙醯肟)或此等之一組合。 Preferably, the other radical-type photoinitiator (E-2) is 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-acetone, 2-benzyl Methyl-2-nitro, nitro-dimethylamine-1- (4-morpholinophenyl) -1-butanone, 2,2'-bis (o-chlorophenyl) -4,4 ', 5, 5'-tetraphenyldiimidazole, acetone, 1- [9-ethyl-6- (2-methylbenzylidene) -9hydro-carbazole-3-substituent]-, 1- ( Oxygen-acetamoxime) or one of these combinations.
本發明之其它自由基型光起始劑(E-2)可進一步添加下列之化合物：噻噸酮(thioxanthone)、2,4-二乙基噻噸酮(2,4-diethyl-thioxanthanone)、噻噸酮-4-碸(thioxanthone-4-sulfone)、二苯甲酮(benzophenone)、4,4’-雙(二甲胺)二苯甲酮〔4,4’-bis(dimethylamino)benzophenone〕、4,4’-雙(二乙胺)二苯甲酮〔4,4’-bis(diethylamino)benzophenone〕等之二苯甲酮(benzophenone)類化合物；苯偶醯(benzil)、乙醯基(acetyl)等之α-二酮(α-diketone)類化合物；二苯乙醇酮(benzoin)等之酮醇(acyloin)類化合物；二苯乙醇酮甲醚(benzoin methylether)、二苯乙醇酮***(benzoin ethylether)、二苯乙醇酮異丙醚(benzoin isopropyl ether)等之酮醇醚(acyloin ether)類化合物；2,4,6-三甲基苯醯二苯基膦氧化物(2,4,6-trimethyl-benzoyl-diphenyl-phosphineoxide)、雙-(2,6-二甲氧基苯醯)-2,4,4-三甲基苯基膦氧化物〔bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethyl-benzyl-phosphineoxide〕等之醯膦氧化物(acylphosphineoxide)類化合物；蒽醌(anthraquinone)、1,4-萘醌(1,4-naphthoquinone)等之醌(quinone)類化合物；苯醯甲基氯(phenacyl chloride)、三溴甲基苯碸(tribromomethyl-phenylsulfone)、三(三氯甲基)-s-三嗪〔tris(trichloromethyl)-s-triazine〕等之鹵化物；以及二-第三丁基過氧化物(di-tertbutylperoxide)等之過氧化物。其中，以二苯甲酮(benzophenone)類化合物較佳，尤以4,4’-雙(二乙胺)二苯甲酮為最佳。 Other free radical photoinitiators (E-2) of the present invention may further add the following compounds: thioxanthone, 2,4-diethyl-thioxanthanone, Thioxanthone-4-sulfone, benzophenone, 4,4'-bis (dimethylamine) benzophenone [4,4'-bis (dimethylamino) benzophenone] , 4,4'-bis (diethylamine) benzophenone [4,4'-bis (diethylamino) benzophenone], and other benzophenone compounds; benzil, acetamyl α -diketone compounds such as (acetyl); acyloin compounds such as benzoin; benzoin methylether, benzophenone ether acyloin ether compounds such as (benzoin ethylether) and benzoin isopropyl ether; 2,4,6-trimethylphenylphosphonium diphenylphosphine oxide (2,4 , 6-trimethyl-benzoyl-diphenyl-phosphineoxide), bis- (2,6-dimethoxyphenylhydrazone) -2,4,4-trimethylphenylphosphine oxide [bis- (2,6-dimethoxy -benzoyl) -2,4,4-trimethyl-benzyl-phosphineoxide) (acylphosphineoxide) compounds; quinone compounds such as anthraquinone, 1,4-naphthoquinone; phenacyl chloride, tribromomethyl phenylhydrazone (tribromomethyl-phenylsulfone), tris (trichloromethyl) -s-triazine, and other halides; and di-tertbutylperoxide peroxide. Among them, benzophenone compounds are preferred, and 4,4'-bis (diethylamine) benzophenone is most preferred.
上述其它自由基型光起始劑(E-2)可單獨一種或混合複數種使用。 The other radical-type photoinitiators (E-2) may be used alone or in combination.
於本發明之具體例中，基於該鹼可溶性樹脂(C)之使用量為100重量份，該其它自由基型光起始劑(E-2)之使用量為0重量份至95重量 份；較佳為5重量份至90重量份；更佳為10重量份至85重量份。 In a specific example of the present invention, based on the used amount of the alkali-soluble resin (C) being 100 parts by weight, the used amount of the other radical photoinitiator (E-2) is 0 to 95 parts by weight 5 parts by weight to 90 parts by weight; more preferably 10 parts by weight to 85 parts by weight.
基於該鹼可溶性樹脂(C)之使用量為100重量份，該光起始劑(E)之使用量為5至100重量份；較佳為10至95重量份；更佳為15至90重量份。 Based on the use amount of the alkali-soluble resin (C) being 100 parts by weight, the use amount of the photoinitiator (E) is 5 to 100 parts by weight; preferably 10 to 95 parts by weight; more preferably 15 to 90 parts by weight Serving.
根據本發明之具有式(1)所示結構之化合物(F)，如下所示：
於式(1)中：A1表示五員環或六員環之烴環或雜環；R1f各自獨立表示鹵素原子、氰基、羥基、硝基、羧基、可具有取代基之碳數為1至40之烷基、碳數為6至20之芳基、碳數為7至20之芳烷基或碳數為2至20之含雜環之基；R2f各自獨立表示碳數為1至20之烷基、碳數為2至20之烯基、碳數為6至20之芳基、碳數為7至20之芳烷基、碳數為2至20之含雜環之基或三烷基矽烷基；其中，R1f及R2f所示之烷基或芳烷基中之亞甲基可被選自由碳-碳雙鍵、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR'-、-S-S-及-SO2-之基所組成之群或前述基在氧原子不相鄰條件下之組合所取代，R'表示氫原子或碳數為1至8之烷基；複數個R1f彼此可鍵結形成苯環或萘環；
複數個R1f及R2f彼此可分別相同或不同；h表示1至10之整數；e表示1至4之整數；f表示1至3之整數；D表示直接鍵、氮原子、氧原子、硫原子、磷原子、下述式(2)所示之基、>C=O、>NR3f、-OR3f、-SR3f、-NR3fR4f或具有與h為相同價數之可具有取代基之碳數為1至120之脂肪族烴基、可具有取代基之碳數為6至35之含芳香環之烴基、可具有取代基之碳數為2至35之含雜環之基，其中R3f及R4f表示氫原子、可具有取代基之碳數為1至35之脂肪族烴基、可具有取代基之碳數為6至35之含芳香環之烴基或可具有取代基之碳數為2至35之含雜環之基，該脂肪族烴基、含芳香環之烴基及含雜環之基可被選自由碳-碳雙鍵、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR'-、-S-S-、-SO2-及氮原子所組成之群之基所組成之群或前述基在氧原子不相鄰條件下之組合所間雜，上述芳香環或雜環可與其他環縮合；其中，當D為氮原子、磷原子或下述式(2)所示之基時，h為3；當D為氧原子或硫原子時，h為2；當D為>C=O、-NH-CO-、-CO-NH-或>NR3f時，h為2；當D為-OR3f、-SR3f或-NR3fR4f時，h為1；其中，D可與A1一起形成環；
該式(1)所示結構之化合物(F)具有D所表示之h價之特定之原子或基上鍵結有h個特定之基的結構。該h個基可相互相同亦可不同。h之值為1至10，就合成容易性之方面而言，較佳為2至6。另外，當h之值為 3至10時，該感光性樹脂組成物所形成之彩色濾光片無泡狀顯示缺陷表現更佳。 The compound (F) of the structure represented by the formula (1) has a structure in which h specific groups are bonded to a specific atom or group having an valence of h represented by D. The h groups may be the same as or different from each other. The value of h is 1 to 10, and in terms of ease of synthesis, 2 to 6 is preferred. In addition, when the value of h When it is 3 to 10, the color filter formed by the photosensitive resin composition exhibits better non-bubble display defects.
於上述式(1)中，A1表示五員環之芳香環，可列舉環戊二烯、二茂鐵等；作為五員環之雜環，可列舉呋喃、噻吩、吡咯、吡咯啶、吡唑啶、吡唑、咪唑、咪唑啶、噁唑(oxazole)、異噁唑、異噁唑啶、噻唑、異噻唑、異噻唑啶(isothiazolidine)等；作為六員環之芳香環，可列舉苯、萘、蒽、茀、苝、芘等；作為六員環之雜環，可列舉哌啶、哌嗪(piperazine)、嗎啉(morpholine)、硫代嗎啉、吡啶、吡嗪(pyrazine)、嘧啶、嗒嗪(pyridazine)、三嗪(triazine)等，該等環亦可與其他環縮合或經取代，可列舉喹啉、異喹啉、吲哚、咯啶、苯并噁唑、苯并***、薁等。 In the above formula (1), A 1 represents a five-membered aromatic ring, including cyclopentadiene, ferrocene, and the like; and the five-membered hetero ring includes furan, thiophene, pyrrole, pyrrolidine, and pyridine Azodin, pyrazole, imidazole, imidazolidine, oxazole, isoxazole, isoxazole, thiazole, isothiazol, isothiazolidine, etc .; as the aromatic ring of six members, benzene , Naphthalene, anthracene, pyrene, pyrene, fluorene, etc .; as the heterocyclic ring of six members, piperidine, piperazine, morpholine, thiomorpholine, pyridine, pyrazine, Pyrimidine, pyridazine, triazine, etc. These rings can also be condensed or substituted with other rings. Examples include quinoline, isoquinoline, indole, pyridine, benzoxazole, and benzo. Triazole, rhenium, etc.
於上述式(1)中，R1f表示之鹵素原子，可列舉：氟、氯、溴、碘等。 Examples of the halogen atom represented by R 1f in the formula (1) include fluorine, chlorine, bromine, and iodine.
作為R1f表示之碳數為1至40之烷基，可列舉：甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基、異丁基、戊基、異戊基、第三戊基、環戊基、己基、2-己基、3-己基、環己基、4-甲基環己基、庚基、2-庚基、3-庚基、異庚基、第三庚基、1-辛基、異辛基、第三辛基、金剛烷基等。 Examples of the alkyl group having 1 to 40 carbon atoms represented by R 1f include methyl, ethyl, propyl, isopropyl, butyl, second butyl, third butyl, isobutyl, and pentyl. , Isopentyl, third pentyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl , Third heptyl, 1-octyl, isooctyl, third octyl, adamantyl and the like.
作為R1f表示之碳數為1至8之烷氧基，可列舉：甲氧基、乙氧基、異丙氧基、丁氧基、第二丁氧基、第三丁氧基、異丁氧基、烯丙氧基、異烯丙氧基、第三烯丙氧基、己氧基、2-己氧基、3-己氧基、環己氧基、4-甲基環己氧基、庚氧基、2-庚氧基、3-庚氧基、異庚氧基、第三庚氧基、1-辛氧基、異辛氧基、第三辛氧基等。 Examples of the alkoxy group having 1 to 8 carbon atoms represented by R 1f include a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, a second butoxy group, a third butoxy group, and an isobutyl group. Oxy, allyloxy, isoallyloxy, third allyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy , Heptyloxy, 2-heptyloxy, 3-heptyloxy, isoheptyloxy, third heptyloxy, 1-octyloxy, isooctyloxy, third octyloxy and the like.
作為對R1f表示之碳數為1至8之烷基及烷氧基進行取代之取代基，可列舉：乙烯基、烯丙基、丙烯酸基、甲基丙烯酸基等乙烯性不飽 和基；氟、氯、溴、碘等鹵素原子；乙醯基、2-氯乙醯基、丙醯基、辛醯基、丙烯醯基、甲基丙烯醯基、苯基羰基(苯甲醯基)、鄰苯二甲醯基、4-三氟甲基苯甲醯基、新戊醯基、水楊醯基、草醯基、硬脂醯基、甲氧基羰基、乙氧基羰基、第三丁氧基羰基、正十八烷氧基羰基、胺甲醯基等醯基；乙醯氧基、苯甲醯氧基等醯氧基；胺基、乙基胺基、二甲基胺基、二乙基胺基、丁基胺基、環戊基胺基、2-乙基己基胺基、十二烷基胺基、苯胺基、氯苯基胺基、甲苯胺基、甲氧苯胺基、N-甲基-苯胺基、二苯基胺基、萘基胺基、2-吡啶基胺基、甲氧基羰基胺基、苯氧基羰基胺基、乙醯基胺基、苯甲醯基胺基、甲醯基胺基、新戊醯基胺基、月桂醯基胺基、胺甲醯基胺基、N,N-二甲基胺基羰基胺基、N,N-二乙基胺基羰基胺基、嗎啉基羰基胺基(morpholinocarbonylamino)、甲氧基羰基胺基、乙氧基羰基胺基、第三丁氧基羰基胺基、正十八烷氧基羰基胺基、N-甲基-甲氧基羰基胺基、苯氧基羰基胺基、胺磺醯基胺基、N,N-二甲基胺基磺醯基胺基、甲基磺醯基胺基、丁基磺醯基胺基、苯基磺醯基胺基等經取代之胺基；磺醯胺基、磺醯基、羧基、氰基、磺基、羥基、硝基、巰基、醯亞胺基、胺甲醯基、磺醯胺基、膦酸基、磷酸基或羧基、磺基、膦酸基、磷酸基之鹽等。 Examples of the substituent that substitutes an alkyl group and an alkoxy group having a carbon number of 1 to 8 represented by R 1f include ethylenically unsaturated groups such as vinyl, allyl, acrylic, and methacrylic groups; fluorine , Chlorine, bromine, iodine and other halogen atoms; ethenyl, 2-chloroethenyl, propionyl, octyl, propenyl, methacryl, phenylcarbonyl (benzyl), orthophthalein Formamyl, 4-trifluoromethylbenzyl, neopentyl, salicyl, sulfonyl, stearyl, methoxycarbonyl, ethoxycarbonyl, tertiary butoxycarbonyl, n- Stearyl groups such as octadecyloxycarbonyl and carbamoyl; ethoxy groups such as ethynyloxy and benzyloxy; amine, ethylamino, dimethylamino, diethylamino, Butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, aniline, chlorophenylamino, tolylamino, methoxyaniline, N-methyl-aniline Group, diphenylamino group, naphthylamino group, 2-pyridylamino group, methoxycarbonylamino group, phenoxycarbonylamino group, ethenylamino group, benzamylamino group, formamyl group Amino group, neopentylamino group, Laurylamino, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino, methylamine Oxycarbonylamino, ethoxycarbonylamino, tertiary butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino , Sulfamoylamino, N, N-dimethylaminosulfoamidoamino, methylsulfoamidoamino, butylsulfoamidoamino, phenylsulfoamidoamino, etc. Amino groups; sulfoamido, sulfoamido, carboxyl, cyano, sulfo, hydroxy, nitro, mercapto, amidoimino, carbamate, sulfoamido, phosphonic acid, phosphate, or carboxyl , Sulfo, phosphonic acid, phosphate salts, etc.
作為R2f表示之碳數為6至20之芳基，可列舉：苯基、萘基、蒽基等。 Examples of the aryl group having 6 to 20 carbon atoms represented by R 2f include phenyl, naphthyl, and anthracenyl.
作為R2f表示之碳數為7至20之芳烷基，可列舉：苄基、茀基、茚基、9-茀基甲基等。 Examples of the aralkyl group having 7 to 20 carbon atoms represented by R 2f include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, and the like.
作為R2f表示之碳數為2至20之含雜環之基，可列舉：吡啶基、嘧啶基、嗒嗪基、哌啶基、吡喃基、吡唑基、三嗪基、吡咯基、喹啉基、異喹啉基、咪唑基、苯并咪唑基、***基、聯呋喃甲醯基(furil)、呋喃基(furanyl)、苯并呋喃基、噻吩基(thienyl)、苯硫基(thiophenyl)、苯并噻吩 基、噻二唑基、噻唑基、苯并噻唑基、噁唑基、苯并噁唑基、異噻唑基、異噁唑基、吲哚基、2-吡咯啶酮-1-基、2-哌啶酮-1-基、2,4-二氧基咪唑啶-3-基、2,4-二氧基噁唑啶-3-基等。 Examples of the heterocyclic group containing 2 to 20 carbon atoms represented by R 2f include pyridyl, pyrimidinyl, pyrazinyl, piperidinyl, pyranyl, pyrazolyl, triazinyl, pyrrolyl, Quinolinyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furilyl, furanyl, benzofuranyl, thienyl, phenylthio (thiophenyl), benzothienyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidone 1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazol-3-yl, 2,4-dioxyoxazol-3-yl, and the like.
作為R2f表示之三烷基矽烷基，可列舉：三甲基矽烷、三乙基矽烷、乙基二甲基矽烷等。 Examples of the trialkylsilyl group represented by R 2f include trimethylsilane, triethylsilane, and ethyldimethylsilane.
較佳地，R2f表示碳數為1至8之烷基之氧原子側末端上鍵結有-CO-O-者。 Preferably, R 2f represents a group having -CO-O- bonded to an oxygen atom-side end of an alkyl group having 1 to 8 carbon atoms.
作為上述式(1)中，D、R3f及R4f表示之可具有取代基之碳數為1至35之一價脂肪族烴基，例如可列舉：甲基、乙基、丙基、異丙基、環丙基、丁基、第二丁基、第三丁基、異丁基、戊基、異戊基、第三戊基、環戊基、己基、2-己基、3-己基、環己基、雙環己基、1-甲基環己基、庚基、2-庚基、3-庚基、異庚基、第三庚基、正辛基、異辛基、第三辛基、2-乙基己基、壬基、異壬基、癸基等烷基；甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、第二丁氧基、第三丁氧基、異丁氧基、戊氧基、異戊氧基、第三戊氧基、己氧基、環己氧基、庚氧基、異庚氧基、第三庚氧基、正辛氧基、異辛氧基、第三辛氧基、2-乙基己氧基、壬氧基、癸氧基等烷氧基；甲硫基、乙硫基、丙硫基、異丙硫基、丁硫基、第二丁硫基、第三丁硫基、異丁硫基、戊硫基、異戊硫基、第三戊硫基、己硫基、環己硫基、庚硫基、異庚硫基、第三庚硫基、正辛硫基、異辛硫基、第三辛硫基、2-乙基己硫基等烷硫基；乙烯基、1-甲基乙烯基、2-甲基乙烯基、2-丙烯基、1-甲基-3-丙烯基、3-丁烯基、1-甲基-3-丁烯基、異丁烯基、3-戊烯基、4-己烯基、環己烯基、雙環己烯基、庚烯基、辛烯基、癸烯基、十五烯基、二十烯基、三十烯基等烯基等；作為可具有取代基之碳原子數6至35之一價含芳香環之烴基，可列舉：苄基、苯乙基、二苯基甲基、三苯基甲基、苯乙烯基、苯 烯丙基(cinnamyl)等芳烷基；苯基、萘基等芳基；苯氧基、萘氧基等芳氧基；苯硫基、萘硫基等芳硫基等；作為可具有取代基之碳數為2至35之一價含雜環之基，可列舉：吡啶基、嘧啶基、嗒嗪基、哌啶基、吡喃基、吡唑基、三嗪基、吡咯基、喹啉基、異喹啉基、咪唑基、苯并咪唑基、***基、聯呋喃甲醯基(furil)、呋喃基(furanyl)、苯并呋喃基、噻吩基(thienyl)、苯硫基(thiophenyl)、苯并噻吩基、噻二唑基、噻唑基、苯并噻唑基、噁唑基、苯并噁唑基、異噻唑基、異噁唑基、吲哚基、2-吡咯啶酮-1-基、2-哌啶酮-1-基、2,4-二氧基咪唑啶-3-基、2,4-二氧基噁唑啶-3-基、苯并***基等。 As the monovalent aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent represented by D, R 3f, and R 4f in the above formula (1), examples include methyl, ethyl, propyl, and isopropyl Base, cyclopropyl, butyl, second butyl, third butyl, isobutyl, pentyl, isopentyl, third pentyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclo Hexyl, dicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, third heptyl, n-octyl, isooctyl, third octyl, 2-ethyl Alkyl groups such as hexyl, nonyl, isononyl, decyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy, second butoxy, third butoxy, iso Butoxy, pentyloxy, isopentyloxy, third pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, third heptyloxy, n-octyloxy, isooctyl Alkoxy groups such as ethoxy, third octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy; methylthio, ethylthio, propylthio, isopropylthio, butylthio, Second butylthio, third butylthio, isobutylthio, pentylthio, isopentylthio, third pentylthio , Hexylthio, cyclohexylthio, heptylthio, isoheptylthio, third heptylthio, n-octylthio, isooctylthio, third octylthio, 2-ethylhexylthio, etc. Thio; vinyl, 1-methylvinyl, 2-methylvinyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butene Base, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, dicyclohexenyl, heptenyl, octenyl, decenyl, pentaenyl, eicosyl, tris Alkenyl groups such as decaenyl and the like; Examples of the monovalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may have a substituent include benzyl, phenethyl, diphenylmethyl, and triphenylmethyl , Arylalkyl such as styryl, cinnamyl; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthyloxy; arylthio groups such as phenylthio and naphthylthio ; Examples of the monovalent heterocyclic group containing 2 to 35 carbon atoms which may have a substituent include pyridyl, pyrimidinyl, pyrazinyl, piperidinyl, pyranyl, pyrazolyl, and triazinyl , Pyrrolyl, quinolinyl, isoquinolinyl, imidazolyl, benzimidazolyl, triazolyl, Furil, furanyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothienyl, thiadiazolyl, thiazolyl, benzothiazolyl, Oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidone-1-yl, 2-piperidone-1-yl, 2,4-dioxy Imidazol-3-yl, 2,4-dioxyoxazol-3-yl, benzotriazole and the like.
作為取代基，可列舉：乙烯基、烯丙基、丙烯基、甲基丙烯基等乙烯性不飽和基；氟、氯、溴、碘等鹵素原子；乙醯基、2-氯乙醯基、丙醯基、辛醯基、丙烯醯基、甲基丙烯醯基、苯基羰基(苯甲醯基)、鄰苯二甲醯基、4-三氟甲基苯甲醯基、特戊醯基、水楊醯基、草醯基、硬脂醯基、甲氧基羰基、乙氧基羰基、第三丁氧基羰基、正十八烷氧基羰基、胺甲醯基等醯基；乙醯氧基、苯甲醯氧基等醯氧基；胺基、乙基胺基、二甲基胺基、二乙基胺基、丁基胺基、環戊基胺基、2-乙基己基胺基、十二烷基胺基、苯胺基、氯苯基胺基、甲苯胺基、甲氧苯胺基、N-甲基-苯胺基、二苯基胺基、萘基胺基、2-吡啶基胺基、甲氧基羰基胺基、苯氧基羰基胺基、乙醯基胺基、苯甲醯基胺基、甲醯基胺基、特戊醯基胺基、月桂醯基胺基、胺甲醯基胺基、N,N-二甲基胺基羰基胺基、N,N-二乙基胺基羰基胺基、嗎啉基羰基胺基、甲氧基羰基胺基、乙氧基羰基胺基、第三丁氧基羰基胺基、正十八烷氧基羰基胺基、N-甲基-甲氧基羰基胺基、苯氧基羰基胺基、胺磺醯基胺基、N,N-二甲基胺基磺醯基胺基、甲基磺醯基胺基、丁基磺醯基胺基、苯基磺醯基胺基等經取代之胺基；磺醯胺基、磺醯基、羧基、氰基、磺基、羥基、硝基、巰基、醯亞胺基、胺甲醯基、磺醯胺基、膦酸 基、磷酸基或羧基、磺基、膦酸基、磷酸基之鹽等，該等基亦可進而經取代。又，羧基及磺基亦可形成鹽。 Examples of the substituent include ethylenically unsaturated groups such as a vinyl group, an allyl group, a propenyl group, and a methacryl group; halogen atoms such as fluorine, chlorine, bromine, and iodine; ethenyl, 2-chloroethenyl, Propionyl, octyl, propenyl, methacryl, phenylcarbonyl (benzyl), phthalyl, 4-trifluoromethylbenzyl, pentamyl, water Stilbene groups such as myringyl, sulfonyl, stearyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl, and carbamoyl; ethoxy Methoxy, such as methyloxy; amine, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, twelve Alkylamino, aniline, chlorophenylamino, toluidine, methoxyaniline, N-methyl-aniline, diphenylamino, naphthylamino, 2-pyridylamine, methylamine Oxycarbonylamino, phenoxycarbonylamino, ethenylamino, benzylamino, methylamido, pentamylamino, laurylamino, carbamoylamine N, N-dimethylaminocarbonylamine , N, N-diethylaminocarbonylamino, morpholinylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, third butoxycarbonylamino, n-octadecyloxy Carbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N, N-dimethylaminosulfoamidoamine, methylsulfoamido Substituted amino groups such as amine, butylsulfonylamino, phenylsulfonylamino; sulfonamido, sulfonamido, carboxyl, cyano, sulfo, hydroxyl, nitro, thiol, hydrazone Imino, carbamoyl, sulfamidino, phosphonic acid Group, phosphate group or carboxyl group, sulfo group, phosphonate group, phosphate group salt, etc., these groups may be further substituted. Moreover, a carboxyl group and a sulfo group may form a salt.
於本發明之具體例中，該式(1)所示結構之化合物(F)較佳為式(F-1)至式(F-5)所示之基團：
於式(F-1)中，A2表示六員環之脂環、芳香環或雜環；R11f、R12f、R13f、R14f及R15f表示氫原子、鹵素原子、氰基、羥基、硝基、羧基、可具有取代基之碳數為1至40之烷基、碳數為6至20之芳基、碳數為7至20之芳烷基、碳數為2至20之含雜環之基或-O-R2f，其中R11f、R12f、R13f、R14f及R15f至少一個不為氫原子；R2f之定義如前所述，在此不另贅述。 In formula (F-1), A 2 represents an alicyclic ring, an aromatic ring or a heterocyclic ring of six members; R 11f , R 12f , R 13f , R 14f and R 15f represent a hydrogen atom, a halogen atom, a cyano group, and a hydroxyl group , Nitro, carboxyl, optionally substituted alkyl having 1 to 40 carbons, aryl having 6 to 20 carbons, aralkyl having 7 to 20 carbons, and 2 to 20 carbons inclusive A heterocyclic group or -OR 2f , wherein at least one of R 11f , R 12f , R 13f , R 14f and R 15f is not a hydrogen atom; the definition of R 2f is as described above, and is not repeated here.
於式(F-2)中，D11表示式(a)所示結構；R16f、R17f、R18f及R19f表示氫原子、鹵素原子、氰基、羥基、硝基、羧基、可具有取代基之碳數為1至40之烷基、碳數為6至20之芳基、碳數為7至20之芳烷基或碳數為2至20之含雜環之基，其中R16f、R17f、R18f及R19f至少一個不為氫原子；A2及R2f之定義如前所述，在此不另贅述。 In formula (F-2), D 11 represents the structure represented by formula (a); R 16f , R 17f , R 18f, and R 19f represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, and may have Substituents having 1 to 40 carbons, 6 to 20 carbons, 7 to 20 carbons or 2 to 20 carbons containing heterocyclic groups, wherein R 16f At least one of R 17f , R 18f, and R 19f is not a hydrogen atom; the definitions of A 2 and R 2f are as described above, and are not repeated here.
*-Z1f-X1f-Z2f-* 式(a) * -Z 1f -X 1f -Z 2f- * Formula (a)
於式(a)中，X1f表示-CR30fR31f-、-NR32f-、二價之碳數為1至35之脂肪族 烴基、碳數6至35之含芳香環之烴基或碳數為2至35之含雜環之基、或下述式(a-1)至式(a-3)所示之任一取代基，該脂肪族烴基可經選自由-O-、-S-、-CO-、-COO-、-OCO-及-NH-之基所組成之群或前述基在氧原子不相鄰條件下之組合所間雜；R30f及R31f表示氫原子、碳數為1至8之烷基、碳數為6至20之芳基或碳數為7至20之芳烷基；Z1f及Z2f分別獨立地表示直接鍵、-O-、-S-、>CO、-CO-O-、-O-CO-、-SO2-、-SS-、-SO-或>NR33f；R32f及R33f表示氫原子、可具有取代基之碳數為1至35之脂肪族烴基、可具有取代基之碳數為6至35之含芳香環之烴基或可具有取代基之碳數為2至35之含雜環之基。 In formula (a), X 1f represents -CR 30f R 31f- , -NR 32f- , a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group or carbon number having 6 to 35 carbon atoms It is a heterocyclic group containing 2 to 35, or any one of the following formulae (a-1) to (a-3). The aliphatic hydrocarbon group may be selected from -O-, -S- The group consisting of the groups of -CO-, -COO-, -OCO-, and -NH- or the combination of the aforementioned groups under conditions where the oxygen atoms are not adjacent to each other; R 30f and R 31f represent hydrogen atoms and carbon numbers as An alkyl group of 1 to 8, an aryl group of 6 to 20 carbons, or an aralkyl group of 7 to 20 carbons; Z 1f and Z 2f each independently represent a direct bond, -O-, -S-,> CO , -CO-O-, -O-CO-, -SO 2- , -SS-, -SO- or> NR 33f ; R 32f and R 33f represent a hydrogen atom, and the number of carbons which may have a substituent is 1 to 35 The aliphatic hydrocarbon group may be an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may have a substituent or the heterocyclic group-containing hydrocarbon group having 2 to 35 carbon atoms which may have a substituent.
於式(a-1)中，R21f表示氫原子、可具有取代基之苯基、或碳數為3至10之環烷基；R22f表示碳數為1至10之烷基、碳數為1至10之烷氧基、碳數為2至10之烯基或鹵素原子，上述烷基、烷氧基及烯基亦可具有取代基；及fa為0至5之整數。 In formula (a-1), R 21f represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms; R 22f represents an alkyl group having 1 to 10 carbon atoms and carbon number an alkoxy group of 1 to 10 carbon atoms or an alkenyl group of 2 to 10 halogen atoms, the above alkyl, alkoxy and alkenyl group may have a substituent; and f a is an integer of 0-5.
於式(a-3)中，上述式中，R23f及R24f分別獨立地表示可具有取代基之碳數為1至10之烷基、可具有取代基之碳數為6至20之芳基、可具有取代基之碳數為6至20之芳氧基、可具有取代基之碳數為6至20之芳硫基、可具有取代基之碳數為6至20之芳烯基、可具有取代基之碳數為7至20之芳烷基、可具有取代基之碳數為2至20之含雜環之基或鹵素原子，該烷基及芳烷基中之亞甲基亦可被取代為不飽和鍵、-O-或-S-，R23f亦可以鄰接之R23f彼此形成環；fb表示0至4之數，fc表示0至8之數，fg表示0至4之數，fh表示0至4之數，fg與fh之數合計為2至4。 In the formula (a-3), in the above formula, R 23f and R 24f each independently represent an alkyl group having 1 to 10 carbon atoms which may have a substituent, and an aromatic group having 6 to 20 carbon atoms which may have a substituent. Group, an aryloxy group having 6 to 20 carbons which may have a substituent, an arylthio group having 6 to 20 carbons which may have a substituent, an arylalkenyl group having 6 to 20 carbons which may have a substituent, Aryl groups having 7 to 20 carbons which may have a substituent, heterocyclic groups or halogen atoms having 2 to 20 carbons which may have a substituent, and the methylene groups in the alkyl group and the aralkyl group are also May be substituted with unsaturated bond, -O- or -S-, R 23f may also be adjacent R 23f to form a ring with each other; f b represents a number from 0 to 4, f c represents a number from 0 to 8, and f g represents 0 Numbers from 4 to 4, f h represents a number from 0 to 4, and numbers from f g and f h add up to 2 to 4.
於式(F-3)中，fm表示2至6之數；當fm表示2時，D3表示上述式(a)所示之基；當fm表示3時，D3表示下述式(b)所示之基；當fm表示4時，D3表示下述式(c)所示之基；當fm表示5時，D3表示下述式(d)所示之基；當fm表示6時，D3表示下述式(e)所示之基；R25f、R26f、R27f及R28f表示氫原子、鹵素原子、氰基、羥基、硝基、羧基、可具有取代基之碳數為1至40之烷基、碳數為6至20之芳基、碳數為7至20之芳烷基或碳數為2至20之含雜環之基，其中R25f、R26f、R27f及R28f至少一個不為氫原子；A2及R2f之定義如前所述，在 此不另贅述。 In formula (F-3), f m represents a number from 2 to 6; when f m represents 2, D 3 represents a base represented by the above formula (a); when f m represents 3, D 3 represents the following When f m represents 4, D 3 represents a base represented by the following formula (c); When f m represents 5, D 3 represents a base represented by the following formula (d) ; When f m represents 6, D 3 represents a group represented by the following formula (e); R 25f , R 26f , R 27f and R 28f represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, It may have an alkyl group having 1 to 40 carbons, an aryl group having 6 to 20 carbons, an aralkyl group having 7 to 20 carbons or a heterocyclic group containing 2 to 20 carbons in which At least one of R 25f , R 26f , R 27f and R 28f is not a hydrogen atom; the definitions of A 2 and R 2f are as described above, and will not be repeated here.
式(b)中，Y11f表示三價之碳數為3至35之脂肪族烴基、碳數為3至35之脂環族烴基、碳數為6至35之含芳香族之烴基或碳數為2至35之含雜環之基，Z1f、Z2f及Z3f分別獨立地表示直接鍵、-O-、-S-、>CO、-CO-O-、-O-CO-、-SO2-、-SS-、-SO-、>NR32f、>PR32f或可具有取代基之碳數為1至35之脂肪族烴基、可具有取代基之碳數為6至35之含芳香族之烴基或可具有取代基之碳數為2至35之含雜環之基，R32f表示氫原子、可具有取代基之碳數為1至35之脂肪族烴基、可具有取代基之碳數為6至35之含芳香族之烴基或可具有取代基之碳數為2至35之含雜環之基，該脂肪族烴基亦可經選自由碳-碳雙鍵、-O-、-S-、-CO-、-O-CO-、-CO-O-及-SO2-所組成之基或前述基之組合所間雜。 In formula (b), Y 11f represents a trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, and an aromatic-containing hydrocarbon group or carbon number having 6 to 35 carbon atoms. Is a heterocyclic group containing 2 to 35, and Z 1f , Z 2f and Z 3f each independently represent a direct bond, -O-, -S-,> CO, -CO-O-, -O-CO-,- SO 2- , -SS- , -SO-,> NR 32f ,> PR 32f or an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, and aromatic containing 6 to 35 carbon atoms which may have a substituent Group hydrocarbon group or heterocyclic group containing 2 to 35 carbons which may have a substituent, R 32f represents a hydrogen atom, aliphatic hydrocarbon group having 1 to 35 carbons which may have a substituent, carbon which may have substituents The aromatic hydrocarbon group having a number of 6 to 35 or the heterocyclic group having a carbon number of 2 to 35 which may have a substituent. The aliphatic hydrocarbon group may also be selected from carbon-carbon double bonds, -O-,- The groups consisting of S-, -CO-, -O-CO-, -CO-O-, and -SO 2 -or the combination of the foregoing groups are intermixed.
式(c)中，Y12f表示碳原子、四價之碳數為1至35之脂肪族烴基、碳數為6至35之含芳香族之烴基或碳數為2至35之含雜環之基，該脂肪族烴基亦可經選自由-COO-、-O-、-OCO-、-NHCO-、-NH-及-CONH-所組成之基或前述基之組合所間雜，Z1f至Z4f分別獨立為與上述式(b)中Z1f至Z3f之定義相同，在此不另贅述。 In formula (c), Y 12f represents a carbon atom, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group containing 6 to 35 carbon atoms, or a heterocyclic ring containing 2 to 35 carbon atoms. The aliphatic hydrocarbon group may be selected from the group consisting of -COO-, -O-, -OCO-, -NHCO-, -NH-, and -CONH- or a combination of the foregoing groups, Z 1f to Z 4f is independently the same as the definition of Z 1f to Z 3f in the above formula (b), and is not repeated here.
式(d)中，Y13f表示五價之碳數為2至35之脂肪族烴基、碳數為6至30之含芳香族之烴基或碳數為2至30之含雜環之基，該脂肪族烴基亦可經選自由-COO-、-O-、-OCO-、-NHCO-、-NH-及-CONH-所組成之基或前述基之組合所間雜，Z1f至Z5f分別獨立為與上述式(b)中Z1f至Z3f之定義相同，在此不另贅述。 In the formula (d), Y 13f represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group containing 6 to 30 carbon atoms or a heterocyclic ring containing group having 2 to 30 carbon atoms. The aliphatic hydrocarbon group may also be interspersed by a group selected from the group consisting of -COO-, -O-, -OCO-, -NHCO-, -NH-, and -CONH-, or a combination of the foregoing groups, and Z 1f to Z 5f are each independently It is the same as the definition of Z 1f to Z 3f in the above formula (b), and is not repeated here.
式(e)中，Y14f表示六價之碳數為2至35之脂肪族烴基、碳數為6至35之含芳香族之烴基或碳數為2至35之含雜環之基，該脂肪族烴基亦可經選自由-COO-、-O-、-OCO-、-NHCO-、-NH-及-CONH-所組成之基或前述基之組合所間雜，Z1f至Z6f分別獨立為與上述式(b)中Z1f至Z3f之定義相同，在此不另贅述。 In the formula (e), Y 14f represents a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group containing 2 to 35 carbon atoms. The aliphatic hydrocarbon group may also be interspersed by a group selected from the group consisting of -COO-, -O-, -OCO-, -NHCO-, -NH-, and -CONH-, or a combination of the foregoing groups, and Z 1f to Z 6f are each independently It is the same as the definition of Z 1f to Z 3f in the above formula (b), and is not repeated here.
於式(F-4)中，fm表示2至6之數；當fm表示2時，D4表示上述式(a)所示之基；當fm表示3時，D4表示上述式(b)所示之基；當fm表示4時，D4表示上述式(c)所示之基；當fm表示5時，D4表示上述式(d)所示之基；當fm表示6時， D4表示上述式(e)所示之基；R205f、R206f、R207f及R208f表示氫原子、鹵素原子、氰基、羥基、硝基、羧基、可具有取代基之碳數為1至40之烷基、碳數為6至20之芳基、碳數為7至20之芳烷基或碳數為2至20之含雜環之基，其中R205f、R206f、R207f及R208f至少一個不為氫原子；A2及R2f之定義如前所述，在此不另贅述。 In formula (F-4), f m represents a number from 2 to 6; when f m represents 2, D 4 represents a base represented by the above formula (a); when f m represents 3, D 4 represents the above formula (b) a base; when f m represents 4, D 4 represents the base represented by the above formula (c); when f m represents 5, D 4 represents the base represented by the above formula (d); when f When m represents 6, D 4 represents a group represented by the formula (e); R 205f , R 206f , R 207f, and R 208f represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, and may have a substituent. An alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms, of which R 205f , R At least one of 206f , R 207f, and R 208f is not a hydrogen atom; the definitions of A 2 and R 2f are as described above, and are not repeated here.
於式(F-5)中，fm表示3至6之數；當fm表示3時，D5表示上述式(b)所示之基；當fm表示4時，D5表示上述式(c)所示之基；當fm表示5時，D5表示上述式(d)所示之基；當fm表示6時，D5表示上述式(e)所示之基；R305f、R306f、R307f及R308f表示氫原子、鹵素原子、氰基、羥基、硝基、羧基、可具有取代基之碳數為1至40之烷基、碳數為6至20之芳基、碳數為7至20之芳烷基或碳數為2至20之含雜環之基，其中R305f、R306f、R307f及R308f至少一個不為氫原子；A2及R2f之定義如前所述，在此不另贅述。 In formula (F-5), f m represents a number from 3 to 6; when f m represents 3, D 5 represents a base represented by the above formula (b); when f m represents 4, D 5 represents the above formula (c) a base; when f m represents 5, D 5 represents the base represented by the above formula (d); when f m represents 6, D 5 represents the base represented by the above formula (e); R 305f , R 306f , R 307f and R 308f represent a hydrogen atom, a halogen atom, a cyano group, a hydroxy group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms Aralkyl groups having 7 to 20 carbon atoms or heterocyclic containing groups having 2 to 20 carbon atoms, wherein at least one of R 305f , R 306f , R 307f, and R 308f is not a hydrogen atom; of A 2 and R 2f The definition is the same as above, and it will not be repeated here.
於本發明之具體例中，該具有式(1)所示結構之化合物(F)包含但不限於如下所示之化合物：
上述結構中，n'表示1至5之數；n"表示1至3之數。 In the above structure, n 'represents a number from 1 to 5; n "represents a number from 1 to 3.
基於該鹼可溶性樹脂(C)之使用量為100重量份，該具有式(1)所示結構之化合物(F)之使用量為0.1至20重量份；較佳為0.3至18重量份；更佳為0.5至15重量份。當未同時使用環戊二酮肟酯化合物(E-1)及該具有式(1)所示結構之化合物(F)時，該感光性樹脂組成物所形成之彩色濾光片具有易發生UV黃變之問題。 Based on the use amount of the alkali-soluble resin (C) being 100 parts by weight, the use amount of the compound (F) having the structure represented by the formula (1) is 0.1 to 20 parts by weight; preferably 0.3 to 18 parts by weight; more It is preferably 0.5 to 15 parts by weight. When the cyclopentadione oxime ester compound (E-1) and the compound (F) having the structure represented by the formula (1) are not used at the same time, the color filter formed by the photosensitive resin composition has a tendency to generate UV. The problem of yellowing.
本發明該感光性樹脂組成物的製備，通常是先將該顏料(A)以外的各成份溶解於溶劑(G)中，調製成液狀組成物，再加入顏料(A)均勻混合。溶劑(G)需選擇可溶解染料(B)、鹼可溶性樹脂(C)、具有乙烯性不飽和基之化合物(D)、光起始劑(E)以及具有式(1)所示結構之化合物(F)，且需不與該等成份相互反應並具有適當揮發性者。 In the preparation of the photosensitive resin composition of the present invention, generally, components other than the pigment (A) are first dissolved in a solvent (G) to prepare a liquid composition, and then the pigment (A) is added and mixed uniformly. As the solvent (G), a soluble dye (B), an alkali-soluble resin (C), an ethylenically unsaturated compound (D), a photoinitiator (E), and a compound having a structure represented by the formula (1) must be selected. (F), and those that do not react with these ingredients and have appropriate volatility.
基於該鹼可溶性樹脂(C)之使用量為100重量份，該溶劑(G)之使用量為500至5000重量份；較佳為800至4500重量份；更佳為1000至4000重量份。 Based on the use amount of the alkali-soluble resin (C) being 100 parts by weight, the use amount of the solvent (G) is 500 to 5000 parts by weight; preferably 800 to 4500 parts by weight; more preferably 1000 to 4000 parts by weight.
此外，溶劑(G)可與製備鹼可溶性樹脂(C)所使用的溶劑相同，在此不再贅述。較佳地，該溶劑(G)是擇自於丙二醇甲醚醋酸酯、環己酮或3-乙氧基丙酸乙酯。 In addition, the solvent (G) may be the same as the solvent used for preparing the alkali-soluble resin (C), and details are not described herein again. Preferably, the solvent (G) is selected from propylene glycol methyl ether acetate, cyclohexanone or ethyl 3-ethoxypropionate.
於本發明之較佳具體例中，該感光性樹脂組成物還包括添加劑(H)，例如：填充劑、鹼可溶性樹脂(C)以外的高分子化合物、密著促進劑、抗氧化劑、紫外線吸收劑、防凝集劑等。 In a preferred embodiment of the present invention, the photosensitive resin composition further includes an additive (H), for example, a filler, a polymer compound other than the alkali-soluble resin (C), an adhesion promoter, an antioxidant, and ultraviolet absorption. Agent, anti-aggregation agent, etc.
該添加劑(H)可單獨或混合使用，且該添加劑(H)包含但不限於玻璃、鋁等填充劑；聚乙烯醇、聚乙二醇單烷基醚、聚氟丙烯酸烷酯等鹼可溶性樹脂(C)以外的高分子化合物；乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧乙氧基)矽烷、氮-(2-胺基乙基)-3-胺基丙基甲 基二甲氧基矽烷、氮-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-環氧丙醇丙基三甲氧基矽烷、3-環氧丙醇丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯氧基丙基三甲氧基矽烷、3-硫醇基丙基三甲氧基矽烷等密著促進劑；2,2-硫代雙(4-甲基-6-第三丁基苯酚)、2,6-二-第三丁基苯酚等抗氧化劑；2-(3-第三丁基-5-甲基-2-羥基苯基)-5-氯苯基疊氮、烷氧基苯酮等紫外線吸收劑；及聚丙烯酸鈉等防凝集劑。 The additive (H) can be used singly or in combination, and the additive (H) includes, but is not limited to, fillers such as glass and aluminum; polyvinyl alcohol, polyethylene glycol monoalkyl ether, and polyfluoroacrylates and other alkali-soluble resins Polymer compounds other than (C); vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, nitrogen- (2-aminoethyl) -3 -Aminopropylmethyl Dimethoxysilane, nitrogen- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidylpropyltrimethylsilane Oxysilane, 3-glycidyl propylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxy Adhesion promoters such as silane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-thiolpropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and other antioxidants; 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) ) -5-chlorophenyl azide, alkoxy phenone and other ultraviolet absorbers; and anti-aggregation agents such as sodium polyacrylate.
基於該鹼可溶性樹脂(C)之使用量為100重量份，該添加劑(H)之使用量為0.1至10重量份；較佳為0.3至7重量份；更佳為0.5至4重量份。 Based on the use amount of the alkali-soluble resin (C) being 100 parts by weight, the use amount of the additive (H) is 0.1 to 10 parts by weight; preferably 0.3 to 7 parts by weight; more preferably 0.5 to 4 parts by weight.
本發明亦提供一種彩色濾光片之製造方法，其係使用前述之彩色濾光片用感光性樹脂組成物，以於基板上形成一畫素層。 The present invention also provides a method for manufacturing a color filter, which uses the aforementioned photosensitive resin composition for a color filter to form a pixel layer on a substrate.
本發明又提供一種彩色濾光片，其係由前述之方法所製得。 The present invention also provides a color filter, which is prepared by the aforementioned method.
本發明之彩色濾光片之製造方法，主要係藉由迴轉塗佈、流延塗佈、噴墨塗佈(ink-jet)或輥式塗佈等塗佈方式，將混合成溶液狀態之前述彩色濾光片用感光性組成物塗佈在基板上。塗佈後，先以減壓乾燥之方式，去除大部分之溶劑，再以預烤(pre-bake)方式將溶劑去除而形成一預烤塗膜。其中，減壓乾燥及預烤之條件，依各成份之種類，配合比率而異，通常，減壓乾燥乃是在0至200mmHg之壓力下進行1秒鐘至60秒鐘，而預烤乃是在70至110℃溫度下進行1分鐘至15分鐘。預烤後，該預烤塗膜於所指定之光罩(mask)下曝光，於23±2℃溫度下浸漬於顯影液15秒至5分鐘進行顯影，除去不要之部分而形成圖案。曝光使用之光線，以g線、h線、i線等之紫外線為佳，而紫外線裝置可為(超)高壓水銀燈或金屬鹵素燈。 The manufacturing method of the color filter of the present invention is mainly a method of mixing the solution into a solution by spin coating, cast coating, ink-jet coating, or roll coating. A photosensitive composition for a color filter is coated on a substrate. After coating, first remove most of the solvent by drying under reduced pressure, and then remove the solvent by pre-bake to form a pre-bake coating film. Among them, the conditions of reduced pressure drying and pre-baking vary according to the type of each component and the blending ratio. Generally, the reduced pressure drying is performed at a pressure of 0 to 200 mmHg for 1 second to 60 seconds, while pre-baking is It is performed at a temperature of 70 to 110 ° C for 1 minute to 15 minutes. After pre-baking, the pre-baking coating film is exposed under a designated mask, and immersed in a developing solution at a temperature of 23 ± 2 ° C. for 15 seconds to 5 minutes for development, removing unnecessary portions to form a pattern. The light used for exposure is preferably ultraviolet rays such as g-line, h-line, i-line, etc., and the ultraviolet device can be a (super) high-pressure mercury lamp or a metal halide lamp.
前述基板之具體例如：用於液晶顯示裝置之無鹼玻璃、鈉鈣玻璃、硬質玻璃(派勒斯玻璃)、石英玻璃、鈉玻璃以及於此等玻璃上所附著的透明導電膜；或用於固體攝影裝置等之光電變換裝置基板(如：矽基板)等等。此等基板一般係先形成隔離各畫素著色層之黑色矩陣(black matrix)。 Specific examples of the aforementioned substrate include: alkali-free glass, soda-lime glass, hard glass (Pales glass), quartz glass, soda glass, and transparent conductive films attached to these glasses for liquid crystal display devices; or Photoelectric conversion device substrates (such as silicon substrates) for solid-state imaging devices and the like. These substrates are generally formed with a black matrix that isolates each pixel color layer.
再者，顯影液之具體例如：氫氧化鈉，氫氧化鉀，碳酸鈉，碳酸氫鈉，碳酸鉀，碳酸氫鉀，矽酸鈉，甲基矽酸鈉，氨水，乙胺，二乙胺，二甲基乙醇胺，氫氧化四甲銨，氫氧化四乙銨，膽鹼，吡咯，呱啶，1,8-二氮雜二環-(5,4,0)-7-十一烯等鹼性化合物所構成之鹼性水溶液，其濃度一般為0.001至10重量%，較佳為0.005至5重量%，更佳為0.01至1重量%。 Moreover, specific examples of the developing solution include: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methylsilicate, ammonia, ethylamine, diethylamine, Dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, pyridine, 1,8-diazabicyclo- (5,4,0) -7-undecene and other bases The concentration of the alkaline aqueous solution composed of a neutral compound is generally 0.001 to 10% by weight, preferably 0.005 to 5% by weight, and more preferably 0.01 to 1% by weight.
使用前述鹼性水溶液所構成之顯影液時，一般係於顯影後再以水洗淨，其次以壓縮空氣或壓縮氮氣將圖案風乾。 When using a developing solution composed of the aforementioned alkaline aqueous solution, it is generally washed with water after development, and then the pattern is air-dried with compressed air or compressed nitrogen.
風乾後之具有光硬化塗膜層的基板，利用熱板或烘箱等加熱裝置，在溫度100至280℃下加熱1至15分鐘，將塗膜中的揮發性成分去除，並且使塗膜中未反應的乙烯性不飽和雙鍵進行熱硬化反應。使用各色(主要包括紅、綠、藍三色)之感光性樹脂組成物在預定的畫素上以同樣的步驟重複操作三次，即可得到紅、綠、藍三色之畫素著色層。 After air-drying, the substrate with the light-hardened coating film layer is heated at a temperature of 100 to 280 ° C for 1 to 15 minutes using a heating device such as a hot plate or an oven to remove the volatile components in the coating film and make the coating film The reacted ethylenically unsaturated double bond undergoes a thermosetting reaction. Using the photosensitive resin composition of each color (mainly including three colors of red, green, and blue) on a predetermined pixel, the same procedure is repeated three times to obtain a pixel colored layer of three colors of red, green, and blue.
其次，在畫素著色層上，以220℃至250℃溫度於真空下形成ITO(氧化銦錫)蒸鍍膜，必要時，對ITO蒸鍍膜施行蝕刻暨佈線之後，再塗佈液晶配向膜用聚醯亞胺，進而燒成之，即可作為液晶顯示器用之彩色濾光片。 Next, an ITO (indium tin oxide) vapor-deposited film is formed on the pixel color layer under a vacuum at a temperature of 220 ° C to 250 ° C. If necessary, the ITO vapor-deposited film is subjected to etching and wiring, and then a polycrystalline silicon alignment film is coated. Perylene imine, which can be further fired, can be used as a color filter for liquid crystal displays.
再者，前述使用的液晶配向膜，係用於限制液晶分子之配向，此處並未特別限定，舉凡無機物或有機物任一者均可。至於形成液晶配向膜之技術為本發明所屬技術領域中任何具有通常知識者所熟知，且非 為本發明的重點，故不另贅述。 In addition, the liquid crystal alignment film used in the foregoing is used to restrict the alignment of liquid crystal molecules, which is not particularly limited here, and any inorganic or organic substance may be used. As for the technique of forming a liquid crystal alignment film, it is well known to anyone with ordinary knowledge in the technical field to which the present invention belongs, and is not This is the focus of the present invention, so it will not be repeated here.
本發明又一目的在於提供一種液晶顯示元件，該液晶顯示元件包含前述彩色濾光片。 Another object of the present invention is to provide a liquid crystal display element including the aforementioned color filter.
本發明之液晶顯示元件，主要係藉由上述彩色濾光片形成方法所形成之彩色濾光片基板，以及設置有薄膜電晶體(TFT，Thin Film Transistor)之驅動基板所構成，其中，在2片基板間介入間隙(晶胞間隔；cell gap)作對向配置，2片基板的周圍部位用封止劑貼合，在基板表面以及封止劑所區分出的間隙內充填注入液晶，封住注入孔而構成液晶晶胞(cell)。然後，在液晶晶胞的外表面，亦即構成液晶晶胞的各個基板的其他側面上，貼合偏光板而製得液晶顯示元件。 The liquid crystal display element of the present invention is mainly composed of a color filter substrate formed by the above-mentioned color filter forming method, and a driving substrate provided with a thin film transistor (TFT, Thin Film Transistor). The interposition gap (cell gap; cell gap) between the substrates is oppositely arranged, and the peripheral parts of the two substrates are bonded with a sealing agent. The liquid crystal is filled into the gap separated by the substrate surface and the sealing agent, and the injection is sealed. Holes to form a liquid crystal cell. Then, on the outer surface of the liquid crystal cell, that is, on the other side of each substrate constituting the liquid crystal cell, a polarizing plate is bonded to prepare a liquid crystal display element.
至於前述使用的液晶，亦即液晶化合物或液晶組成物，此處並未特別限定，惟可使用任何一種液晶化合物及液晶組成物。 As for the liquid crystal used above, that is, a liquid crystal compound or a liquid crystal composition, it is not particularly limited here, but any liquid crystal compound and liquid crystal composition may be used.
茲以下列實例予以詳細說明本發明，唯並不意謂本發明僅侷限於此等實例所揭示之內容。 The following examples are used to explain the present invention in detail, but it is not meant to limit the present invention to the contents disclosed in these examples.
<合成例> <Synthesis example>
製備第一鹼可溶性樹脂(C) Preparation of the first alkali-soluble resin (C)
合成例C-1-1 Synthesis Example C-1-1
將100重量份的芴環氧化合物(型號ESF-300，新日鐵化學製；環氧當量231)、30重量份的丙烯酸、0.3重量份的氯化苄基三乙基銨、0.1重量份的2,6-二第三丁基對甲酚及130重量份的丙二醇甲醚醋酸酯連續添加至500mL的四口燒瓶中，且入料速度控制在25重量份/分鐘，將溫度維持在100℃至110℃的範圍內，反應15小時後，即可獲得固體成分濃度為50wt%之淡黃色透明混合液。 100 parts by weight of a rhenium epoxy compound (model ESF-300, manufactured by Nippon Steel Chemical; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, and 0.1 parts by weight of 2,6-Di-tert-butyl p-cresol and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500 mL four-necked flask, and the feeding speed was controlled at 25 parts by weight / minute, and the temperature was maintained at 100 ° C. Within the range of 110 ° C, a light yellow transparent mixed solution having a solid content concentration of 50% by weight can be obtained after 15 hours of reaction.
接著，將100重量份的上述混合液溶於25重量份的乙二醇乙 醚醋酸酯中，同時添加6重量份的四氫鄰苯二甲酸酐及13重量份的二苯甲酮四甲酸二酐，並加熱至110℃至115℃，反應2小時後，即可獲得酸價為98.0mgKOH/g，且數目平均分子量為1,623之第一鹼可溶性樹脂(C-1-1)。 Next, 100 parts by weight of the mixed solution was dissolved in 25 parts by weight of ethylene glycol. Add 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of benzophenonetetracarboxylic dianhydride to the ether acetate, and heat to 110 ° C to 115 ° C. After reacting for 2 hours, the acid can be obtained The first alkali-soluble resin (C-1-1) having a valence of 98.0 mgKOH / g and a number average molecular weight of 1,623.
合成例C-1-2 Synthesis Example C-1-2
將100重量份的芴環氧化合物(型號ESF-300，新日鐵化學製；環氧當量231)、30重量份的丙烯酸、0.3重量份的氯化苄基三乙基銨、0.1重量份的2,6-二第三丁基對甲酚及130重量份的丙二醇甲醚醋酸酯連續添加至500mL的四口燒瓶中，且入料速度控制在25重量份/分鐘，將溫度維持在100℃至110℃的範圍內，反應15小時後，即可獲得固體成分濃度為50wt%之淡黃色透明混合液。 100 parts by weight of a rhenium epoxy compound (model ESF-300, manufactured by Nippon Steel Chemical; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, and 0.1 parts by weight of 2,6-Di-tert-butyl p-cresol and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500 mL four-necked flask, and the feeding speed was controlled at 25 parts by weight / minute, and the temperature was maintained at 100 ° C. Within the range of 110 ° C, a light yellow transparent mixed solution having a solid content concentration of 50% by weight can be obtained after 15 hours of reaction.
接著，將100重量份的上述混合液溶於25重量份的乙二醇***醋酸酯中，同時添加13重量份的二苯甲酮四甲酸二酐，在90℃至95℃下反應2小時，接著，添加6重量份的四氫鄰苯二甲酸酐，並於90℃至95℃下反應4小時，即可獲得酸價為99.0mgKOH/g，且數目平均分子量為2,162之第一鹼可溶性樹脂(C-1-2)。 Next, 100 parts by weight of the above mixed solution was dissolved in 25 parts by weight of ethylene glycol ether acetate, and 13 parts by weight of benzophenonetetracarboxylic dianhydride was added at the same time, and the reaction was performed at 90 ° C to 95 ° C for 2 hours. Next, by adding 6 parts by weight of tetrahydrophthalic anhydride and reacting at 90 ° C to 95 ° C for 4 hours, a first alkali-soluble resin having an acid value of 99.0 mgKOH / g and a number average molecular weight of 2,162 can be obtained. (C-1-2).
合成例C-1-3 Synthesis Example C-1-3
將400重量份的環氧化合物(型號NC-3000，日本化藥(株)製；環氧當量288)、102重量份的丙烯酸、0.3重量份的甲氧基酚(methoxyphenol)、5重量份的三苯基膦及264重量份的丙二醇甲醚醋酸酯置於反應瓶中，將溫度維持在95℃，反應9小時後，即可獲得酸價為2.2mgKOH/g之中間產物。接著，加入151重量份的四氫鄰苯二甲酸酐(tetrahydrophthalic anhydride)，在95℃下反應4小時，即可獲得酸價為102mgKOH/g，且數目平均分子量為2,589之第一鹼可溶性樹脂(C-1-3)。 400 parts by weight of an epoxy compound (model NC-3000, manufactured by Nippon Kayaku Co., Ltd .; epoxy equivalent 288), 102 parts by weight of acrylic acid, 0.3 parts by weight of methoxyphenol, and 5 parts by weight of Triphenylphosphine and 264 parts by weight of propylene glycol methyl ether acetate were placed in a reaction flask, and the temperature was maintained at 95 ° C. After 9 hours of reaction, an intermediate product having an acid value of 2.2 mgKOH / g was obtained. Next, 151 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain a first alkali-soluble resin having an acid value of 102 mgKOH / g and a number average molecular weight of 2,589 ( C-1-3).
合成例C-1-4 Synthesis Example C-1-4
將200重量份的環氧化合物(型號NC-3000，日本化藥(株)製；環氧當量288)、60重量份的丙烯酸、0.15重量份的甲氧基酚(methoxyphenol)、2.5重量份的三苯基膦及200重量份的丙二醇甲醚醋酸酯置於反應瓶中，將溫度維持在95℃，反應9小時後，即可獲得酸價為2.5mgKOH/g之中間產物。接著，加入85重量份的四氫鄰苯二甲酸酐(tetrahydrophthalic anhydride)，在95℃下反應4小時，即可獲得酸價為105mgKOH/g，且數目平均分子量為3,410之第一鹼可溶性樹脂(C-1-4)。 200 parts by weight of an epoxy compound (model NC-3000, manufactured by Nippon Kayaku Co., Ltd .; epoxy equivalent 288), 60 parts by weight of acrylic acid, 0.15 parts by weight of methoxyphenol, and 2.5 parts by weight of Triphenylphosphine and 200 parts by weight of propylene glycol methyl ether acetate were placed in a reaction flask, and the temperature was maintained at 95 ° C. After 9 hours of reaction, an intermediate product having an acid value of 2.5 mgKOH / g was obtained. Next, 85 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain a first alkali-soluble resin having an acid value of 105 mgKOH / g and a number average molecular weight of 3,410 ( C-1-4).
製備第二鹼可溶性樹脂(C-2) Preparation of the second alkali-soluble resin (C-2)
合成例C-2-1 Synthesis Example C-2-1
在一四頸錐瓶上設置攪拌器、溫度計、冷凝管及氮氣入口，並導入氮氣。然後，加入100重量份之丙二醇甲醚醋酸酯(簡稱為PGMEA)，並將溫度升溫至100℃。接著，將25重量份之2-甲基丙烯醯乙氧基丁二酸酯(簡稱為HOMS)、70重量份之甲基丙烯酸2-羥基乙酯(簡稱為HEMA)、15重量份之甲基丙烯酸3,4-環氧環己基甲酯(ECMMA)、10重量份之鄰-乙烯基苯甲基環氧丙醚(簡稱為VBGE)，以及4.5重量份之2,2'-偶氮雙-2-甲基丁腈(簡稱為AMBN)溶於100重量份之丙二醇甲醚醋酸酯中，並將此混合溶液於2小時內逐滴滴入上述四頸錐瓶中。於100℃反應6.5小時後，將5重量份之丙烯酸(簡稱為AA)加至充滿氮氣之四頸錐瓶中，並將溫度上升至110℃。反應6小時後，即可製得合成例C-2-1之第二鹼可溶性樹脂。 A four-necked conical flask was provided with a stirrer, a thermometer, a condenser tube, and a nitrogen inlet, and nitrogen was introduced. Then, 100 parts by weight of propylene glycol methyl ether acetate (abbreviated as PGMEA) was added, and the temperature was raised to 100 ° C. Next, 25 parts by weight of 2-methacrylic acid ethoxysuccinate (abbreviated as HOMS), 70 parts by weight of 2-hydroxyethyl methacrylate (abbreviated as HEMA), and 15 parts by weight of methyl 3,4-epoxycyclohexyl methyl acrylate (ECMMA), 10 parts by weight of o-vinylbenzyl glycidyl ether (abbreviated as VBGE), and 4.5 parts by weight of 2,2'-azobis- 2-methylbutyronitrile (abbreviated as AMBN) was dissolved in 100 parts by weight of propylene glycol methyl ether acetate, and the mixed solution was dropped into the four-necked conical flask dropwise within 2 hours. After reacting at 100 ° C for 6.5 hours, 5 parts by weight of acrylic acid (referred to as AA) was added to a four-necked conical flask filled with nitrogen, and the temperature was raised to 110 ° C. After 6 hours of reaction, the second alkali-soluble resin of Synthesis Example C-2-1 was obtained.
合成例C-2-2至C-2-6之製造方法 Production method of Synthesis Examples C-2-2 to C-2-6
合成例C-2-2至C-2-6是以與合成例C-2-1相同的步驟來製備第二鹼可溶性樹脂(C-2)，不同的地方在於：改變反應溫度、聚合時間、成份的種類及使用量，且詳載於表1。 Synthesis Examples C-2-2 to C-2-6 were prepared using the same procedure as Synthesis Example C-2-1 to prepare a second alkali-soluble resin (C-2), except that the reaction temperature and polymerization time were changed. The types and amounts of ingredients are listed in Table 1.
<實施例> <Example>
製備感光性樹脂組成物 Preparation of photosensitive resin composition
實施例1 Example 1
將前述合成例所得之100重量份的第二鹼可溶性樹脂(C-2-1)、80重量份的C.I.顏料紅254(以下簡稱A-1)、20重量份的C.I.酸性紅37(以下簡稱B-2-1)、60重量份的EO改質之三甲基丙烯酸三羥甲基丙酯(以下簡稱D-1)、25重量份的式(I-11)所示之化合物(以下簡稱E-1-1)、10重量份的下列(F-1)所示之化合物，加入800重量份的3-乙氧基丙酸乙酯(以下簡稱G-1)後，以搖動式攪拌器，加以溶解混合，即可調製而得感光性樹脂組成物，該感光性樹脂組成物以下述之各測定評價方式進行評價，所得結果如表2所示。 100 parts by weight of the second alkali-soluble resin (C-2-1) obtained in the aforementioned Synthesis Example, 80 parts by weight of CI Pigment Red 254 (hereinafter referred to as A-1), and 20 parts by weight of CI Acid Red 37 (hereinafter referred to as B-2-1), 60 parts by weight of EO modified trimethylolpropyl trimethacrylate (hereinafter referred to as D-1), and 25 parts by weight of a compound represented by formula (I-11) (hereinafter referred to as E-1-1), 10 parts by weight of the compound shown in the following (F-1), 800 parts by weight of ethyl 3-ethoxypropionate (hereinafter referred to as G-1) was added, and then a shaker was used. After dissolving and mixing, a photosensitive resin composition can be prepared, and the photosensitive resin composition is evaluated by the following measurement and evaluation methods. The results are shown in Table 2.
實施例2至16及比較例1至4 Examples 2 to 16 and Comparative Examples 1 to 4
實施例2至16及比較例1至4係使用與實施例1之感光性樹脂組成物的製作方法相同之製備方法，不同之處在於實施例2至16及比較例1至4係改變感光性樹脂組成物中原料的種類及使用量，且其配方及評價結果分別如表2即表3所示，在此不另贅述。 Examples 2 to 16 and Comparative Examples 1 to 4 use the same preparation method as that of the photosensitive resin composition of Example 1, except that Examples 2 to 16 and Comparative Examples 1 to 4 change the sensitivity. The types and amounts of raw materials in the resin composition, and their formulations and evaluation results are shown in Table 2 and Table 3, respectively, and are not repeated here.
表2及表3中：
比較例5 Comparative Example 5
將167重量份的C.I.顏料紅177、100重量份的由MAA/MGMA/HEMA/BzMA(聚合重量比：15/16.5/15/53.5，Mw=9000，Mn=4500)聚合而得之鹼可溶性樹脂、67重量份的二季戊四醇六丙烯酸酯、17重量份的2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基二咪唑、17重量份的4,4’-雙(二乙胺)二苯甲酮、83重量份的2-苄基-2-氮，氮-二甲胺-1-(4-嗎啉代苯基)-1-丁酮、8重量份的2-氫硫苯并噻唑，加入1667重量份的3-乙氧基丙酸乙酯後，以搖動式攪拌器，加以溶解混合，即可調製而得感光性樹脂組成物，該感光性樹脂組成物以下述之各測定評價方式進行評價，評價結果耐UV黃變性為×。 167 parts by weight of CI Pigment Red 177 and 100 parts by weight of an alkali-soluble resin obtained by polymerization of MAA / MGMA / HEMA / BzMA (polymerization weight ratio: 15 / 16.5 / 15 / 53.5, Mw = 9000, Mn = 4500) 67 parts by weight of dipentaerythritol hexaacrylate, 17 parts by weight of 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyldiimidazole, 17 parts by weight Parts of 4,4'-bis (diethylamine) benzophenone, 83 parts by weight of 2-benzyl-2-nitro, nitro-dimethylamine-1- (4-morpholinophenyl) -1 -Butanone, 8 parts by weight of 2-hydrothiobenzothiazole, and after adding 1667 parts by weight of ethyl 3-ethoxypropionate, the mixture is dissolved and mixed with a shaker to prepare a photosensitive resin. The composition and the photosensitive resin composition were evaluated by the following measurement and evaluation methods, and the results of the evaluation were UV yellowing resistance ×.
<評價方式> <Evaluation method>
耐UV黃變性 UV yellowing resistance
將感光性樹脂組成物以旋轉塗佈之方式，塗佈在100mm×100mm之玻璃基板上，先進行減壓乾燥，壓力100mmHg、時間30秒鐘，然後再進行預烤，溫度90℃、時間2分鐘，可形成一膜厚1.2μm之預烤塗膜，再將預烤塗膜以紫外光(曝光機Canon PLA-501F)100mJ/cm2之光量照射該預烤塗膜後，再浸漬於23℃之顯影液1分鐘，以純水洗淨，再以230℃後烤30分鐘，即可在玻璃基板上形成一膜厚1.0μm之畫素著色層。 The photosensitive resin composition was spin-coated on a 100 mm × 100 mm glass substrate, and then dried under reduced pressure, with a pressure of 100 mmHg for 30 seconds, and then pre-baked at a temperature of 90 ° C. and a time of 2 After a minute, a pre-baking coating film with a thickness of 1.2 μm can be formed. The pre-baking coating film is irradiated with 100 mJ / cm 2 of UV light (exposure machine Canon PLA-501F), and then immersed in 23 The developing solution at ℃ for 1 minute, washed with pure water, and then baked at 230 ℃ for 30 minutes, then a pixel-colored layer with a film thickness of 1.0 μm can be formed on the glass substrate.
所得之畫素著色層，於L*a*b*所表示之色系，以分光測色計CM-600d(Konica Minolta Sensing社製)測定L1*,a1*,b1*值，接著，將此畫素著色層再進一步以紫外光1680mJ/cm2之光量照射後，再次測定L2*,a2*,b2*值。 The obtained pixel-colored layer was measured for a value of L 1 *, a 1 *, b 1 * using a spectrophotometer CM-600d (manufactured by Konica Minolta Sensing) in the color system represented by L * a * b *, and then After further irradiating the pixel-colored layer with a light amount of 1680 mJ / cm 2 of ultraviolet light, the values of L 2 *, a 2 *, and b 2 * were measured again.
計算色差△Eab*=[(△L*)^2+(△a*)^2+(△b*)^2]^1/2 Calculate color difference △ E ab * = [(△ L *) ^ 2+ (△ a *) ^ 2+ (△ b *) ^ 2] ^ 1/2
△L*=L2*-L1*,△a*=a2*-a1*,△b*=b2*-b1* △ L * = L 2 * -L 1 *, △ a * = a 2 * -a 1 *, △ b * = b 2 * -b 1 *
◎：△Eab*<3 ◎: △ E ab * <3
○：3≦△Eab*<6 ○: 3 ≦ △ E ab * <6
△：6≦△Eab*<9 △: 6 ≦ △ E ab * <9
×：△Eab*≧9 ×: △ E ab * ≧ 9
上述實施例僅為說明本發明之原理及其功效，而非限制本發明。習於此技術之人士對上述實施例所做之修改及變化仍不違背本發明之精神。本發明之權利範圍應如後述之申請專利範圍所列。 The above embodiments are only for explaining the principle of the present invention and its effects, but not for limiting the present invention. Modifications and changes made by those skilled in the art to the above embodiments still do not violate the spirit of the present invention. The scope of rights of the present invention should be listed in the scope of patent application described later.
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