TW201604243A - Colored curable resin composition - Google Patents
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Description
本發明係關於一種著色硬化性樹脂組合物。 The present invention relates to a color hardening resin composition.
著色硬化性樹脂組合物例如係用於製造液晶顯示裝置等之彩色濾光片。作為著色硬化性樹脂組合物，於日本專利特開2010-211198號公報中揭示有：含有選自由黃色顏料、橙色顏料及紅色顏料所組成之群中之至少一種顏料與二苯并吡喃染料作為著色劑之著色硬化性樹脂組合物。 The colored curable resin composition is used, for example, for producing a color filter such as a liquid crystal display device. As a coloring curable resin composition, it is disclosed in Japanese Laid-Open Patent Publication No. 2010-211198 that at least one pigment selected from the group consisting of a yellow pigment, an orange pigment, and a red pigment is used as a dibenzopyran dye. A colored curable resin composition for a colorant.
本發明提供以下[1]~[7]。 The present invention provides the following [1] to [7].
[1]一種著色硬化性樹脂組合物，其含有著色劑(A)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D)，著色劑(A)含有紅色顏料(A-1)及染料(A-2)，染料(A-2)含有二苯并吡喃染料及香豆素染料。 [1] A color-curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) contains a red pigment (A- 1) and dye (A-2), the dye (A-2) contains a dibenzopyran dye and a coumarin dye.
[2]如[1]之著色硬化性樹脂組合物，其中紅色顏料(A-1)係選自由顏料紅177、顏料紅242及顏料紅254所組成之群中之至少一種顏料。 [2] The colored curable resin composition according to [1], wherein the red pigment (A-1) is at least one selected from the group consisting of Pigment Red 177, Pigment Red 242, and Pigment Red 254.
[3]如[1]或[2]之著色硬化性樹脂組合物，其中二苯并吡喃染料係式(1a)所表示之化合物，
[4]如[1]至[3]中任一項之著色硬化性樹脂組合物，其中香豆素染料係式(Ad2)所表示之化合物，
[5]如[1]至[4]中任一項之著色硬化性樹脂組合物，其中二苯并吡喃染料及香豆素染料之含有比(二苯并吡喃染料：香豆素染料)以質量基準計為60：40~99：1。 [5] The colored curable resin composition according to any one of [1] to [4] wherein the content ratio of the dibenzopyran dye and the coumarin dye (dibenzopyran dye: coumarin dye) ) 60:40~99:1 on a mass basis.
[6]一種彩色濾光片，其係由如[1]至[5]中任一項之著色硬化性樹脂組合物所形成者。 [6] A color filter formed by the color hardening resin composition according to any one of [1] to [5].
[7]一種液晶顯示裝置，其係含有如[6]之彩色濾光片者。 [7] A liquid crystal display device comprising the color filter of [6].
本發明之著色硬化性樹脂組合物含有著色劑(A)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D)。 The color-curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
著色劑(A)含有紅色顏料(A-1)及染料(A-2)，染料(A-2)含有二苯并吡喃染料及香豆素染料。 The colorant (A) contains a red pigment (A-1) and a dye (A-2), and the dye (A-2) contains a dibenzopyran dye and a coumarin dye.
較佳為二苯并吡喃染料及香豆素染料之含有比(二苯并吡喃染料：香豆素染料)以質量基準計為60：40~99：1。 Preferably, the content ratio of the dibenzopyran dye and the coumarin dye (dibenzopyran dye: coumarin dye) is 60:40 to 99:1 on a mass basis.
較佳為本發明之著色硬化性樹脂組合物進而含有選自由溶劑(E)及調平劑(F)所組成之群中之至少一種。 It is preferable that the colored curable resin composition of the present invention further contains at least one selected from the group consisting of a solvent (E) and a leveling agent (F).
本發明之著色硬化性樹脂組合物可進而含有聚合起始助劑(D1)。 The colored curable resin composition of the present invention may further contain a polymerization initiation aid (D1).
於本說明書中，作為各成分而例示之化合物若無特別說明，則可單獨或組合複數種使用。 In the present specification, the compounds exemplified as the respective components may be used singly or in combination of plural kinds unless otherwise specified.
作為紅色顏料(A-1)，並無特別限定，可使用公知之顏料，例如可列舉：染料索引(The Society of Dyers and Colourists(染色家協會)出版)中分類為顏料之紅色顏料。 The red pigment (A-1) is not particularly limited, and a known pigment can be used. For example, a red pigment classified as a pigment in the dye index (published by The Society of Dyers and Colourists) can be cited.
作為紅色顏料，例如可列舉：C.I.顏料紅9(以下，省略C.I.顏料之記載，僅記載編號；其他亦相同)、97、105、122、123、144、149、166、168、176、177、180、192、207、209、215、216、224、242、254、255、264、265、272，較佳可列舉：C.I.顏料紅149、176、177、207、242、254、255、264、272，進而較佳可列舉：C.I.顏料紅177、 242、254。 Examples of the red pigment include CI Pigment Red 9 (hereinafter, the description of the CI pigment is omitted, only the number is described; the others are the same), 97, 105, 122, 123, 144, 149, 166, 168, 176, and 177. 180, 192, 207, 209, 215, 216, 224, 242, 254, 255, 264, 265, 272, preferably, CI Pigment Red 149, 176, 177, 207, 242, 254, 255, 264, 272, further preferably, CI Pigment Red 177, 242, 254.
於本發明之著色硬化性樹脂組合物中，含有C.I.顏料紅149、176、177、207、242、254、255、264、272等作為紅色顏料(A-1)之情形時，作為紅色濾光片之透射光譜之最佳化較容易，彩色濾光片之亮度變得良好。 When the coloring curable resin composition of the present invention contains CI Pigment Red 149, 176, 177, 207, 242, 254, 255, 264, 272 or the like as the red pigment (A-1), it is used as a red color filter. The optimization of the transmission spectrum of the sheet is easier, and the brightness of the color filter becomes good.
進而，本發明之著色硬化性樹脂組合物亦可含有紅色顏料(A-1)以外之顏料(A-3)。 Further, the colored curable resin composition of the present invention may contain a pigment (A-3) other than the red pigment (A-1).
作為顏料(A-3)，可列舉：C.I.顏料黃1、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、137、138、139、147、148、150、153、154、166、173、194、214等黃色顏料；C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等橙色顏料等。 As the pigment (A-3), CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, Yellow pigments such as 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments.
該等顏料可配合所需之彩色濾光片之分光光譜而適宜選擇。該等顏料可單獨使用亦可混合兩種以上而使用。 These pigments can be suitably selected in accordance with the spectral spectrum of the desired color filter. These pigments may be used singly or in combination of two or more.
顏料視需要亦可實施松香處理、使用有導入有酸性基或鹼性基之顏料衍生物等之表面處理、利用高分子化合物等所進行之對顏料表面之接枝處理、藉由硫酸微粒化法等所進行之微粒化處理、或藉由用以去除雜質之有機溶劑或水等所進行之清洗處理、藉由離子交換法等所進行之離子性雜質之去除處理等。 The pigment may be subjected to a rosin treatment, a surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment on the surface of the pigment by a polymer compound, or the like, and a sulfuric acid micronization method. The micronization treatment performed by the microparticles, the cleaning treatment by an organic solvent or water for removing impurities, the removal treatment of ionic impurities by an ion exchange method, or the like.
顏料較佳為粒徑均勻。藉由含有顏料分散劑而進行分散處理，可獲得顏料於溶液中均勻分散之狀態之顏料分散液。 The pigment preferably has a uniform particle size. By performing a dispersion treatment by containing a pigment dispersant, a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained.
作為顏料分散劑，例如可列舉：陽離子系、陰離子系、非離子系、兩性、聚酯系、聚胺系、丙烯酸系等之界面活性劑等。該等顏料分散劑可單獨使用亦可組合兩種以上而使用。作為顏料分散劑，可列舉：商品名KP(信越化學工業(股份)製造)、Flowlen(共榮社化學(股份)製造)、Solsperse(Zeneca(股份)製造)、EFKA(註冊商標)(BASF公司製造)、 Ajisper(Ajinomoto Fine-Techno(股份)製造)、Disperbyk(註冊商標)(BYK-Chemie公司製造)等。 Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used singly or in combination of two or more. Examples of the pigment dispersant include a product name KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca), and EFKA (registered trademark) (BASF Corporation). Manufacturing), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), and the like.
於使用顏料分散劑之情形時，其使用量相對於顏料之總量，較佳為1質量%以上、100質量%以下，更佳為5質量%以上、50質量%以下。若顏料分散劑之使用量為上述範圍，則存在獲得均勻分散狀態之顏料分散液之傾向。 In the case of using a pigment dispersant, the amount thereof to be used is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 50% by mass or less based on the total amount of the pigment. When the amount of the pigment dispersant used is in the above range, there is a tendency to obtain a pigment dispersion liquid in a uniformly dispersed state.
紅色顏料(A-1)之含量相對於著色劑(A)之總量，較佳為1~99質量%，更佳為5~98質量%，進而較佳為10~95質量%。 The content of the red pigment (A-1) is preferably from 1 to 99% by mass, more preferably from 5 to 98% by mass, even more preferably from 10 to 95% by mass, based on the total amount of the coloring agent (A).
於含有顏料(A-3)之情形時，其含有率相對於著色劑(A)之總量，較佳為0.5~50質量%，更佳為1~40質量%。 In the case of containing the pigment (A-3), the content thereof is preferably from 0.5 to 50% by mass, more preferably from 1 to 40% by mass, based on the total amount of the coloring agent (A).
染料(A-2)含有二苯并吡喃染料及香豆素染料。 The dye (A-2) contains a dibenzopyran dye and a coumarin dye.
二苯并吡喃染料係含有於分子內具有二苯并吡喃骨架之化合物之染料。作為二苯并吡喃染料，可列舉：C.I.酸性紅51、52、87、92、94、289、388，C.I.酸性紫9、30、102，C.I.鹼性紅1(玫瑰紅6G)、2、3、4、8，C.I.鹼性紅10(玫瑰紅B)、11，C.I.鹼性紫10、11、25，C.I.溶劑紅218，C.I.媒介紅27，C.I.反應性紅36(孟加拉玫瑰紅B)，酸性玫瑰紅G，日本專利特開2010-32999號公報中揭示之二苯并吡喃染料及日本專利第4492760號公報中揭示之二苯并吡喃染料等。 The dibenzopyran dye is a dye containing a compound having a dibenzopyran skeleton in the molecule. Examples of the dibenzopyran dyes include CI Acid Red 51, 52, 87, 92, 94, 289, 388, CI Acid Violet 9, 30, 102, CI Basic Red 1 (Rose Red 6G), 2. 3, 4, 8, CI alkaline red 10 (Rose red B), 11, CI alkaline purple 10, 11, 25, CI solvent red 218, CI medium red 27, CI reactive red 36 (Bangladesh rose red B) The acid rosacem G, the dibenzopyran dye disclosed in Japanese Patent Laid-Open Publication No. 2010-32999, and the dibenzopyran dye disclosed in Japanese Patent No. 4492760.
作為二苯并吡喃染料，較佳為含有式(1a)所表示之化合物(以下有時稱為「化合物(1a)」)之染料。化合物(1a)亦可為其互變異構物。 The dibenzopyran dye is preferably a dye containing a compound represented by the formula (1a) (hereinafter sometimes referred to as "compound (1a)"). Compound (1a) can also be a tautomer thereof.
於本發明之著色硬化性樹脂組合物中，含有化合物(1a)作為二苯并吡喃染料之情形時，二苯并吡喃染料中之化合物(1a)之含量較佳為50質量%以上，更佳為70質量%以上，進而較佳為90質量%以上。尤其，作為二苯并吡喃染料，較佳為僅使用化合物(1a)。 When the compound (1a) is used as the dibenzopyran dye in the colored curable resin composition of the present invention, the content of the compound (1a) in the dibenzopyran dye is preferably 50% by mass or more. More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more. In particular, as the dibenzopyran dye, it is preferred to use only the compound (1a).
[式(1a)中，R1~R4相互獨立地表示氫原子、可具有取代基之碳數1~20之1價飽和烴基或可具有取代基之碳數6~10之1價芳香族烴基，該飽和烴基中所含之-CH2-可被取代為-O-、-CO-或-NR11-；R1及R2亦可相互鍵結，與該等所鍵結之氮原子一併形成含有氮原子之環，R3及R4亦可相互鍵結，與該等所鍵結之氮原子一併形成含有氮原子之環；R5表示-OH、-SO3 -、-SO3H、-SO3 -Z+、-CO2H、-CO2 -Z+、-CO2R8、-SO3R8或-SO2NR9R10；R6及R7相互獨立地表示氫原子或碳數1~6之烷基；m表示0~5之整數；m為2以上時，複數個R5可相同亦可不同；a表示0或1之整數；X表示鹵素原子；Z+表示+N(R11)4、Na+或K+；R8表示碳數1~20之1價飽和烴基，該飽和烴基中所含之氫原子可被取代為鹵素原子；R9及R10相互獨立地表示氫原子或可具有取代基之碳數1~20之1價飽和烴基，該飽和脂肪族烴基中所含之-CH2-可被取代為-O-、-CO-、-NH-或-NR8-，R9及R10亦可相互鍵結，與該等所鍵結之氮原子一併形成3~10員含氮雜環；R11相互獨立地表示氫原子、碳數1~20之1價飽和烴基或碳數7~10之芳烷基] 作為R1~R4及R8~R11所表示之碳數1~20之1價飽和烴基，可列舉：甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十二烷基、十六烷基、二十烷基等直鏈狀烷基；異丙基、異丁基、異戊基、新戊基、2-乙基己基等支鏈狀烷基；環丙基、環戊基、環己基、環庚基、環辛基、三環癸基等碳數3~20之脂環式飽和烴基。 In the formula (1a), R 1 to R 4 each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic group having 6 to 10 carbon atoms which may have a substituent a hydrocarbon group, -CH 2 - contained in the saturated hydrocarbon group may be substituted with -O-, -CO- or -NR 11 -; R 1 and R 2 may also be bonded to each other, and the bonded nitrogen atom A ring containing a nitrogen atom is formed together, and R 3 and R 4 may be bonded to each other to form a ring containing a nitrogen atom together with the nitrogen atom to be bonded; R 5 represents -OH, -SO 3 - , - SO 3 H, -SO 3 - Z + , -CO 2 H, -CO 2 - Z + , -CO 2 R 8 , -SO 3 R 8 or -SO 2 NR 9 R 10 ; R 6 and R 7 are independent of each other The ground represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents an integer of 0 to 5; when m is 2 or more, plural R 5 's may be the same or different; a represents an integer of 0 or 1; and X represents a halogen atom. ; Z + represents + N (R 11) 4, Na + or K +; R 8 is a C 1-20 monovalent saturated hydrocarbon group of 1, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom; R 9 and R 10 each independently represent a hydrogen atom or a substituent group having a carbon number of 1 to 20. the monovalent saturated hydrocarbon group, the saturated aliphatic hydrocarbon Contains the -CH 2 - may be substituted with -O -, - CO -, - NH- or -NR 8 -, R 9 and R 10 may be bonded to each other, such that the nitrogen atom bonded together with the 3 to 10 members of a nitrogen-containing heterocyclic ring are formed; R 11 independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms] as R 1 to R 4 and R 8 ~ The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 11 may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group or a fluorene group. a linear alkyl group such as an alkyl group, a hexadecyl group or an eicosyl group; a branched alkyl group such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group or a 2-ethylhexyl group; a cyclopropyl group; An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclic fluorenyl group.
R1~R4之碳數1~20之1價飽和烴基中所含之氫原子可被取代為苯基等碳數6~10之芳香族烴基、氟原子等鹵素原子等。 The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms of R 1 to R 4 may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group or a halogen atom such as a fluorine atom.
R9及R10之碳數1~20之1價飽和烴基中所含之氫原子例如可被取代為羥基或鹵素原子。 The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms of R 9 and R 10 may be substituted, for example, with a hydroxyl group or a halogen atom.
作為R1~R4所表示之碳數6~10之1價芳香族烴基，可列舉：苯基、甲苯甲醯基、二甲苯基、基、丙基苯基及丁基苯基。 Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R 1 to R 4 include a phenyl group, a tolylmethyl group, and a xylyl group. Base, propyl phenyl and butyl phenyl.
作為該芳香族烴基可具有之取代基，可列舉：鹵素原子、-R8a、-OH、-OR8a、-SO3 -、-SO3H、-SO3 -Z+、-CO2H、-CO2R8a、-SR8a、-SO2R8a、-SO3R8a及-SO2NR9aR10a。該等之中，作為取代基，較佳為-SO3 -、-SO3H、-SO3 -Za +及-SO2NR9aR10a，更佳為-SO3 -Za +及-SO2NR9aR10a。作為該情形時之-SO3 -Za +，較佳為-SO3 -+N(R11a)4。 Examples of the substituent which the aromatic hydrocarbon group may have include a halogen atom, -R 8a , -OH, -OR 8a , -SO 3 - , -SO 3 H, -SO 3 - Z + , -CO 2 H, -CO 2 R 8a , -SR 8a , -SO 2 R 8a , -SO 3 R 8a and -SO 2 NR 9a R 10a . Among these, as the substituent, -SO 3 - , -SO 3 H, -SO 3 - Z a + and -SO 2 NR 9a R 10a are preferred, and -SO 3 - Z a + and - are more preferred. SO 2 NR 9a R 10a . As this case, -SO 3 - Z a + is preferably -SO 3 -+ N(R 11a ) 4 .
含有R1~R4為該等基之化合物(1a)之本發明之著色硬化性樹脂組合物於彩色濾光片形成時較少產生異物，並且，所獲得之彩色濾光片之耐熱性優異。 The colored curable resin composition of the present invention containing the compound (1a) in which R 1 to R 4 are the groups is less likely to generate foreign matter when the color filter is formed, and the color filter obtained is excellent in heat resistance. .
作為R1及R2與氮原子一同形成之環、以及R3及R4與氮原子一同形成之環，可列舉以下者。 Examples of the ring formed by R 1 and R 2 together with a nitrogen atom and the ring formed by R 3 and R 4 together with a nitrogen atom include the following.
R8a、R9a及R10a分別表示碳數1~20之1價飽和烴基，該飽和烴基中 所含之氫原子可被取代為鹵素原子。作為R8a所表示之飽和烴基，可列舉關於R8所例示之直鏈狀烷基、支鏈狀烷基、脂環式飽和烴基。 R 8a , R 9a and R 10a each represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. The saturated hydrocarbon group represented by R 8a may, for example, be a linear alkyl group, a branched alkyl group or an alicyclic saturated hydrocarbon group exemplified as R 8 .
作為-OR8及-OR8a，分別可列舉：甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、2-乙基己氧基及二十烷氧基等碳數1~20，較佳為碳數1~8之烷氧基。 Examples of -OR 8 and -OR 8a include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, and a 2-ethyl group. The oxy group and the eicosyloxy group have a carbon number of 1 to 20, preferably an alkoxy group having 1 to 8 carbon atoms.
作為-CO2R8及-CO2R8a，分別可列舉：甲氧基羰基、乙氧基羰基、丙氧基羰基、第三丁氧基羰基、己氧基羰基及二十烷氧基羰基。 Examples of -CO 2 R 8 and -CO 2 R 8a include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a third butoxycarbonyl group, a hexyloxycarbonyl group, and an eicosyloxycarbonyl group. .
作為-SR8及-SR8a，分別可列舉：甲基硫基、乙基硫基、丁基硫基、己基硫基、癸基硫基及二十烷基硫基。 Examples of -SR 8 and -SR 8a include a methylthio group, an ethylthio group, a butylthio group, a hexylthio group, a mercaptothio group, and an eicosylthio group.
作為-SO2R8及-SO2R8a，分別可列舉：甲基磺醯基、乙基磺醯基、丁基磺醯基、己基磺醯基、癸基磺醯基及二十烷基磺醯基。 Examples of -SO 2 R 8 and -SO 2 R 8a include methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl and eicosyl groups. Sulfonyl.
作為-SO3R8及-SO2R8a，分別可列舉：甲氧基磺醯基、乙氧基磺醯基、丙氧基磺醯基、第三丁氧基磺醯基、己氧基磺醯基及二十烷氧基磺醯基。 Examples of -SO 3 R 8 and -SO 2 R 8a include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a third butoxysulfonyl group, and a hexyloxy group. Sulfhydryl and eicosyloxysulfonyl.
作為-SO2NR9R10及-SO2NR9aR10a，可列舉：胺磺醯基；N-甲基胺磺醯基、N-乙基胺磺醯基、N-丙基胺磺醯基、N-異丙基胺磺醯基、N-丁基胺磺醯基、N-異丁基胺磺醯基、N-第二丁基胺磺醯基、N-第三丁基胺磺醯基、N-戊基胺磺醯基、N-(1-乙基丙基)胺磺醯基、N-(1,1-二甲基丙基)胺磺醯基、N-(1,2-二甲基丙基)胺磺醯基、N-(2,2-二甲基丙基)胺磺醯基、N-(1-甲基丁基)胺磺醯基、N-(2-甲基丁基)胺磺醯基、N-(3-甲基丁基)胺磺醯基、N-環戊基胺磺醯基、N-己基胺磺醯基、N-(1,3-二甲基丁基)胺磺醯基、N-(3,3-二甲基丁基)胺磺醯基、N-庚基胺磺醯基、N-(1-甲基己基)胺磺醯基、N-(1,4-二甲基戊基)胺磺醯基、N-辛基胺磺醯基、N-(2-乙基己基)胺磺醯基、N-(1,5-二甲基)己基胺磺醯基、N-(1,1,2,2-四甲基丁基)胺磺醯基等N-1取代胺磺醯基； N,N-二甲基胺磺醯基、N,N-乙基甲基胺磺醯基、N,N-二乙基胺磺 醯基、N,N-丙基甲基胺磺醯基、N,N-異丙基甲基胺磺醯基、N,N-第三丁基甲基胺磺醯基、N,N-丁基乙基胺磺醯基、N,N-雙(1-甲基丙基)胺磺醯基、N,N-庚基甲基胺磺醯基等N,N-2取代胺磺醯基。 Examples of -SO 2 NR 9 R 10 and -SO 2 NR 9a R 10a include an amine sulfonyl group; N-methylamine sulfonyl group, N-ethylamine sulfonyl group, and N-propylamine sulfonate. Base, N-isopropylamine sulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-butylbutylsulfonyl, N-tert-butylamine sulfonate Sulfhydryl, N-pentylamine sulfonyl, N-(1-ethylpropyl)amine sulfonyl, N-(1,1-dimethylpropyl)amine sulfonyl, N-(1, 2-dimethylpropyl)aminesulfonyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2 -Methylbutyl)aminesulfonyl, N-(3-methylbutyl)aminesulfonyl, N-cyclopentylaminesulfonyl, N-hexylaminesulfonyl, N-(1,3 - dimethylbutyl)amine sulfonyl, N-(3,3-dimethylbutyl)amine sulfonyl, N-heptylamine sulfonyl, N-(1-methylhexyl)amine sulfonate Sulfhydryl, N-(1,4-dimethylpentyl)amine sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5 -N-methyl hexylamine sulfonyl group, N-substituted sulfonyl group such as N-(1,1,2,2-tetramethylbutyl)amine sulfonyl group; N,N-dimethylamine Sulfonyl, N,N-ethylmethylaminesulfonyl, N,N-diethylamine Indenyl, N,N-propylmethylaminesulfonyl, N,N-isopropylmethylaminesulfonyl, N,N-tert-butylmethylaminesulfonyl, N,N-butyl N,N-2 substituted amine sulfonyl group such as sulfamidino, N,N-bis(1-methylpropyl)amine sulfonyl, N,N-heptylmethylamine sulfonyl.
R9、R10、R9a及R10a所表示之碳數1~20之1價飽和烴基可具有取代基。作為該取代基，可列舉羥基及鹵素原子。 The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 9 , R 10 , R 9a and R 10a may have a substituent. Examples of the substituent include a hydroxyl group and a halogen atom.
R9、R10、R9a及R10a可相互鍵結與氮原子一同形成3~10員含氮雜環(環內含有1個以上氮原子之雜環)。 R 9 , R 10 , R 9a and R 10a may be bonded to each other to form a 3 to 10 member nitrogen-containing heterocyclic ring (a heterocyclic ring containing one or more nitrogen atoms in the ring) together with a nitrogen atom.
作為該雜環，例如可列舉以下者。 Examples of the hetero ring include the following.
作為R5，較佳為-CO2H、-CO2 -Z+、-CO2R8、-SO3 -、-SO3 -Z+、-SO3H及SO2NHR9，更佳為SO3 -、-SO3 -Z+、-SO3H及SO2NHR9。 R 5 is preferably -CO 2 H, -CO 2 - Z + , -CO 2 R 8 , -SO 3 - , -SO 3 - Z + , -SO 3 H and SO 2 NHR 9 , more preferably SO 3 - , -SO 3 - Z + , -SO 3 H and SO 2 NHR 9 .
m較佳為1~4之整數，更佳為1及2。 m is preferably an integer of 1 to 4, more preferably 1 or 2.
作為R6及R7所表示之碳數1~6之烷基，可列舉：上述列舉之烷基中，碳數1~6之烷基。 Examples of the alkyl group having 1 to 6 carbon atoms represented by R 6 and R 7 include an alkyl group having 1 to 6 carbon atoms among the alkyl groups listed above.
作為R8及R11之碳數7~10之芳烷基，可列舉：苄基、苯基乙基及苯基丁基。 Examples of the aralkyl group having 7 to 10 carbon atoms of R 8 and R 11 include a benzyl group, a phenylethyl group, and a phenylbutyl group.
Z+及Za +分別為+N(R11)4、Na+或K+，較佳為+N(R11)4。 Z + and Z a + are respectively + N(R 11 ) 4 , Na + or K + , preferably + N(R 11 ) 4 .
作為上述+N(R11)4，較佳為4個R11中，至少2個為碳數5~20之1價飽和烴基，更佳為碳數5~10之烷基。又，4個R11之總碳數較佳為20~80，更佳為20~60。於化合物(1a)中存在+N(R11)4之情形時，若R11為該等基，則可自含有化合物(1a)之本發明之著色硬化性樹脂組合物形成異物較少之彩色濾光片。 As the above + N(R 11 ) 4 , at least two of the four R 11 are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms, more preferably an alkyl group having 5 to 10 carbon atoms. Further, the total carbon number of the four R 11 is preferably from 20 to 80, more preferably from 20 to 60. In the case where + N(R 11 ) 4 is present in the compound (1a), if R 11 is such a group, the colored curing resin composition of the present invention containing the compound (1a) can be formed into a color having less foreign matter. Filter.
上述+N(R11a)4中之R11a較佳為具有與R11相同範圍內之碳數。作為 R11a所表示之飽和烴基之具體例，可列舉關於R11所例示之飽和烴基。 Above + N (R 11a) 4 in the R 11a preferably having a carbon number within the same range of R 11. Specific examples of the saturated hydrocarbon group represented by R 11a include a saturated hydrocarbon group exemplified for R 11 .
作為化合物(1a)，例如可列舉式(1-1)~式(1-63)所表示之化合物。式中，R86及R100表示碳數1~20之1價飽和烴基，作為其具體例，可列舉關於R11所例示之飽和烴基。R86及R100較佳為碳數6~12之支鏈狀烷基，進而較佳為2-乙基己基。 The compound (1a) is, for example, a compound represented by the formula (1-1) to the formula (1-63). In the formula, R 86 and R 100 each represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof include a saturated hydrocarbon group exemplified for R 11 . R 86 and R 100 are preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably 2-ethylhexyl group.
作為化合物(1a)，較佳為R1、R2、R3及R4為氫原子或碳數1~8之烷基，R6及R7為氫原子，R5為-SO3 -、-SO3H、-SO3 -Z+、-SO3R8b或-SO2NR9bR10b(R8b、R9b及R10b分別為碳數1~4之烷基)，a為0的式(1a)之化合物，更佳為式(1-41)~式(1-60)之化合物，進而較佳為式(1-41)、式(1-43)、式(1-45)、式(1-47)、式(1-49)、式(1-51)、式(1-53)、式(1-55)、式(1-57)及式(1-59)之化合物。 As the compound (1a), R 1 , R 2 , R 3 and R 4 are preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 6 and R 7 are a hydrogen atom, and R 5 is -SO 3 - , -SO 3 H, -SO 3 - Z + , -SO 3 R 8b or -SO 2 NR 9b R 10b (R 8b , R 9b and R 10b are each an alkyl group having 1 to 4 carbon atoms), and a is 0. The compound of the formula (1a) is more preferably a compound of the formula (1-41) to the formula (1-60), and further preferably a formula (1-41), a formula (1-43), and a formula (1-45). , formula (1-47), formula (1-49), formula (1-51), formula (1-53), formula (1-55), formula (1-57), and formula (1-59) Compound.
二苯并吡喃染料可使用市售之二苯并吡喃染料(例如，中外化成(股份)製造之「Chugai Aminol Fast Pink R-H/C」、田岡化學工業(股份)製造之「Rhodamin 6G」)。亦可將市售之二苯并吡喃染料作為起始原料，參考日本專利特開2010-32999號公報而合成。 As the dibenzopyran dye, a commercially available dibenzopyran dye (for example, "Chugai Aminol Fast Pink RH/C" manufactured by Chugao Chemicals Co., Ltd., and "Rhodamin 6G" manufactured by Takooka Chemical Industry Co., Ltd.) can be used. . A commercially available dibenzopyran dye can also be used as a starting material, and is synthesized by referring to JP-A-2010-32999.
香豆素染料係含有於分子內具有香豆素骨架之化合物之染料。作為香豆素染料，可列舉：C.I.酸性黃227、250，C.I.分散黃82、184， C.I.溶劑橙112，C.I.溶劑黃160、172，日本專利第1299948號公報中揭示之香豆素染料等。 The coumarin dye is a dye containing a compound having a coumarin skeleton in the molecule. As the coumarin dye, C.I. Acid Yellow 227, 250, C.I. Disperse Yellow 82, 184, C.I. Solvent Orange 112, C.I. Solvent Yellow 160, 172, coumarin dyes disclosed in Japanese Patent No. 1299948, and the like.
該等之中，作為香豆素染料，較佳為式(Ad2)所表示之化合物(以下有時稱為「化合物(Ad2)」)，亦包含其互變異構物或該等之鹽。 Among these, the coumarin dye is preferably a compound represented by the formula (Ad2) (hereinafter sometimes referred to as "compound (Ad2)"), and also includes a tautomer or a salt thereof.
式(Ad2)中，LC表示碳數1~20之2價烴基或磺醯基，該烴基中所含之氫原子可被取代為氟原子。 In the formula (Ad2), L C represents a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group, and a hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom.
XC表示氧原子或硫原子。 X C represents an oxygen atom or a sulfur atom.
R1C及R2C分別獨立地表示可具有取代基之苯基或碳數1~20之烷基，於構成該烷基之碳原子間亦可***氧原子。 R 1C and R 2C each independently represent a phenyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms, and an oxygen atom may be interposed between carbon atoms constituting the alkyl group.
R7C~R13C分別獨立地表示氫原子、鹵素原子、氰基、硝基、胺甲醯基、胺磺醯基、-SO3MC、-CO2MC、羥基、甲醯基、胺基、碳數1~20之1價烴基，於構成該烴基之碳原子間亦可***氧原子、硫原子、-N(R14C)-、磺醯基或羰基，該烴基中所含之氫原子可被取代為鹵素原子、氰基、硝基、胺甲醯基、胺磺醯基、-SO3MC、-CO2MC、羥基、甲醯基或胺基。於-SO3MC及-CO2MC分別存在複數個之情形時，該等可相同亦可不同。 R 7C to R 13C each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amine carbenyl group, an amine sulfonyl group, -SO 3 M C , -CO 2 M C , a hydroxyl group, a methyl group, an amine. a monovalent hydrocarbon group having 1 to 20 carbon atoms, and an oxygen atom, a sulfur atom, -N(R 14C )-, a sulfonyl group or a carbonyl group may be interposed between carbon atoms constituting the hydrocarbon group, and hydrogen contained in the hydrocarbon group The atom may be substituted with a halogen atom, a cyano group, a nitro group, an amine carbenyl group, an amine sulfonyl group, -SO 3 M C , -CO 2 M C , a hydroxyl group, a decyl group or an amine group. When there are a plurality of cases in which -SO 3 M C and -CO 2 M C respectively exist, the same may be the same or different.
R14C表示氫原子或碳數1~20之1價烴基。於-N(R14C)-存在複數個之情形時，該等可相同亦可不同。 R 14C represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When there are a plurality of cases where -N(R 14C )-, there may be the same or different.
MC表示氫原子或鹼金屬原子。 M C represents a hydrogen atom or an alkali metal atom.
作為LC所表示之碳數1~20之2價烴基，可列舉：亞甲基、伸乙基、 伸丙基、伸丁基等直鏈狀烷基；伸異丙基、伸異丁基等支鏈狀烷基；伸環丙基、伸環己基等碳數3~20之脂環式飽和烴基；伸苯基、伸萘基等芳香族烴基等。 Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by L C include a linear alkyl group such as a methylene group, an exoethyl group, a propyl group or a butyl group; and an isopropyl group and an isobutyl group; The branched-chain alkyl group; an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group or a cyclohexylene group; an aromatic hydrocarbon group such as a phenyl group or a naphthyl group;
LC較佳為可經氟原子取代之碳數1~5之2價烴基或磺醯基，更佳為丙-2,2-二基、六氟丙-2,2-二基或磺醯基。 L C is preferably a divalent hydrocarbon group or a sulfonyl group having 1 to 5 carbon atoms which may be substituted by a fluorine atom, more preferably a propane-2,2-diyl group, a hexafluoropropane-2,2-diyl group or a sulfonium group. base.
XC較佳為氧原子。 X C is preferably an oxygen atom.
作為R1C及R2C所表示之碳數1~20之烷基，可列舉：甲基、乙基、丙基、丁基、戊基、己基等直鏈狀烷基；異丙基、異丁基、2-乙基己基等支鏈狀烷基等。作為該烷基，較佳為碳數1~8之烷基。 Examples of the alkyl group having 1 to 20 carbon atoms represented by R 1C and R 2C include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group; an isopropyl group and an isobutyl group; A branched alkyl group such as a 2-ethylhexyl group or the like. The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms.
作為R1C及R2C之苯基可具有之取代基，可列舉：鹵素原子(氟原子等)、氰基、硝基、胺甲醯基、胺磺醯基、-SO3MC、-CO2MC、羥基、甲醯基、胺基、碳數1~20之1價烴基(較佳為碳數1~4之烷基)等。 Examples of the substituent which the phenyl group of R 1C and R 2C may have include a halogen atom (such as a fluorine atom), a cyano group, a nitro group, an amine carbaryl group, an amine sulfonyl group, -SO 3 M C or -CO. 2 M C , a hydroxyl group, a decyl group, an amine group, a monovalent hydrocarbon group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 4 carbon atoms).
作為R1C及R2C，分別較佳為碳數1~8之烷基及可經碳數1~4之烷基取代之苯基。 R 1C and R 2C are each preferably an alkyl group having 1 to 8 carbon atoms and a phenyl group substituted by an alkyl group having 1 to 4 carbon atoms.
作為R7C~R14C所表示之烴基，可列舉：作為式(1a)之R1~R4及R8~R11所表示之飽和烴基所列舉之直鏈狀烷基、支鏈狀烷基及脂環式飽和烴基，以及苯基、萘基等芳香族烴基。 The hydrocarbon group represented by R 7C to R 14C may, for example, be a linear alkyl group or a branched alkyl group as the saturated hydrocarbon group represented by R 1 to R 4 and R 8 to R 11 in the formula (1a). And an alicyclic saturated hydrocarbon group, and an aromatic hydrocarbon group such as a phenyl group or a naphthyl group.
作為MC所表示之鹼金屬原子，可列舉：鈉原子、鉀原子等。 Examples of the alkali metal atom represented by M C include a sodium atom and a potassium atom.
R7C~R14C分別較佳為氫原子或碳數1~4之烷基，更佳為氫原子。 R 7C to R 14C are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom.
作為化合物(Ad2)，例如可列舉下式所表示之化合物。 The compound (Ad2) is, for example, a compound represented by the following formula.
作為香豆素染料之製造方法，例如可依據Dyes and Plgments(2008),77,556-558.中揭示之方法而製造。 As a method for producing the coumarin dye, for example, it can be produced according to the method disclosed in Dyes and Plgments (2008), 77, 556-558.
香豆素染料可為僅由化合物(Ad2)構成之染料，亦可含有其他香豆素染料。香豆素染料較佳為以70~100質量%之比例含有化合物(Ad2)。 The coumarin dye may be a dye composed only of the compound (Ad2), and may also contain other coumarin dyes. The coumarin dye preferably contains the compound (Ad2) in a ratio of 70 to 100% by mass.
染料(A-2)之含有率相對於著色劑(A)之總量，較佳為1~99質量%，更佳為2~95質量%，進而較佳為5~90質量%。 The content of the dye (A-2) is preferably from 1 to 99% by mass, more preferably from 2 to 95% by mass, even more preferably from 5 to 90% by mass, based on the total amount of the coloring agent (A).
染料(A-2)中，二苯并吡喃染料與香豆素染料之含量比以質量基準計，通常為60：40~99：1，較佳為65：35~99：1，更佳為70：30~98：2。 In the dye (A-2), the content ratio of the dibenzopyran dye to the coumarin dye is usually 60:40 to 99:1, preferably 65:35 to 99:1, more preferably on a mass basis. It is 70:30~98:2.
著色劑(A)之含有率相對於固形物成分之總量，較佳為5~70質量%，更佳為10~60質量%，進而較佳為10~55質量%。若著色劑(A)之含有率為上述範圍內，則可獲得所需之分光或色濃度。 The content of the colorant (A) is preferably from 5 to 70% by mass, more preferably from 10 to 60% by mass, even more preferably from 10 to 55% by mass, based on the total amount of the solid content component. When the content of the coloring agent (A) is within the above range, the desired spectral or color density can be obtained.
本說明書中所謂「固形物成分之總量」，係指自本發明之著色硬化性樹脂組合物去除溶劑(E)之成分之合計量。固形物成分之總量及相對於其之各成分之含量可藉由液相層析法或氣相層析法等公知之分析方法而測定。 In the present specification, the "total amount of the solid content component" means the total amount of the components from which the solvent (E) is removed from the colored curable resin composition of the present invention. The total amount of the solid content component and the content of each component relative thereto can be measured by a known analytical method such as liquid chromatography or gas chromatography.
樹脂(B)並無特別限定，較佳為鹼可溶性樹脂，更佳為具有源自選自由不飽和羧酸及不飽和羧酸酐所組成之群中至少一種之結構單元之加成聚合物。作為此種樹脂，可列舉以下之樹脂[K1]~[K6]等。 The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably an addition polymer derived from a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. Examples of such a resin include the following resins [K1] to [K6].
樹脂[K1]選自由不飽和羧酸及不飽和羧酸酐所組成之群中之至少一種(a)(以下有時稱為「(a)」)與具有碳數2~4之環狀醚結構與乙烯性不飽和鍵之單體(b)(以下有時稱為「(b)」)之共聚物；樹脂[K2](a)、與(b)、及可與(a)共聚合之單體(c)(其中，與(a)及(b)不同)(以下有時稱為「(c)」)之共聚物；樹脂[K3](a)與(c)之共聚物；樹脂[K4]使(a)與(c)之共聚物與(b)反應而獲得之樹脂；樹脂[K5]使(b)與(c)之共聚物與(a)反應而獲得之樹脂； 樹脂[K6]使(b)與(c)之共聚物與(a)反應，進而與羧酸酐反應而獲得之樹脂。 The resin [K1] is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter sometimes referred to as "(a)") and a cyclic ether structure having a carbon number of 2 to 4. a copolymer of a monomer (b) (hereinafter sometimes referred to as "(b)")) having an ethylenically unsaturated bond; a resin [K2] (a), and (b), and copolymerizable with (a) a copolymer of a monomer (c) (which is different from (a) and (b)) (hereinafter sometimes referred to as "(c)"); a copolymer of the resin [K3] (a) and (c); a resin [K4] a resin obtained by reacting the copolymer of (a) and (c) with (b); a resin obtained by reacting the copolymer of (b) and (c) with (a); Resin [K6] A resin obtained by reacting the copolymer of (b) and (c) with (a) and further reacting with a carboxylic acid anhydride.
作為(a)，具體而言，例如可列舉：丙烯酸，甲基丙烯酸，丁烯酸，鄰-、間-、對-乙烯基苯甲酸等不飽和單羧酸；順丁烯二酸、反丁烯二酸、甲基順丁烯二酸、甲基反丁烯二酸、伊康酸、3-乙烯基鄰苯二甲酸、4-乙烯基鄰苯二甲酸、3,4,5,6-四氫鄰苯二甲酸、1,2,3,6-四氫鄰苯二甲酸、二甲基四氫鄰苯二甲酸、1,4-環己烯二羧酸等不飽和二羧酸；甲基-5-降烯-2,3-二羧酸、5-羧基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯、5-羧基-5-甲基雙環[2.2.1]庚-2-烯、5-羧基-5-乙基雙環[2.2.1]庚-2-烯、5-羧基-6-甲基雙環[2.2.1]庚-2-烯、5-羧基-6-乙基雙環[2.2.1]庚-2-烯等含有羧基之雙環不飽和化合物；順丁烯二酸酐、甲基順丁烯二酸酐、伊康酸酐、3-乙烯基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐、5,6-二羧基雙環[2.2.1]庚-2-烯酐等不飽和二羧酸酐；琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯等2元以上之多元羧酸之不飽和單[(甲基)丙烯醯氧基烷基]酯；如α-(羥基甲基)丙烯酸之同一分子中含有羥基及羧基之不飽和丙烯酸酯等。 Specific examples of (a) include acrylic acid, methacrylic acid, crotonic acid, unsaturated monocarboxylic acid such as o-, m-, p-vinylbenzoic acid, and maleic acid and anti-butylene. Aenedioic acid, methyl maleic acid, methyl fumaric acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6- An unsaturated dicarboxylic acid such as tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid or 1,4-cyclohexene dicarboxylic acid; Base-5-down Alkene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-A Bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2 - a bicyclic unsaturated compound containing a carboxyl group such as a olefin, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, methyl maleic anhydride, itaconic anhydride, 3 -vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , dimethyltetrahydrophthalic anhydride, unsaturated dicarboxylic anhydride such as 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; succinic acid mono [2-(methyl) propylene oxime Unsaturated mono[(methyl)acryloxyalkylene group of a polyvalent carboxylic acid having two or more kinds, such as a ethyl ethyl ester] or a mono [2-(methyl) propylene oxyethyl ester] phthalic acid An ester; an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule of α-(hydroxymethyl)acrylic acid.
該等之中，自共聚合反應性之方面或所獲得之樹脂對鹼性水溶液之溶解性之方面而言，較佳為丙烯酸、甲基丙烯酸、順丁烯二酸酐等。 Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of the copolymerization reactivity or the solubility of the obtained resin to the alkaline aqueous solution.
(b)係指具有碳數2~4之環狀醚結構(例如選自由環氧乙烷環、氧雜環丁烷環及四氫呋喃環所組成之群中之至少一種)與乙烯性不飽和鍵之聚合性化合物。(b)較佳為具有碳數2~4之環狀醚與(甲基)丙烯醯 氧基之單體。 (b) means a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. A polymeric compound. (b) preferably a cyclic ether having a carbon number of 2 to 4 and (meth)acrylic acid A monomer of an oxy group.
於本說明書中，所謂「(甲基)丙烯酸」係表示選自由丙烯酸及甲基丙烯酸所組成之群中至少一種。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等表述亦具有相同含義。 In the present specification, the term "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth)acryloyl" and "(meth)acrylate" have the same meaning.
作為(b)，可列舉：具有環氧乙烷基與乙烯性不飽和鍵之單體(b1)(以下有時稱為「(b1)」)、具有氧雜環丁基與乙烯性不飽和鍵之單體(b2)(以下有時稱為「(b2)」)、具有四氫呋喃基與乙烯性不飽和鍵之單體(b3)(以下有時稱為「(b3)」)等。 (b): a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), having an oxetanyl group and an ethylenic unsaturated group The monomer (b2) of the bond (hereinafter sometimes referred to as "(b2)"), the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)")).
作為(b1)，可列舉：具有直鏈狀或支鏈狀之脂肪族不飽和烴經環氧化之結構之單體、具有脂環式不飽和烴經環氧化之結構之單體。 Examples of (b1) include a monomer having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and a monomer having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.
作為(b2)，較佳為具有氧雜環丁基與(甲基)丙烯醯氧基之單體。作為(b2)，可列舉：3-甲基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-甲基-3-丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-丙烯醯氧基乙基氧雜環丁烷等。 As (b2), a monomer having an oxetanyl group and a (meth) acryloxy group is preferable. Examples of (b2) include 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, and 3- Ethyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methylpropene oxime Ethyloxyoxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 3 Ethyl-3-propenyloxyethyloxetane and the like.
作為(b3)，較佳為具有四氫呋喃基與(甲基)丙烯醯氧基之單體。作為(b3)，具體可列舉：丙烯酸四氫糠酯(Viscoat V # 150，大阪有機化學工業(股份)製造)、甲基丙烯酸四氫糠酯等。 As (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group is preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (Viscoat V #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.
作為(b)，自進一步提高彩色濾光片之耐熱性、耐化學品性等可靠性之方面而言，較佳為(b1)。 (b) is preferably (b1) from the viewpoint of further improving the reliability of heat resistance and chemical resistance of the color filter.
作為(c)，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、 (甲基)丙烯酸2-甲基環己酯、(甲基)丙烯酸三環[5.2.1.02,6]癸-8-基酯(於該技術領域中，作為慣用名被稱為「(甲基)丙烯酸二環戊酯」；又，有時稱為「(甲基)丙烯酸三環癸酯」)、(甲基)丙烯酸三環[5.2.1.02,6]癸烯-8-基酯(於該技術領域中，作為慣用名被稱為「(甲基)丙烯酸二環戊烯酯」)、(甲基)丙烯酸二環戊氧基乙酯、(甲基)丙烯酸異酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸酯；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯等含羥基之(甲基)丙烯酸酯；順丁烯二酸二乙酯、反丁烯二酸二乙酯、伊康酸二乙酯等二羧酸二酯；雙環[2.2.1]庚-2-烯、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、5-羥基雙環[2.2.1]庚-2-烯、5-羥基甲基雙環[2.2.1]庚-2-烯、5-(2'-羥基乙基)雙環[2.2.1]庚-2-烯、5-甲氧基雙環[2.2.1]庚-2-烯、5-乙氧基雙環[2.2.1]庚-2-烯、5,6-二羥基雙環[2.2.1]庚-2-烯、5,6-二(羥基甲基)雙環[2.2.1]庚-2-烯、5,6-二(2'-羥基乙基)雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[2.2.1]庚-2-烯、5,6-二乙氧基雙環[2.2.1]庚-2-烯、5-羥基-5-甲基雙環[2.2.1]庚-2-烯、5-羥基-5-乙基雙環[2.2.1]庚-2-烯、5-羥基甲基-5-甲基雙環[2.2.1]庚-2-烯、5-第三丁氧基羰基雙環[2.2.1]庚-2-烯、5-環己氧基羰基雙環[2.2.1]庚-2-烯、5-苯氧基羰基雙環[2.2.1]庚-2-烯、5,6-雙(第三丁氧基羰基)雙環[2.2.1]庚-2-烯、5,6-雙(環己氧基羰基)雙環[2.2.1]庚-2-烯等雙環不飽和化合物；N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺、N-丁二醯亞胺基-3-順丁烯二醯亞胺苯甲酸酯、N-丁二醯亞胺基-4-順丁烯二醯亞胺丁酸酯、N-丁二醯亞胺基-6-順丁烯二醯亞胺己酸酯、N-丁二醯亞胺基-3-順丁烯二醯亞胺丙酸酯、N-(9-吖啶基)順 丁烯二醯亞胺等二羰基醯亞胺衍生物；苯乙烯、α-甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、對甲氧基苯乙烯、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、乙酸乙烯酯、1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等。 Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentane (meth)acrylate Ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ]non-8-yl (meth)acrylate (in the technical field) In the conventional name, it is called "dicyclopentanyl (meth)acrylate"; it is sometimes called "tricyclodecyl (meth)acrylate), and tricyclo(meth)acrylate [5.2.1.0 2,6 ]decene-8-yl ester (in the technical field, it is called "dicyclopentenyl (meth)acrylate" as a conventional name), dicyclopentyloxyethyl (meth)acrylate (meth)acrylic acid Ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (meth)acrylic acid (meth) acrylate such as benzyl ester; hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; diethyl maleate a dicarboxylic acid diester such as diethyl fumarate or diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene , 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5 -(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]g 2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di (2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[ 2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methyl bicyclic [2.2.1] Hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclo) a bicyclic unsaturated compound such as hexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl maleimide, N-cyclohexylmethyleneimine, N-benzyl Maleimide, N-butylimidazolyl-3-methyleneimine benzoate, N-butanediamine-4-butyleneimine Acid ester, N-butyl diimide imino-6-m-butylene imide hexanoate, N-butyl diimide imino-3-butane diimide propionate, N-( 9-Acridine-based dicarbonyl ruthenium derivatives such as maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and para Oxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2, 3-dimethyl-1,3-butadiene and the like.
該等之中，自共聚合反應性及耐熱性之方面而言，較佳為苯乙烯、乙烯基甲苯、(甲基)丙烯酸苄酯、(甲基)丙烯酸三環[5.2.1.02,6]癸-8-基酯、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苄基順丁烯二醯亞胺、雙環[2.2.1]庚-2-烯。 Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyl toluene, benzyl (meth)acrylate, and trimethyl (meth)acrylate [5.2.1.0 2,6 are preferred.癸-8-yl ester, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, bicyclo [2.2.1] Hept-2-ene.
樹脂[K1]例如可參考文獻「高分子合成之實驗法」(大津隆行著 發行所(股份)化學同人 第1版第1次印刷1972年3月1日發行)中所記載之方法及該文獻中所記載之引用文獻而製造。 For example, the resin [K1] can be referred to the "Experimental Method for Polymer Synthesis" (the method described in the first print of the first edition of the Otsuka Ryokan (Shares) Chemicals, the first print, March 1, 1972) and the literature. Manufactured from the cited documents described in the above.
具體可列舉：將特定量之(a)及(b)、聚合起始劑及溶劑等裝入反應容器中，例如以氮氣置換氧氣，藉此成為脫氧環境，一邊攪拌一邊加熱及保溫的方法。再者，此處所使用之聚合起始劑及溶劑等並無特別限定，可使用該領域中通常使用者。作為聚合起始劑，可列舉：偶氮化合物(2,2'-偶氮二異丁腈、2,2'-偶氮雙(2,4-二甲基戊腈)等)或有機過氧化物(過氧化苯甲醯等)，作為溶劑，若為溶解各單體者即可，可列舉作為本發明之著色硬化性樹脂組合物之溶劑(E)之下述溶劑等。 Specifically, a method in which a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction container, for example, by replacing oxygen with nitrogen, thereby providing a deoxidizing environment and heating and holding while stirring. In addition, the polymerization initiator, the solvent, and the like used herein are not particularly limited, and a general user in the field can be used. Examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxidation. In the solvent (E), the solvent (E) may be exemplified as the solvent (E) of the colored curable resin composition of the present invention.
所獲得之共聚物可直接使用反應後之溶液，亦可使用濃縮或稀釋之溶液，亦可使用藉由再沈澱等方法而作為固體(粉體)提取者。作為該聚合時之溶劑，使用本發明之著色硬化性樹脂組合物中所含之溶劑，藉此可將反應後之溶液直接用於本發明之著色硬化性樹脂組合物之製備，故而可簡化本發明之著色硬化性樹脂組合物之製造步驟。 The obtained copolymer may be directly used as a solution after the reaction, or a concentrated or diluted solution may be used, or a solid (powder) extractor may be used by a method such as reprecipitation. By using the solvent contained in the colored curable resin composition of the present invention as the solvent in the polymerization, the solution after the reaction can be directly used for the preparation of the colored curable resin composition of the present invention, so that the present invention can be simplified. A manufacturing step of the inventive color-curable resin composition.
作為樹脂(B)，具體可列舉：(甲基)丙烯酸3,4-環氧環己基甲酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸3,4-環氧三環[5.2.1.02.6]癸酯/(甲基)丙 烯酸共聚物等樹脂[K1]；(甲基)丙烯酸縮水甘油酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸縮水甘油酯/苯乙烯/(甲基)丙烯酸共聚物、(甲基)丙烯酸3,4-環氧三環[5.2.1.02.6]癸酯/(甲基)丙烯酸/N-環己基順丁烯二醯亞胺共聚物、(甲基)丙烯酸3,4-環氧三環[5.2.1.02.6]癸酯/(甲基)丙烯酸/乙烯基甲苯共聚物、3-甲基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷/(甲基)丙烯酸/苯乙烯共聚物等樹脂[K2]；(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、苯乙烯/(甲基)丙烯酸共聚物、(甲基)丙烯酸苄酯/(甲基)丙烯酸三環癸酯/(甲基)丙烯酸共聚物等樹脂[K3]；(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物上加成(甲基)丙烯酸縮水甘油酯之樹脂、(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸共聚物上加成(甲基)丙烯酸縮水甘油酯之樹脂、(甲基)丙烯酸三環癸酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物上加成(甲基)丙烯酸縮水甘油酯之樹脂等樹脂[K4]；(甲基)丙烯酸三環癸酯/(甲基)丙烯酸縮水甘油酯之共聚物與(甲基)丙烯酸反應而獲得之樹脂、(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸縮水甘油酯之共聚物與(甲基)丙烯酸反應而獲得之樹脂等樹脂[K5]；(甲基)丙烯酸三環癸酯/(甲基)丙烯酸縮水甘油酯之共聚物與(甲基)丙烯酸反應而獲得之樹脂進而與四氫鄰苯二甲酸酐反應而獲得之樹脂等樹脂[K6]等。 Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer and (meth)acrylic acid 3,4-epoxytricyclo[5.2. 1.0 2.6 ]Resin such as oxime ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (meth)acrylic acid shrinkage ester / styrene / (meth) acrylic acid copolymer, (meth) acrylate, 3,4-epoxy-tricyclo [5.2.1.0 2.6] decyl acrylate / (meth) acrylic acid / N- cyclohexyl maleate醯imine copolymer, 3,4-epoxytricyclo(5.sup.3-epoxy)[5.2.1.0 2.6 ] decyl ester / (meth) acrylate / vinyl toluene copolymer, 3-methyl-3- (methyl Resin such as acryloxymethyloxetane/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(A) Resin such as acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylate copolymer [K3]; benzyl (meth) acrylate / (meth) acrylate Addition of a resin of glycidyl (meth)acrylate to a copolymer, tricyclo(meth)acrylate Addition of an ester/styrene/(meth)acrylic acid copolymer to a resin of glycidyl (meth)acrylate, tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer A resin such as a resin of glycidyl (meth)acrylate is added to the material [K4]; a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate is reacted with (meth)acrylic acid to obtain a resin such as a resin obtained by reacting a copolymer of tricyclodecyl methacrylate/styrene/glycidyl (meth)acrylate with (meth)acrylic acid [K5]; (meth)acrylic acid A resin such as a resin obtained by reacting a copolymer of cyclodecyl ester/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting with tetrahydrophthalic anhydride to obtain a resin such as a resin [K6].
樹脂(B)較佳為選自由樹脂[K1]、樹脂[K2]及樹脂[K3]所組成之群中之一種，更佳為選自由樹脂[K2]及樹脂[K3]所組成之群中之一種。若為該等樹脂，則著色硬化性樹脂組合物之顯影性優異。就自著色硬化性樹脂組合物獲得之彩色濾光片與基板之密接性之觀點而言，進而較佳為樹脂[K2]。 The resin (B) is preferably one selected from the group consisting of a resin [K1], a resin [K2], and a resin [K3], and more preferably selected from the group consisting of a resin [K2] and a resin [K3]. One of them. When it is such a resin, the coloring curable resin composition is excellent in developability. The resin [K2] is further preferable from the viewpoint of the adhesion between the color filter obtained from the colored curable resin composition and the substrate.
樹脂(B)之聚苯乙烯換算之重量平均分子量較佳為3,000~100,000，更佳為5,000~50,000，進而較佳為5,000~30,000。若分子量為上述範圍，則存在塗膜硬度提高、殘膜率亦較高、未曝光部對顯影 液之溶解性良好、且著色圖案之解像度提高之傾向。 The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 5,000 to 30,000. When the molecular weight is in the above range, the hardness of the coating film is increased, the residual film ratio is also high, and the unexposed portion is developed. The solubility of the liquid is good, and the resolution of the colored pattern tends to increase.
樹脂(B)之分子量分佈[重量平均分子量(Mw)/數量平均分子量(Mn)]較佳為1.1~6，更佳為1.2~4。 The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6, more preferably from 1.2 to 4.
樹脂(B)之酸值較佳為50~170mg-KOH/g，更佳為60~150mg-KOH/g，進而較佳為70~135mg-KOH/g。此處酸值係作為中和樹脂(B)1g所需之氫氧化鉀之量(mg)而測定之值，例如可藉由使用氫氧化鉀水溶液進行滴定而求得。 The acid value of the resin (B) is preferably from 50 to 170 mg-KOH/g, more preferably from 60 to 150 mg-KOH/g, still more preferably from 70 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be obtained, for example, by titration with an aqueous potassium hydroxide solution.
樹脂(B)之含量相對於固形物成分之總量，較佳為7~65質量%，更佳為13~60質量%，進而較佳為17~55質量%。若樹脂(B)之含量為上述範圍，則可形成著色圖案，又存在著色圖案之解像度及殘膜率提高之傾向。 The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, even more preferably from 17 to 55% by mass, based on the total amount of the solid content component. When the content of the resin (B) is in the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film ratio tend to increase.
聚合性化合物(C)係可藉由自聚合起始劑(D)產生之活性自由基及/或酸而聚合之化合物。作為該聚合性化合物(C)，可列舉具有聚合性之乙烯性不飽和鍵之化合物等，較佳為(甲基)丙烯酸酯化合物。 The polymerizable compound (C) is a compound which can be polymerized by an active radical and/or an acid generated from the polymerization initiator (D). The polymerizable compound (C) may, for example, be a compound having a polymerizable ethylenically unsaturated bond, and is preferably a (meth) acrylate compound.
作為具有1個乙烯性不飽和鍵之聚合性化合物，例如可列舉：壬基苯基卡必醇丙烯酸酯、丙烯酸2-羥基-3-苯氧基丙酯、2-乙基己基卡必醇丙烯酸酯、丙烯酸2-羥基乙酯、N-乙烯基吡咯啶酮等以及上述(a)、(b)及(c)。 Examples of the polymerizable compound having one ethylenically unsaturated bond include mercaptophenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexyl carbitol acrylic acid. Ester, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc., and the above (a), (b) and (c).
作為具有2個乙烯性不飽和鍵之聚合性化合物，例如可列舉：1,6-己二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、雙酚A之雙(丙烯醯氧基乙基)醚、3-甲基戊二醇二(甲基)丙烯酸酯等。 Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, and neopentyl glycol di( Methyl) acrylate, triethylene glycol di(meth) acrylate, bisphenol A bis(acryloxyethyl) ether, 3-methyl pentanediol di(meth) acrylate, and the like.
聚合性化合物(C)較佳為具有3個以上之乙烯性不飽和鍵之聚合性化合物。作為此種聚合性化合物，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、 二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三季戊四醇八(甲基)丙烯酸酯、三季戊四醇七(甲基)丙烯酸酯、四季戊四醇十(甲基)丙烯酸酯、四季戊四醇九(甲基)丙烯酸酯、異氰尿酸三(2-(甲基)丙烯醯氧基乙基)酯、乙二醇改性季戊四醇四(甲基)丙烯酸酯、乙二醇改性二季戊四醇六(甲基)丙烯酸酯、丙二醇改性季戊四醇四(甲基)丙烯酸酯、丙二醇改性二季戊四醇六(甲基)丙烯酸酯、己內酯改性季戊四醇四(甲基)丙烯酸酯、己內酯改性二季戊四醇六(甲基)丙烯酸酯等。 The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, Pentaerythritol nine (meth) acrylate, tris(2-(meth) propylene methoxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified Pentaerythritol hexa(meth) acrylate, propylene glycol modified pentaerythritol tetra(meth) acrylate, propylene glycol modified dipentaerythritol hexa(meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, Ester-modified dipentaerythritol hexa(meth) acrylate or the like.
其中，較佳為二季戊四醇五(甲基)丙烯酸酯及二季戊四醇六(甲基)丙烯酸酯。 Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.
聚合性化合物(C)之重量平均分子量較佳為150以上、2,900以下，更佳為250~1,500以下。 The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 to 1,500 or less.
聚合性化合物(C)之含量相對於固形物成分之總量，較佳為7~65質量%，更佳為13~60質量%，進而較佳為17~55質量%。 The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, even more preferably from 17 to 55% by mass, based on the total amount of the solid content component.
樹脂(B)與聚合性化合物(C)之含量比[樹脂(B)：聚合性化合物(C)]以質量基準計，較佳為20：80~80：20，更佳為35：65~80：20。 The content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is preferably 20:80 to 80:20, more preferably 35:65 by mass. 80:20.
若聚合性化合物(C)之含量為上述範圍內，則存在著色圖案形成時之殘膜率及彩色濾光片之耐化學品性提高之傾向。 When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of formation of the colored pattern and the chemical resistance of the color filter tend to be improved.
聚合起始劑(D)若為可藉由光或熱之作用而產生活性自由基、酸等，使聚合開始之化合物，則並無特別限定，可使用公知之聚合起始劑。 The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat, and a known polymerization initiator can be used.
作為聚合起始劑(D)，可列舉：O-醯基肟化合物、烷基苯酮化合物、聯咪唑化合物、三化合物及醯基氧化膦化合物等。 Examples of the polymerization initiator (D) include an O-indenyl hydrazine compound, an alkyl phenone compound, a biimidazole compound, and three. a compound, a fluorenylphosphine oxide compound, and the like.
作為O-醯基肟化合物，可列舉：N-苯甲醯氧基-1-(4-苯基硫基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫基苯基)-3-環戊基丙烷-1-酮-2-亞胺、 N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-{2-甲基-4-(3,3-二甲基-2,4-二氧雜環戊基甲基氧基)苯甲醯基}-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-亞胺、N-苯甲醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-酮-2-亞胺等。亦可使用Irgacure(註冊商標)OXE01、OXE02(以上，BASF公司製造)，N-1919(ADEKA公司製造)等市售品。其中，較佳為選自由N-苯甲醯氧基-1-(4-苯基硫基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺及N-苯甲醯氧基-1-(4-苯基硫基苯基)-3-環戊基丙烷-1-酮-2-亞胺所組成之群中之至少一種，更佳為N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺。 The O-indenyl hydrazine compound may, for example, be N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine or N-benzylideneoxy group. 1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclopentyl Propane-1-one-2-imine, N-Ethyloxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1-imine, N-acetoxy 1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolanylmethyloxy)benzylidene}- 9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-carbazole- 3-yl]-3-cyclopentylpropane-1-imine, N-benzylideneoxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole 3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF Corporation), and N-1919 (made by ADEKA Co., Ltd.) can also be used. Wherein, it is preferably selected from the group consisting of N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzylideneoxy-1-( 4-phenylthiophenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1 At least one selected from the group consisting of keto-2-imine, more preferably N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine .
作為烷基苯酮化合物，可列舉：2-甲基-2-啉基-1-(4-甲基硫基苯基)丙烷-1-酮、2-二甲基胺基-1-(4-啉基苯基)-2-苄基丁烷-1-酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-啉基)苯基]丁烷-1-酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、2-羥基-2-甲基-1-[4-(2-羥基乙氧基)苯基]丙烷-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-(4-異丙烯基苯基)丙烷-1-酮之寡聚物、α,α-二乙氧基苯乙酮、苄基二甲基縮酮等。亦可使用Irgacure(註冊商標)369、907、379(以上，BASF公司製造)等市售品。 As the alkylphenone compound, 2-methyl-2- can be mentioned Lolinyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1-(4- Phenylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Phenyl)phenyl]butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl Oligomerization of ethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one , α,α-diethoxyacetophenone, benzyldimethylketal, and the like. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF Corporation) can also be used.
作為聯咪唑化合物，可列舉：2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2,3-二氯苯基)-4,4',5,5'-四苯基聯咪唑(參考日本專利特開平6-75372號公報、日本專利特開平6-75373號公報等)、2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(烷氧基苯基)聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(二烷氧基苯基)聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(三烷氧基苯基)聯咪唑(參考日本專利特公昭48-38403號公報、日本專利特開昭62-174204號公報等)、4,4',5,5'-位之 苯基經烷氧羰基取代之咪唑化合物(參考日本專利特開平7-10913號公報等)等。其中，較佳為下述式所表示之化合物及該等之混合物。 As the biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-di) Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (refer to Japanese Patent Laid-Open No. Hei 6-75372, Japanese Patent Laid-Open No. Hei 6-75373, etc.), 2, 2'-double (2-Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra Alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (refer to Japanese Patent Publication No. Sho 48-38403, Japanese Patent Laid-Open No. 62-174204 No., etc.), 4, 4', 5, 5'-position An imidazole compound in which a phenyl group is substituted with an alkoxycarbonyl group (refer to Japanese Laid-Open Patent Publication No. Hei 7-10913, etc.). Among them, preferred are compounds represented by the following formulas and mixtures thereof.
作為三化合物，可列舉：2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三、2,4-雙(三氯甲基)-6-向日葵基-1,3,5-三、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三等。 As three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-sunflower-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.
作為醯基氧化膦化合物，可列舉：2,4,6-三甲基苯甲醯基二苯基氧化膦等。 The fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or the like.
進而，作為聚合起始劑(D)，可列舉：安息香、安息香甲醚、安息香***、安息香異丙醚、安息香異丁醚等安息香化合物；二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4'-甲基二苯硫醚、3,3',4,4'-四(過氧化第三丁基羰基)二苯甲酮、2,4,6-三甲基二苯甲酮等二苯甲酮化合物；9,10-菲醌、2-乙基蒽醌、樟腦醌等醌化合物；10-丁基-2-氯吖啶酮、二苯基乙二酮、苯基乙醛酸甲酯、二茂鈦化合物等。該等較佳為與下述聚合起始助劑(D1)(尤其胺化合物)組合使用。 Further, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone and methyl benzoyl benzoate; , 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(t-butylcarbonyl)diphenyl peroxide Benzophenone compound such as ketone or 2,4,6-trimethylbenzophenone; anthracene compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine, camphorquinone; 10-butyl-2-chloro Acridone, diphenylethylenedione, methyl phenylglyoxylate, titanocene compound, and the like. These are preferably used in combination with the following polymerization starting assistant (D1) (especially an amine compound).
聚合起始劑(D)較佳為含有選自由烷基苯酮化合物、三化合物、 醯基氧化膦化合物、O-醯基肟化合物及聯咪唑化合物所組成之群中之至少一種之聚合起始劑，更佳為含有O-醯基肟化合物之聚合起始劑。 The polymerization initiator (D) preferably contains a compound selected from the group consisting of alkyl phenones, three The polymerization initiator of at least one of the group consisting of a compound, a mercaptophosphine oxide compound, an O-mercaptopurine compound, and a biimidazole compound is more preferably a polymerization initiator containing an O-mercaptopurine compound.
聚合起始劑(D)之含量相對於樹脂(B)及聚合性化合物(C)之總量100質量份，較佳為0.1~40質量份，更佳為1~30質量份。 The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts by mass, per 100 parts by mass of the total of the resin (B) and the polymerizable compound (C).
聚合起始助劑(D1)係為促進可藉由聚合起始劑而開始聚合之聚合性化合物之聚合而使用之化合物或增感劑。於含有聚合起始助劑(D1)之情形時，通常與聚合起始劑(D)組合使用。 The polymerization initiation aid (D1) is a compound or a sensitizer which is used to promote polymerization of a polymerizable compound which can be polymerized by a polymerization initiator. In the case of containing the polymerization starting assistant (D1), it is usually used in combination with the polymerization initiator (D).
作為聚合起始助劑(D1)，可列舉：胺化合物、烷氧基蒽化合物、9-氧硫化合物及羧酸化合物等。 Examples of the polymerization initiation assistant (D1) include an amine compound, an alkoxy fluorene compound, and 9-oxosulfuric acid. Compounds, carboxylic acid compounds, and the like.
作為胺化合物，可列舉：三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、苯甲酸2-二甲基胺基乙酯、4-二甲基胺基苯甲酸2-乙基己酯、N,N-二甲基對甲苯胺、4,4'-雙(二甲基胺基)二苯甲酮(通稱米其勒酮)、4,4'-雙(二乙基胺基)二苯甲酮、4,4'-雙(乙基甲基胺基)二苯甲酮等，其中較佳為4,4'-雙(二乙基胺基)主苯甲酮。亦可使用EAB-F(保土谷化學工業(股份)製造)等市售品。 The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate or 4-dimethyl group. Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4 '-Bis(dimethylamino)benzophenone (commonly known as Michlerone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis (ethyl group) Aminoamino)benzophenone or the like, of which 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.
作為烷氧基蒽化合物，可列舉：9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽、2-乙基-9,10-二乙氧基蒽、9,10-二丁氧基蒽、2-乙基-9,10-二丁氧基蒽等。 As the alkoxy ruthenium compound, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.
作為9-氧硫化合物，可列舉：2-異丙基-9-氧硫、4-異丙基-9-氧硫、2,4-二乙基-9-氧硫、2,4-二氯-9-氧硫、1-氯-4-丙氧基-9-氧硫等。 9-oxosulfur Compounds can be exemplified by 2-isopropyl-9-oxosulfur 4-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 1-chloro-4-propoxy-9-oxosulfur Wait.
作為羧酸化合物，可列舉：苯基硫基乙酸、甲基苯基硫基乙酸、乙基苯基硫基乙酸、甲基乙基苯基硫基乙酸、二甲基苯基硫基乙酸、甲氧基苯基硫基乙酸、二甲氧基苯基硫基乙酸、氯苯基硫基乙酸、二 氯苯基硫基乙酸、N-苯基甘胺酸、苯氧基乙酸、萘基硫代乙酸、N-萘基甘胺酸、萘氧基乙酸等。 Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and A. Oxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, two Chlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.
於使用該等聚合起始助劑(D1)之情形時，其含量相對於樹脂(B)及聚合性化合物(C)之總量100質量份，較佳為0.1~30質量份，更佳為1~20質量份。若聚合起始助劑(D1)之量為該範圍內，則存在可以更高感度形成著色圖案，提高彩色濾光片之生產性之傾向。 When the polymerization initiator (D1) is used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, the coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.
溶劑(E)並無特別限定，可使用該領域中通常使用之溶劑。例如，酯溶劑(分子內含有-COO-且不含-O-之溶劑)、醚溶劑(分子內含有-O-且不含-COO-之溶劑)、醚酯溶劑(分子內含有-COO-與-O-之溶劑)、酮溶劑(分子內含有-CO-且不含-COO-之溶劑)、醇溶劑(分子內含有OH且不含-O-、-CO-及-COO-之溶劑)、芳香族烴溶劑、醯胺溶劑、二甲基亞碸等。 The solvent (E) is not particularly limited, and a solvent which is usually used in the field can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and containing no -O-), an ether solvent (a solvent containing -O- in the molecule and containing no -COO-), an ether ester solvent (containing -COO- in the molecule) a solvent with -O-), a ketone solvent (a solvent containing -CO- in the molecule and containing no -COO-), an alcohol solvent (a solvent containing OH in the molecule and not containing -O-, -CO- and -COO-) ), an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl alum, and the like.
作為酯溶劑，可列舉：乳酸甲酯、乳酸乙酯、乳酸丁酯、2-羥基異丁酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、環己醇乙酸酯、γ-丁內酯等。 Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, ring Hexanol acetate, γ-butyrolactone, and the like.
作為醚溶劑，可列舉：乙二醇單甲醚、乙二醇單***、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚、3-甲氧基-1-丁醇、3-甲氧基-3-甲基丁醇、四氫呋喃、四氫吡喃、1,4-二烷、二乙二醇二甲醚、二乙二醇二***、二乙二醇甲基乙基醚、二乙二醇二丙醚、二乙二醇二丁醚、苯甲醚、苯***、甲基苯甲醚等。 Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and two. Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether, Methyl anisole and the like.
作為醚酯溶劑，可列舉：甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲 氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、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、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯、二丙二醇甲醚乙酸酯等。 Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, and A. Butyl oxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropanoate, 3-methoxybutyl acetate , 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and the like.
作為酮溶劑，可列舉：4-羥基-4-甲基-2-戊酮、丙酮、2-丁酮、2-庚酮、3-庚酮、4-庚酮、4-甲基-2-戊酮、環戊酮、環己酮、異佛酮等。 Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.
作為醇溶劑，可列舉：甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇、丙三醇等。 Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.
作為芳香族烴溶劑，可列舉：苯、甲苯、二甲苯、均三甲苯等。 Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.
作為醯胺溶劑，可列舉：N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等。 Examples of the guanamine solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.
該等溶劑可單獨使用亦可併用兩種以上。 These solvents may be used singly or in combination of two or more.
其中，較佳為：丙二醇單甲醚乙酸酯、乳酸乙酯、丙二醇單甲醚、3-乙氧基丙酸乙酯、乙二醇單甲醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單***、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇、4-羥基-4-甲基-2-戊酮、N,N-二甲基甲醯胺、N-甲基吡咯啶酮等，更佳為：丙二醇單甲醚乙酸酯、丙二醇單甲醚、乙二醇單丁醚、二丙二醇甲醚乙酸酯、乳酸乙酯、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇、3-乙氧基丙酸乙酯、N-甲基吡咯啶酮等。 Among them, preferred are: propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol Alcohol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone, etc., more preferably: propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, Ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N-methylpyrrolidone, and the like.
溶劑(E)之含量相對於著色硬化性樹脂組合物之總量，較佳為70~95質量%，更佳為75~92質量%。換言之，著色硬化性樹脂組合物之固形物成分較佳為5~30質量%，更佳為8~25質量%。 The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass based on the total amount of the colored curable resin composition. In other words, the solid content component of the colored curable resin composition is preferably from 5 to 30% by mass, more preferably from 8 to 25% by mass.
若溶劑(F)之含量為上述範圍，則存在塗佈時之平坦性變得良好，又形成彩色濾光片時不會產生色濃度不足故而顯示特性變得良好的傾向。 When the content of the solvent (F) is in the above range, the flatness at the time of coating becomes good, and when the color filter is formed, the color density is insufficient, and the display characteristics tend to be good.
本發明之著色硬化性樹脂組合物中亦可含有調平劑(F)。 The coloring resin composition of the present invention may further contain a leveling agent (F).
作為調平劑(F)，可列舉：聚矽氧系界面活性劑、氟系界面活性劑及具有氟原子之聚矽氧系界面活性劑等。該等可於側鏈具有聚合性基。 Examples of the leveling agent (F) include a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.
作為聚矽氧系界面活性劑，可列舉：分子內具有矽氧烷鍵之界面活性劑等。具體可列舉：Toray Silicone DC3PA、Toray Silicone SH7PA、Toray Silicone DC11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、Toray Silicone SH8400(商品名，東麗道康寧(股份)製造)，KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業(股份)製造)，TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF4446、TSF4452及TSF4460(邁圖高新材料日本有限公司製造)等。 Examples of the polyoxymethylene-based surfactant include a surfactant having a decane bond in the molecule. Specific examples include: Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name, manufactured by Toray Dow Corning (share)), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (made by Momentive Advanced Materials Japan Co., Ltd.).
作為氟系界面活性劑，可列舉：分子內具有氟碳鏈之界面活性劑等。具體可列舉：Fluorad(註冊商標)FC430、Fluorad FC431(Sumitomo 3M(股份)製造)，MEGAFAC(註冊商標)F142D、MEGAFAC F171、MEGAFAC F172、MEGAFAC F173、MEGAFAC F177、MEGAFAC F183、MEGAFAC F554、MEGAFAC R30、MEGAFAC RS-718-K(DIC(股份)製造)，Eftop(註冊商標)EF301、Eftop EF303、Eftop EF351、Eftop EF352(三菱綜合材料電子化成(股份)製造)，Surflon(註冊商標)S381、Surflon S382、Surflon SC101、Surflon SC105(旭硝子(股份)製造)及E5844(大金精密化學研究所(股份)製造)等。 Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples include Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M (share), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (Mitsubishi Integrated Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Surflon S382 , Surflon SC101, Surflon SC105 (made by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Institute of Precision Chemistry (stock)).
作為具有氟原子之聚矽氧系界面活性劑，可列舉：分子內具有矽氧烷鍵及氟碳鏈之界面活性劑等。具體可列舉：MEGAFAC(註冊商 標)R08、MEGAFAC BL20、MEGAFAC F475、MEGAFAC F477及MEGAFAC F443(DIC(股份)製造)等。 Examples of the polyfluorene-based surfactant having a fluorine atom include a surfactant having a decane bond and a fluorocarbon chain in the molecule. Specific examples: MEGAFAC (registrar Standard) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (manufactured by DIC).
調平劑(F)之含量相對於著色硬化性樹脂組合物之總量，較佳為0.001質量%以上、0.2質量%以下，較佳為0.002質量%以上、0.1質量%以下，更佳為0.005質量%以上、0.07質量%以下。若調平劑(F)之含量為上述範圍內，則可使彩色濾光片之平坦性變得良好。 The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more, 0.1% by mass or less, and even more preferably 0.005%, based on the total amount of the coloring curable resin composition. The mass% or more and 0.07 mass% or less. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.
本發明之著色硬化性樹脂組合物視需要可含有填充劑、其他高分子化合物、密接促進劑、抗氧化劑、光穩定劑、鏈轉移劑等該技術領域中公知之添加劑。 The colored curable resin composition of the present invention may contain additives such as a filler, another polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent, as is known in the art, as needed.
本發明之著色硬化性樹脂組合物例如可藉由混合著色劑(A)、樹脂(B)、聚合性化合物(C)、聚合起始劑(D)以及視需要使用之溶劑(E)、調平劑(F)、聚合起始助劑(D1)及其他成分而製備。 The colored curable resin composition of the present invention can be prepared, for example, by mixing a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and optionally a solvent (E). It is prepared by a flat agent (F), a polymerization starting aid (D1) and other ingredients.
紅色顏料較佳為預先混合該顏料與溶劑(E)之一部分或全部，使用珠磨機等使之分散直至該顏料之平均粒徑成為0.2μm以下之程度。 The red pigment is preferably a part or all of the pigment and the solvent (E), and is dispersed in a bead mill or the like until the average particle diameter of the pigment is 0.2 μm or less.
此時，視需要可調配顏料分散劑、樹脂(B)之一部分或全部。於如此獲得之顏料分散液中以成為特定濃度之方式混合剩餘成分，藉此可製備目標之著色硬化性樹脂組合物。 At this time, a part or all of the pigment dispersant and the resin (B) may be optionally provided. The target coloring curable resin composition can be prepared by mixing the remaining components in a pigment dispersion thus obtained at a specific concentration.
染料(A-2)較佳為預先溶解於溶劑(E)之一部分或全部中而製備溶液。較佳為以孔徑0.01~1μm左右之過濾器過濾該溶液。 The dye (A-2) is preferably prepared by dissolving in part or all of the solvent (E) in advance. Preferably, the solution is filtered through a filter having a pore diameter of about 0.01 to 1 μm.
較佳為利用孔徑為0.01~10μm左右之過濾器對混合後之著色硬化性樹脂組合物進行過濾。 Preferably, the mixed color-curable resin composition is filtered using a filter having a pore diameter of about 0.01 to 10 μm.
本發明之彩色濾光片係由本發明之著色硬化性樹脂組合物所形成。該彩色濾光片可為具有著色圖案之塗膜，亦可為下述著色塗膜。 The color filter of the present invention is formed from the colored curable resin composition of the present invention. The color filter may be a coating film having a colored pattern, or may be a colored coating film described below.
作為由本發明之著色硬化性樹脂組合物而製造著色圖案之方法，可列舉：光微影法、噴墨法、印刷法等。其中，較佳為光微影法。 The method of producing a colored pattern by the colored curable resin composition of the present invention includes a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred.
光微影法係將上述著色硬化性樹脂組合物塗佈於基板上，使之乾燥而形成著色組合物層，經由光罩將該著色組合物層曝光，並進行顯影之方法。於光微影法中可藉由曝光時不使用光罩及/或不顯影，而形成作為上述著色組合物層之硬化物之著色塗膜。 In the photolithography method, the colored curable resin composition is applied onto a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask to develop the film. In the photolithography method, a color coating film which is a cured product of the coloring composition layer can be formed by using no mask and/or no development during exposure.
彩色濾光片之膜厚並無特別限定，可根據目的或用途等而適宜調整，例如為0.1~30μm，較佳為0.1~20μm，進而較佳為0.5~6μm。 The film thickness of the color filter is not particularly limited, and can be appropriately adjusted depending on the purpose, use, and the like, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.
作為基板，可使用石英玻璃、硼矽酸玻璃、氯矽酸鹽玻璃、表面塗佈有二氧化矽之鈉鈣玻璃等玻璃板，或聚碳酸酯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯等樹脂板，矽，於上述基板上形成有鋁、銀、銀/銅/鈀合金薄膜等者。該等基板上亦可形成其他之彩色濾光片層、樹脂層、電晶體、電路等。 As the substrate, a glass plate such as quartz glass, borosilicate glass, chlorite glass, or soda-lime glass coated with cerium oxide, or polycarbonate, polymethyl methacrylate or poly-p-phenylene can be used. A resin plate such as ethylene formate is formed on the substrate, and an aluminum, silver, silver/copper/palladium alloy film or the like is formed on the substrate. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on the substrates.
藉由光微影法所進行之彩色濾光片之形成可利用公知或慣用之裝置或者條件而進行。例如可藉由下述方式製作。 The formation of the color filter by photolithography can be carried out using known or conventional devices or conditions. For example, it can be produced by the following method.
首先，將著色硬化性樹脂組合物塗佈於基板上，藉由加熱乾燥(預烘烤)及/或減壓乾燥而去除溶劑等揮發成分，使之乾燥，而獲得平滑之著色組合物層。 First, the colored curable resin composition is applied onto a substrate, and the volatile components such as a solvent are removed by heat drying (prebaking) and/or drying under reduced pressure, and dried to obtain a smooth colored composition layer.
作為塗佈方法，可列舉：旋轉塗佈法、狹縫塗佈法、狹縫與旋轉塗佈法等。 Examples of the coating method include a spin coating method, a slit coating method, a slit and a spin coating method, and the like.
進行加熱乾燥之情形時之溫度較佳為30~120℃，更佳為50~110℃。又，作為加熱時間，較佳為10秒鐘~60分鐘，更佳為30秒鐘~30分鐘。 The temperature at the time of heat drying is preferably from 30 to 120 ° C, more preferably from 50 to 110 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.
進行減壓乾燥之情形時，較佳為於50~150Pa之壓力下、20~25℃之溫度範圍內進行。 In the case of drying under reduced pressure, it is preferably carried out at a temperature of from 50 to 150 Pa and at a temperature of from 20 to 25 °C.
著色組合物層之膜厚並無特別限定，可根據目標彩色濾光片之膜 厚而適宜選擇。 The film thickness of the coloring composition layer is not particularly limited, and may be a film according to a target color filter. Thick and suitable for selection.
其次，對於著色組合物層，經由用以形成目標著色圖案之光罩進行曝光。該光罩上之圖案並無特別限定，可使用根據目標用途之圖案。 Next, for the colored composition layer, exposure is performed via a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use can be used.
作為曝光中所使用之光源，較佳為產生250~450nm之波長之光之光源。例如，對於未達350nm之光，使用截取該波長區域之過濾器進行截取；或者對於436nm附近、408nm附近、365nm附近之光，使用提取該等波長區域之帶通濾波器進行選擇性地提取。具體而言，可列舉：水銀燈、發光二極體、金屬鹵素燈、鹵素燈等。 As the light source used in the exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, for light that is less than 350 nm, a filter that intercepts the wavelength region is used for interception; or for light near 436 nm, near 408 nm, and near 365 nm, a band pass filter that extracts the wavelength regions is used for selective extraction. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.
為了對曝光面整體均勻照射平行光線、或可進行光罩與形成有著色組合物層之基板之正確之位置對準，較佳為使用光罩對準曝光機及步進式曝光機等曝光裝置。 In order to uniformly illuminate the entire surface of the exposed surface, or to align the correct position of the reticle with the substrate on which the colored composition layer is formed, it is preferable to use an exposure apparatus such as a reticle alignment machine and a stepper. .
藉由使曝光後之著色組合物層與顯影液接觸進行顯影，而於基板上形成著色圖案。藉由顯影，著色組合物層之未曝光部溶解於顯影液中而去除。作為顯影液，較佳為氫氧化鉀、碳酸氫鈉、碳酸鈉、氫氧化四甲基銨等鹼性化合物之水溶液。鹼性化合物之水溶液中之濃度較佳為0.01~10質量%，更佳為0.03~5質量%。進而，顯影液可含有界面活性劑。 The coloring pattern is formed on the substrate by developing the exposed coloring composition layer in contact with the developing solution. By development, the unexposed portion of the colored composition layer is dissolved in the developer to be removed. As the developer, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferred. The concentration in the aqueous solution of the basic compound is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass. Further, the developer may contain a surfactant.
顯影方法可為覆液法、浸漬法及噴霧法等之任一者。進而顯影時可將基板傾斜任意角度。 The development method may be any of a liquid coating method, a dipping method, and a spraying method. Further, the substrate can be tilted at an arbitrary angle during development.
顯影後較佳為進行水洗。 It is preferred to carry out water washing after development.
進而，較佳為對所獲得之著色組合物層進行後烘烤。後烘烤溫度較佳為150~250℃，更佳為160~235℃。後烘烤時間較佳為1~120分鐘，更佳為10~60分鐘。 Further, it is preferred to post-bake the obtained coloring composition layer. The post-baking temperature is preferably from 150 to 250 ° C, more preferably from 160 to 235 ° C. The post-baking time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.
根據本發明，可提供可製造耐溶劑性或耐熱性優異之彩色濾光片之著色硬化性樹脂組合物。自本發明之著色硬化性樹脂組合物形成之彩色濾光片亦歸為本發明之範疇。 According to the present invention, it is possible to provide a color-curable resin composition which can produce a color filter excellent in solvent resistance or heat resistance. A color filter formed from the colored curable resin composition of the present invention is also within the scope of the present invention.
該彩色濾光片可較佳地用於顯示裝置(液晶顯示裝置、有機EL(Electroluminescence，電致發光)裝置、電子紙等)及固體拍攝元件中。 The color filter can be preferably used in a display device (a liquid crystal display device, an organic EL (electroluminescence) device, an electronic paper, etc.) and a solid-state imaging device.
其次，列舉實施例，更具體地說明本發明。例中之「%」及「份」只要無特別說明，則表示質量%及質量份。 Next, the present invention will be described more specifically by way of examples. In the examples, "%" and "parts" mean % by mass and parts by mass unless otherwise stated.
於以下之合成例中，化合物之結構係利用NMR(JMM-ECA-500；日本電子(股份)製造)進行鑑定。 In the following synthesis examples, the structure of the compound was identified by NMR (JMM-ECA-500; manufactured by JEOL Ltd.).
樹脂之聚苯乙烯換算之重量平均分子量(Mw)及數量平均分子量(Mn)之測定係藉由GPC法並於以下條件下進行。 The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene of the resin was carried out by the GPC method under the following conditions.
裝置：HLC-8120GPC(Tosoh(股份)製造) Device: HLC-8120GPC (manufactured by Tosoh)
管柱：TSK-GELG2000HXL Column: TSK-GELG2000HXL
管柱溫度：40℃ Column temperature: 40 ° C
溶劑：四氫呋喃[THF] Solvent: tetrahydrofuran [THF]
流速：1.0mL/分鐘 Flow rate: 1.0 mL/min
受檢液固形物成分濃度：0.001~0.01質量% The concentration of the solid content of the test liquid: 0.001~0.01% by mass
注入量：50μL Injection volume: 50μL
檢測器：R1 Detector: R1
校正用標準物質：TSK標準聚苯乙烯F-40、F-4、F-288、A-2500、A-500(Tosoh(股份)製造) Standard materials for calibration: TSK standard polystyrene F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh)
將上述所獲得之聚苯乙烯換算之重量平均分子量及數量平均分子量之比(Mw/Mn)設為分子量分佈。 The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained above was defined as a molecular weight distribution.
將雙(3-胺基-4-羥基苯基)六氟丙烷10.1份與甲醇51份混合，一面攪拌一面於5℃以下添加3-乙氧基-3-亞胺基丙酸乙酯鹽酸鹽12.6份。其後，將反應混合物於10℃以下攪拌5小時，於室溫下攪拌24小時， 於60℃下攪拌24小時。將上述反應混合物冷卻至室溫後，添加水300份與乙酸乙酯270份，分取乙酸乙酯層。於水層中添加乙酸乙酯135份，分取乙酸乙酯層。於水層中添加乙酸乙酯135份，分取乙酸乙酯層。合併乙酸乙酯層，以水300份清洗3次，以硫酸鎂進行乾燥，並過濾。蒸餾去除濾液之溶劑而獲得殘渣。將該殘渣以管柱層析法進行純化，而獲得式(pt1)所表示之化合物14.5份。 10.1 parts of bis(3-amino-4-hydroxyphenyl)hexafluoropropane was mixed with 51 parts of methanol, and 3-ethoxy-3-iminopropyl propionate hydrochloride was added thereto at 5 ° C or lower while stirring. The salt was 12.6 parts. Thereafter, the reaction mixture was stirred at 10 ° C or lower for 5 hours and at room temperature for 24 hours. Stir at 60 ° C for 24 hours. After cooling the reaction mixture to room temperature, 300 parts of water and 270 parts of ethyl acetate were added, and the ethyl acetate layer was separated. 135 parts of ethyl acetate was added to the aqueous layer, and the ethyl acetate layer was separated. 135 parts of ethyl acetate was added to the aqueous layer, and the ethyl acetate layer was separated. The ethyl acetate layer was combined, washed three times with 300 portions of water, dried over magnesium sulfate and filtered. The solvent of the filtrate was distilled off to obtain a residue. The residue was purified by column chromatography to obtain 14.5 parts of the compound of formula (pt1).
<式(pt1)所表示之化合物之鑑定> <Identification of the compound represented by formula (pt1)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 559.1 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 559.1
精確質量(Exact Mass)：558.1 Exact Mass: 558.1
於氮氣環境下，將二甲基亞碸75份、氫氧化鉀8.45份混合，於室溫下攪拌0.5小時。於該混合物中添加3-甲氧基二苯胺25份，於室溫下攪拌0.5小時。於該混合物中添加碘乙烷21.5份，於室溫下攪拌2小時。於所獲得之混合物中添加氫氧化鉀4.23份，於室溫下攪拌1小時後，添加碘乙烷10.8份，於室溫下攪拌12小時。於所獲得之混合物中添加氫氧化鉀4.23份，於室溫下攪拌1小時後，添加碘乙烷10.8份，於室溫下攪拌2小時。於所獲得之混合物中添加氫氧化鉀4.23份，於室溫下攪拌1小時後，添加碘乙烷10.8份，於室溫下攪拌13小時。於所獲得之混合物中添加水158份與乙酸乙酯135份，分取乙酸乙酯層。於水層中添加乙酸乙酯90份，分取乙酸乙酯層。合併乙酸乙酯層，以水100份清洗3次。將該乙酸乙酯溶液以硫酸鎂進行乾燥，並過濾。蒸餾去除該濾液之溶劑，而獲得式(pt3-1)所表示之化合物28.4份。 75 parts of dimethyl hydrazine and 8.45 parts of potassium hydroxide were mixed under a nitrogen atmosphere, and stirred at room temperature for 0.5 hour. To the mixture was added 25 parts of 3-methoxydiphenylamine, and the mixture was stirred at room temperature for 0.5 hour. 21.5 parts of iodoethane was added to the mixture, and the mixture was stirred at room temperature for 2 hours. 4.23 parts of potassium hydroxide was added to the obtained mixture, and the mixture was stirred at room temperature for 1 hour, and then 10.8 parts of ethyl iodide was added thereto, and the mixture was stirred at room temperature for 12 hours. To the obtained mixture, 4.23 parts of potassium hydroxide was added, and after stirring at room temperature for 1 hour, 10.8 parts of ethyl iodide was added, and the mixture was stirred at room temperature for 2 hours. To the obtained mixture, 4.23 parts of potassium hydroxide was added, and after stirring at room temperature for 1 hour, 10.8 parts of ethyl iodide was added, and the mixture was stirred at room temperature for 13 hours. To the obtained mixture, 158 parts of water and 135 parts of ethyl acetate were added, and the ethyl acetate layer was separated. 90 parts of ethyl acetate was added to the aqueous layer, and the ethyl acetate layer was separated. The ethyl acetate layer was combined and washed 3 times with 100 parts of water. The ethyl acetate solution was dried over magnesium sulfate and filtered. The solvent of the filtrate was distilled off to obtain 28.4 parts of the compound represented by the formula (pt3-1).
<式(pt3-1)所表示之化合物之鑑定> <Identification of the compound represented by formula (pt3-1)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 228.1 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 228.1
精確質量：227.1 Exact quality: 227.1
於氮氣環境下，混合式(pt3-1)所表示之化合物28.4份與二氯甲烷302份。一面將該混合物保持為4~10℃，一面添加三溴化硼44.8份後，於室溫下攪拌12小時。一面將水341份與二氯甲烷302份之混合物之溫度保持為4~19℃，一面於水341份與二氯甲烷302份之混合物中添加所獲得之混合物。將該混合物於室溫下攪拌2小時，分取二氯甲烷層。將該二氯甲烷溶液以10wt%食鹽水227份清洗4次，以硫酸鎂進行乾燥，並過濾。蒸餾去除該濾液之溶劑，獲得式(pt4-1)所表示之化合物23.3份。 28.4 parts of the compound represented by the formula (pt3-1) and 302 parts of dichloromethane were mixed under a nitrogen atmosphere. While maintaining the mixture at 4 to 10 ° C, 44.8 parts of boron tribromide was added thereto, followed by stirring at room temperature for 12 hours. While maintaining the temperature of the mixture of 341 parts of water and 302 parts of dichloromethane at 4 to 19 ° C, the obtained mixture was added to a mixture of 341 parts of water and 302 parts of dichloromethane. The mixture was stirred at room temperature for 2 hours and the dichloromethane layer was separated. The dichloromethane solution was washed 4 times with 227 parts of 10 wt% saline, dried over magnesium sulfate, and filtered. The solvent of the filtrate was distilled off to obtain 23.3 parts of the compound represented by the formula (pt4-1).
<式(pt4-1)所表示之化合物之鑑定> <Identification of the compound represented by formula (pt4-1)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 214.1 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 214.1
精確質量：213.1 Exact quality: 213.1
於氮氣環境下，一面將溫度保持為6~15℃，一面於N,N-二甲基 甲醯胺47.7份中添加磷醯氯25.1份。一面將該混合物之溫度保持為6~25℃，一面於該混合物中添加式(pt4-1)所表示之化合物23.3份與N,N-二甲基甲醯胺31.4份之混合物。將該混合物於40℃下攪拌2小時後，冷卻至室溫。一面將溫度保持為14~19℃，一面將所獲得之混合物添加至48wt%氫氧化鈉水溶液109份與水410份之混合物中，攪拌1小時。一面將溫度保持為12~17℃，一面於所獲得之混合物中添加35wt%鹽酸67.2份。於所獲得之混合物中添加乙酸乙酯210份與矽藻土，加以過濾。將所獲得之濾液以10wt%食鹽水233份清洗2次，以硫酸鎂進行乾燥，並過濾。蒸餾去除所獲得之濾液之溶劑而獲得殘渣。將該殘渣以管柱層析法加以純化，而獲得式(pt5-1)所表示之化合物23.9份。 Maintain a temperature of 6 to 15 ° C on one side and a N, N-dimethyl group under a nitrogen atmosphere. 25.1 parts of phosphonium chloride was added to 47.7 parts of methotrexate. While maintaining the temperature of the mixture at 6 to 25 ° C, a mixture of 23.3 parts of the compound represented by the formula (pt4-1) and 31.4 parts of N,N-dimethylformamide was added to the mixture. The mixture was stirred at 40 ° C for 2 hours and then cooled to room temperature. While maintaining the temperature at 14 to 19 ° C, the obtained mixture was added to a mixture of 109 parts of a 48 wt% aqueous sodium hydroxide solution and 410 parts of water, and stirred for 1 hour. While maintaining the temperature at 12 to 17 ° C, 67.2 parts of 35 wt% hydrochloric acid was added to the obtained mixture. To the obtained mixture, 210 parts of ethyl acetate and diatomaceous earth were added and filtered. The obtained filtrate was washed twice with 233 parts of 10 wt% saline, dried over magnesium sulfate, and filtered. The solvent of the obtained filtrate was distilled off to obtain a residue. The residue was purified by column chromatography to obtain 23.9 parts of the compound of formula (pt5-1).
<式(pt5-1)所表示之化合物之鑑定> <Identification of the compound represented by formula (pt5-1)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 242.1 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 242.1
精確質量：241.1 Exact quality: 241.1
於氮氣環境下，混合式(pt5-1)所表示之化合物10.9份、式(pt1)所表示之化合物12.0份、哌啶0.915份及甲苯83.8份。將該混合物於100℃下攪拌19小時。蒸餾去除該混合液之溶劑而獲得殘渣。將該殘渣以管柱層析法加以純化，而獲得式(Ad2-12)所表示之化合物10.6份。 10.9 parts of the compound represented by the formula (pt5-1), 12.0 parts of the compound represented by the formula (pt1), 0.915 parts of piperidine, and 83.8 parts of toluene were mixed under a nitrogen atmosphere. The mixture was stirred at 100 ° C for 19 hours. The solvent of the mixture was distilled off to obtain a residue. The residue was purified by column chromatography to give 10.6 parts of the compound of formula (Ad2-12).
<式(Ad2-12)所表示之化合物之鑑定> <Identification of the compound represented by the formula (Ad2-12)>
1H-NMR(CDCl3,270MHz)δ 1.31(6H),3.84(4H),6.58-6.61(4H),7.16-7.24(4H),7.31-7.39(6H),7.46-7.52(4H),7.55(2H),7.99(2H),8.63(2H) 1 H-NMR (CDCl 3 , 270 MHz) δ 1.31 (6H), 3.84 (4H), 6.58-6.61 (4H), 7.16-7.24 (4H), 7.31-7.39 (6H), 7.46-7.52 (4H), 7.55 (2H), 7.99 (2H), 8.63 (2H)
混合2,4-二甲基苯胺42.4份、三乙胺35.4份及N,N-二甲基甲醯胺132份，於50℃下攪拌。一面將該混合物之溫度保持為50~60℃，一面添加碘乙烷56.8份，其後，於60℃下攪拌65小時。將該混合物放冷至室溫後，添加水1000份與甲苯433份，分取甲苯層。將該甲苯層以飽和氯化鈉水溶液1000份清洗3次後，以旋轉蒸發器蒸餾去除溶劑。將所獲得之殘渣以管柱層析法加以純化，而獲得式(pt2-2)所表示之化合物18.8份。 42.4 parts of 2,4-dimethylaniline, 35.4 parts of triethylamine and 132 parts of N,N-dimethylformamide were mixed and stirred at 50 °C. While maintaining the temperature of the mixture at 50 to 60 ° C, 56.8 parts of ethyl iodide was added thereto, followed by stirring at 60 ° C for 65 hours. After the mixture was allowed to cool to room temperature, 1000 parts of water and 433 parts of toluene were added, and the toluene layer was separated. The toluene layer was washed three times with 1000 parts of a saturated aqueous sodium chloride solution, and then the solvent was distilled off by a rotary evaporator. The residue obtained was purified by column chromatography to obtain 18.8 parts of the compound represented by formula (pt2-2).
<式(pt2-2)所表示之化合物之鑑定> <Identification of the compound represented by formula (pt2-2)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 150.1 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 150.1
精確質量：149.1 Exact quality: 149.1
於氮氣環境下，混合式(pt2-2)所表示之化合物29.8份、3-溴苯甲醚37.4份、乙酸鈀(II)1.35份、第三丁醇鉀33.7份、2,8,9-三異丙基-2,5,8,9-四氮雜-1-磷雜雙環[3.3.3]十一烷(1M甲苯溶液)3.42份及甲苯520份，於100℃下攪拌6小時。將該混合液放冷至室溫後，添加水1000 份。過濾該混合液後，分取甲苯層。將該甲苯溶液以飽和碳酸氫鈉水溶液加以清洗，以硫酸鎂加以乾燥後，過濾。將該濾液以旋轉蒸發器蒸餾去除溶劑，將所獲得之殘渣以管柱層析法加以純化，而獲得式(pt3-2)所表示之化合物41.9份。 29.8 parts of the compound represented by the formula (pt2-2), 37.4 parts of 3-bromoanisole, 1.35 parts of palladium acetate (II), 33.7 parts of potassium t-butoxide, 2,8,9- under a nitrogen atmosphere. 3.42 parts of triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane (1 M in toluene) and 520 parts of toluene were stirred at 100 ° C for 6 hours. After the mixture was allowed to cool to room temperature, water 1000 was added. Share. After filtering the mixture, the toluene layer was taken. The toluene solution was washed with a saturated aqueous sodium hydrogencarbonate solution, dried over magnesium sulfate and filtered. The filtrate was distilled off by a rotary evaporator to remove the solvent, and the obtained residue was purified by column chromatography to obtain 41.9 parts of the compound of formula (pt3-2).
<式(pt3-2)所表示之化合物之鑑定> <Identification of the compound represented by formula (pt3-2)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 256.2 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 256.2
精確質量：255.2 Exact quality: 255.2
除於合成例1中，將式(pt3-1)所表示之化合物替代為式(pt3-2)所表示之化合物以外，以與合成例1相同之方式實施，獲得式(pt4-2)、式(pt5-2)及式(Ad2-14)所表示之化合物。 In the same manner as in Synthesis Example 1, except that the compound represented by the formula (pt3-1) was replaced by the compound represented by the formula (pt3-2), the formula (pt4-2) was obtained. A compound represented by the formula (pt5-2) and the formula (Ad2-14).
<各化合物之鑑定> <Identification of each compound>
式(pt4-2)所表示之化合物 a compound represented by the formula (pt4-2)
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 242.2 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 242.2
精確質量：241.2 Exact quality: 241.2
式(pt5-2)所表示之化合物 a compound represented by the formula (pt5-2)
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 270.2 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 270.2
精確質量：269.1 Exact quality: 269.1
式(Ad2-14)所表示之化合物 a compound represented by the formula (Ad2-14)
1H-NMR(CDCl3,270MHz)δ 1.30(6H),2.09(6H),2.39(6H),3.59(2H),3.86(2H),6.42(4H),7.00(2H),7.12(2H),7.18(2H),7.30-7.37(4H),7.54(2H),7.98(2H),8.62(2H) 1 H-NMR (CDCl 3 , 270MHz) δ 1.30 (6H), 2.09 (6H), 2.39 (6H), 3.59 (2H), 3.86 (2H), 6.42 (4H), 7.00 (2H), 7.12 (2H) , 7.18(2H), 7.30-7.37(4H), 7.54(2H), 7.98(2H), 8.62(2H)
將4-(二丁基胺基)柳醛(2.49g，10mmol)、氰基乙酸乙酯(1.13g，10mmol)及2,2-雙(3-胺基-4-羥基苯基)六氟丙烷(1.83g，5mmol)溶解於正戊醇(22g，250mmol)中，添加苯甲酸(0.41g，3.4mmol)，於氮氣流下於135℃下攪拌7小時。反應結束後，減壓蒸餾去除正戊醇，將殘渣溶解於甲苯中，以水加以清洗。將甲苯層以硫酸鈉加以乾燥後濃縮，以矽膠管柱層析法(己烷/乙酸乙酯)加以純化，以30%之產率獲得式(4-44)所表示之化合物(1.39g，1.5mmol)。以1H-NMR確認式(Ad2-11)所表示之化合物之結構。 4-(Dibutylamino) salicylaldehyde (2.49 g, 10 mmol), ethyl cyanoacetate (1.13 g, 10 mmol) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro Propane (1.83 g, 5 mmol) was dissolved in n-pentanol (22 g, 250 mmol), benzoic acid (0.41 g, 3.4 mmol) was added, and the mixture was stirred at 135 ° C for 7 hours under a nitrogen stream. After completion of the reaction, n-pentanol was distilled off under reduced pressure, and the residue was dissolved in toluene and washed with water. The toluene layer was dried over sodium sulfate, concentrated, and purified by silica gel column chromatography (hexane/ethyl acetate) to afford the compound of formula (4-44) (1.39 g, 1.5 mmol). The structure of the compound represented by the formula (Ad2-11) was confirmed by 1 H-NMR.
<式(Ad2-11)所表示之化合物之鑑定> <Identification of the compound represented by the formula (Ad2-11)>
1H-NMR(400MHz,CDCl3)：0.99(12H,t),1.36-1.42(8H,m),1.59-1.67(8H,m),3.37(8H,t),6.51(2H,d),6.63(2H,dd),7.32(2H,d),7.41(2H,d),7.54(2H,d),7.99(2H,s),8.61(2H,s) 1 H-NMR (400 MHz, CDCl 3 ): 0.99 (12H, t), 1.36-1.42 (8H, m), 1.59-1.67 (8H, m), 3.37 (8H, t), 6.51 (2H, d), 6.63 (2H, dd), 7.32 (2H, d), 7.41 (2H, d), 7.54 (2H, d), 7.99 (2H, s), 8.61 (2H, s)
混合雙(3-胺基-4-羥基苯基)碸4.98份與甲醇28.1份，一面攪拌一面於10℃以下緩慢添加3-乙氧基-3-亞胺基丙酸乙酯鹽酸鹽8.18份。其後，將反應混合物於10℃以下攪拌7小時，於室溫下攪拌24小時，於60℃下攪拌24小時。將上述反應混合物冷卻至室溫後，作為抽氣過濾之殘渣而獲得析出之結晶。將該殘渣以甲醇加以清洗，於60℃下減壓乾燥，獲得式(pt2)所表示之化合物6.77份。 4.98 parts of bis(3-amino-4-hydroxyphenyl)phosphonium and 28.1 parts of methanol were mixed, and 3-ethoxy-3-iminopropionate ethyl ester hydrochloride 8.18 was slowly added while stirring at 10 ° C or less. Share. Thereafter, the reaction mixture was stirred at 10 ° C or lower for 7 hours, at room temperature for 24 hours, and at 60 ° C for 24 hours. After the reaction mixture was cooled to room temperature, the precipitated crystals were obtained as a residue obtained by suction filtration. The residue was washed with methanol and dried under reduced pressure at 60 ° C to yield 6.77 parts of the compound of formula (pt2).
<式(pt2)所表示之化合物之鑑定> <Identification of the compound represented by formula (pt2)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 473.1 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 473.1
精確質量：472.1 Exact quality: 472.1
混合2,4-二甲基苯胺42.4份(0.35莫耳)、三乙胺35.4份(0.35莫耳)及N,N-二甲基甲醯胺132份，於50℃下加以攪拌。一面將該混合物之溫度保持為50~60℃，一面添加1-溴-2-乙基己烷70.2份(0.364莫耳)，其後，於60℃下攪拌65小時。將該混合物放冷至室溫後，添加水1000份與甲苯433份，分取甲苯層。將該甲苯層以飽和氯化鈉水溶液1000份清洗3次後，以旋轉蒸發器蒸餾去除溶劑。將所獲得之殘渣以管柱層析法加以純化，而獲得式(pt2-1)所表示之化合物50.6份。 42.4 parts (0.35 mol) of 2,4-dimethylaniline, 35.4 parts of triethylamine (0.35 mol) and 132 parts of N,N-dimethylformamide were mixed and stirred at 50 °C. While maintaining the temperature of the mixture at 50 to 60 ° C, 70.2 parts (0.364 mol) of 1-bromo-2-ethylhexane was added thereto, followed by stirring at 60 ° C for 65 hours. After the mixture was allowed to cool to room temperature, 1000 parts of water and 433 parts of toluene were added, and the toluene layer was separated. The toluene layer was washed three times with 1000 parts of a saturated aqueous sodium chloride solution, and then the solvent was distilled off by a rotary evaporator. The residue obtained was purified by column chromatography to obtain 50.6 parts of the compound of formula (pt2-1).
<式(pt2-1)所表示之化合物之鑑定> <Identification of the compound represented by formula (pt2-1)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 234.2 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 234.2
精確質量：233.2 Exact quality: 233.2
於氮氣環境下，混合式(pt2-1)所表示之化合物46.7份(0.2莫耳)、3-溴苯甲醚37.4份(0.2莫耳)、乙酸鈀(II)1.35份(0.006莫耳)、第三丁醇鉀33.7份(0.3莫耳)、2,8,9-三異丙基-2,5,8,9-四氮雜-1-磷雜雙環[3.3.3]十一烷(1.0M甲苯溶液)3.42份(0.01莫耳)及甲苯520份，於100℃下攪拌6小時。將該混合液放冷至室溫後，添加至水1000份中。過濾該混合液後，分取甲苯層。將該甲苯溶液以飽和碳酸氫鈉水溶液加以清洗，以硫酸鎂加以乾燥後，過濾。將該濾液以旋轉蒸發器蒸餾去除溶劑，將所獲得之殘渣以管柱層析法加以純化，而獲得式(pt3-3)所表示之化合物30.9份。 46.7 parts (0.2 mol) of compound represented by (pt2-1), 37.4 parts of 3-bromoanisole (0.2 mol), and 1.35 parts of palladium acetate (II) (0.006 mol) under nitrogen atmosphere. 33.7 parts (0.3 moles) of potassium butoxide, 2,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane (1.0 M toluene solution) 3.42 parts (0.01 mol) and 520 parts of toluene were stirred at 100 ° C for 6 hours. After the mixture was allowed to cool to room temperature, it was added to 1000 parts of water. After filtering the mixture, the toluene layer was taken. The toluene solution was washed with a saturated aqueous sodium hydrogencarbonate solution, dried over magnesium sulfate and filtered. The filtrate was distilled off by a rotary evaporator to remove the solvent, and the obtained residue was purified by column chromatography to obtain 30.9 parts of the compound of formula (pt3-3).
<式(pt3-3)所表示之化合物之鑑定> <Identification of the compound represented by the formula (pt3-3)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 340.3 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 340.3
精確質量：339.3 Exact quality: 339.3
於氮氣環境下，混合式(pt3-3)所表示之化合物17.0份(0.05莫耳)與二氯甲烷199份，一面將該混合液保持為15~23℃，一面以三溴化硼與式(pt3-3)所表示之化合物成為相同莫耳數之份數(0.05莫耳)添加三溴化硼(1.0M二氯甲烷溶液)。其後，將該混合液於室溫下攪拌8小時。 17.2 parts (0.05 mol) of the compound represented by the formula (pt3-3) and 199 parts of methylene chloride were mixed under a nitrogen atmosphere, while maintaining the mixture at 15 to 23 ° C while using boron tribromide and The compound represented by (pt3-3) was divided into the same molar number (0.05 mol) and boron tribromide (1.0 M dichloromethane solution) was added. Thereafter, the mixture was stirred at room temperature for 8 hours.
將該混合物添加至冰水250份中，分取二氯甲烷層。將該二氯甲烷層以水250份加以清洗，以硫酸鎂進行乾燥，並過濾。將所獲得之濾液以旋轉蒸發器蒸餾去除溶劑。將所獲得之殘渣以管柱層析法加以純化，而獲得式(pt4-3)所表示之化合物13.9份。 The mixture was added to 250 parts of ice water, and the dichloromethane layer was separated. The dichloromethane layer was washed with 250 parts of water, dried over magnesium sulfate and filtered. The obtained filtrate was distilled off by a rotary evaporator to remove the solvent. The residue obtained was purified by column chromatography to obtain 13.9 parts of the compound of formula (pt4-3).
<式(pt4-3)所表示之化合物之鑑定> <Identification of the compound represented by the formula (pt4-3)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 326.3 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 326.3
精確質量：325.2 Exact quality: 325.2
混合式(pt4-3)所表示之化合物13.9份(0.0427莫耳)與N,N-二甲基甲醯胺26.4份。一面將該混合物保持為23~55℃，一面添加磷醯氯13.1份(0.0854莫耳)。其後，將該混合物於60℃下攪拌6小時。將該混合物放冷至室溫後，添加至冰水150份中，以48%氫氧化鈉水溶液加以中和。於該混合物中添加乙酸乙酯300份，過濾，自所獲得之濾液分取乙酸乙酯層。將該乙酸乙酯溶液以水300份加以清洗，以硫酸鎂進行乾燥，並過濾。將所獲得之濾液以旋轉蒸發器蒸餾去除溶劑。將所獲得之殘渣以管柱層析法加以純化，而獲得式(pt5-3)所表示之化合物11.6份。 13.9 parts (0.0427 mol) of the compound represented by the mixed formula (pt4-3) and 26.4 parts of N,N-dimethylformamide. While maintaining the mixture at 23 to 55 ° C, 13.1 parts (0.0854 mol) of phosphonium chloride was added. Thereafter, the mixture was stirred at 60 ° C for 6 hours. After the mixture was cooled to room temperature, it was added to 150 parts of ice water and neutralized with a 48% aqueous sodium hydroxide solution. To the mixture was added 300 parts of ethyl acetate, and the mixture was filtered. The ethyl acetate solution was washed with 300 parts of water, dried over magnesium sulfate, and filtered. The obtained filtrate was distilled off by a rotary evaporator to remove the solvent. The residue obtained was purified by column chromatography to obtain 11.6 parts of the compound of formula (pt5-3).
<式(pt5-3)所表示之化合物之鑑定> <Identification of the compound represented by formula (pt5-3)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 354.2 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 354.2
精確質量：353.2 Exact mass: 353.2
於氮氣環境下，混合式(pt5-3)所表示之化合物9.65份(0.0273莫耳)、式(pt2)所表示之化合物6.14份(0.013莫耳)、哌啶0.553份(0.0065莫耳)及甲苯51.1份。將該混合物於100℃下攪拌19小時。將該混合液添加至甲醇231份中。藉由去除上清液而獲得產生之沈澱物。於該沈澱物中添加甲醇231份加以攪拌後，將該混合液加以抽氣過濾。將所獲得之殘渣以甲醇20份加以清洗，作為抽氣過濾之殘渣而獲得。將該殘渣以管柱層析法加以純化，而獲得式(Ad2-2)所表示之化合物9.1份。 9.64 parts (0.0273 mol) of the compound represented by the formula (pt5-3), 6.14 parts (0.013 mol) of the compound represented by the formula (pt2), 0.553 parts (0.0065 mol) of piperidine, and the compound represented by the formula (pt5-3) under a nitrogen atmosphere. 51.1 parts of toluene. The mixture was stirred at 100 ° C for 19 hours. This mixture was added to 231 parts of methanol. The resulting precipitate is obtained by removing the supernatant. After adding 231 parts of methanol to the precipitate and stirring, the mixture was suction-filtered. The obtained residue was washed with 20 parts of methanol and obtained as a residue of suction filtration. The residue was purified by column chromatography to give 9.1 part of the compound of formula (Ad2-2).
<式(Ad2-2)所表示之化合物之鑑定> <Identification of the compound represented by the formula (Ad2-2)>
1H-NMR(CDCl3,270MHz)δ 0.82-0.92(12H,m),1.26-1.52(16H,brm),1.77(2H,brs),2.05(6H,s),2.38(6H,s),3.32-3.42(2H,m),3.71-3.78(2H,m),6.42-6.45(4H,m),7.02(2H,d),7.11(2H,d),7.15(2H,s),7.33(2H,d),7.66(2H,d),7.96(2H,dd),8.39(2H,d),8.62(2H, s) 1 H-NMR (CDCl 3 , 270 MHz) δ 0.82-0.92 (12H, m), 1.26-1.52 (16H, brm), 1.77 (2H, brs), 2.05 (6H, s), 2.38 (6H, s), 3.32-3.42 (2H, m), 3.71-3.78 (2H, m), 6.42-6.45 (4H, m), 7.02 (2H, d), 7.11 (2H, d), 7.15 (2H, s), 7.33 ( 2H,d), 7.66(2H,d), 7.96(2H,dd),8.39(2H,d),8.62(2H, s)
除將1-溴-2-乙基己烷替代為1-溴辛烷以外，以與合成例1相同之方式，獲得式(pt2-3)、式(pt3-3)、式(pt4-4)、式(pt5-4)及式(Ad2-4)所表示之化合物。 Formula (pt2-3), formula (pt3-3), and formula (pt4-4) were obtained in the same manner as in Synthesis Example 1, except that 1-bromo-2-ethylhexane was replaced by 1-bromooctane. a compound represented by the formula (pt5-4) and the formula (Ad2-4).
<式(pt2-3)、式(pt3-3)、式(pt4-4)及式(pt5-4)所表示之化合物之鑑定> Identification of Compounds Represented by Formula (pt2-3), Formula (pt3-3), Formula (pt4-4), and Formula (pt5-4) >
<式(Ad2-4)所表示之化合物之鑑定> <Identification of the compound represented by formula (Ad2-4)>
1H-NMR(CDCl3,270MHz)δ 0.88(6H,t),1.28-1.32(20H,m),1.72(4H,brs),2.07(6H,s),2.38(6H,s),3.44(2H,brm),3.77(2H,brm),6.39(4H,brs),6.99(2H,d),7.12(2H,d),7.17(2H,s),7.34(2H,d),7.66(2H,d),7.96(2H,dd),8.39(2H,d),8.62(2H,s) 1 H-NMR (CDCl 3 , 270 MHz) δ 0.88 (6H, t), 1.28-1.32 (20H, m), 1.72 (4H, brs), 2.07 (6H, s), 2.38 (6H, s), 3.44 ( 2H,brm),3.77(2H,brm),6.39(4H,brs),6.99(2H,d),7.12(2H,d),7.17(2H,s),7.34(2H,d),7.66(2H , d), 7.96 (2H, dd), 8.39 (2H, d), 8.62 (2H, s)
混合間苯二酚(東京化成工業(股份)製造)275份與正己胺(東京化成工業(股份)製造)101份，一面於150~155℃下去除生成之水一面攪拌20小時。放冷後，將反應混合物溶解於甲苯433份中，將該甲苯溶液以40℃之溫水1000份清洗3次。於該甲苯溶液中添加無水硫酸鎂50份加以攪拌後，過濾。蒸餾去除濾液之溶劑而獲得粗產物。將該粗產物溶解於甲苯234份中，於0℃以下加以攪拌，過濾收集晶析物。將該晶析物於50℃下減壓乾燥，獲得式(pt3)所表示之化合物95.7份。 275 parts of resorcinol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 101 parts of n-hexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and the resulting water was removed while being heated at 150 to 155 ° C for 20 hours. After allowing to cool, the reaction mixture was dissolved in 433 parts of toluene, and the toluene solution was washed three times with 1000 parts of warm water of 40 °C. To the toluene solution, 50 parts of anhydrous magnesium sulfate was added and stirred, followed by filtration. The solvent of the filtrate was distilled off to obtain a crude product. This crude product was dissolved in 234 parts of toluene, stirred at 0 ° C or lower, and the crystallization was collected by filtration. The crystallization product was dried under reduced pressure at 50 ° C to obtain 95.7 parts of the compound of formula (pt3).
<式(pt3)所表示之化合物之鑑定> <Identification of the compound represented by formula (pt3)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 194.2 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 194.2
精確質量：193.2 Exact mass: 193.2
混合式(pt3)所表示之化合物95.3份與水48份，於80℃下加以攪拌。繼而，一面添加1-溴-2-乙基己烷(東京化成工業(股份)製造)107份，一面於80℃下攪拌3小時後，添加48%氫氧化鈉水溶液22.4份。將該混合物於110℃下攪拌18小時。放冷後，使用10%氫氧化鈉水溶液將反應混合物之pH值調整為5，添加甲苯130份加以攪拌，萃取甲苯層。將甲 苯萃取液以溫水500份清洗2次，添加無水硫酸鎂25.0份加以攪拌，過濾。蒸餾去除濾液之溶劑，獲得含有式(pt4)所表示之化合物作為主成分之殘渣154份。 95.3 parts of the compound represented by the mixed formula (pt3) and 48 parts of water were stirred at 80 °C. Then, 107 parts of 1-bromo-2-ethylhexane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 80 ° C for 3 hours, and then 22.4 parts of a 48% aqueous sodium hydroxide solution was added. The mixture was stirred at 110 ° C for 18 hours. After allowing to cool, the pH of the reaction mixture was adjusted to 5 using a 10% aqueous sodium hydroxide solution, and 130 parts of toluene was added thereto and stirred to extract a toluene layer. Will The benzene extract was washed twice with 500 parts of warm water, and 25.0 parts of anhydrous magnesium sulfate was added thereto, stirred, and filtered. The solvent of the filtrate was distilled off to obtain 154 parts of a residue containing a compound represented by the formula (pt4) as a main component.
<式(pt4)所表示之化合物之鑑定> <Identification of the compound represented by formula (pt4)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 306.3 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 306.3
精確質量：305.3 Exact quality: 305.3
混合含有(pt4)所表示之化合物作為主成分之殘渣154份與N,N-二甲基甲醯胺597份，於-6℃~3℃下加以攪拌。一面將液溫保持為-6℃~3℃，一面於其中添加磷醯氯(和光純藥工業(股份)製造)258份。將該混合物於室溫下攪拌1小時後，於60℃下攪拌4小時。放冷後，將反應混合物添加至冰1500份中，使用48%氫氧化鈉水溶液加以中和。於其中添加甲苯867份，萃取甲苯層。將該甲苯萃取液以15%氯化鈉水溶液1200份清洗2次。於該甲苯萃取液中添加無水硫酸鎂60份加以攪拌後，過濾。蒸餾去除濾液之溶劑而獲得殘渣。將該殘渣以管柱層析法加以純化，而獲得式(pt5)所表示之化合物94.4份。 154 parts of a residue containing the compound represented by (pt4) as a main component and 597 parts of N,N-dimethylformamide were mixed and stirred at -6 ° C to 3 ° C. While maintaining the liquid temperature at -6 ° C to 3 ° C, 258 parts of phosphonium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) were added thereto. The mixture was stirred at room temperature for 1 hour and then stirred at 60 ° C for 4 hours. After allowing to cool, the reaction mixture was added to 1500 portions of ice and neutralized using a 48% aqueous sodium hydroxide solution. To the mixture was added 867 parts of toluene, and the toluene layer was extracted. The toluene extract was washed twice with 1200 parts of a 15% aqueous sodium chloride solution. 60 parts of anhydrous magnesium sulfate was added to the toluene extract, stirred, and filtered. The solvent of the filtrate was distilled off to obtain a residue. The residue was purified by column chromatography to give 94.4 parts of the compound of formula (pt5).
<式(pt5)所表示之化合物之鑑定> <Identification of the compound represented by formula (pt5)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 334.3 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 334.3
精確質量：333.3 Exact quality: 333.3
混合雙(3-胺基-4-羥基苯基)碸(東京化成工業(股份)製造)10.6份、式(pt5)所表示之化合物25.3份、苯甲酸(東京化成工業(股份)製造)3.2份、1-戊醇(東京化成工業(股份)製造)184份及氰基乙酸乙酯(東京化成工業(股份)製造)8.59份，於120℃下攪拌3小時。於該反應溶液中混合式(pt5)所表示之化合物25.4份、苯甲酸(東京化成工業(股份)製造)3.21份、1-戊醇(東京化成工業(股份)製造)90份及氰基乙酸乙酯(東京化成工業(股份)製造)8.59份，於120℃下攪拌12小時。將上述反應液冷卻至室溫後，添加至甲醇1800份中，作為抽氣過濾之殘渣而獲得析出之結晶。將該殘渣以管柱層析法加以純化，而獲得式(Ad2-10)所表示之化合物20.6份。藉由1H-NMR確認結構。 10.6 parts of a mixture of bis(3-amino-4-hydroxyphenyl) oxime (manufactured by Tokyo Chemical Industry Co., Ltd.), 25.3 parts of a compound represented by the formula (pt5), and benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.2 184 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 8.59 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 120 ° C for 3 hours. 25.4 parts of the compound represented by the formula (pt5), 3.21 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 90 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and cyanoacetic acid were mixed in the reaction solution. Ethyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was 8.59 parts, and stirred at 120 ° C for 12 hours. After cooling the reaction liquid to room temperature, it was added to 1800 parts of methanol, and the precipitated crystal was obtained as a residue by suction filtration. The residue was purified by column chromatography to obtain 20.6 parts of the compound of formula (Ad2-10). The structure was confirmed by 1 H-NMR.
<式(Ad2-10)所表示之化合物之鑑定> <Identification of the compound represented by the formula (Ad2-10)>
1H-NMR(500MHz,DMSO-d6)：0.85(6H,t),0.87(6H,t),0.87(6H,t),1.20~1.40(28H),1.56(4H,tt),1.75(2H,ttt),3.34(4H,d),3.43(4H,t),6.55(2H,d),6.79(2H,dd),7.64(2H,d),7.91(2H,d),8.01(2H,dd),8.36(2H,d),8.73(2H,s) 1 H-NMR (500MHz, DMSO -d 6): 0.85 (6H, t), 0.87 (6H, t), 0.87 (6H, t), 1.20 ~ 1.40 (28H), 1.56 (4H, tt), 1.75 ( 2H, ttt), 3.34 (4H, d), 3.43 (4H, t), 6.55 (2H, d), 6.79 (2H, dd), 7.64 (2H, d), 7.91 (2H, d), 8.01 (2H , dd), 8.36 (2H, d), 8.73 (2H, s)
<7-二乙基胺基香豆素之合成> Synthesis of <7-diethylamino coumarin>
將式(pp"1-1)所表示之4-二乙基胺基柳醛1.93g(10mmol)與式(pp"5-1)所表示之丙二酸二乙酯3.2g(20mmol)與哌啶1mL溶解於50mL之無水乙醇中。繼而，一面於回流條件下攪拌6小時一面進行反應。反應結束後，減壓蒸餾去除乙醇，於反應混合物中添加濃鹽酸10mL與冰乙酸10mL，進而攪拌6小時。將反應混合物冷卻至室溫後，裝入200mL之冰水中進而冷卻，繼而，於反應混合物中滴加30質量%氫氧化鈉水溶液，藉此將反應混合物之pH值調整為約5。將反應混合物攪拌30分鐘後，過濾生成之沈澱物，以水清洗加以乾燥。將所獲得之沈澱物以甲苯再結晶，藉此獲得式(pp"2-1)所表示之7-二乙基胺基香豆素。產量為1.74g(8mmol)，產率為80%。 1.93 g (10 mmol) of 4-diethylaminosulphonate represented by the formula (pp"1-1) and 3.2 g (20 mmol) of diethyl malonate represented by the formula (pp"5-1) 1 mL of piperidine was dissolved in 50 mL of absolute ethanol. Then, the reaction was carried out while stirring under reflux for 6 hours. After completion of the reaction, ethanol was distilled off under reduced pressure, and 10 mL of concentrated hydrochloric acid and 10 mL of glacial acetic acid were added to the reaction mixture, followed by stirring for 6 hours. After cooling the reaction mixture to room temperature, it was placed in 200 mL of ice water and then cooled, and then, a 30 mass% aqueous sodium hydroxide solution was added dropwise to the reaction mixture, whereby the pH of the reaction mixture was adjusted to about 5. After the reaction mixture was stirred for 30 minutes, the resulting precipitate was filtered, washed with water and dried. The obtained precipitate was recrystallized from toluene, whereby 7-diethylamino coumarin represented by the formula (pp"2-1) was obtained, and the yield was 1.74 g (8 mmol) in a yield of 80%.
<7-二乙基胺基香豆素-3-醛之合成> Synthesis of <7-diethylamino coumarin-3-aldehyde>
於裝有磷醯氯2mL之反應容器中，於0℃、氮氣環境下緩慢滴加脫水二甲基甲醯胺2mL後，升溫至室溫攪拌30分鐘。繼而，將式(pp"2-1)所表示之7-二乙基胺基香豆素1.5g(6.91mmol)溶解於脫水二甲基甲醯胺10mL中，裝入反應容器中，於50℃下攪拌12小時。將反應混合物裝入200mL之冰水中，添加20質量%氫氧化鈉水溶液。過濾生成之沈澱物，以水清洗加以乾燥。將所獲得之沈澱物以乙醇再結晶，藉此獲得式(pp"3-1)所表示之7-二乙基胺基香豆素-3-醛。產量為1.2g(4.89mmol)，產率為70%。 In a reaction vessel containing 2 mL of phosphonium chloride, 2 mL of dehydrated dimethylformamide was slowly added dropwise at 0 ° C under a nitrogen atmosphere, and the mixture was heated to room temperature and stirred for 30 minutes. Then, 1.5 g (6.91 mmol) of 7-diethylamine coumarin represented by the formula (pp"2-1) was dissolved in 10 mL of dehydrated dimethylformamide, and placed in a reaction vessel at 50 The mixture was stirred for 12 hours at ° C. The reaction mixture was poured into 200 mL of ice water, and a 20% by mass aqueous sodium hydroxide solution was added thereto, and the resulting precipitate was filtered, washed with water and dried, and the obtained precipitate was recrystallized from ethanol. 7-Diethylamino coumarin-3-aldehyde represented by the formula (pp"3-1) is obtained. The yield was 1.2 g (4.89 mmol) and the yield was 70%.
<化合物(Ad2-16)之合成> <Synthesis of Compound (Ad2-16)>
將式(pp"3-1)所表示之7-二乙基胺基香豆素-3-醛2g(8.15mmol)與式(pp"4-1)所表示之2,2-雙(3-胺基-4-羥基苯基)六氟丙烷1.49g(4.08mmol)與乙酸鈉12.6g(163mmol)溶解於冰乙酸40mL中，於90℃下攪拌10小時。繼而，將反應混合物裝入200mL之水中。過濾生成之沈澱物，溶解於二氯甲烷中，與水一同裝入分液漏斗中加以清洗。將自分液漏斗回收之二氯甲烷層以硫酸鈉加以乾燥後，以矽膠管柱層析法加以純化，藉此獲得化合物(Ad2-16)。產量為1.67g(2.04mmol)，產率為50%。 7-diethylamino coumarin-3-aldehyde represented by the formula (pp"3-1) 2g (8.15 mmol) and 2,2-bis (3) represented by the formula (pp"4-1) 1.49 g (4.08 mmol) of -amino-4-hydroxyphenyl)hexafluoropropane and 12.6 g (163 mmol) of sodium acetate were dissolved in 40 mL of glacial acetic acid, and stirred at 90 ° C for 10 hours. The reaction mixture was then charged to 200 mL of water. The resulting precipitate was filtered, dissolved in dichloromethane, and placed in a separating funnel with water and washed. The methylene chloride layer recovered from the separatory funnel was dried over sodium sulfate, and then purified by silica gel column chromatography to obtain compound (Ad2-16). The yield was 1.67 g (2.04 mmol) and the yield was 50%.
混合雙(3-胺基-4-羥基苯基)碸4.98份與甲醇28.1份，一面攪拌一面於10℃以下緩慢添加3-乙氧基-3-亞胺基丙酸乙酯鹽酸鹽8.18份。其後，將反應混合物於10℃以下攪拌7小時，於室溫下攪拌24小時，於60℃下攪拌24小時。將上述反應混合物冷卻至室溫後，作為抽氣過濾之殘渣而獲得析出之結晶。將該殘渣以甲醇加以清洗，於60℃下減壓乾燥，獲得式(pt2)所表示之化合物6.77份。 4.98 parts of bis(3-amino-4-hydroxyphenyl)phosphonium and 28.1 parts of methanol were mixed, and 3-ethoxy-3-iminopropionate ethyl ester hydrochloride 8.18 was slowly added while stirring at 10 ° C or less. Share. Thereafter, the reaction mixture was stirred at 10 ° C or lower for 7 hours, at room temperature for 24 hours, and at 60 ° C for 24 hours. After the reaction mixture was cooled to room temperature, the precipitated crystals were obtained as a residue obtained by suction filtration. The residue was washed with methanol and dried under reduced pressure at 60 ° C to yield 6.77 parts of the compound of formula (pt2).
<式(pt2)所表示之化合物之鑑定> <Identification of the compound represented by formula (pt2)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 473.1 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 473.1
精確質量：472.1 Exact quality: 472.1
於氮氣環境下，混合間甲氧苯胺24份、4-碘-間二甲苯99.7份、碳酸鉀117份、銅粉末27.3份、18-冠醚-64.64份、鄰二氯苯511份，於175℃下攪拌19小時。其後，添加碳酸鉀35.1份、銅粉末8.19份、18-冠醚-61.39份、鄰二氯苯22.0份，於175℃下攪拌17小時。將上述混合物放冷至室溫後，過濾。於濾液中添加乙酸乙酯450份，以2N鹽酸450份清洗3次，以18wt%氯化鈉水溶液470份清洗3次。將所獲得之乙酸乙酯溶液以硫酸鎂進行乾燥，並過濾。將濾液以旋轉蒸發器蒸餾去除溶劑後，將所獲得之殘渣以管柱層析法加以純化，而獲得式(pt6)所表示之化合物64.1份。 24 parts of m-m-aniline, 99.7 parts of 4-iodo-m-xylene, 117 parts of potassium carbonate, 27.3 parts of copper powder, -64.64 parts of 18-crown ether, and 511 parts of o-dichlorobenzene were mixed in a nitrogen atmosphere. Stir at ° C for 19 hours. Thereafter, 35.1 parts of potassium carbonate, 8.19 parts of copper powder, -61.39 parts of 18-crown ether, and 22.0 parts of o-dichlorobenzene were added, and the mixture was stirred at 175 ° C for 17 hours. The mixture was allowed to cool to room temperature and then filtered. 450 parts of ethyl acetate was added to the filtrate, and the mixture was washed three times with 450 parts of 2N hydrochloric acid, and washed three times with 470 parts of an aqueous solution of 18 wt% of sodium chloride. The obtained ethyl acetate solution was dried over magnesium sulfate and filtered. After the filtrate was distilled off by a rotary evaporator to remove the solvent, the obtained residue was purified by column chromatography to obtain 64.1 parts of the compound of formula (pt6).
<式(pt6)所表示之化合物之鑑定> <Identification of the compound represented by formula (pt6)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 332.2 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 332.2
精確質量：331.2 Exact quality: 331.2
於氮氣環境下0℃下混合式(pt6)所表示之化合物31.7份與脫水二氯甲烷190份。繼而，添加17wt%三溴化硼二氯甲烷溶液199份，攪拌1小時。其後，於室溫下攪拌12小時。將該混合物添加至冰水1100份中後，添加氯仿740份，萃取氯仿層。將所獲得之氯仿溶液以18wt%氯化鈉水溶液470份清洗2次後，以硫酸鎂進行乾燥，並過濾。將濾液以旋轉蒸發器蒸餾去除溶劑後，將所獲得之殘渣以管柱層析法加以純化，而獲得式(pt7)所表示之化合物30份。 31.7 parts of the compound represented by the formula (pt6) and 190 parts of dehydrated dichloromethane were mixed at 0 ° C under a nitrogen atmosphere. Then, 199 parts of a 17 wt% boron tribromide dichloromethane solution was added, and the mixture was stirred for 1 hour. Thereafter, it was stirred at room temperature for 12 hours. After the mixture was added to 1100 parts of ice water, 740 parts of chloroform was added, and the chloroform layer was extracted. The obtained chloroform solution was washed twice with 470 parts of an 18 wt% aqueous sodium chloride solution, dried over magnesium sulfate, and filtered. After the filtrate was distilled off by a rotary evaporator to remove the solvent, the obtained residue was purified by column chromatography to obtain 30 parts of the compound of formula (pt7).
<式(pt7)所表示之化合物之鑑定> <Identification of the compound represented by formula (pt7)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 318.2 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 318.2
精確質量：317.2 Exact quality: 317.2
於氮氣環境下5~10℃下混合式(pt7)所表示之化合物7.46份與N,N-二甲基甲醯胺14.4份。一面將該混合物之溫度保持為5~10℃，一 面添加磷醯氯7.21份。其後，於10℃以下攪拌1小時，於室溫下攪拌1小時，於80℃下攪拌1小時。將該反應混合物放冷至室溫後，添加冰水100份，以48%氫氧化鈉水溶液中和。於該混合物中添加乙酸乙酯180份，繼而添加矽藻土加以攪拌。過濾該混合物，萃取乙酸乙酯層。將該乙酸乙酯層以硫酸鎂進行乾燥，並過濾。將該濾液以旋轉蒸發器蒸餾去除溶劑後，將所獲得之殘渣以管柱層析法加以純化，而獲得式(pt8)所表示之化合物6.26份。 7.46 parts of the compound represented by the formula (pt7) and 14.4 parts of N,N-dimethylformamide were mixed at 5 to 10 ° C under a nitrogen atmosphere. Keep the temperature of the mixture at 5~10 °C, one 7.21 parts of phosphonium chloride were added to the surface. Thereafter, the mixture was stirred at 10 ° C or lower for 1 hour, at room temperature for 1 hour, and at 80 ° C for 1 hour. After the reaction mixture was allowed to cool to room temperature, 100 parts of ice water was added and then neutralized with a 48% aqueous sodium hydroxide solution. To the mixture was added 180 parts of ethyl acetate, followed by addition of diatomaceous earth and stirring. The mixture was filtered and the ethyl acetate layer was extracted. The ethyl acetate layer was dried over magnesium sulfate and filtered. After the filtrate was distilled off by a rotary evaporator to remove the solvent, the obtained residue was purified by column chromatography to obtain 6.26 parts of the compound of formula (pt8).
<式(pt8)所表示之化合物之鑑定> <Identification of the compound represented by formula (pt8)>
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 346.2 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 346.2
精確質量：345.2 Exact quality: 345.2
混合式(pt8)所表示之化合物6.01份、式(pt2)所表示之化合物4.04份、哌啶0.357份及甲苯33.4份，於105℃下攪拌6小時。將該混合物放冷至室溫後，添加至甲醇153份中。作為抽氣過濾之殘渣而獲得沈澱物。將所獲得之殘渣以管柱層析法加以純化，而獲得式(Ad2-13)所表示之化合物7.76份。 6.01 parts of the compound represented by the formula (pt8), 4.04 parts of the compound represented by the formula (pt2), 0.357 parts of piperidine and 33.4 parts of toluene were stirred at 105 ° C for 6 hours. The mixture was allowed to cool to room temperature and then added to 153 portions of methanol. A precipitate was obtained as a residue of suction filtration. The residue obtained was purified by column chromatography to obtain 7.76 parts of the compound represented by formula (Ad2-13).
<式(Ad2-13)所表示之化合物之鑑定> <Identification of the compound represented by the formula (Ad2-13)>
1H-NMR(CDCl3,270MHz)δ 2.13(12H),2.34(12H),6.38(2H),6.52(2H),6.92-7.02(8H),7.10(4H),7.37(2H),7.67(2H),7.98(2H),8.40(2H),8.64(2H) 1 H-NMR (CDCl 3, 270MHz) δ 2.13 (12H), 2.34 (12H), 6.38 (2H), 6.52 (2H), 6.92-7.02 (8H), 7.10 (4H), 7.37 (2H), 7.67 ( 2H), 7.98 (2H), 8.40 (2H), 8.64 (2H)
於室溫下混合式(X-1)所表示之化合物50份、異丙醇(和光純藥工業(股份)製造)350份，於不超過20℃之溫度下於混合物中滴加二乙胺(東京化成工業(股份)製造)18.1份，於20℃下攪拌3小時。將反應液投入10%鹽酸2100份中。作為抽氣過濾之殘渣而獲取所獲得之析出物，以離子交換水373份清洗後加以乾燥，獲得式(X-3)所表示之化合物23.6份。產率為43%。 50 parts of the compound represented by the formula (X-1) and 350 parts of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, and diethylamine was added dropwise to the mixture at a temperature not exceeding 20 ° C. (manufactured by Tokyo Chemical Industry Co., Ltd.) 18.1 parts, and stirred at 20 ° C for 3 hours. The reaction solution was poured into 2100 parts of 10% hydrochloric acid. The obtained precipitate was obtained as a residue obtained by suction filtration, washed with 373 parts of ion-exchanged water, and dried to obtain 23.6 parts of the compound represented by the formula (X-3). The yield was 43%.
式(X-3)所表示之化合物之鑑定 Identification of compounds represented by formula (X-3)
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 442.1 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 442.1
精確質量：441.1 Exact quality: 441.1
於室溫下混合式(X-3)所表示之化合物5.0份、N-甲基吡咯啶酮(和光純藥工業(股份)製造)35份，於不超過20℃之溫度下於混合物中滴加二丙胺(東京化成工業(股份)製造)3.4份，升溫至80℃攪拌3小時。將反應液冷卻至室溫後，添加濃鹽酸3.4份，將所獲得之混合物投入飽和食鹽水315份中。作為抽氣過濾之殘渣而獲取所獲得之析出物，以離子交換水630份清洗後加以乾燥，獲得式(1-51)所表示之化合物3.9份。產率為69%。 Mixing 5.0 parts of the compound represented by the formula (X-3) and N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature, and dropping it in the mixture at a temperature not exceeding 20 ° C 3.4 parts of dipropylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was heated to 80 ° C and stirred for 3 hours. After cooling the reaction solution to room temperature, 3.4 parts of concentrated hydrochloric acid was added, and the obtained mixture was poured into 315 parts of saturated brine. The obtained precipitate was obtained as a residue obtained by suction filtration, washed with 630 parts of ion-exchanged water, and dried to obtain 3.9 parts of the compound represented by the formula (1-51). The yield was 69%.
式(1-51)所表示之化合物之鑑定 Identification of compounds represented by formula (1-51)
(質量分析)離子化模式=ESI+：m/z=[M+H]+ 507.7 (mass analysis) ionization mode = ESI +: m / z = [M + H] + 507.7
精確質量：506.7 Exact mass: 506.7
於具備回流冷卻器、滴液漏斗及攪拌機之燒瓶內適量流通氮氣而成為氮氣環境，投入丙二醇單甲醚乙酸酯100份，一面攪拌一面加熱至 85℃。繼而，使用滴加泵以約5小時於該燒瓶內滴加將甲基丙烯酸19份、3,4-環氧三環[5.2.1.02,6]癸-8-基丙烯酸酯及3,4-環氧三環[5.2.1.02,6]癸-9-基丙烯酸酯之混合物(含有比以莫耳比計為50：50)(商品名「E-DCPA」，Daicel股份有限公司製造)171份溶解於丙二醇單甲醚乙酸酯40份中之溶液。另一方面，使用其他之滴加泵以約5小時於燒瓶內滴加將聚合起始劑2,2'-偶氮雙(2,4-二甲基戊腈)26份溶解於丙二醇單甲醚乙酸酯120份中之溶液。聚合起始劑之滴加結束後，約3小時保持為同溫度，其後冷卻至室溫，獲得固形物成分43.5%之共聚物(樹脂B1)之溶液。所獲得之樹脂B1之重量平均分子量為8000，分子量分佈為1.98，固形物成分換算之酸值為53mg-KOH/g。 A suitable amount of nitrogen gas was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to obtain a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated to 85 ° C while stirring. Then, 19 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 2,6 ]癸-8-yl acrylate and 3,4 were added dropwise to the flask using a dropping pump for about 5 hours. - a mixture of epoxy tricyclo[5.2.1.0 2,6 ]癸-9-yl acrylate (containing 50:50 by molar ratio) (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) 171 parts of a solution dissolved in 40 parts of propylene glycol monomethyl ether acetate. On the other hand, 26 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in propylene glycol monomethylate by dropwise addition to the flask using another dropping pump for about 5 hours. A solution of 120 parts of ether acetate. After completion of the dropwise addition of the polymerization initiator, the mixture was kept at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin B1) having a solid content of 43.5%. The obtained resin B1 had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value of 53 mg-KOH/g in terms of solid content.
[著色硬化性樹脂組合物之製備] [Preparation of Colored Curable Resin Composition]
混合混合著色劑(A)：C.I.顏料紅254(顏料) 36.7份、丙烯酸系顏料分散劑 15.9份、樹脂(B)：樹脂B1(固形物成分換算) 13.7份、及溶劑(E)：丙二醇單甲醚乙酸酯 265.5份，使用珠磨機使顏料充分分散之顏料分散液；著色劑(A)：式(1-51)所表示之化合物 8.8份； 著色劑(A)：式(Ad2-16)所表示之化合物 2.4份；樹脂(B)：樹脂B1(固形物成分換算) 36.3份；聚合性化合物(C)：二季戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA；日本化藥(股份)製造) 50份；聚合起始劑(D)：N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01；BASF公司製造；O-醯基肟化合物) 17份；溶劑(E)：丙二醇單甲醚乙酸酯 311.6份；溶劑(E)：4-羥基-4-甲基-2-戊酮 247.3份；以及調平劑(F)：聚醚改性聚矽油(Toray Silicone SH8400；Dow Corning Toray(股份)製造) 0.1份，獲得著色硬化性樹脂組合物。 Mixed coloring agent (A): CI Pigment Red 254 (pigment) 36.7 parts, acrylic pigment dispersant 15.9 parts, resin (B): resin B1 (solid content conversion) 13.7 parts, and solvent (E): propylene glycol single 265.5 parts of methyl ether acetate, a pigment dispersion liquid which sufficiently disperses a pigment using a bead mill; a coloring agent (A): 8.8 parts of a compound represented by the formula (1-51); Coloring agent (A): 2.4 parts of the compound represented by the formula (Ad2-16); Resin (B): Resin B1 (in terms of solid content) 36.3 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD ( Registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 50 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one -2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 17 parts; solvent (E): propylene glycol monomethyl ether acetate 311.6 parts; solvent (E): 4 -hydroxy-4-methyl-2-pentanone 247.3 parts; and leveling agent (F): polyether modified polyphthalate oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) 0.1 part to obtain a colored curable resin combination.
混合混合著色劑(A)：C.I.顏料紅254(顏料) 37.8份、丙烯酸系顏料分散劑 16.4份、樹脂(B)：樹脂B1(固形物成分換算) 14.1份、及溶劑(E)：丙二醇單甲醚乙酸酯 272.9份，使用珠磨機使顏料充分分散之顏料分散液；著色劑(A)：式(1-51)所表示之化合物 8.9份；著色劑(A)：式(Ad2-12)所表示之化合物 2.5份；樹脂(B)：樹脂B1(固形物成分換算) 35.9份；聚合性化合物(C)：二季戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA；日本化藥(股份)製造) 50份；聚合起始劑(D)：N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01；BASF公司製造；O-醯基肟化合物) 17份；溶劑(E)：丙二醇單甲醚乙酸酯 309.3份；溶劑(E)：4-羥基-4-甲基-2-戊酮 249.5份；以及調平劑(F)：聚醚改性聚矽油(Toray Silicone SH8400；Dow Corning Toray(股份)製造) 0.1份，獲得著色硬化性樹脂組合物。 Mixed coloring agent (A): CI Pigment Red 254 (pigment) 37.8 parts, acrylic pigment dispersant 16.4 parts, resin (B): resin B1 (solid content conversion) 14.1 parts, and solvent (E): propylene glycol single 272.9 parts of methyl ether acetate, a pigment dispersion liquid which sufficiently disperses a pigment using a bead mill; a coloring agent (A): 8.9 parts of a compound represented by the formula (1-51); a coloring agent (A): a formula (Ad2- 12) 2.5 parts of the compound represented; resin (B): resin B1 (converted solid content) 35.9 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Chemical Co., Ltd. )) 50 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-mercaptopurine compound) 17 parts; solvent (E): propylene glycol monomethyl ether acetate 309.3 parts; solvent (E): 4-hydroxy-4-methyl-2-pentanone 249.5 parts; and leveling agent (F): polyether modified Toray Silicone SH8400 (manufactured by Dow Corning Toray Co., Ltd.) was used in an amount of 0.1 part to obtain a colored curable resin composition.
混合混合著色劑(A)：C.I.顏料紅254(顏料) 37.5份、丙烯酸系顏料分散劑 16.3份、樹脂(B)：樹脂B1(固形物成分換算) 14份、及溶劑(E)：丙二醇單甲醚乙酸酯 271份，使用珠磨機使顏料充分分散之顏料分散液；著色劑(A)：式(1-51)所表示之化合物 8.9份；著色劑(A)：式(Ad2-14)所表示之化合物 2.4份；樹脂(B)：樹脂B1(固形物成分換算) 36份；聚合性化合物(C)：二季戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA；日本化藥(股份)製造) 50份；聚合起始劑(D)：N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01；BASF公司製造；O-醯基肟化合物) 17份；溶劑(E)：丙二醇單甲醚乙酸酯 310份；溶劑(E)：4-羥基-4-甲基-2-戊酮 249份；以及調平劑(F)：聚醚改性聚矽油(Toray Silicone SH8400；Dow Corning Toray(股份)製造) 0.1份，獲得著色硬化性樹脂組合物。 Mixed coloring agent (A): CI Pigment Red 254 (pigment) 37.5 parts, acrylic pigment dispersant 16.3 parts, resin (B): resin B1 (solid content conversion) 14 parts, and solvent (E): propylene glycol single 271 parts of methyl ether acetate, a pigment dispersion liquid in which a pigment is sufficiently dispersed using a bead mill; a coloring agent (A): 8.9 parts of a compound represented by the formula (1-51); a coloring agent (A): a formula (Ad2- 14) The compound represented by 2.4 parts; Resin (B): Resin B1 (converted solid content) 36 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Chemical Co., Ltd. )) 50 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-mercaptopurine compound) 17 parts; solvent (E): propylene glycol monomethyl ether acetate 310 parts; solvent (E): 4-hydroxy-4-methyl-2- 249 parts of pentanone; and leveling agent (F): 0.1 part of polyether modified polyphthalate oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) to obtain a colored curable resin composition.
混合混合著色劑(A)：C.I.顏料紅254(顏料) 37.5份、丙烯酸系顏料分散劑 16.3份、樹脂(B)：樹脂B1(固形物成分換算) 14份、及溶劑(E)：丙二醇單甲醚乙酸酯 271份，使用珠磨機使顏料充分分散之顏料分散液；著色劑(A)：式(1-51)所表示之化合物 8.9份；著色劑(A)：式(Ad2-11)所表示之化合物 2.4份；樹脂(B)：樹脂B1(固形物成分換算) 36份；聚合性化合物(C)：二季戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA；日本化藥(股份)製造) 50份；聚合起始劑(D)：N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01；BASF公司製造；O-醯基肟化合物) 17份；溶劑(E)：丙二醇單甲醚乙酸酯 310份；溶劑(E)：4-羥基-4-甲基-2-戊酮 249份；以及調平劑(F)：聚醚改性聚矽油(Toray Silicone SH8400；Dow Corning Toray(股份)製造) 0.1份，獲得著色硬化性樹脂組合物。 Mixed coloring agent (A): CI Pigment Red 254 (pigment) 37.5 parts, acrylic pigment dispersant 16.3 parts, resin (B): resin B1 (solid content conversion) 14 parts, and solvent (E): propylene glycol single 271 parts of methyl ether acetate, a pigment dispersion liquid in which a pigment is sufficiently dispersed using a bead mill; a coloring agent (A): 8.9 parts of a compound represented by the formula (1-51); a coloring agent (A): a formula (Ad2- 11) 2.4 parts of the compound represented; resin (B): resin B1 (converted solid content) 36 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Chemical Co., Ltd. )) 50 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-mercaptopurine compound) 17 parts; solvent (E): propylene glycol monomethyl ether acetate 310 parts; solvent (E): 4-hydroxy-4-methyl-2- 249 parts of pentanone; and leveling agent (F): 0.1 part of polyether modified polyphthalate oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) to obtain a colored curable resin composition.
混合混合著色劑(A)：C.I.顏料紅254(顏料) 38.7份、丙烯酸系顏料分散劑 16.8份、樹脂(B)：樹脂B1(固形物成分換算) 14.4份、及溶劑(E)：丙二醇單甲醚乙酸酯 279.4份， 使用珠磨機使顏料充分分散之顏料分散液；著色劑(A)：式(1-51)所表示之化合物 8.9份；著色劑(A)：式(Ad2-10)所表示之化合物 2.5份；樹脂(B)：樹脂B1(固形物成分換算) 35.6份；聚合性化合物(C)：二季戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA；日本化藥(股份)製造) 50份；聚合起始劑(D)：N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01；BASF公司製造；O-醯基肟化合物) 17份；溶劑(E)：丙二醇單甲醚乙酸酯 307份；溶劑(E)：4-羥基-4-甲基-2-戊酮 251.3份；以及調平劑(F)：聚醚改性聚矽油(Toray Silicone SH8400；Dow Corning Toray(股份)製造) 0.1份，獲得著色硬化性樹脂組合物。 Mixed coloring agent (A): CI pigment red 254 (pigment) 38.7 parts, acrylic pigment dispersing agent 16.8 parts, resin (B): resin B1 (solid content conversion) 14.4 parts, and solvent (E): propylene glycol single 279.4 parts of methyl ether acetate, a pigment dispersion liquid in which a pigment is sufficiently dispersed using a bead mill; a coloring agent (A): 8.9 parts of a compound represented by the formula (1-51); a coloring agent (A): 2.5 parts of a compound represented by the formula (Ad2-10) Resin (B): Resin B1 (converted in solid content) 35.6 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 50 parts; Starting agent (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF ; O-mercaptopurine compound) 17 parts; solvent (E): propylene glycol monomethyl ether acetate 307 parts; solvent (E): 4-hydroxy-4-methyl-2-pentanone 251.3 parts; and leveling Agent (F): 0.1 parts of a polyether modified polyanthracene oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) to obtain a colored curable resin composition.
混合混合著色劑(A)：C.I.顏料紅254(顏料) 39.2份、丙烯酸系顏料分散劑 17份、樹脂(B)：樹脂B1(固形物成分換算) 14.6份、及溶劑(E)：丙二醇單甲醚乙酸酯 283.5份，使用珠磨機使顏料充分分散之顏料分散液；著色劑(A)：式(1-51)所表示之化合物 8.9份；著色劑(A)：式(Ad2-13)所表示之化合物 2.5份；樹脂(B)：樹脂B1(固形物成分換算) 35.4份；聚合性化合物(C)：二季戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA；日本化藥(股份)製造) 50份； 聚合起始劑(D)：N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01；BASF公司製造；O-醯基肟化合物) 17份；溶劑(E)：丙二醇單甲醚乙酸酯 305.6份；溶劑(E)：4-羥基-4-甲基-2-戊酮 252.4份；以及調平劑(F)：聚醚改性聚矽油(Toray Silicone SH8400；Dow Corning Toray(股份)製造) 0.1份，獲得著色硬化性樹脂組合物。 Mixed coloring agent (A): CI Pigment Red 254 (pigment) 39.2 parts, acrylic pigment dispersant 17 parts, resin (B): Resin B1 (solid content conversion) 14.6 parts, and solvent (E): propylene glycol single 283.5 parts of methyl ether acetate, a pigment dispersion liquid which sufficiently disperses a pigment using a bead mill; a coloring agent (A): 8.9 parts of a compound represented by the formula (1-51); a coloring agent (A): a formula (Ad2- 13) 2.5 parts of the compound represented; resin (B): resin B1 (in terms of solid content) 35.4 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Chemical Co., Ltd. ) manufacturing) 50 parts; Polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF Company made; O-mercaptopurine compound) 17 parts; solvent (E): propylene glycol monomethyl ether acetate 305.6 parts; solvent (E): 4-hydroxy-4-methyl-2-pentanone 252.4 parts; Leveling agent (F): 0.1 part of a polyether modified polyphthalate oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) to obtain a colored curable resin composition.
混合混合著色劑(A)：C.I.顏料紅254(顏料) 38.1份、丙烯酸系顏料分散劑 16.5份、樹脂(B)：樹脂B1(固形物成分換算) 14.2份、及溶劑(E)：丙二醇單甲醚乙酸酯 275.3份，使用珠磨機使顏料充分分散之顏料分散液；著色劑(A)：式(1-51)所表示之化合物 8.9份；著色劑(A)：式(Ad2-2)所表示之化合物 2.5份；樹脂(B)：樹脂B1(固形物成分換算) 35.8份；聚合性化合物(C)：二季戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA；日本化藥(股份)製造) 50份；聚合起始劑(D)：N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01；BASF公司製造；O-醯基肟化合物) 17份；溶劑(E)：丙二醇單甲醚乙酸酯 308.3份；溶劑(E)：4-羥基-4-甲基-2-戊酮 250.1份；以及調平劑(F)：聚醚改性聚矽油(Toray Silicone SH8400；Dow Corning Toray(股份)製造) 0.1份，獲得著色硬化性樹脂組合物。 Mixed coloring agent (A): CI Pigment Red 254 (pigment) 38.1 parts, acrylic pigment dispersant 16.5 parts, resin (B): Resin B1 (solid content conversion) 14.2 parts, and solvent (E): propylene glycol single 275.3 parts of methyl ether acetate, a pigment dispersion liquid in which a pigment is sufficiently dispersed using a bead mill; a coloring agent (A): 8.9 parts of a compound represented by the formula (1-51); a coloring agent (A): a formula (Ad2- 2) 2.5 parts of the compound represented; resin (B): resin B1 (converted solid content) 35.8 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Chemical Co., Ltd. )) 50 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-mercaptopurine compound) 17 parts; solvent (E): propylene glycol monomethyl ether acetate 308.3 parts; solvent (E): 4-hydroxy-4-methyl-2- 250.1 parts of pentanone; and leveling agent (F): polyether modified polyphthalate oil (Toray Silicone SH8400; Dow Corning Toray (manufactured by Toray Co., Ltd.) was 0.1 part, and a colored curable resin composition was obtained.
混合混合著色劑(A)：C.I.顏料紅254(顏料) 38.4份、丙烯酸系顏料分散劑 16.6份、樹脂(B)：樹脂B1(固形物成分換算) 14.3份、及溶劑(E)：丙二醇單甲醚乙酸酯 277.4份，使用珠磨機使顏料充分分散之顏料分散液；著色劑(A)：式(1-51)所表示之化合物 8.9份；著色劑(A)：式(Ad2-4)所表示之化合物 2.5份；樹脂(B)：樹脂B1(固形物成分換算) 35.7份；聚合性化合物(C)：二季戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA；日本化藥(股份)製造) 50份；聚合起始劑(D)：N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01；BASF公司製造；O-醯基肟化合物) 17份；溶劑(E)：丙二醇單甲醚乙酸酯 307.6份；溶劑(E)：4-羥基-4-甲基-2-戊酮 250.7份；以及調平劑(F)：聚醚改性聚矽油(Toray Silicone SH8400；Dow Corning Toray(股份)製造) 0.1份，獲得著色硬化性樹脂組合物。 Mixed coloring agent (A): 38.4 parts of CI Pigment Red 254 (pigment), 16.6 parts of acrylic pigment dispersant, Resin (B): Resin B1 (converted in solid content) 14.3 parts, and solvent (E): Propylene glycol 277.4 parts of methyl ether acetate, a pigment dispersion liquid which sufficiently disperses a pigment using a bead mill; a coloring agent (A): 8.9 parts of a compound represented by the formula (1-51); a coloring agent (A): a formula (Ad2- 4) 2.5 parts of the compound represented; resin (B): resin B1 (converted solid content) 35.7 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Chemical Co., Ltd. )) 50 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-mercaptopurine compound) 17 parts; solvent (E): propylene glycol monomethyl ether acetate 307.6 parts; solvent (E): 4-hydroxy-4-methyl-2- 250.7 parts of pentanone; and leveling agent (F): 0.1 part of polyether modified polyphthalate oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) to obtain a colored curable resin composition.
混合混合著色劑(A)：C.I.顏料紅254(顏料) 14.8份、丙烯酸系顏料分散劑 6.4份、 樹脂(B)：樹脂B1(固形物成分換算) 5.5份、及溶劑(E)：丙二醇單甲醚乙酸酯 107.0份，使用珠磨機使顏料充分分散顏料分散液；著色劑(A)：式(1-51)所表示之化合物 11.6份；著色劑(A)：式(Ad2-16)所表示之化合物 7份；樹脂(B)：樹脂B1(固形物成分換算) 44.5份；聚合性化合物(C)：二季戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA；日本化藥(股份)製造) 50份；聚合起始劑(D)：N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01；BASF公司製造；O-醯基肟化合物) 17份；溶劑(E)：丙二醇單甲醚乙酸酯 404.5份；溶劑(E)：4-羥基-4-甲基-2-戊酮 203.4份；以及調平劑(F)：聚醚改性聚矽油(Toray Silicone SH8400；Dow Corning Toray(股份)製造) 0.1份，獲得著色硬化性樹脂組合物。 Mixed mixed colorant (A): C.I. Pigment Red 254 (pigment) 14.8 parts, acrylic pigment dispersant 6.4 parts, Resin (B): Resin B1 (in terms of solid content) 5.5 parts, and solvent (E): 107.0 parts of propylene glycol monomethyl ether acetate, and the pigment dispersion liquid was sufficiently dispersed by a bead mill; coloring agent (A): 11.6 parts of the compound represented by the formula (1-51); coloring agent (A): 7 parts of the compound represented by the formula (Ad2-16); resin (B): resin B1 (in terms of solid content) 44.5 parts; Compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 50 parts; polymerization initiator (D): N-benzylidene-1-(4-) Phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 17 parts; solvent (E): propylene glycol monomethyl 404.5 parts of ether acetate; solvent (E): 203.4 parts of 4-hydroxy-4-methyl-2-pentanone; and leveling agent (F): polyether modified polyphthalate oil (Toray Silicone SH8400; Dow Corning Toray (manufactured by the company) 0.1 part, and a colored curable resin composition was obtained.
混合混合著色劑(A)：C.I.顏料紅254(顏料) 40.5份、丙烯酸系顏料分散劑 17.6份、樹脂(B)：樹脂B1(固形物成分換算) 15.1份、及溶劑(E)：丙二醇單甲醚乙酸酯 292.6份，使用珠磨機使顏料充分分散之顏料分散液；著色劑(A)：式(1-51)所表示之化合物 9.1份；著色劑(A)：式(Ad2-16)所表示之化合物 0.5份；樹脂(B)：樹脂B1(固形物成分換算) 34.9份； 聚合性化合物(C)：二季戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA；日本化藥(股份)製造) 50份；聚合起始劑(D)：N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01；BASF公司製造；O-醯基肟化合物) 17份；溶劑(E)：丙二醇單甲醚乙酸酯 305.0份；溶劑(E)：4-羥基-4-甲基-2-戊酮 243.8份；以及調平劑(F)：聚醚改性聚矽油(Toray Silicone SH8400；Dow Corning Toray(股份)製造) 0.1份，獲得著色硬化性樹脂組合物。 Mixed coloring agent (A): CI pigment red 254 (pigment) 40.5 parts, acrylic pigment dispersant 17.6 parts, resin (B): resin B1 (solid content conversion) 15.1 parts, and solvent (E): propylene glycol single 292.6 parts of methyl ether acetate, a pigment dispersion liquid in which a pigment is sufficiently dispersed using a bead mill; a coloring agent (A): 9.1 parts of a compound represented by the formula (1-51); a coloring agent (A): a formula (Ad2- 16) 0.5 parts of the compound represented; resin (B): resin B1 (converted solid content) 34.9 parts; Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 50 parts; polymerization initiator (D): N-benzylidene-1-( 4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 17 parts; solvent (E): propylene glycol 305.0 parts of monomethyl ether acetate; solvent (E): 243.8 parts of 4-hydroxy-4-methyl-2-pentanone; and leveling agent (F): polyether modified polyterpene oil (Toray Silicone SH8400; Dow Corning Toray (manufactured by the company) 0.1 parts, a colored curable resin composition was obtained.
混合混合著色劑(A)：C.I.顏料紅254(顏料) 17.8份、丙烯酸系顏料分散劑 7.7份、樹脂(B)：樹脂B1(固形物成分換算) 6.7份、及溶劑(E)：丙二醇單甲醚乙酸酯 128.9份，使用珠磨機使顏料充分分散之顏料分散液；混合著色劑(A)：C.I.顏料黃138(顏料) 7.4份、丙烯酸系顏料分散劑 3.1份、樹脂(B)：樹脂B1(固形物成分換算) 3.1份、及溶劑(E)：丙二醇單甲醚乙酸酯 47.7份，使用珠磨機使顏料充分分散之顏料分散液；著色劑(A)：式(1-51)所表示之化合物 11.9份；樹脂(B)：樹脂B1(固形物成分換算) 40.2份；聚合性化合物(C)：二季戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA；日本化藥(股份)製造) 50份； 聚合起始劑(D)：N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01；BASF公司製造；O-醯基肟化合物) 17份；溶劑(E)：丙二醇單甲醚乙酸酯 349.9份；溶劑(E)：4-羥基-4-甲基-2-戊酮 225.6份；以及調平劑(F)：聚醚改性聚矽油(Toray Silicone SH8400；Dow Corning Toray(股份)製造) 0.1份，獲得著色硬化性樹脂組合物。 Mixed coloring agent (A): CI Pigment Red 254 (pigment) 17.8 parts, 7.7 parts of acrylic pigment dispersant, resin (B): Resin B1 (solid content conversion) 6.7 parts, and solvent (E): propylene glycol single 128.9 parts of methyl ether acetate, a pigment dispersion which sufficiently disperses the pigment using a bead mill; mixed coloring agent (A): 7.4 parts of CI Pigment Yellow 138 (pigment), 3.1 parts of acrylic pigment dispersant, and resin (B) : Resin B1 (converted in solid content) 3.1 parts, and solvent (E): 47.7 parts of propylene glycol monomethyl ether acetate, a pigment dispersion liquid in which a pigment is sufficiently dispersed using a bead mill; coloring agent (A): formula (1) -51) 11.9 parts of the compound represented; Resin (B): Resin B1 (in terms of solid content) 40.2 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Chemical ( Share) manufacturing) 50 copies; Polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF Company made; O-mercaptopurine compound) 17 parts; solvent (E): propylene glycol monomethyl ether acetate 349.9 parts; solvent (E): 4-hydroxy-4-methyl-2-pentanone 225.6 parts; Leveling agent (F): 0.1 part of a polyether modified polyphthalate oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) to obtain a colored curable resin composition.
混合混合著色劑(A)：C.I.顏料紅254(顏料) 53.1份、丙烯酸系顏料分散劑 23份、樹脂(B)：樹脂B1(固形物成分換算) 19.8份、及溶劑(E)：丙二醇單甲醚乙酸酯 383.5份，使用珠磨機使顏料充分分散之顏料分散液；著色劑(A)：式(1-51)所表示之化合物 9份；樹脂(B)：樹脂B1(固形物成分換算) 30.2份；聚合性化合物(C)：二季戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA；日本化藥(股份)製造) 50份；聚合起始劑(D)：N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01；BASF公司製造；O-醯基肟化合物) 17份；溶劑(E)：丙二醇單甲醚乙酸酯 261.2份；溶劑(E)：4-羥基-4-甲基-2-戊酮 276.3份；以及調平劑(F)：聚醚改性聚矽油(Toray Silicone SH8400；Dow Corning Toray(股份)製造) 0.1份， 獲得著色硬化性樹脂組合物。 Mixed coloring agent (A): CI Pigment Red 254 (pigment) 53.1 parts, acrylic pigment dispersant 23 parts, resin (B): Resin B1 (solid content conversion) 19.8 parts, and solvent (E): propylene glycol single 383.5 parts of methyl ether acetate, a pigment dispersion liquid in which a pigment is sufficiently dispersed using a bead mill; a coloring agent (A): 9 parts of a compound represented by the formula (1-51); a resin (B): a resin B1 (solid substance) Component conversion) 30.2 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 50 parts; polymerization initiator (D): N-benzamide Oxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 17 parts; Solvent (E): propylene glycol monomethyl ether acetate 261.2 parts; solvent (E): 4-hydroxy-4-methyl-2-pentanone 276.3 parts; and leveling agent (F): polyether modified polyphthalate (Toray Silicone SH8400; manufactured by Dow Corning Toray) A colored curable resin composition was obtained.
藉由旋塗法於2英吋見方之玻璃基板(Eagle XG；康寧公司製造)上分別塗佈實施例1~10及比較例1~2之著色硬化性樹脂組合物後，於100℃下預烘烤3分鐘，而形成著色組合物層。 The colored curable resin compositions of Examples 1 to 10 and Comparative Examples 1 and 2 were applied to a glass substrate (Eagle XG; manufactured by Corning Incorporated) of 2 inches square by a spin coating method, and then preliminarily prepared at 100 ° C. Bake for 3 minutes to form a colored composition layer.
冷卻至室溫後，將形成有著色組合物層之基板與石英玻璃製之光罩之間隔設為200μm，使用曝光機(TME-150RSK；TOPCON(股份)製造)，於大氣環境下，以60mJ/cm2之曝光量(365nm基準)進行曝光。再者，光罩係使用形成100μm之線與間隙圖案者。 After cooling to room temperature, the distance between the substrate on which the colored composition layer was formed and the mask made of quartz glass was set to 200 μm, and an exposure machine (TME-150RSK; TOPCON (manufactured by COP)) was used, and in an atmosphere, 60 mJ. The exposure amount of /cm 2 (365 nm reference) was exposed. Further, the photomask is formed by forming a line and gap pattern of 100 μm.
將曝光後之著色組合物層於25℃下於含有非離子系界面活性劑0.12%與氫氧化鉀0.04%之水溶液中浸漬70秒而進行顯影，水洗後，於烘箱中，於230℃下後烘烤25分鐘，藉此獲得著色圖案。 The exposed coloring composition layer was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C for development for 70 seconds, washed with water, and then placed in an oven at 230 ° C. Bake for 25 minutes, thereby obtaining a colored pattern.
對所獲得之著色圖案，使用膜厚測定裝置(DEKTAK3；日本真空技術(股份)製造)測定膜厚。將結果示於表2。 The film thickness of the obtained coloring pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 2.
對所獲得之著色圖案，使用測色機(OSP-SP-200；Olympus(股份)製造)測定分光，使用C光源之特性函數測定CIE之XYZ表色系統中之xy色度座標(x，y)與三刺激值Y。Y之值越大，表示亮度越高。將結果示於表2。 For the obtained color pattern, the color measurement was measured using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinate (x, y) in the XYZ color system of CIE was measured using the characteristic function of the C light source. ) with a tristimulus value of Y. The larger the value of Y, the higher the brightness. The results are shown in Table 2.
除不經由光罩進行曝光以外，以與著色圖案之製作相同之順序，製作於230℃下後烘烤25分鐘後之膜厚為2.5μm之著色塗膜。 A color coat film having a film thickness of 2.5 μm after post-baking at 230 ° C for 25 minutes was prepared in the same order as the production of the colored pattern, except that the film was not exposed through the mask.
將該著色塗膜於230℃下加熱2小時，使用測色機(OSP-SP-200；OLYMPUS公司製造)測定其加熱前後之著色塗膜之色差(△Eab*)。△Eab值越小，耐熱性越好。將結果示於表2。 The colored coating film was heated at 230 ° C for 2 hours, and the color difference (ΔEab*) of the colored coating film before and after heating was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS Co., Ltd.). The smaller the ΔEab value, the better the heat resistance. The results are shown in Table 2.
除不經由光罩進行曝光以外，以與著色圖案之製作相同之順序，製作於230℃下後烘烤25分鐘後之膜厚為2.5μm之著色塗膜。 A color coat film having a film thickness of 2.5 μm after post-baking at 230 ° C for 25 minutes was prepared in the same order as the production of the colored pattern, except that the film was not exposed through the mask.
於著色塗膜上配置紫外線截止濾光片(COLORED OPTICAL GLASS L38；HOYA公司製造；截止380nm以下之光)，利用耐光性試驗機(SUNTEST CPS+：東洋精機公司製造)，照射氙氣燈光48小時。 An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by HOYA Co., Ltd.; light of 380 nm or less) was placed on the colored coating film, and a xenon lamp was irradiated for 48 hours using a light resistance tester (SUNTEST CPS+: manufactured by Toyo Seiki Co., Ltd.).
於照射前後測定xy色度座標(x，y)及Y，藉由JIS Z 8730：2009(7.色差之計算方法)中所記載之方法，由該測定值計算色差△Eab*，將結果示於表2。△Eab*越小，表示色變化越小，若△Eab*為5以下，則可謂該著色塗膜作為彩色濾光片於實用上無問題。 The xy chromaticity coordinates (x, y) and Y are measured before and after the irradiation, and the color difference ΔEab* is calculated from the measured value by the method described in JIS Z 8730:2009 (7. Calculation method of color difference), and the result is shown. In Table 2. The smaller the ΔEab* is, the smaller the color change is. If ΔEab* is 5 or less, it can be said that the colored coating film is practically no problem as a color filter.
將結果示於表2。 The results are shown in Table 2.
除不經由光罩進行曝光以外，以與著色圖案之製作相同之順序，製作於230℃下後烘烤25分鐘後之膜厚為2.5μm之著色塗膜。 A color coat film having a film thickness of 2.5 μm after post-baking at 230 ° C for 25 minutes was prepared in the same order as the production of the colored pattern, except that the film was not exposed through the mask.
使用測色機(OSP-SP-200；OLYMPUS公司製造)測定所獲得之著色塗膜之色度。繼而，將該著色塗膜浸漬於固定保持為23℃之大量過剩之N-甲基-2-吡咯啶酮中30分鐘，以同樣方式測定浸漬後之著色塗膜之色度。 The color of the obtained colored coating film was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS Co., Ltd.). Then, the colored coating film was immersed in a large excess of N-methyl-2-pyrrolidone fixed at 23 ° C for 30 minutes, and the chromaticity of the colored coating film after the immersion was measured in the same manner.
作為色差之評價基準，若△Eab*為2以下則幾乎無色相變化，作為彩色濾光片顯示良好特性，若△Eab*超過2且5以下，則可見若干之色相變化，但為彩色濾光片之實用上無問題之水平，若△Eab*為5以上，則可確認明顯之色相變化，為作為彩色濾光片有問題之水平。將結果示於表2。 As a criterion for evaluating chromatic aberration, when ΔEab* is 2 or less, there is almost no hue change, and good characteristics are exhibited as a color filter. When ΔEab* exceeds 2 and 5 or less, a plurality of hue changes are observed, but color filtering is performed. When the film has no problem in practical use, if ΔEab* is 5 or more, it is possible to confirm a significant hue change, which is a problem that is problematic as a color filter. The results are shown in Table 2.
根據本發明之著色硬化性樹脂組合物，可提供耐溶劑性優異之彩色濾光片。自該著色硬化性樹脂組合物製造之彩色濾光片之耐溶劑性優異，故而可較佳用於液晶顯示裝置、有機EL裝置、電子紙等顯示裝置或固體拍攝元件中。 According to the colored curable resin composition of the present invention, a color filter excellent in solvent resistance can be provided. Since the color filter produced from the colored curable resin composition is excellent in solvent resistance, it can be preferably used in a display device such as a liquid crystal display device, an organic EL device, or an electronic paper, or a solid-state imaging device.
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| TWI804801B (en) * | 2021-01-20 | 2023-06-11 | 住華科技股份有限公司 | Photosensitive resin composition, and color filter formed therefrom |
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| KR101857083B1 (en) * | 2015-12-29 | 2018-05-11 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter, and image display apparatus comprising the same |
| KR20170084498A (en) * | 2016-01-12 | 2017-07-20 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter, and image display apparatus comprising the same |
| JP6654526B2 (en) * | 2016-08-12 | 2020-02-26 | 大日精化工業株式会社 | Method for producing coloring composition, coloring composition, and coloring agent |
| JP7046777B2 (en) * | 2017-11-10 | 2022-04-04 | 東友ファインケム株式会社 | Color curable resin composition, color filter and display device |
| WO2019117134A1 (en) * | 2017-12-14 | 2019-06-20 | 三菱鉛筆株式会社 | Colored particle aqueous dispersion |
| US20210277248A1 (en) | 2018-02-26 | 2021-09-09 | Sumitomo Chemical Company, Limited | Green colored resin composition |
| JP6901513B2 (en) * | 2018-03-26 | 2021-07-14 | 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． | Light conversion resin composition and light conversion laminated base material, image display device using this |
| JP7497998B2 (en) | 2019-03-25 | 2024-06-11 | 住友化学株式会社 | Colored curable resin composition, color filter and solid-state imaging device |
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| JP5021046B2 (en) * | 2009-02-26 | 2012-09-05 | エルジー ケム． エルティーディ． | Photosensitive resin composition |
| JP2013037336A (en) * | 2011-07-13 | 2013-02-21 | Dainippon Printing Co Ltd | Liquid crystal display device |
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| JP6461453B2 (en) * | 2011-12-09 | 2019-01-30 | 住友化学株式会社 | Red colored curable resin composition |
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| TWI804801B (en) * | 2021-01-20 | 2023-06-11 | 住華科技股份有限公司 | Photosensitive resin composition, and color filter formed therefrom |
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