TWI674303B - Colored curable resin composition - Google Patents
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Abstract
本發明提供一種具有良好之耐熱性與良好之亮度之彩色濾光片。 The present invention provides a color filter having good heat resistance and good brightness.
本發明之著色硬化性樹脂組合物含有藍色顏料(A1)、下述式(I)所表示之化合物、樹脂(B)、聚合性化合物(C)及聚合起始劑(D),
[式(I)中,R1、R2、R3及R4分別獨立地表示可具有取代基之碳數3~10之一價飽和烴基或可具有取代基之芳基;R51、R52及R53分別獨立地表示氫原子、-SO3 -、-SO3H或-SO3 -Z+;X+及Z+分別獨立地表示+N(R13)4、Na+或K+,R13表示氫原子或碳數1~20之一價飽和烴基;+N(R13)4中之4個R13互相可相同,亦可不同;a表示1~4之整數]。 [In the formula (I), R 1 , R 2 , R 3 and R 4 each independently represent a monovalent saturated hydrocarbon group having 3 to 10 carbon atoms which may have a substituent or an aryl group which may have a substituent; R 51 , R 52 and R 53 each independently represent a hydrogen atom, -SO 3 -, -SO 3 H or -SO 3 - Z +; X + and Z + each independently represent a + N (R 13) 4, Na + or K + , R 13 represents a hydrogen atom or one having 1 to 20 carbon atoms, monovalent saturated hydrocarbon group; + N (R 13) 4 in each of the four R 13 may be identical or different; A represents an integer of] of 1 to 4.
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 coloring curable resin composition.
由著色硬化性樹脂組合物形成之彩色濾光片係用於液晶顯示面板、電致發光面板及電漿顯示面板等顯示裝置,要求具有良好之亮度、良好之對比度、良好之解像度之彩色濾光片。為了實現具有良好之亮度、良好之對比度、良好之解像度之彩色濾光片,而對含有染料作為著色劑之著色硬化性樹脂組合物進行研究,但有會因含有染料而導致耐熱性、耐化學品性等降低之問題。 A color filter formed of a coloring curable resin composition is used for display devices such as a liquid crystal display panel, an electroluminescent panel, and a plasma display panel, and requires a color filter having good brightness, good contrast, and good resolution. sheet. In order to realize a color filter with good brightness, good contrast, and good resolution, a color-hardening resin composition containing a dye as a colorant has been studied. However, heat resistance and chemical resistance may be caused by containing the dye. The problem of reduced character and so on.
專利文獻1中記載有一種著色硬化性樹脂組合物,其含有C.I.顏料藍15:6、C.I.酸性紅52及下述式所表示之染料作為著色劑,且C.I.酸性紅52之含量相對於100質量份之C.I.顏料藍15:6為14.7質量份。 Patent Document 1 describes a coloring curable resin composition containing CI Pigment Blue 15: 6, CI Acid Red 52, and a dye represented by the following formula as a colorant, and the content of CI Acid Red 52 is 100 mass%. Parts of CI Pigment Blue 15: 6 are 14.7 parts by mass.
[專利文獻1]日本專利特開2013-144724號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2013-144724
本發明之著色硬化性樹脂組合物之目的在於獲得耐熱性或亮度優異之彩色濾光片。 An object of the colored curable resin composition of the present invention is to obtain a color filter excellent in heat resistance or brightness.
本發明包括以下發明。 The present invention includes the following inventions.
[1]一種著色硬化性樹脂組合物,其含有藍色顏料(A1)、下述式(I)所表示之化合物、樹脂(B)、聚合性化合物(C)及聚合起始劑(D)。
[2]如[1]記載之著色硬化性樹脂組合物,其進而含有藍色或紫色染料(A2)。 [2] The colored curable resin composition according to [1], which further contains a blue or purple dye (A2).
[3]如[1]記載之著色硬化性樹脂組合物,其中藍色顏料(A1)為C.I.顏料藍15:6。
[4]如[2]記載之著色硬化性樹脂組合物,其中藍色或紫色染料(A2)係選自由:式(I)所表示之化合物以外之染料(A3)、三芳基甲烷染料(A4)、式(A7):
[5]如[4]記載之著色硬化性樹脂組合物,其中藍色或紫色染料(A2)係選自由:三芳基甲烷染料(A4)、 式(A7)所表示之染料、及含有由上述式(A7)所表示之染料衍生之結構單元之聚合物所組成之群中之至少一種。 [5] The colored curable resin composition according to [4], wherein the blue or violet dye (A2) is selected from the group consisting of a triarylmethane dye (A4), At least one of a dye represented by the formula (A7) and a polymer containing a structural unit derived from the dye represented by the formula (A7).
[6]一種著色劑,其含有三芳基甲烷染料(A4)、藍色顏料(A1)及式(I)所表示之化合物,且三芳基甲烷染料(A4)為聚合物。
[7]一種著色劑,其包含選自由式(A7)
[8]如[6]或[7]記載之著色劑,其中藍色顏料(A1)為C.I.顏料藍15:6。 [8] The coloring agent according to [6] or [7], wherein the blue pigment (A1) is C.I. Pigment Blue 15: 6.
[9]一種彩色濾光片,其係由如[1]至[5]中任一項記載之著色硬化性樹脂組合物所形成。 [9] A color filter formed of the coloring curable resin composition according to any one of [1] to [5].
[10]一種顯示裝置,其包含如[9]記載之彩色濾光片。 [10] A display device including the color filter according to [9].
根據本發明之著色硬化性樹脂組合物,可製造具有良好之耐熱性與良好之亮度之彩色濾光片。 According to the colored curable resin composition of the present invention, a color filter having good heat resistance and good brightness can be manufactured.
本發明之著色硬化性樹脂組合物含有藍色顏料(A1)、上述式(I)所表示之化合物、樹脂(B)、聚合性化合物(C)及聚合起始劑(D)。 The colored curable resin composition of the present invention contains a blue pigment (A1), a compound represented by the formula (I), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
較佳為本發明之著色硬化性樹脂組合物含有選自溶劑(E)及調平劑(F)中之至少一者。 The colored curable resin composition of the present invention preferably 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含有聚合起始助劑(D1)。 The colored curable resin composition of the present invention may contain a polymerization initiator (D1).
於本案說明書中,於任一式表示之化合物可形成互變異構物之情形時,該式所表示之化合物只要無損及本發明之特徵,則為亦包括其互變異構物之概念。 In the description of the present case, when a compound represented by any formula can form a tautomer, the compound represented by the formula includes the concept of a tautomer as long as it does not impair the characteristics of the present invention.
於本發明之著色硬化性樹脂組合物中,通常含有藍色顏料(A1)及式(I)所表示之化合物作為著色劑(A)。 The colored curable resin composition of the present invention usually contains a blue pigment (A1) and a compound represented by the formula (I) as a colorant (A).
該著色硬化性樹脂組合物可進而含有藍色或紫色染料(A2)(以下有時稱為「染料(A2)」)。 This colored curable resin composition may further contain a blue or purple dye (A2) (hereinafter sometimes referred to as "dye (A2)").
該著色硬化性樹脂組合物可進而含有與藍色顏料(A1)不同之顏料(以下有時稱為「顏料(Ad)」)、或與藍色或紫色染料(A2)不同之染料(Ac)(以下有時稱為「染料(Ac)」)。 This colored curable resin composition may further contain a pigment different from the blue pigment (A1) (hereinafter sometimes referred to as "pigment (Ad)") or a dye (Ac) different from the blue or purple dye (A2). (Hereinafter sometimes referred to as "dye (Ac)").
再者,於本案中,「C.I.」意指色指數(C.I)。 Furthermore, in this case, "C.I." means color index (C.I).
作為藍色顏料(A1),可列舉C.I.顏料藍15、15:3、15:4、15:6、60,較佳為C.I.顏料藍15:3及15:6,更佳為C.I.顏料藍15:6。 Examples of the blue pigment (A1) include CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60, preferably CI Pigment Blue 15: 3 and 15: 6, and more preferably CI Pigment Blue 15 : 6.
藍色顏料(A1)可含有兩種以上。 The blue pigment (A1) may contain two or more kinds.
[式(I)中,R1、R2、R3及R4分別獨立地表示可具有取代基之碳數3~10之一價飽和烴基或可具有取代基之芳基;R51、R52及R53分別獨立地表示氫原子、-SO3 -、-SO3H或-SO3 -Z+;X+及Z+分別獨立地表示+N(R13)4、Na+或K+,R13表示氫原子或碳數1~20之一價飽和烴基;+N(R13)4中之4個R13互相可相同,亦可不 同;a表示1~4之整數] [In the formula (I), R 1 , R 2 , R 3 and R 4 each independently represent a monovalent saturated hydrocarbon group having 3 to 10 carbon atoms which may have a substituent or an aryl group which may have a substituent; R 51 , R 52 and R 53 each independently represent a hydrogen atom, -SO 3 -, -SO 3 H or -SO 3 - Z +; X + and Z + each independently represent a + N (R 13) 4, Na + or K + , R 13 represents a hydrogen atom or one having 1 to 20 carbon atoms, monovalent saturated hydrocarbon group; + N (R 13) 4 in each of the four R 13 may be identical or different; A 1 represents an integer of 1-4]
其中,式(I)之化合物之價數為0。 The valence of the compound of formula (I) is 0.
作為R1、R2、R3及R4所表示之碳數3~10之一價飽和烴基,可列舉:正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、正己基、正庚基、正辛基、癸基、1-甲基丁基、3-甲基丁基、4-甲基戊基、1,1,3,3-四甲基丁基、1,5-二甲基己基、1,6-二甲基庚基、2-乙基己基、1,1,5,5-四甲基己基等碳數3~10之直鏈或支鏈狀烷基;環丙基、環丁基、環戊基、環己基、金剛烷基等碳數3~10之環烷基,較佳為正丙基、正丁基、2-乙基己基。 Examples of the monovalent saturated hydrocarbon group having 3 to 10 carbon atoms represented by R 1 , R 2 , R 3 and R 4 include n-propyl, isopropyl, n-butyl, second butyl, and third butyl. , N-pentyl, n-hexyl, n-heptyl, n-octyl, decyl, 1-methylbutyl, 3-methylbutyl, 4-methylpentyl, 1,1,3,3-tetramethyl Straight chains with 3 to 10 carbon atoms such as butyl, 1,5-dimethylhexyl, 1,6-dimethylheptyl, 2-ethylhexyl, 1,1,5,5-tetramethylhexyl Or branched chain alkyl groups; cycloalkyl groups having 3 to 10 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl, preferably n-propyl, n-butyl, and 2-ethyl Kihiki.
R1、R2、R3及R4所表示之碳數3~10之一價飽和烴基所含之氫原子可經羥基、烷氧基或鹵素原子取代。 A hydrogen atom contained in a monovalent saturated hydrocarbon group having 3 to 10 carbon atoms represented by R 1 , R 2 , R 3 and R 4 may be substituted with a hydroxyl group, an alkoxy group or a halogen atom.
作為鹵素原子,可列舉:氟原子、氯原子、溴原子及碘原子。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
作為烷氧基,例如可列舉: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之烷氧基。 Examples of the alkoxy group 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, a 2-ethylhexyloxy group, and a bisoxy group. Alkoxy having 1 to 20 carbons such as decaalkoxy.
作為經鹵素原子取代之碳數1~10之一價飽和烴基,可列舉:七氟丙基、1,1-二氟丙基、3,3,3-三氟丙基、九氟丁基、2,2-二氟丁基、十一氟戊基、3-(三氟甲基)-3,4,4,4-五氟丁基、6,6,6-三氟己基、七氯丙基、七溴丙基、3,3,3-三碘丙基、2,2-二氯-3,3,3-三氟丙基等,較佳為下述式所表示之基。 Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom include heptafluoropropyl, 1,1-difluoropropyl, 3,3,3-trifluoropropyl, nonafluorobutyl, 2,2-difluorobutyl, undecylpentyl, 3- (trifluoromethyl) -3,4,4,4-pentafluorobutyl, 6,6,6-trifluorohexyl, heptachloropropane Group, heptabromopropyl, 3,3,3-triiodopropyl, 2,2-dichloro-3,3,3-trifluoropropyl and the like are preferably a group represented by the following formula.
(*表示鍵結鍵) (* Indicates bond key)
作為R1、R2、R3及R4所表示之芳基,可列舉:苯基、萘基等碳數 6~10之芳香族烴基;苄基、苯乙基等碳數6~10之芳烷基等,較佳為苯基。 Examples of the aryl group represented by R 1 , R 2 , R 3, and R 4 include aromatic hydrocarbon groups having 6 to 10 carbon atoms such as phenyl and naphthyl; and 6 to 10 carbon atoms such as benzyl and phenethyl. Aralkyl and the like are preferably phenyl.
R1、R2、R3及R4所表示之芳基可經如下基取代:甲基、乙基、正丙基等碳數1~20之烷基;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之烷氧基;羥基等。 The aryl groups represented by R 1 , R 2 , R 3 and R 4 may be substituted by the following groups: alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, and n-propyl; methoxy, ethoxy, and propyl 1-20 carbon alkoxy groups such as oxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and eicosyloxy; hydroxy, etc.
作為R1、R2、R3及R4所表示之芳基所具有之取代基,較佳為碳數1~20之烷基,更佳為碳數1~10之烷基。 As a substituent of the aryl group represented by R 1 , R 2 , R 3 and R 4 , an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred.
作為R13所表示之碳數1~20之一價飽和烴基,可列舉:甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十二烷基、正十六烷基及正二十烷基等碳數1~20之直鏈狀烷基;異丙基、異丁基、第二丁基、第三丁基、異戊基、新戊基及2-乙基己基等碳數3~20之支鏈狀烷基;環丙基、環戊基、環己基、環庚基、環辛基及三環癸基等碳數3~20之脂環式飽和烴基,較佳為1~5之直鏈狀烷基,更佳為甲基或乙基。 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 13 include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and n- Nonyl, n-decyl, n-dodecyl, n-hexadecyl and n-eicosyl linear alkyl groups having 1 to 20 carbon atoms; isopropyl, isobutyl, second butyl, Third butyl, isopentyl, neopentyl, 2-ethylhexyl and other branched alkyl groups having 3 to 20 carbon atoms; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and A cycloaliphatic saturated hydrocarbon group having 3 to 20 carbon atoms such as tricyclodecyl group, is preferably a linear alkyl group having 1 to 5, and more preferably a methyl group or an ethyl group.
X+及Z+分別獨立地表示+N(R13)4、Na+或K+,+N(R13)4中之4個R13互相可相同,亦可不同。X+較佳為Na+或K+。 X + Z + and each independently represent a + N (R 13) 4, Na + or K +, + N (R 13 ) 4 in each of the four R 13 may be the same or different. X + is preferably Na + or K + .
作為R51、R52及R53中之-SO3 -Z+,較佳為-SO3 -+N(R13)4。 As -SO 3 - Z + among R 51 , R 52 and R 53 , -SO 3- + N (R 13 ) 4 is preferred.
較佳為R1、R2、R3及R4分別獨立為碳數3~10之烷基或可具有取代基之苯基,更佳為分別獨立為碳數3~8之烷基或可經碳數1~10之烷基取代之苯基,進而較佳為分別獨立為碳數3~8之直鏈狀烷基或可經碳數1~3之烷基取代之苯基。 Preferably, R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 3 to 10 carbon atoms or a phenyl group which may have a substituent, and more preferably an independent alkyl group having 3 to 8 carbon atoms or may be independently The phenyl substituted with an alkyl group having 1 to 10 carbon atoms is more preferably a linear alkyl group independently having 3 to 8 carbon atoms or a phenyl group which can be substituted with an alkyl group having 1 to 3 carbon atoms.
於R1、R2、R3及R4中,較佳為R1與R3為相同之基,且較佳為R2與R4為相同之基。更佳為R1、R2、R3及R4全部相同。 Among R 1 , R 2 , R 3 and R 4 , it is preferable that R 1 and R 3 are the same base, and it is more preferable that R 2 and R 4 are the same base. More preferably, all of R 1 , R 2 , R 3 and R 4 are the same.
a表示1~4之整數,較佳為1或2,更佳為1。 a represents an integer of 1 to 4, preferably 1 or 2, and more preferably 1.
較佳為R51、R52及R53全部相同,更佳為全部為氫原子。 R 51 , R 52 and R 53 are preferably all the same, and more preferably all of them are a hydrogen atom.
化合物(I)例如可依照WO2013/050431而製造。 The compound (I) can be produced, for example, according to WO2013 / 050431.
作為化合物(I)之具體例,可列舉下述所表示之化合物。下述式中,R26表示2-乙基己基。 Specific examples of the compound (I) include the compounds shown below. In the following formula, R 26 represents 2-ethylhexyl.
作為化合物(I),較佳為式(I-1)所表示之化合物~式(I-20)所表示之化合物,更佳為式(I-1)所表示之化合物~式(I-8)所表示之化合物、式(I-17)所表示之化合物~式(I-18)所表示之化合物,進而較佳為式(I-1)所表示之化合物~式(I-2)所表示之化合物、式(I-5)所表示之化合物~式(I-6)所表示之化合物。 The compound (I) is preferably a compound represented by the formula (I-1) ~ a compound represented by the formula (I-20), and more preferably a compound represented by the formula (I-1) ~ formula (I-8) ), A compound represented by formula (I-17) ~ a compound represented by formula (I-18), and more preferably a compound represented by formula (I-1) ~ formula (I-2) Compounds represented by the formula, compounds represented by the formula (I-5) ~ compounds represented by the formula (I-6).
化合物(I)之含量相對於藍色顏料(A1)100質量份,較佳為0.1~10質量份,更佳為0.1~8質量份,進而較佳為1~8質量份。 The content of the compound (I) is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and still more preferably 1 to 8 parts by mass based on 100 parts by mass of the blue pigment (A1).
所謂藍色或紫色染料意指在氯仿溶液中於560nm以上且650nm以下之範圍具有最大吸收波長之染料。藍色或紫色染料較佳為於580nm以上且650nm以下之範圍具有最大吸收波長之染料,更佳為於600nm以上且645nm以下之範圍具有最大吸收波長之染料。 The blue or violet dye means a dye having a maximum absorption wavelength in a chloroform solution in a range from 560 nm to 650 nm. The blue or purple dye is preferably a dye having a maximum absorption wavelength in a range of 580 nm to 650 nm, and more preferably a dye having a maximum absorption wavelength in a range of 600 nm to 645 nm.
藍色或紫色染料(A2)較佳為選自由式(I)所表示之化合物以外之 染料(A3)、三芳基甲烷染料(A4)、四氮雜卟啉染料(A5)、蒽醌染料(A6)及式(A7)所表示之染料(以下有時稱為染料(A7))所組成之群中之至少一種,更佳為選自由式(I)所表示之化合物以外之染料(A3)、三芳基甲烷染料(A4)、式(A7)所表示之染料、及含有由上述式(A7)所表示之染料衍生之結構單元之聚合物所組成之群中之至少一種,進而較佳為選自由三芳基甲烷染料(A4)、式(A7)所表示之染料、及含有由上述式(A7)所表示之染料衍生之結構單元之聚合物所組成之群中之至少一種。 The blue or violet dye (A2) is preferably selected from compounds other than the compound represented by formula (I) Dyes (A3), triarylmethane dyes (A4), tetraazaporphyrin dyes (A5), anthraquinone dyes (A6), and dyes represented by formula (A7) (hereinafter sometimes referred to as dyes (A7)) At least one of the constituent groups is more preferably selected from compounds other than the compound represented by formula (I) At least one of the group consisting of a dye (A3), a triarylmethane dye (A4), a dye represented by formula (A7), and a polymer containing a structural unit derived from the dye represented by formula (A7), Further preferably, it is at least one selected from the group consisting of a triarylmethane dye (A4), a dye represented by the formula (A7), and a polymer containing a structural unit derived from the dye represented by the formula (A7). .
染料(A2)可含有兩種以上。 The dye (A2) may contain two or more kinds.
所謂式(I)所表示之化合物以外之染料(A3)係含有分子內具有骨架之化合物且與化合物(I)不同之染料。較佳之染料(A3)包括式(A3-1)所表示之化合物、式(A3-2)所表示之化合物、式(A3-3)所表示之化合物等。再者,於下述化合物整體為陰離子之情形時,下述化合物表示與抗衡陽離子或抗衡陰離子一併形成鹽之態樣之一部分。 Other than the compounds represented by formula (I) Dye (A3) contains A skeleton compound and a dye different from the compound (I). Better The dye (A3) includes a compound represented by the formula (A3-1), a compound represented by the formula (A3-2), a compound represented by the formula (A3-3), and the like. In addition, when the following compounds are anions as a whole, the following compounds represent a part of the state of forming a salt together with a counter cation or a counter anion.
(式中,R1C及R2C分別獨立地表示氫原子、可具有取代基之芳基、可具有取代基之烷基、或具有乙烯性雙鍵之基;R3C及R4C分別獨立地表示氫原子、可具有取代基之芳基、可具有取代基之烷基、或具有乙烯性雙鍵之基,於R3C為烷基之情形時,可與R1C鍵結而形成環,於R4C為烷基之情形時,可與R2C鍵結而形成環;R5C表示O-或OH;R6C及R7C相同或不同,表示O-、OH、烷氧基、或胺基;R8C表示氧原子或硫原子;m及n相同或不同,為0、1、2、或3,m與n之合計為1以上且3以下;t為0或1;R9C及R10C相同或不同,表示氫原子或烷氧基;其中,自式(A3-2)化合物中去除式(A3-1)化合物)R1C~R4C之芳基包括苯基、萘基、苄基等。作為其取代基,可例 示:甲基、乙基等烷基;磺酸基;2-乙基己基胺基磺醯基等磺醯胺基;甲氧基磺醯基等磺酸酯基;烷氧基;硫代烷基;硫代烷氧基等。作為具有取代基之芳基,可列舉:甲苯基、二甲苯基、基、乙基苯基等烷基取代苯基;苯基、苄基或上述烷基取代苯基上鍵結有磺酸基或磺醯胺基之基;乙氧基苯基等鍵結有烷氧基之苯基;甲硫基苯基等鍵結有烷硫基之苯基等,較佳為苯基、烷基取代苯基、或者苯基、苄基或上述烷基取代苯基上鍵結有磺酸基或磺醯胺基之基。 (In the formula, R 1C and R 2C each independently represent a hydrogen atom, an aryl group which may have a substituent, an alkyl group which may have a substituent, or a group having an ethylenic double bond; R 3C and R 4C each independently represent A hydrogen atom, an aryl group which may have a substituent, an alkyl group which may have a substituent, or a group having an ethylenic double bond. When R 3C is an alkyl group, it may be bonded to R 1C to form a ring. 4C is the case where an alkyl group, and R 2C can be bonded to form a ring; R 5C represents O - or OH; R 6C and R 7C are the same or different, represent O -, OH, alkoxy, or amino; R & lt 8C represents an oxygen atom or a sulfur atom; m and n are the same or different and are 0, 1, 2, or 3; the total of m and n is 1 or more and 3 or less; t is 0 or 1; R 9C and R 10C are the same or Different, it represents a hydrogen atom or an alkoxy group; wherein, the aryl group of R 1C to R 4C excluding the compound of formula (A3-1) from the compound of formula (A3-2) includes phenyl, naphthyl, benzyl, and the like. Examples of the substituent include alkyl groups such as methyl and ethyl groups; sulfonic acid groups; sulfonylamino groups such as 2-ethylhexylaminosulfonyl; sulfonate groups such as methoxysulfonyl; Oxy; thioalkyl; thioalkoxy and the like. Examples of the aryl group having a substituent include tolyl, xylyl, Alkyl, phenyl and other alkyl-substituted phenyl groups; phenyl, benzyl, or the above alkyl-substituted phenyl groups are bonded with a sulfonic acid group or a sulfonamido group; ethoxyphenyl groups are bonded with an alkyl group An phenyl group of an oxy group; a phenyl group of an alkylthio group and the like, such as a methylthiophenyl group, preferably a phenyl group, an alkyl-substituted phenyl group, or a phenyl group, a benzyl group, or the above alkyl-substituted phenyl bond A sulfonic or sulfonamide group is bound.
R1C~R4C之烷基可列舉:甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基等碳數1~20之直鏈狀烷基;異丙基、異丁基、第二丁基、第三丁基、異戊基、新戊基及2-乙基己基等碳數3~20之支鏈狀烷基。作為其取代基,包括苯基、萘基等。又,取代基亦可為磺酸基、2-乙基己基胺基磺醯基等磺醯胺基、甲氧基磺醯基等磺酸酯基等,鍵結有該等之苯基或萘基亦包括於取代基中。較佳為碳數1~10之直鏈狀烷基,更佳為碳數1~5之直鏈狀烷基,進而較佳為甲基或乙基。 Examples of the alkyl group of R 1C to R 4C include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl linear alkyl groups having 1 to 20 carbon atoms. Groups; isopropyl, isobutyl, second butyl, third butyl, isopentyl, neopentyl, and 2-ethylhexyl branched alkyl groups having 3 to 20 carbon atoms. Examples of the substituent include a phenyl group and a naphthyl group. The substituent may be a sulfonyl group such as a sulfonic acid group, a 2-ethylhexylaminosulfonyl group, and a sulfonate group such as a methoxysulfonyl group. A phenyl group or a naphthalene group may be bonded thereto. The group is also included in the substituent. A linear alkyl group having 1 to 10 carbon atoms is preferred, a linear alkyl group having 1 to 5 carbon atoms is more preferred, and a methyl or ethyl group is more preferred.
R1C~R4C之具有乙烯性雙鍵之基包括乙烯基、(甲基)丙烯醯基等。該等乙烯基、(甲基)丙烯醯基等亦可鍵結於烷基上,例如可列舉:烯丙基(乙烯基甲基)、乙烯基乙基等鍵結有乙烯基之烷基;(甲基)丙烯醯基甲基、(甲基)丙烯醯基乙基等鍵結有(甲基)丙烯醯基之烷基。進而,亦可例示該鍵結有(甲基)丙烯醯基之烷基鍵結於連結基上而成之基作為該具有乙烯性雙鍵之基。作為該連結基,例如可列舉下述式之基。 Examples of the R 1C to R 4C group having an ethylenic double bond include a vinyl group, a (meth) acrylfluorenyl group, and the like. The vinyl group, (meth) acryl fluorenyl group and the like may be bonded to an alkyl group, and examples thereof include an alkyl group having a vinyl group such as an allyl (vinylmethyl) and vinylethyl group; (Meth) acrylfluorenylmethyl, (meth) acrylfluorenylethyl and the like are bonded to a (meth) acrylfluorenyl alkyl group. Furthermore, as the group having an ethylenic double bond, a group in which an alkyl group having a (meth) acrylfluorenyl group is bonded to a linking group can be exemplified. Examples of the linking group include a group of the following formula.
(式中,R11C表示亞甲基、伸乙基等碳數為1~8之伸烷基;*1表示與鍵結有(甲基)丙烯醯基之烷基之鍵結鍵,*2表示與N原子之鍵結鍵) (In the formula, R 11C represents an alkylene group having 1 to 8 carbon atoms, such as methylene and ethylene; * 1 represents a bond with an alkyl group having a (meth) acrylfluorenyl group, * 2 (Indicates a bond with an N atom)
R11C較佳為碳數1~4之伸烷基,更佳為亞甲基或伸乙基。 R 11C is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably methylene or ethylene.
又,*1較佳為鍵結於(甲基)丙烯醯基甲基或(甲基)丙烯醯基乙基上。 * 1 is preferably bonded to (meth) acrylfluorenylmethyl or (meth) acrylfluorenylethyl.
於R1C及R3C形成環之情形時,或於R2C及R4C形成環之情形時,上述式(A3-1)~(A3-3)中之基R1CR3CN-*或R2CR4CN-*例如如以下般,較佳為式(R-5)所表示之基~式(R-10)所表示之基,更佳為式(R-5)所表示之基、式(R-6)所表示之基、式(R-7)所表示之基、式(R-9)所表示之基。 When R 1C and R 3C form a ring, or when R 2C and R 4C form a ring, the groups R 1C R 3C N- * or R in the above formulae (A3-1) to (A3-3) 2C R 4C N- * is, for example, as follows, preferably the base represented by formula (R-5) to the base represented by formula (R-10), more preferably the base represented by formula (R-5), The base represented by formula (R-6), the base represented by formula (R-7), and the base represented by formula (R-9).
R6C、R7C、R9C及R10C之烷氧基包括甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、第二丁氧基、第三丁氧基、戊氧基等碳數1~6之烷氧基,較佳為碳數1~3之烷氧基。 The alkoxy groups of R 6C , R 7C , R 9C and R 10C include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, third The alkoxy group having 1 to 6 carbons such as butoxy and pentoxy is preferably an alkoxy group having 1 to 3 carbons.
R6C及R7C之胺基包括:N-甲基胺基、N-乙基胺基、N-(1-乙基丙基)胺基、N-(2-乙基己基)胺基等碳數1~20之N-烷基胺基;N,N-二甲胺基、N,N-乙基甲基胺基等碳數1~20之N,N-二烷基胺基等,較佳為碳數1~10之N-烷基胺基,更佳為碳數3~10之N-烷基胺基。 The amino groups of R 6C and R 7C include: carbons such as N-methylamino, N-ethylamino, N- (1-ethylpropyl) amino, N- (2-ethylhexyl) amino N-alkylamino groups of 1-20; N, N-dimethylamino, N, N-ethylmethylamino groups, etc. N-N-dialkylamino groups of 1-20, etc. It is preferably an N-alkylamino group having 1 to 10 carbon atoms, and more preferably an N-alkylamino group having 3 to 10 carbon atoms.
R8C更佳為硫原子。t為0或1,較佳為0。 R 8C is more preferably a sulfur atom. t is 0 or 1, preferably 0.
R9C及R10C較佳為R9C及R10C中一者為烷氧基、另一者為氫原子。 R 9C and R 10C are preferably one in which R 9C and R 10C are an alkoxy group and the other is a hydrogen atom.
m及n相同或不同,較佳為0、1、或2,更佳為0或1。 m and n are the same or different, preferably 0, 1, or 2, and more preferably 0 or 1.
m與n之合計較佳為1以上且2以下,更佳為1。 The total of m and n is preferably 1 or more and 2 or less, and more preferably 1.
抗衡陽離子例如包括式(I)之X+所表示者。 Counter cations include, for example, those represented by X + of formula (I).
作為抗衡陰離子,可列舉鹵化物離子、式(x1)及式(x2)所表示之抗衡離子。 Examples of the counter anion include a halide ion, and a counter ion represented by the formula (x1) and the formula (x2).
作為鹵化物離子,可列舉氟化物離子、氯化物離子、溴化物離子及碘化物離子。 Examples of the halide ion include fluoride ion, chloride ion, bromide ion, and iodide ion.
[於式(x1)中,R51x表示碳數1~12之氟化烷基;於式(x2)中,R52x及R53x互相獨立地表示鹵素原子或碳數1~12之氟化烷基] [In formula (x1), R 51x represents a fluorinated alkyl group having 1 to 12 carbon atoms; in formula (x2), R 52x and R 53x independently represent a halogen atom or a fluorinated alkyl group having 1 to 12 carbon atoms base]
作為R51x所表示之碳數1~12之氟化烷基,具體而言,可列舉:氟甲基、二氟甲基、三氟甲基、1,1,2,2,2-五氟乙基、2,2,2-三氟乙基、3-(三氟甲基)-3,4,4,4-五氟丁基、全氟乙基、全氟丙基、全氟異丙基、全氟丁基、全氟第二丁基、全氟第三丁基、全氟戊基及全氟己基,較佳可列舉氫原子全部被取代為氟原子之碳數1~12之全氟烷基,更佳可列舉-CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-CF2CF2CF2CF3、-CF2CF(CF3)2、-C(CF3)3等碳數1~4之全氟烷基。 Examples of the fluorinated alkyl group having 1 to 12 carbon atoms represented by R 51x include fluoromethyl, difluoromethyl, trifluoromethyl, and 1,1,2,2,2-pentafluoro Ethyl, 2,2,2-trifluoroethyl, 3- (trifluoromethyl) -3,4,4,4-pentafluorobutyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl Group, perfluorobutyl group, perfluorosecond butyl group, perfluorothird butyl group, perfluoropentyl group and perfluorohexyl group, and preferably all hydrogen atoms are substituted with fluorine atoms of 1 to 12 carbon atoms. Examples of the fluoroalkyl group include -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF (CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ) Perfluoroalkyl groups having 1 to 4 carbon atoms such as 2 and -C (CF 3 ) 3 .
R51x所表示之氟化烷基之碳數較佳為1~6,更佳為1~4。 The carbon number of the fluorinated alkyl group represented by R 51x is preferably 1 to 6, more preferably 1 to 4.
作為R52x及R53x所表示之鹵素原子,可列舉氟原子、氯原子、溴原子及碘原子,較佳為氟原子。 Examples of the halogen atom represented by R 52x and R 53x include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.
作為R52x及R53x所表示之碳數1~12之氟化烷基,可列舉與R51x所表示之氟化烷基相同者,較佳可列舉碳數1~12之全氟烷基,更佳可列舉-CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-CF2CF2CF2CF3、-CF2CF(CF3)2、-C(CF3)3等碳數1~4之全氟烷基。 Examples of the fluorinated alkyl group having 1 to 12 carbon atoms represented by R 52x and R 53x include the same as the fluorinated alkyl group represented by R 51x , and preferably a perfluoroalkyl group having 1 to 12 carbon atoms. More preferably, -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF (CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ) 2 , -C (CF 3 ) 3 and other perfluoroalkyl groups having 1 to 4 carbon atoms.
R52x及R53x可互相鍵結而形成含有-SO2-N--SO2-之環。 R 52x and R 53x may be bonded to each other to form a ring containing -SO 2 -N -- SO 2- .
作為染料(A3),可列舉下述所記載之化合物。下述式中,R26及R40分別表示2-乙基己基。 As Examples of the dye (A3) include compounds described below. In the following formula, R 26 and R 40 each represent a 2-ethylhexyl group.
作為染料(A3),較佳為式(1-1)所表示之化合物~式(1-10)所表示之化合物、式(1-24)所表示之化合物~式(1-47)所表示之化合物,更佳為式(1-1)所表示之化合物~式(1-8)所表示之化合物、式(1-24)所表示之化合物、式(1-44)所表示之化合物~式(1-47)所表示之化合物,進而較佳為式(1-1)所表示之化合物~式(1-8)所表示之化合物、式(1-24)所表示之化合物。 As The dye (A3) is preferably a compound represented by the formula (1-1) ~ a compound represented by the formula (1-10), a compound represented by the formula (1-24) ~ a compound represented by the formula (1-47) The compound is more preferably a compound represented by formula (1-1) ~ a compound represented by formula (1-8), a compound represented by formula (1-24), or a compound represented by formula (1-44) ~ formula The compound represented by (1-47) is more preferably a compound represented by formula (1-1) to a compound represented by formula (1-8), or a compound represented by formula (1-24).
作為染料(A3),亦可列舉市售之染料(例如,中外化成股份有限公司製造之「Chugai Aminol Fast Pink R-H/C」、田岡化學工業股份有限公司製造之「Rhodamin 6G」)。又,亦可以市售之染料作為起始原料,以日本專利特開2010-32999號公報作為參考而進行合成。 As Dyes (A3), also available commercially Dyes (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Sinochem Chemical Co., Ltd., and "Rhodamin 6G" manufactured by Taoka Chemical Industry Co., Ltd.). Alternatively, a commercially available dye may be used as a starting material, and synthesized by using Japanese Patent Laid-Open No. 2010-32999 as a reference.
三芳基甲烷染料(A4)係含有分子內具有三芳基甲烷骨架之化合物之染料。 Triarylmethane dye (A4) is a dye containing a compound having a triarylmethane skeleton in the molecule.
較佳之三芳基甲烷染料(A4)包括式(A4-1)所表示之化合物、式(A4-2)所表示之化合物等。再者,於下述化合物整體為陰離子之情形時,下述化合物表示與抗衡陽離子或抗衡陰離子一併形成鹽之態樣之一部分。抗衡陽離子例如包括式(I)之X+所表示者。抗衡陰離子例如包括式(x1)及式(x2)所表示之抗衡離子。 Preferred triarylmethane dyes (A4) include compounds represented by formula (A4-1), compounds represented by formula (A4-2), and the like. In addition, when the following compounds are anions as a whole, the following compounds represent a part of the state of forming a salt together with a counter cation or a counter anion. Counter cations include, for example, those represented by X + of formula (I). The counter anion includes, for example, counter ions represented by the formula (x1) and the formula (x2).
(式中,R1D~R6D分別獨立地表示氫原子、可具有取代基之芳基、可具有取代基之烷基、或具有乙烯性雙鍵之基;R7D~R9D分別獨立地表示氫原子、甲基、或氟原子) (In the formula, R 1D to R 6D each independently represent a hydrogen atom, an aryl group which may have a substituent, an alkyl group which may have a substituent, or a group having an ethylenic double bond; R 7D to R 9D each independently represent Hydrogen, methyl, or fluorine)
R1D~R6D之芳基包括苯基、萘基、苄基等。作為其取代基,可例示:甲基、乙基等烷基;磺酸基;2-乙基己基胺基磺醯基等磺醯胺基;甲氧基磺醯基等磺酸酯基;烷氧基;硫代烷基;硫代烷氧基等。 作為具有取代基之芳基,可列舉:甲苯基、二甲苯基、基、乙基苯基等烷基取代苯基;苯基、苄基或上述烷基取代苯基上鍵結有磺酸基或磺醯胺基之基;乙氧基苯基等鍵結有烷氧基之苯基;甲硫基苯基等鍵結有烷硫基之苯基等,較佳為苯基、烷基取代苯基、或者苯基、苄基或上述烷基取代苯基上鍵結有磺酸基或磺醯胺基之基。 The aryl groups of R 1D to R 6D include phenyl, naphthyl, benzyl and the like. Examples of the substituent include alkyl groups such as methyl and ethyl groups; sulfonic acid groups; sulfonylamino groups such as 2-ethylhexylaminosulfonyl; sulfonate groups such as methoxysulfonyl; Oxy; thioalkyl; thioalkoxy and the like. Examples of the aryl group having a substituent include tolyl, xylyl, Alkyl, phenyl and other alkyl-substituted phenyl groups; phenyl, benzyl, or the above alkyl-substituted phenyl groups are bonded with a sulfonic acid group or a sulfonamido group; ethoxyphenyl groups are bonded with an alkyl group An phenyl group of an oxy group; a phenyl group of an alkylthio group and the like, such as a methylthiophenyl group, preferably a phenyl group, an alkyl-substituted phenyl group, or a phenyl group, a benzyl group, or the above alkyl-substituted phenyl bond A sulfonic or sulfonamide group is bound.
R1D~R6D之烷基可列舉:甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基等碳數1~20之直鏈狀烷基;異丙基、異丁基、第二丁基、第三丁基、異戊基、新戊基及2-乙基己基等碳數3~20之支鏈狀烷基。作為其取代基,包括苯基、萘基等。又,取代基亦可為磺酸基、2-乙基己基胺基磺醯基等磺醯胺基、甲氧基磺醯基等磺酸酯基等,鍵結有該等之苯基或萘基亦包括於取代基中。較佳為碳數1~10之直鏈狀烷基,更佳為碳數1~5之直鏈狀烷基,進而較佳為甲基或乙基。 Examples of the alkyl group of R 1D to R 6D include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl linear alkyl groups having 1 to 20 carbon atoms. Groups; isopropyl, isobutyl, second butyl, third butyl, isopentyl, neopentyl, and 2-ethylhexyl branched alkyl groups having 3 to 20 carbon atoms. Examples of the substituent include a phenyl group and a naphthyl group. The substituent may be a sulfonyl group such as a sulfonic acid group, a 2-ethylhexylaminosulfonyl group, and a sulfonate group such as a methoxysulfonyl group. A phenyl group or a naphthalene group may be bonded thereto. The group is also included in the substituent. A linear alkyl group having 1 to 10 carbon atoms is preferred, a linear alkyl group having 1 to 5 carbon atoms is more preferred, and a methyl or ethyl group is more preferred.
R1D~R6D之具有乙烯性雙鍵之基包括乙烯基、(甲基)丙烯醯基等。該等乙烯基、(甲基)丙烯醯基等亦可鍵結於烷基上,例如可列舉:烯丙基(乙烯基甲基)、乙烯基乙基等鍵結有乙烯基之烷基;(甲基)丙烯醯基甲基、(甲基)丙烯醯基乙基等鍵結有(甲基)丙烯醯基之烷基。進而,亦可例示該鍵結有(甲基)丙烯醯基之烷基鍵結於連結基上而成之基作為該具有乙烯性雙鍵之基。作為該連結基,例如可列舉下述式之基。 Examples of R 1D to R 6D having a vinylic double bond include a vinyl group, a (meth) acrylfluorenyl group, and the like. The vinyl group, (meth) acryl fluorenyl group and the like may be bonded to an alkyl group, and examples thereof include an alkyl group having a vinyl group such as an allyl (vinylmethyl) and vinylethyl group; (Meth) acrylfluorenylmethyl, (meth) acrylfluorenylethyl and the like are bonded to a (meth) acrylfluorenyl alkyl group. Furthermore, as the group having an ethylenic double bond, a group in which an alkyl group having a (meth) acrylfluorenyl group is bonded to a linking group can be exemplified. Examples of the linking group include a group of the following formula.
(式中,R10D表示亞甲基、伸乙基等碳數為1~8之伸烷基;*1表示與鍵結有(甲基)丙烯醯基之烷基之鍵結鍵,*2表示與N原子之鍵結 鍵) (In the formula, R 10D represents an alkylene group having 1 to 8 carbon atoms such as methylene and ethylene; * 1 represents a bond with an alkyl group having a (meth) acrylfluorenyl group, * 2 (Indicates a bond with an N atom)
R10D較佳為碳數1~4之伸烷基,更佳為亞甲基或伸乙基。 R 10D is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably methylene or ethylene.
又,*1較佳為鍵結於(甲基)丙烯醯基甲基或(甲基)丙烯醯基乙基上。 * 1 is preferably bonded to (meth) acrylfluorenylmethyl or (meth) acrylfluorenylethyl.
作為三芳基甲烷染料(A4),例如可列舉:C.I.酸性紫(以下省略C.I.酸性紫之記載,僅記載編號)15、16、17、19、21、23、24、25、38、49、72;C.I.酸性藍1、3、5、7、9、11、13、15、17、22、24、26、34、38、48、75、83、84、86、88、90、90:1、91、93、93:1、99、100、103、104、108、109、110、119、123、147、213、269;C.I.鹼性藍7、81、83、88、89;C.I.鹼性紫2;C.I.直接藍1、3、28、29、41、42、47、52、55;C.I.食用紫3;C.I.媒染紫1、1:1、3、6、8、10、11、15、16、17、18、19、21、23、27、28、33、36、39、49等。 Examples of the triarylmethane dye (A4) include: CI Acid Violet (hereinafter, the description of CI Acid Violet is omitted and only the number is described) 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, 72 ; CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 22, 24, 26, 34, 38, 48, 75, 83, 84, 86, 88, 90, 90: 1, 91, 93, 93: 1, 99, 100, 103, 104, 108, 109, 110, 119, 123, 147, 213, 269; CI Basic Blue 7, 81, 83, 88, 89; CI Basic Violet 2; CI Direct Blue 1, 3, 28, 29, 41, 42, 47, 52, 55; CI Edible Violet 3; CI Mordant Violet 1, 1: 1, 3, 6, 8, 10, 11, 15, 16 , 17, 18, 19, 21, 23, 27, 28, 33, 36, 39, 49, etc.
作為三芳基甲烷染料(A4),亦可列舉下述所記載之化合物。 Examples of the triarylmethane dye (A4) include compounds described below.
作為三芳基甲烷染料(A4),較佳為式(4-5)所表示之化合物、式(4-9)所表示之化合物、式(2b-2)所表示之化合物~式(2b-5)所表示之化合物、式(2b-14)所表示之化合物~式(2b-15)所表示之化合物,更佳為式(4-5)所表示之化合物。 The triarylmethane dye (A4) is preferably a compound represented by the formula (4-5), a compound represented by the formula (4-9), or a compound represented by the formula (2b-2) ~ formula (2b-5 The compound represented by), the compound represented by formula (2b-14) ~ the compound represented by formula (2b-15), and more preferably the compound represented by formula (4-5).
四氮雜卟啉染料(A5)係含有分子內具有四氮雜卟啉骨架之化合物之染料。又,於四氮雜卟啉染料為酸性染料或鹼性染料之情形時,亦可與任意陽離子或陰離子形成鹽。 The tetraazaporphyrin dye (A5) is a dye containing a compound having a tetraazaporphyrin skeleton in the molecule. When the tetraazaporphyrin dye is an acid dye or a basic dye, it may form a salt with any cation or anion.
較佳之四氮雜卟啉染料(A5)包括式(A5-1)所表示之化合物、式 (A5-2)所表示之化合物等。再者,於下述化合物整體為陰離子之情形時,下述化合物表示與抗衡陽離子或抗衡陰離子一併形成鹽之態樣之一部分。抗衡陽離子例如包括式(I)之X+所表示者。抗衡陰離子例如包括式(x1)及式(x2)所表示之抗衡離子。 Preferred tetraazaporphyrin dyes (A5) include compounds represented by formula (A5-1), compounds represented by formula (A5-2), and the like. In addition, when the following compounds are anions as a whole, the following compounds represent a part of the state of forming a salt together with a counter cation or a counter anion. Counter cations include, for example, those represented by X + of formula (I). The counter anion includes, for example, counter ions represented by the formula (x1) and the formula (x2).
(式中,R1E~R24E分別獨立地表示氫原子、鹵素原子、氰基、可具有取代基之烷基、可具有取代基之芳基、胺基、磺酸基、磺酸鹽基、或具有乙烯性雙鍵之基;R25E~R32E分別獨立地表示單鍵、氧原子或硫原子;M1E表示金屬原子或金屬氧化物) ( Wherein R 1E to R 24E each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an amine group, a sulfonic acid group, a sulfonate group, Or a group having an ethylenic double bond; R 25E to R 32E each independently represents a single bond, an oxygen atom, or a sulfur atom; M 1E represents a metal atom or a metal oxide)
R1E~R24E之鹵素原子包括氟原子、氯原子、溴原子等,較佳為氟原子或氯原子。 The halogen atom of R 1E to R 24E includes a fluorine atom, a chlorine atom, a bromine atom, and the like, and is preferably a fluorine atom or a chlorine atom.
R1E~R24E之烷基可列舉:甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基等碳數1~20之直鏈狀烷基;異丙基、異丁基、第二丁基、第三丁基、異戊基、新戊基及2-乙基己基等碳數3~20之支鏈狀烷基。其取代基包括氟原子等鹵素原子、羥基、磺酸基、磺酸鹽基、芳基、烷基取代苯基等。 Examples of the alkyl group of R 1E to R 24E include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl linear alkane having 1 to 20 carbon atoms. Groups; isopropyl, isobutyl, second butyl, third butyl, isopentyl, neopentyl, and 2-ethylhexyl branched alkyl groups having 3 to 20 carbon atoms. The substituent includes a halogen atom such as a fluorine atom, a hydroxyl group, a sulfonic acid group, a sulfonate group, an aryl group, an alkyl-substituted phenyl group, and the like.
R1E~R24E之芳基包括苯基、萘基、苄基等。作為其取代基,可 例示:氟原子、氯原子等鹵素原子;甲基、乙基、丙基、丁基等烷基;磺酸基、2-乙基己基胺基磺醯基、環己基胺基磺醯基、胺基戊基胺基磺醯基等磺醯胺基;甲氧基磺醯基等磺酸酯基、烷氧基、硫代烷氧基等。作為具有取代基之芳基,可列舉:甲苯基、二甲苯基、基、乙基苯基等烷基取代苯基;苯基、苄基或上述烷基取代苯基上鍵結有磺酸基或磺醯胺基之基;乙氧基苯基等鍵結有烷氧基之苯基;甲硫基苯基等鍵結有烷硫基之苯基;氟苯基、氯苯基等苯基、苄基或上述烷基取代苯基上鍵結有鹵素原子之基等,較佳為:苯基、烷基取代苯基;苯基、苄基或上述烷基取代苯基上鍵結有磺酸基或磺醯胺基之基;或者苯基、苄基或上述烷基取代苯基上鍵結有鹵素原子之基。 The aryl groups of R 1E to R 24E include phenyl, naphthyl, benzyl and the like. Examples of the substituent include halogen atoms such as a fluorine atom and a chlorine atom; alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group; a sulfonic acid group, a 2-ethylhexylaminosulfofluorenyl group, and a cyclohexylamine Sulfosulfenyl groups such as sulfosulfonyl, aminopentylaminosulfonyl; sulfonate groups such as methoxysulfonyl, alkoxy, thioalkoxy and the like. Examples of the aryl group having a substituent include tolyl, xylyl, Alkyl, phenyl and other alkyl-substituted phenyl groups; phenyl, benzyl, or the above alkyl-substituted phenyl groups are bonded with a sulfonic acid group or a sulfonamido group; ethoxyphenyl groups are bonded with an alkyl group An phenyl group of an oxy group; a phenyl group having an alkylthio group bonded to a methylthiophenyl group; a phenyl group such as a fluorophenyl group, a chlorophenyl group, a benzyl group, or the above alkyl-substituted phenyl group to which a halogen atom is bonded Etc., preferably: phenyl, alkyl-substituted phenyl; phenyl, benzyl, or the alkyl-substituted phenyl group having a sulfonic or sulfonylamino group bonded thereto; or phenyl, benzyl, or the above An alkyl-substituted phenyl group has a halogen atom bonded to it.
R1E~R24E之胺基包括:單正丁基胺基等單烷基胺基;二烷基胺基;單芳基胺基;二苯基胺基等二芳基胺基;單芳烷基胺基;二芳烷基胺基等。 The amine groups of R 1E to R 24E include: monoalkylamine groups such as mono-n-butylamine group; dialkylamine groups; monoarylamine groups; diarylamine groups such as diphenylamine group; monoaralkyl groups Aminoamino; diaralkylamino and the like.
R1E~R24E之具有乙烯性雙鍵之基包括乙烯基、(甲基)丙烯醯基等。該等乙烯基、(甲基)丙烯醯基等亦可鍵結於烷基上,例如可列舉:烯丙基(乙烯基甲基)、乙烯基乙基等鍵結有乙烯基之烷基;(甲基)丙烯醯基甲基、(甲基)丙烯醯基乙基等鍵結有(甲基)丙烯醯基之烷基。進而,亦可例示該鍵結有(甲基)丙烯醯基之烷基鍵結於連結基上而成之基作為該具有乙烯性雙鍵之基。作為該連結基,例如可列舉下述式之基。 Examples of R 1E to R 24E having a vinylic double bond include vinyl, (meth) acryl, and the like. The vinyl group, (meth) acryl fluorenyl group and the like may be bonded to an alkyl group, and examples thereof include an alkyl group having a vinyl group such as an allyl (vinylmethyl) and vinylethyl group; (Meth) acrylfluorenylmethyl, (meth) acrylfluorenylethyl and the like are bonded to a (meth) acrylfluorenyl alkyl group. Furthermore, as the group having an ethylenic double bond, a group in which an alkyl group having a (meth) acrylfluorenyl group is bonded to a linking group can be exemplified. Examples of the linking group include a group of the following formula.
(式中,R33E表示亞甲基、伸乙基等碳數為1~8之伸烷基;*1表示與鍵結有(甲基)丙烯醯基之烷基之鍵結鍵,*2表示與N原子之鍵結 鍵) (In the formula, R 33E represents an alkylene group having 1 to 8 carbon atoms such as methylene and ethylene; * 1 represents a bond with an alkyl group having a (meth) acrylfluorenyl group, * 2 (Indicates a bond with an N atom)
R33E較佳為碳數1~4之伸烷基,更佳為亞甲基或伸乙基。 R 33E is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably methylene or ethylene.
又,*1較佳為鍵結於(甲基)丙烯醯基甲基或(甲基)丙烯醯基乙基上。 * 1 is preferably bonded to (meth) acrylfluorenylmethyl or (meth) acrylfluorenylethyl.
於R1E~R24E為烷基時,R25E~R32E亦可為氧原子或硫原子,較佳為氧原子。 When R 1E to R 24E is an alkyl group, R 25E to R 32E may also be an oxygen atom or a sulfur atom, preferably an oxygen atom.
M1E包括Mg、Cu、Ni、Co、Pd、VO等,較佳為Cu。 M 1E includes Mg, Cu, Ni, Co, Pd, VO and the like, and Cu is preferred.
於R1E~R8E中,較佳為選自由R1E、R3E、R5E及R7E所組成之群中之至少一者以上為可具有取代基之芳基,且選自由R2E、R4E、R6E及R8E所組成之群中之至少一者以上為氫原子或可具有取代基之烷基,更佳為R1E、R3E、R5E及R7E全部為可具有取代基之芳基,且R2E、R4E、R6E及R8E全部為氫原子或可具有取代基之烷基。 Among R 1E to R 8E , it is preferred that at least one selected from the group consisting of R 1E , R 3E , R 5E and R 7E is an aryl group which may have a substituent, and is selected from R 2E , R At least one of the groups consisting of 4E , R 6E, and R 8E is a hydrogen atom or an alkyl group which may have a substituent, and more preferably R 1E , R 3E , R 5E, and R 7E are all which may have a substituent An aryl group, and all of R 2E , R 4E , R 6E and R 8E are a hydrogen atom or an alkyl group which may have a substituent.
作為四氮雜卟啉染料,可列舉下述所記載之化合物。 Examples of the tetraazaporphyrin dye include the compounds described below.
蒽醌染料(A6)係含有分子內具有蒽醌骨架之化合物之染料。較佳之蒽醌染料(A6)包括式(A6-1)所表示之化合物。 Anthraquinone dye (A6) is a dye containing a compound having an anthraquinone skeleton in the molecule. The preferred anthraquinone dye (A6) includes a compound represented by the formula (A6-1).
(式中,R1F~R4F分別獨立地表示氫原子、可具有取代基之芳 基、可具有取代基之烷基、或具有乙烯性雙鍵之基;R5F及R6F分別獨立地表示氫原子、鹵素原子、腈基、磺酸基、或磺酸鹽基) (In the formula, R 1F to R 4F each independently represent a hydrogen atom, an aryl group which may have a substituent, an alkyl group which may have a substituent, or a group having an ethylenic double bond; R 5F and R 6F each independently represent Hydrogen, halogen, nitrile, sulfonate, or sulfonate)
R1F~R4F之芳基包括苯基、萘基、苄基等。作為其取代基,可例示:甲基、乙基等烷基;氟原子、氯原子等鹵素原子;磺酸基;2-乙基己基胺基磺醯基、環己基胺基磺醯基、胺基戊基胺基磺醯基等磺醯胺基;甲氧基磺醯基等磺酸酯基;烷氧基;硫代烷基;硫代烷氧基等。作為具有取代基之芳基,可列舉:甲苯基、二甲苯基、基、乙基苯基等烷基取代苯基;苯基、苄基或上述烷基取代苯基上鍵結有磺酸基或磺醯胺基之基;氟苯基、氯苯基等苯基、苄基或上述烷基取代苯基上鍵結有鹵素原子之基;乙氧基苯基等鍵結有烷氧基之苯基;甲硫基苯基等鍵結有烷硫基之苯基等,較佳為:苯基、烷基取代苯基;苯基、苄基或上述烷基取代苯基上鍵結有磺酸基或磺醯胺基之基;或者苯基、苄基或上述烷基取代苯基上鍵結有鹵素原子之基。 The aryl groups of R 1F to R 4F include phenyl, naphthyl, benzyl and the like. Examples of the substituent include an alkyl group such as a methyl group and an ethyl group; a halogen atom such as a fluorine atom and a chlorine atom; a sulfonic acid group; a 2-ethylhexylaminosulfonyl group, a cyclohexylaminosulfonyl group, and an amine Sulfonamido groups such as pentylaminosulfonyl; sulfonate groups such as methoxysulfonyl; alkoxy; thioalkyl; thioalkoxy and the like. Examples of the aryl group having a substituent include tolyl, xylyl, Alkyl, phenyl and other alkyl-substituted phenyl groups; phenyl, benzyl, or the alkyl-substituted phenyl groups described above are bonded with sulfonic or sulfonylamino groups; phenyls such as fluorophenyl and chlorophenyl , Benzyl or the above alkyl-substituted phenyl groups are bonded to a halogen atom; ethoxyphenyl and the like are bonded to an alkoxy group; methylthiophenyl and the like are bonded to an alkylthio group Etc., preferably: phenyl, alkyl-substituted phenyl; phenyl, benzyl, or the alkyl-substituted phenyl group having a sulfonic or sulfonylamino group bonded thereto; or phenyl, benzyl, or the above An alkyl-substituted phenyl group has a halogen atom bonded to it.
作為可具有取代基之芳基,可列舉下述所記載之取代基。 Examples of the aryl group which may have a substituent include the substituents described below.
R1F~R4F之烷基可列舉:甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基等碳數1~20之直鏈狀烷基;異丙基、異丁基、第二丁基、第三丁基、異戊基、新戊基及2-乙基己基等碳數3~20之支鏈狀烷基。作為其取代基,包括苯基、萘基等。又,取代 基亦可為羥基磺酸基、2-乙基己基胺基磺醯基等磺醯胺基、甲氧基磺醯基等磺酸酯基等,鍵結有該等之苯基或萘基亦包括於取代基中。較佳為碳數1~10之烷基,更佳為碳數1~5之烷基,進而較佳為甲基、乙基、正丙基、異丙基、1-羥基乙基、或2-羥基乙基。 Examples of the alkyl group of R 1F to R 4F include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl linear alkyl groups having 1 to 20 carbon atoms. Groups; isopropyl, isobutyl, second butyl, third butyl, isopentyl, neopentyl, and 2-ethylhexyl branched alkyl groups having 3 to 20 carbon atoms. Examples of the substituent include a phenyl group and a naphthyl group. Further, the substituent may be a sulfonyl group such as a sulfonic acid group, a 2-ethylhexylaminosulfonyl group, and a sulfonate group such as a methoxysulfonyl group. Naphthyl is also included in the substituent. It is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably methyl, ethyl, n-propyl, isopropyl, 1-hydroxyethyl, or 2 -Hydroxyethyl.
R1F~R4F之具有乙烯性雙鍵之基包括乙烯基、(甲基)丙烯醯基等。該等乙烯基、(甲基)丙烯醯基等亦可鍵結於烷基上,例如可列舉:烯丙基(乙烯基甲基)、乙烯基乙基等鍵結有乙烯基之烷基;(甲基)丙烯醯基甲基、(甲基)丙烯醯基乙基等鍵結有(甲基)丙烯醯基之烷基。進而,亦可例示該鍵結有(甲基)丙烯醯基之烷基鍵結於連結基上而成之基作為該具有乙烯性雙鍵之基。作為該連結基,例如可列舉下述式之基。 Examples of R 1F to R 4F having a vinylic double bond include vinyl, (meth) acryl, and the like. The vinyl group, (meth) acryl fluorenyl group and the like may be bonded to an alkyl group, and examples thereof include an alkyl group having a vinyl group such as an allyl (vinylmethyl) and vinylethyl group; (Meth) acrylfluorenylmethyl, (meth) acrylfluorenylethyl and the like are bonded to a (meth) acrylfluorenyl alkyl group. Furthermore, as the group having an ethylenic double bond, a group in which an alkyl group having a (meth) acrylfluorenyl group is bonded to a linking group can be exemplified. Examples of the linking group include a group of the following formula.
(式中,R7F表示亞甲基、伸乙基等碳數為1~8之伸烷基;*1表示與鍵結有(甲基)丙烯醯基之烷基之鍵結鍵,*2表示與N原子之鍵結鍵) (In the formula, R 7F represents an alkylene group having a carbon number of 1 to 8 such as methylene, ethylidene, etc .; * 1 represents a bond with an alkyl group having a (meth) acrylfluorenyl group, * 2 (Indicates a bond with an N atom)
R7F較佳為碳數1~4之伸烷基,更佳為亞甲基或伸乙基。 R 7F is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably methylene or ethylidene.
又,*1較佳為鍵結於(甲基)丙烯醯基甲基或(甲基)丙烯醯基乙基上。 * 1 is preferably bonded to (meth) acrylfluorenylmethyl or (meth) acrylfluorenylethyl.
作為蒽醌染料(A6),例如可列舉:C.I.溶劑紫11、13、14、26、31、36、37、38、45、47、48、51、59、60;C.I.溶劑藍12、14、18、35、36、45、58、59、59:1、63、68、69、78、79、83、94、97、98、100、101、102、104、105、 111、112、122、128、132、136、139;C.I.酸性紫34;C.I.酸性藍25、27、40、45、78、80、112;C.I.分散紫26、27;C.I.分散藍1、14、56、60;C.I.直接藍40;C.I.媒染藍8等。 Examples of the anthraquinone dye (A6) include: CI solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI solvent blue 12, 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI Acid Violet 34; CI Acid Blue 25, 27, 40, 45, 78, 80, 112; CI Disperse Violet 26, 27; CI Disperse Blue 1, 14, 56, 60; CI Direct Blue 40; CI Mordant Blue 8 and so on.
作為蒽醌染料(A6),亦可列舉下述所記載之化合物。 Examples of the anthraquinone dye (A6) include the compounds described below.
作為蒽醌染料(A6),較佳為式(3-11)所表示之化合物~式(3-12)所表示之化合物。 The anthraquinone dye (A6) is preferably a compound represented by the formula (3-11) to a compound represented by the formula (3-12).
於本說明書中,式(A7)所表示之染料係亦包括式(A7)所表示之化合物之互變異構物之概念。 In this specification, the dye system represented by the formula (A7) also includes the concept of a tautomer of the compound represented by the formula (A7).
[式(A7)中,g表示任意自然數;Gg-表示g價之陰離子;D表示可具有取代基之雜芳香族烴基;R1A、R2A、R3A、R4A、R5A、R6A、R7A及R8A分別獨立地表示氫原子、鹵素原子、硝基、羥基或烷基,該烷基所含之-CH2-可被取代為-O-;R21A及R22A分別獨立地表示可經取代之胺基] [In formula (A7), g represents an arbitrary natural number; G g- represents an anion having a valence of g; D represents a heteroaromatic hydrocarbon group which may have a substituent; R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A, and R 8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group, and -CH 2 -contained in the alkyl group may be substituted with -O-; R 21A and R 22A are independent To represent an optionally substituted amine group]
作為R1A、R2A、R3A、R4A、R5A、R6A、R7A及R8A所表示之烷基,可列舉:甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、己基、庚基、2-乙基己基、辛基、壬基、癸基、十一烷基、十二烷基、環丙基、環丁基、環戊基、環己基、甲基環己基、二甲基環己基、環庚基、環辛基、環壬基、環癸基、十氫萘基、金剛烷基、2-烷基金剛烷-2-基、1-(金剛烷-1-基)烷-1-基、降基、甲基降基及異基等碳數1~20之烷基。較佳為碳數1~8之烷基,更佳為碳數1~6之烷基,進而較佳為碳數1~4之烷基。 Examples of the alkyl group represented by R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A, and R 8A include methyl, ethyl, n-propyl, isopropyl, and n-butyl. , Second butyl, third butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopropyl, cyclobutyl Base, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, decahydronaphthyl, adamantyl, 2-alkyladamantyl Alk-2-yl, 1- (adamantane-1-yl) alk-1-yl, Methyl, methyl Base and different Alkyl group having 1 to 20 carbon atoms. An alkyl group having 1 to 8 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred.
R1A、R2A、R3A、R4A、R5A、R6A、R7A及R8A所表示之烷基所含之-CH2-可被取代為-O-。 -CH 2 -contained in the alkyl group represented by R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A, and R 8A may be substituted with -O-.
作為R1A、R2A、R3A、R4A、R5A、R6A、R7A及R8A所表示之烷基所含之-CH2-被取代為-O-之基,具體而言,可列舉如下所述之基。較佳 為碳數1~10之烷基所含之-CH2-被取代為-O-之基,更佳為碳數1~6之烷基所含之-CH2-被取代為-O-之基。 The -CH 2 -group contained in the alkyl group represented by R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A, and R 8A is substituted with -O-, and specifically, may be The bases are listed below. Preferably, -CH 2 -in the alkyl group having 1 to 10 carbon atoms is substituted with -O-, and more preferably -CH 2 -in the alkyl group having 1 to 6 carbon atoms is substituted with -O. -The base.
作為R1A、R2A、R3A、R4A、R5A、R6A、R7A及R8A所表示之鹵素原子,可列舉氟原子、氯原子、溴原子及碘原子,較佳為氟原子或氯原子。 Examples of the halogen atom represented by R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A, and R 8A include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a fluorine atom is preferred. Chlorine atom.
較佳為R1A、R2A、R3A、R4A、R5A、R6A、R7A及R8A分別獨立為氫原子或碳數1~8之烷基,更佳為分別獨立為氫原子或甲基,進而較佳為分別獨立為氫原子。 Preferably, R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A, and R 8A are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably each is independently a hydrogen atom or The methyl groups are more preferably each independently a hydrogen atom.
R21A及R22A所表示之胺基所含之氫原子可經可具有取代基之芳基、可具有取代基之烷基、或者含有丙烯醯基或甲基丙烯醯基之基取代。 The hydrogen atom contained in the amine group represented by R 21A and R 22A may be substituted with an aryl group which may have a substituent, an alkyl group which may have a substituent, or a group containing an allyl group or a methacryl group.
於可具有取代基之芳基中,作為芳基,可列舉苯基、萘基、蒽基等碳數6~14之芳基,作為該芳基可具有之取代基,可列舉鹵素原子及碳數1~8之烷基。 Among the aryl groups which may have a substituent, examples of the aryl group include aryl groups having 6 to 14 carbon atoms such as phenyl, naphthyl, and anthracenyl groups, and examples of the substituent which the aryl group may have include halogen atoms and carbon Alkyl groups of 1 to 8.
於可具有取代基之烷基中,作為烷基,可列舉:甲基、乙基、 正丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、己基、庚基、2-乙基己基、辛基、壬基、癸基、十一烷基、十二烷基、環丙基、環丁基、環戊基、環己基、甲基環己基、二甲基環己基、環庚基、環辛基、環壬基、環癸基、十氫萘基、金剛烷基、2-烷基金剛烷-2-基、1-(金剛烷-1-基)烷-1-基、降基、甲基降基及異基等碳數1~20之烷基。與該烷基所含之氮原子鄰接之-CH2-以外之-CH2-可被取代為-O-,作為該烷基可具有之取代基,可列舉胺基、經取代之胺基、鹵素原子及含有矽原子之基。 Among the alkyl groups which may have a substituent, examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, pentyl, hexyl, Heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethyl Cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, decahydronaphthyl, adamantyl, 2-alkyladamantane-2-yl, 1- (adamantane-1-yl) Alkan-1-yl Methyl, methyl Base and different Alkyl group having 1 to 20 carbon atoms. -CH 2 -other than -CH 2 -adjacent to the nitrogen atom contained in the alkyl group may be substituted with -O-. Examples of the substituent that the alkyl group may have include an amino group, a substituted amino group, Halogen atoms and radicals containing silicon atoms.
作為鹵素原子,可列舉氟原子、氯原子、溴原子及碘原子。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
作為經取代之胺基,可列舉:甲基胺基、乙基胺基、丙基胺基、異丙基胺基、丁基胺基、第二丁基胺基、第三丁基胺基、二甲胺基、二乙胺基、二丙胺基、乙基甲基胺基等碳數1~8之烷基胺基及碳數1~8之二烷基胺基。 Examples of the substituted amine group include a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, a second butylamino group, a third butylamino group, Alkylamino groups having 1 to 8 carbon atoms and dialkylamino groups having 1 to 8 carbon atoms such as dimethylamino, diethylamino, dipropylamino, and ethylmethylamino groups.
作為含有丙烯醯基或甲基丙烯醯基之基,意指至少具有1個丙烯醯基或甲基丙烯醯基作為基之結構單元之基。 The group containing acrylfluorenyl or methacrylfluorenyl means a group having a structural unit having at least one acrylfluorenyl or methacrylfluorenyl as a base.
含有丙烯醯基或甲基丙烯醯基之基之碳數通常為3~30,較佳為3~20。 The carbon number of the acryl- or methacryl-based group is usually 3 to 30, preferably 3 to 20.
較佳為含有丙烯醯基或甲基丙烯醯基之基為含有丙烯醯氧基或甲基丙烯醯氧基之基。 It is preferable that the group containing a propylene fluorenyl group or a methacryl fluorenyl group is a group containing a propylene fluorenyloxy group or a methacryl fluorenyl group.
較佳為含有丙烯醯基或甲基丙烯醯基之基為式(A7-1)所表示之基。 It is preferable that the group containing an acrylfluorenyl group or a methacrylfluorenyl group is a group represented by Formula (A7-1).
*-R14A-R15A (A7-1) * -R 14A -R 15A (A7-1)
[式(A7-1)中,R15A表示丙烯醯基或甲基丙烯醯基;R14A表示碳數1~8之烷二基,該烷二基所含之-CH2-可被取代為-O-;*表示與氮原 子之鍵結鍵] [In the formula (A7-1), R 15A represents an propylene fluorenyl group or a methacryl fluorenyl group; R 14A indicates an alkanediyl group having 1 to 8 carbon atoms, and -CH 2 -contained in the alkanediyl group may be substituted as -O-; * indicates a bond with a nitrogen atom]
作為R14A所表示之碳數1~8之烷二基,可列舉:亞甲基、伸乙基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基、庚烷-1,7-二基、辛烷-1,8-二基、乙烷-1,1-二基、丙烷-1,1-二基、丙烷-1,2-二基、丙烷-2,2-二基、戊烷-2,4-二基、2-甲基丙烷-1,3-二基、2-甲基丙烷-1,2-二基、戊烷-1,4-二基、2-甲基丁烷-1,4-二基,較佳為碳數1~4之烷二基,更佳為亞甲基或伸乙基,進而較佳為亞甲基。 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by R 14A include methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, and pentane-1. , 5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, ethane-1,1-diyl, propane-1, 1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methyl Propane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, preferably alkanediyl having 1 to 4 carbon atoms, more preferably Methyl or ethylene, more preferably methylene.
作為含有丙烯醯基或甲基丙烯醯基之基,可列舉下述所記載之基。(*表示與氮原子之鍵結鍵) Examples of the group containing an acrylfluorenyl group or a methacrylfluorenyl group include those described below. (* Indicates a bond with a nitrogen atom)
作為R21A及R22A所表示之可經取代之胺基,可列舉:甲基胺基、乙基胺基、丙基胺基、異丙基胺基、丁基胺基、異丁基胺基、第二丁基胺基、第三丁基胺基、戊基胺基、新戊基胺基、己基胺基、二甲胺基、二乙胺基、二丙胺基、二異丙基胺基、乙基甲基胺基、乙基異丙 基胺基、乙基丙基胺基、異丙基甲基胺基、異丙基丙基胺基、甲基丙基胺基、苯基胺基、萘基胺基、2-甲基苯基胺基、4-甲基苯基胺基、3-甲基苯基胺基、3,5-二甲基苯基胺基、4-乙基苯基胺基、N-甲基-N-苯基胺基、丙烯醯氧基甲基胺基、N-(丙烯醯氧基甲基)-N-甲基胺基、N-(丙烯醯氧基乙基)-N-乙基胺基、N-(甲基丙烯醯氧基乙基)-N-乙基胺基、N-(丙烯醯氧基乙基)-N-苯基胺基、N-(丙烯醯氧基乙基)-N-(甲基丙烯醯氧基甲基)胺基、N-(丙烯醯氧基乙氧基甲基)-N-乙基胺基及N-(甲基丙烯醯氧基乙氧基甲基)-N-乙基胺基。 Examples of the replaceable amine group represented by R 21A and R 22A include a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, and an isobutylamino group. , Second butylamino, third butylamino, pentylamino, neopentylamino, hexylamino, dimethylamino, diethylamino, dipropylamino, diisopropylamino , Ethylmethylamino, ethylisopropylamino, ethylpropylamino, isopropylmethylamino, isopropylpropylamino, methylpropylamino, phenylamino , Naphthylamino, 2-methylphenylamino, 4-methylphenylamino, 3-methylphenylamino, 3,5-dimethylphenylamino, 4-ethylbenzene Amino, N-methyl-N-phenylamino, acryloxymethylamino, N- (acryloxymethyl) -N-methylamino, N- (acryloxy (Ethyl) -N-ethylamino, N- (methacryloxyethyl) -N-ethylamino, N- (acryloxyethyl) -N-phenylamino, N -(Acryloxyethyl) -N- (methacryloxymethyl) amino, N- (acryloxyethoxymethyl) -N-ethylamino, and N- (methyl Propylene propylene ethoxyethoxymethyl) -N- Amine group.
D所表示之雜芳香族烴基至少具有1個雜原子即可,作為雜原子,可列舉氮原子、氧原子及硫原子。 The heteroaromatic hydrocarbon group represented by D may have at least one hetero atom, and examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.
D所表示之雜芳香族烴基可為單環,亦可為多環。 The heteroaromatic hydrocarbon group represented by D may be monocyclic or polycyclic.
作為D所表示之雜芳香族烴基,可列舉:吡啶基、咪唑基、吡唑基、唑基、異唑基、噻唑基、異噻唑基、苯并噻唑基、苯并異噻唑基、噻吩基、苯并噻吩基等碳數2~8之雜芳香族烴基,較佳為至少含有1個氮原子或硫原子作為環之構成要素之碳數2~8之雜芳香族烴基。 Examples of the heteroaromatic hydrocarbon group represented by D include pyridyl, imidazolyl, pyrazolyl, Oxazolyl, iso Heteroaromatic hydrocarbon groups having 2 to 8 carbon atoms, such as oxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzoisothiazolyl, thienyl, and benzothienyl, preferably contain at least one nitrogen atom or A heteroaromatic hydrocarbon group having 2 to 8 carbon atoms in which a sulfur atom is a constituent element of a ring.
作為D所表示之雜芳香族烴基可具有之取代基,可列舉可經取代之胺基、碳數1~20之烷基、可具有取代基之芳基,較佳為可經取代之胺基及可具有取代基之芳基。 Examples of the substituent which the heteroaromatic hydrocarbon group represented by D may have include an amine group which may be substituted, an alkyl group having 1 to 20 carbon atoms, and an aryl group which may have a substituent. A substituted amine group is preferred. And an aryl group which may have a substituent.
作為可經取代之胺基,可列舉與R21A及R22A所表示之可經取代之胺基相同者。 Examples of the amine group which may be substituted include the same ones as the amine group which may be substituted represented by R 21A and R 22A .
作為碳數1~20之烷基,可列舉與R1A、R2A、R3A、R4A、R5A、R6A、R7A及R8A所表示之碳數1~20之烷基相同者。 Examples of the alkyl group having 1 to 20 carbon atoms include the same as the alkyl group having 1 to 20 carbon atoms represented by R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A, and R 8A .
作為可具有取代基之芳基,可列舉苯基、萘基、蒽基,作為取代基,可列舉:氟原子、氯原子及溴原子等鹵素原子;碳數1~20之烷基。 Examples of the aryl group which may have a substituent include a phenyl group, a naphthyl group, and an anthryl group. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; and an alkyl group having 1 to 20 carbon atoms.
較佳為D所表示之雜芳香族烴基為式(III)所表示之基。 The heteroaromatic hydrocarbon group represented by D is preferably a group represented by formula (III).
[式(III)中,X表示氧原子或硫原子;R55表示氫原子、碳數1~20之烷基或可具有取代基之芳基;R56表示可經取代之胺基;*表示與碳原子之鍵結鍵] [In formula (III), X represents an oxygen atom or a sulfur atom; R 55 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group which may have a substituent; R 56 represents an amine group which may be substituted; * represents Bonding with a carbon atom]
作為R55所表示之碳數1~20之烷基,可列舉與R1A、R2A、R3A、R4A、R5A、R6A、R7A及R8A所表示之碳數1~20之烷基相同者。 Examples of the alkyl group having 1 to 20 carbon atoms represented by R 55 include those having 1 to 20 carbon atoms represented by R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A, and R 8A . The same alkyl group.
作為R55所表示之可具有取代基之芳基,可列舉苯基。 Examples of the aryl group which may have a substituent represented by R 55 include a phenyl group.
作為R56所表示之可經取代之胺基,可列舉與R21A及R22A所表示之可經取代之胺基相同者。 Examples of the substituted amine group represented by R 56 include the same ones as the substituted amine group represented by R 21A and R 22A .
R55較佳為未經取代或具有取代基之芳基,更佳為未經取代或經鹵素原子取代之芳基。 R 55 is preferably an unsubstituted or substituted aryl group, and more preferably an unsubstituted or substituted aryl group with a halogen atom.
R56較佳為可經取代之胺基。 R 56 is preferably an amine group which may be substituted.
作為D所表示之雜芳香族烴基,可列舉式(III-1)所表示之基~式(III-8)所表示之基,較佳為式(III-1)或式(III-2)所表示之基。 Examples of the heteroaromatic hydrocarbon group represented by D include a group represented by formula (III-1) to a group represented by formula (III-8), and it is preferably formula (III-1) or formula (III-2) The indicated base.
g為任意自然數,較佳為1~2之自然數,更佳為1。 g is an arbitrary natural number, preferably a natural number of 1 to 2, and more preferably 1.
Gg-表示g價之陰離子,只要為由陽離子與g價之陰離子形成鹽者,則並無限定。例如,於g為2以上之自然數之情形時,可具有1個g價之陰離子,亦可具有g個一價之陰離子或一價之陰離子部位。 G g- represents a g-valent anion, and is not limited as long as it is a salt formed by a cation and a g-valent anion. For example, when g is a natural number of 2 or more, it may have 1 g-valent anion, or g monovalent anions or monovalent anion sites.
Gg-較佳為一價之陰離子,例如可列舉:氟化物離子、氯化物離子、溴化物離子及碘化物離子等鹵化物離子;式(y1)所表示之陰離子、式(y2)所表示之陰離子及式(y3)所表示之陰離子。 G g- is preferably a monovalent anion, and examples include halide ions such as fluoride ion, chloride ion, bromide ion, and iodide ion; the anion represented by formula (y1), and the formula (y2) Anion and anion represented by formula (y3).
[於式(y1)中,RB1表示可具有鹵素原子之烴基;於式(y2)中,RB2及RB3分別獨立地表示鹵素原子或鹵化烴基,或 者RB2與RB3互相鍵結而形成含有-SO2-N--SO2-之環;於式(y3)中,M表示鋁原子或硼原子,RB4及RB5分別獨立地表示可具有取代基之苯基] [In formula (y1), R B1 represents a hydrocarbon group which may have a halogen atom; in formula (y2), R B2 and R B3 each independently represent a halogen atom or a halogenated hydrocarbon group, or R B2 and R B3 are bonded to each other and Forms a ring containing -SO 2 -N -- SO 2- ; in formula (y3), M represents an aluminum atom or a boron atom, and R B4 and R B5 each independently represent a phenyl group which may have a substituent]
作為RB1所表示之烴基,可列舉碳數1~8之烷基及碳數6~14之芳香族烴基。 Examples of the hydrocarbon group represented by R B1 include an alkyl group having 1 to 8 carbon atoms and an aromatic hydrocarbon group having 6 to 14 carbon atoms.
作為碳數1~8之烷基,可列舉:甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、己基、庚基、2-乙基己基、辛基、環丙基、環丁基、環戊基、環己基、甲基環己基。 Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, pentyl, hexyl, heptyl, 2 -Ethylhexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl.
作為碳數6~14之芳香族烴基,可列舉苯基及萘基。 Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.
作為鹵素原子,可列舉氟原子、氯原子、溴原子及碘原子,較佳為氟原子。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.
作為碳數1~8之鹵化烷基,可列舉:二氟甲基、三氟甲基、1,1-二氟乙基、2,2-二氟乙基、2,2,2-三氟乙基、全氟乙基、1,1,2,2-四氟丙基、1,1,2,2,3,3-六氟丙基、全氟乙基甲基、1-(三氟甲基)-1,2,2,2-四氟乙基、全氟丙基、1,1,2,2-四氟丁基、1,1,2,2,3,3-六氟丁基、1,1,2,2,3,3,4,4-八氟丁基、全氟丁基、二溴甲基、三溴甲基,較佳為碳數1~8之氟化烷基。 Examples of the halogenated alkyl group having 1 to 8 carbon atoms include difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, and 2,2,2-trifluoro. Ethyl, perfluoroethyl, 1,1,2,2-tetrafluoropropyl, 1,1,2,2,3,3-hexafluoropropyl, perfluoroethylmethyl, 1- (trifluoro (Methyl) -1,2,2,2-tetrafluoroethyl, perfluoropropyl, 1,1,2,2-tetrafluorobutyl, 1,1,2,2,3,3-hexafluorobutane Base, 1,1,2,2,3,3,4,4-octafluorobutyl, perfluorobutyl, dibromomethyl, tribromomethyl, preferably fluorinated alkane having 1 to 8 carbon atoms base.
作為碳數6~14之具有鹵素原子之芳香族烴基,可列舉具有鹵素原子之苯基、具有鹵素原子之萘基。具體而言,可列舉:氟苯基、氯苯基、溴苯基、二氟苯基、1-氟-4-氯苯基、三氟苯基、氟萘基。 Examples of the aromatic hydrocarbon group having a halogen atom having 6 to 14 carbon atoms include a phenyl group having a halogen atom and a naphthyl group having a halogen atom. Specific examples include fluorophenyl, chlorophenyl, bromophenyl, difluorophenyl, 1-fluoro-4-chlorophenyl, trifluorophenyl, and fluoronaphthyl.
RB1較佳為碳數1~8之鹵化烷基,更佳為碳數1~8之氟化烷基。 R B1 is preferably a halogenated alkyl group having 1 to 8 carbon atoms, and more preferably a fluorinated alkyl group having 1 to 8 carbon atoms.
作為RB2及RB3所表示之鹵素原子,可列舉氟原子、氯原子、溴原子及碘原子,較佳為氟原子或氯原子。 Examples of the halogen atom represented by R B2 and R B3 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferred.
作為RB2及RB3所表示之鹵化烴基,可列舉碳數1~8之鹵化烷基、具有鹵素原子之碳數6~14之芳香族烴基。 Examples of the halogenated hydrocarbon group represented by R B2 and R B3 include a halogenated alkyl group having 1 to 8 carbon atoms, and an aromatic hydrocarbon group having 6 to 14 carbon atoms having a halogen atom.
作為碳數1~8之鹵化烷基,可列舉:二氟甲基、三氟甲基、1,1- 二氟乙基、2,2-二氟乙基、2,2,2-三氟乙基、全氟乙基、1,1,2,2-四氟丙基、1,1,2,2,3,3-六氟丙基、全氟乙基甲基、1-(三氟甲基)-1,2,2,2-四氟乙基、全氟丙基、1,1,2,2-四氟丁基、1,1,2,2,3,3-六氟丁基、1,1,2,2,3,3,4,4-八氟丁基、全氟丁基、二溴甲基、三溴甲基,較佳為碳數1~8之氟化烷基。 Examples of the halogenated alkyl group having 1 to 8 carbon atoms include difluoromethyl, trifluoromethyl, and 1,1- Difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 1,1,2,2-tetrafluoropropyl, 1,1,2,2 , 3,3-hexafluoropropyl, perfluoroethylmethyl, 1- (trifluoromethyl) -1,2,2,2-tetrafluoroethyl, perfluoropropyl, 1,1,2, 2-tetrafluorobutyl, 1,1,2,2,3,3-hexafluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, perfluorobutyl, Dibromomethyl and tribromomethyl are preferably fluorinated alkyl groups having 1 to 8 carbon atoms.
作為碳數6~14之具有鹵素原子之芳香族烴基,可列舉具有鹵素原子之苯基、具有鹵素原子之萘基。具體而言,可列舉:氟苯基、氯苯基、溴苯基、二氟苯基、1-氟-4-氯苯基、三氟苯基、氟萘基。 Examples of the aromatic hydrocarbon group having a halogen atom having 6 to 14 carbon atoms include a phenyl group having a halogen atom and a naphthyl group having a halogen atom. Specific examples include fluorophenyl, chlorophenyl, bromophenyl, difluorophenyl, 1-fluoro-4-chlorophenyl, trifluorophenyl, and fluoronaphthyl.
較佳為RB2及RB3為相同之基。 Preferably, R B2 and R B3 are the same group.
RB2及RB3較佳為分別獨立為碳數1~8之氟化烷基,更佳為分別獨立為三氟甲基。 R B2 and R B3 are each preferably independently a fluorinated alkyl group having 1 to 8 carbon atoms, and more preferably each is independently a trifluoromethyl group.
作為RB4及RB5所表示之苯基可具有之取代基,較佳為羥基。 As the substituent which the phenyl group represented by R B4 and R B5 may have, a hydroxyl group is preferred.
較佳為RB4及RB5為相同之基。 Preferably, R B4 and R B5 are the same group.
作為式(y1)所表示之陰離子,可列舉:甲磺酸陰離子、甲苯磺酸陰離子、十二烷基苯磺酸陰離子、三氟甲磺酸陰離子、全氟丁磺酸陰離子、苯基磺酸陰離子、氟苯基磺酸陰離子等。 Examples of the anion represented by the formula (y1) include a methanesulfonic acid anion, a toluenesulfonic acid anion, a dodecylbenzenesulfonic acid anion, a trifluoromethanesulfonic acid anion, a perfluorobutanesulfonic acid anion, and a phenylsulfonic acid. Anions, fluorophenylsulfonic anions, etc.
作為式(y2)所表示之陰離子,可列舉下述所記載之陰離子。 Examples of the anion represented by the formula (y2) include the anions described below.
作為式(y3)所表示之陰離子,可列舉下述所記載之陰離子。 Examples of the anion represented by the formula (y3) include the anions described below.
作為染料(A7),可列舉式(A-I-a1)~(A-I-a15)所表示之化合物。較佳為式(A-I-a5)所表示之化合物~式(A-I-a12)所表示之化合物。 Examples of the dye (A7) include compounds represented by the formulae (A-I-a1) to (A-I-a15). A compound represented by the formula (A-I-a5) to a compound represented by the formula (A-I-a12) is preferable.
染料(A7)例如可藉由韓國公開專利第2014-0026284號公報所記載之方法而製造。 The dye (A7) can be produced, for example, by a method described in Korean Laid-Open Patent Publication No. 2014-0026284.
藍色或紫色染料可為單體,亦可為聚合物。作為藍色或紫色染料之聚合物係含有由藍色或紫色染料衍生之結構單元之聚合物,可為僅含有由藍色或紫色染料衍生之結構單元之聚合物,亦可為含有由藍色或紫色染料衍生之結構單元與其他結構單元之共聚物(以下有時稱為共聚物(a))。 The blue or purple dye may be a monomer or a polymer. The polymer as a blue or purple dye is a polymer containing a structural unit derived from a blue or purple dye, and may be a polymer containing only a structural unit derived from a blue or purple dye, or a polymer containing a blue Or a copolymer of a purple dye-derived structural unit and another structural unit (hereinafter sometimes referred to as a copolymer (a)).
由藍色或紫色染料衍生之結構單元可具有源自藍色或紫色染料之二價以上之基,亦可具有源自藍色或紫色染料之一價基。源自藍色或紫色染料之基可具有陰離子或陽離子。 The structural unit derived from a blue or violet dye may have a bivalent or higher valence group derived from a blue or violet dye, or may have a monovalent group derived from a blue or violet dye. The radical derived from a blue or violet dye may have an anion or a cation.
作為共聚物(a),可列舉除了由藍色或紫色染料衍生之結構單元以外,含有選自由下述式(1)~(3)所表示之結構單元所組成之群中之至少一者之共聚物。 Examples of the copolymer (a) include, in addition to the structural unit derived from a blue or purple dye, at least one selected from the group consisting of a structural unit represented by the following formulae (1) to (3). Copolymer.
又,共聚物(a)亦可為含有由衍生出下文所述之樹脂(B)之單體衍生之結構單元與由藍色或紫色染料衍生之結構單元的共聚物。 The copolymer (a) may be a copolymer containing a structural unit derived from a monomer derived from the resin (B) described below and a structural unit derived from a blue or purple dye.
[式(1)中,R9及R10分別獨立地表示氫原子、可具有取代基之碳數1~30之烷基、可具有取代基之碳數6~30之芳基、可具有取代基之烷基芳基或該等之組合;m'表示0~5之整數] [In formula (1), R 9 and R 10 each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbons which may have a substituent, an aryl group having 6 to 30 carbons which may have a substituent, and may have a substitution Alkylaryl or a combination of these; m 'represents an integer from 0 to 5]
[式(2)中,R11表示氫原子、可具有取代基之碳數1~30之烷基、可具有取代基之碳數6~30之芳基、可具有取代基之烷基芳基或該等之組合;R12表示可具有取代基之碳數1~30之烷基、可具有取代基之碳數6~30之芳基、-CO-R17-COOH或該等之組合;R17表示可具有取代基之碳數1~30之伸烷基或可具有取代基之碳數1~30之伸烷氧基] [In formula (2), R 11 represents a hydrogen atom, an alkyl group having 1 to 30 carbons which may have a substituent, an aryl group having 6 to 30 carbons which may have a substituent, and an alkylaryl group which may have a substituent Or a combination of these; R 12 represents an alkyl group having 1 to 30 carbons which may have a substituent, an aryl group having 6 to 30 carbons which may have a substituent, -CO-R 17 -COOH, or a combination thereof; R 17 represents an alkylene group having 1 to 30 carbon atoms which may have a substituent or an alkoxy group having 1 to 30 carbon atoms which may have a substituent]
[式(3)中,R13及R14分別獨立地表示氫原子、可具有取代基之碳數1~30之烷基、可具有取代基之碳數6~30之芳基、可具有取代基之烷基芳基或該等之組合;R15表示-COOH或-CONHR18;R18表示可具有取代基之碳數1~30之烷基或可具有取代基之碳數6~30之芳基; R16表示-COOH,R15及R16互相鍵結而形成環] [In formula (3), R 13 and R 14 each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbons which may have a substituent, an aryl group having 6 to 30 carbons which may have a substituent, and may have a substituent Alkyl aryl group or a combination of these; R 15 represents -COOH or -CONHR 18 ; R 18 represents an alkyl group having 1 to 30 carbon atoms which may have a substituent or 6 to 30 carbon atoms which may have a substituent Aryl; R 16 represents -COOH, R 15 and R 16 are bonded to each other to form a ring]
作為由藍色或紫色染料衍生之結構單元以外之結構單元,為含有1個以上羧基之乙烯性不飽和單體,具體而言,可列舉丙烯酸、甲基丙烯酸、順丁烯二酸、伊康酸、反丁烯二酸。 The structural unit other than the structural unit derived from a blue or purple dye is an ethylenically unsaturated monomer containing one or more carboxyl groups. Specific examples include acrylic acid, methacrylic acid, maleic acid, and Ikon. Acid, fumaric acid.
含有1個以上羧基之乙烯性不飽和單體之重量比率相對於形成共聚物(a)之單體之總重量,通常為1~50重量%,較佳為3~40重量%,更佳為5~30重量%。 The weight ratio of the ethylenically unsaturated monomer containing more than one carboxyl group with respect to the total weight of the copolymer (a) forming monomer is usually 1 to 50% by weight, preferably 3 to 40% by weight, and more preferably 5 ~ 30% by weight.
又,亦可含有由上述單體以外之單體衍生之結構單元(Z),具體而言,可列舉:苯乙烯、α-甲基苯乙烯、乙烯基甲苯、乙烯基苄基甲醚等烯基芳香族單體;丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸2-羥基乙酯、甲基丙烯酸2-羥基乙酯、丙烯酸2-羥基丁酯、甲基丙烯酸2-羥基丁酯、丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸環己酯、甲基丙烯酸環己酯、丙烯酸苯酯、甲基丙烯酸苯酯等不飽和羧酸酯化合物;丙烯酸2-胺基乙酯、甲基丙烯酸2-胺基乙酯、丙烯酸2-二甲胺基乙酯、甲基丙烯酸2-二甲胺基乙酯等不飽和羧酸胺基烷基酯化合物;乙酸乙烯酯、苯甲酸乙烯酯等羧酸乙烯酯化合物;丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯等不飽和羧酸縮水甘油酯化合物;丙烯腈、甲基丙烯腈等氰化乙烯化合物;丙烯醯胺、甲基丙烯醯胺等不飽和醯胺化合物;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、及該等之組合。 In addition, it may contain a structural unit (Z) derived from a monomer other than the above monomers. Specific examples include styrene, α-methylstyrene, vinyl toluene, vinyl benzyl methyl ether and the like. Aromatic monomers; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate Ester, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, etc. Unsaturated carboxylic acid ester compounds; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, etc. Acid amino alkyl ester compounds; Vinyl carboxylic acid compounds such as vinyl acetate, vinyl benzoate; Unsaturated carboxylic acid glycidyl compounds such as glycidyl acrylate, glycidyl methacrylate; acrylonitrile, methacrylic acid Vinyl cyanide compounds such as nitrile; C Unsaturated fluorenamine compounds such as ketamine, methacrylamide; N-phenylcis butylene diimide, N-cyclohexyl cis butylene diimide, N-benzyl cis butylene diimide Amine, N-butanediimino-3-maleimide diimide benzoate, N-butanebiimino-4-maleimide diimide butyrate, N-butyl Diamidoimino-6-cis-butenediamidoiminohexanoate, N-butadiamidoimino-3-cisbutenediamidoiminopropionate, N- (9-Acridine (Pyridyl) dicarbonylamidoimine derivatives such as maleimide, and combinations thereof.
作為結構單元(Z),較佳為不飽和羧酸酯化合物、二羰基醯亞胺衍生物及該等之組合,更佳為丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸苄酯、甲基丙烯酸苄酯、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及該等之組合,進而較佳為丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸苄酯、甲基丙烯酸苄酯、N-苄基順丁烯二醯亞胺及該等之組合。 The structural unit (Z) is preferably an unsaturated carboxylic acid ester compound, a dicarbonylammonium imine derivative, and a combination thereof, and more preferably methyl acrylate, methyl methacrylate, ethyl acrylate, or methacrylic acid. Ethyl ester, benzyl acrylate, benzyl methacrylate, N-phenylcis-butenedifluorene imine, N-cyclohexylcis-butenedifluoreneimine, N-benzylcis-butenedifluoreneimine and the Combinations such as methyl acrylate, methyl methacrylate, benzyl acrylate, benzyl methacrylate, N-benzyl maleimide, and combinations thereof are more preferred.
於將不飽和羧酸酯化合物及二羰基醯亞胺衍生物組合時,該等之莫耳比(不飽和羧酸酯化合物:二羰基醯亞胺衍生物)較佳為97:3~3:97,更佳為93:7~50:50,進而較佳為90:10~60:40。 When combining an unsaturated carboxylic acid ester compound and a dicarbonylfluorenimine derivative, the molar ratio of these (unsaturated carboxylic acid ester compound: dicarbonylfluorenimine derivative) is preferably 97: 3 to 3: 97, more preferably 93: 7 to 50:50, and still more preferably 90:10 to 60:40.
共聚物(a)所含之由藍色或紫色染料衍生之結構單元較理想為含有具有乙烯性雙鍵之基之由藍色或紫色染料衍生之結構單元,較佳為選自由由染料(A3)衍生之結構單元、由三芳基甲烷染料(A4)衍生之結構單元、及由式(A7)所表示之染料衍生之結構單元所組成之群中之至少一種,更佳為選自由由三芳基甲烷染料(A4)衍生之結構單元、及由式(A7)所表示之染料衍生之結構單元所組成之群中之至少一種。 The structural unit derived from a blue or purple dye contained in the copolymer (a) is preferably a structural unit derived from a blue or purple dye containing a group having an ethylenic double bond, and is preferably selected from the group consisting of At least one selected from the group consisting of a structural unit derived from a dye (A3), a structural unit derived from a triarylmethane dye (A4), and a structural unit derived from a dye represented by formula (A7), more preferably selected from the group consisting of At least one of a structural unit derived from a triarylmethane dye (A4) and a structural unit derived from a dye represented by the formula (A7).
作為由染料(A3)衍生之結構單元,較佳為由含有具有乙烯性雙鍵之基之式(1-45)所表示之化合物~式(1-47)所表示之化合物衍生之各結構單元。 As a cause The structural unit derived from the dye (A3) is preferably each structural unit derived from a compound represented by the formula (1-45) containing a group having an ethylenic double bond to a compound represented by the formula (1-47).
作為由三芳基甲烷染料(A4)衍生之結構單元,較佳為由含有具有乙烯性雙鍵之基之式(2b-1)所表示之化合物~式(2b-19)所表示之化合物衍生之各結構單元。 As the structural unit derived from a triarylmethane dye (A4), it is preferably derived from a compound represented by the formula (2b-1) containing a group having an ethylenic double bond to a compound represented by the formula (2b-19) Each structural unit.
作為由式(A7)所表示之染料衍生之結構單元,較佳為R21A或R22A為經含有丙烯醯基或甲基丙烯醯基之基取代之胺基之式(A7)所表示之染料,更佳為由式(A-I-a15)所表示之化合物衍生之結構單元。 As the structural unit derived from the dye represented by the formula (A7), it is preferable that R 21A or R 22A is a dye represented by the formula (A7) substituted with an amine group containing a propylene fluorenyl group or a methacryl fluorenyl group. , More preferably a structural unit derived from a compound represented by the formula (AI-a15).
於共聚物(a)中,較佳為源自各物質之結構單元之比率於構成共聚物(a)之全部結構單元中,由含有1個以上羧基之乙烯性不飽和單體(具體而言,丙烯酸、甲基丙烯酸、順丁烯二酸、伊康酸、反丁烯二酸)衍生之結構單元:20~50莫耳%(較佳為25~45莫耳%),由藍色或紫色染料衍生之結構單元:0.1~25莫耳%(較佳為0.5~20莫耳%),結構單元(Z);25~79.9莫耳%(較佳為35~74.5莫耳%)。 In the copolymer (a), it is preferable that the ratio of the structural units derived from each substance is from an ethylenically unsaturated monomer (specifically, one or more carboxyl groups) in all the structural units constituting the copolymer (a). , Acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid) derived structural units: 20-50 mol% (preferably 25-45 mol%), blue or Structural units derived from purple dye: 0.1 to 25 mole% (preferably 0.5 to 20 mole%), structural unit (Z); 25 to 79.9 mole% (preferably 35 to 74.5 mole%).
染料(A2)之含量相對於化合物(I)100質量份,通常為80~10000質量份,較佳為80~7500質量份,更佳為80~1000質量份,進而較佳為80~600質量份,進而更佳為80~300質量份。 The content of the dye (A2) is usually 80 to 10,000 parts by mass, preferably 80 to 7,500 parts by mass, more preferably 80 to 1,000 parts by mass, and still more preferably 80 to 600 parts by mass relative to 100 parts by mass of the compound (I). It is more preferably 80 to 300 parts by mass.
作為染料(Ac),可無特別限定地使用公知之染料。 As the dye (Ac), a known dye can be used without particular limitation.
作為顏料(Ad),可無特別限定地使用公知之顏料,例如,可列舉色指數(The Society of Dyers and Colourists出版)中被分類為顏料之顏料。 As the pigment (Ad), known pigments can be used without particular limitation, and examples thereof include pigments classified as pigments in the color index (published by The Society of Dyers and Colourists).
作為顏料,可列舉:C.I.顏料紫1、19、23、29、32、36、38等紫色顏料等。 Examples of the pigment include purple pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, and 38.
著色劑(A)較佳為含有下述所記載之組合之著色劑。 The colorant (A) is preferably a colorant containing a combination described below.
(1)藍色顏料(A1)、化合物(I)及藍色或紫色染料(A2) (1) Blue pigment (A1), compound (I) and blue or purple dye (A2)
(2)藍色顏料(A1)、化合物(I)、及作為聚合物之三芳基甲烷染料(A4) (2) Blue pigment (A1), compound (I), and triarylmethane dye (A4) as polymer
(3)藍色顏料(A1)、化合物(I)、以及選自由式(A7)所表示之染料及含有由上述式(A7)所表示之染料衍生之結構單元之聚合物所組成之群中之至少一種染料 (3) The blue pigment (A1), the compound (I), and a group selected from the group consisting of a dye represented by the formula (A7) and a polymer containing a structural unit derived from the dye represented by the above formula (A7) At least one dye
(4)藍色顏料(A1)、化合物(I)、藍色或紫色染料(A2)及紫色顏料 (Ad) (4) Blue pigment (A1), compound (I), blue or purple dye (A2) and purple pigment (Ad)
著色劑(A)之含量相對於固形物成分之總量,較佳為5~60質量%,更佳為8~55質量%,進而較佳為10~50質量%。若著色劑(A)之含量處於上述範圍,則製成彩色濾光片時之色濃度充分,且可於組合物中含有所需量之樹脂(B)或聚合性化合物(C),因此可形成機械強度充分之圖案。此處,本說明書中之所謂「固形物成分之總量」係指自著色硬化性樹脂組合物之總量中去除溶劑之含量而得之量。固形物成分之總量及相對於其之各成分之含量例如可藉由液相層析法或氣相層析法等公知之分析方法進行測定。 The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and still more preferably 10 to 50% by mass with respect to the total amount of the solid components. If the content of the colorant (A) is in the above range, the color density when the color filter is made is sufficient, and a required amount of the resin (B) or the polymerizable compound (C) can be contained in the composition. Form a pattern with sufficient mechanical strength. Herein, the “total amount of solid components” in the present specification refers to an amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of the solid component and the content of each component relative thereto can be measured, for example, by a known analysis 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。作為樹脂(B),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. Examples of the resin (B) 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之環狀醚結構及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)、(b)及可與(a)共聚之單體(c)(其中,不同於(a)及(b))(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)反應而得之樹脂;樹脂[K5]使(b)與(c)之共聚物與(a)反應而得之樹脂;樹脂[K6]使(b)與(c)之共聚物與(a)反應並進一步與羧酸酐反應而得之樹脂。 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 having 2 to 4 carbon atoms Copolymer of monomer (b) (hereinafter sometimes referred to as "(b)") with structure and ethylenically unsaturated bonds; resin [K2] (a), (b) and monomers copolymerizable with (a) (c) (wherein they are different from (a) and (b)) (hereinafter sometimes referred to as "(c)"); resins [K3] (a) and (c) copolymers; resins [K4 ] Resin obtained by reacting (a) and (c) copolymer with (b); Resin [K5] Resin obtained by reacting (b) and (c) copolymer with (a); Resin [K6 ] A resin obtained by reacting the copolymer of (b) and (c) with (a) and further reacting with a carboxylic anhydride.
作為(a),具體而言,可列舉:例如,丙烯酸、甲基丙烯酸、丁烯酸、鄰乙烯基苯甲酸、間乙烯基苯甲酸、對乙烯基苯甲酸等不飽和單羧酸類;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類;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類;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類酐;丁二酸單[2-(甲基)丙烯醯氧基乙酯]、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙酯]等二價以上之多元羧酸之不飽和單[(甲基)丙烯醯氧基烷基]酯類;如α-(羥基甲基)丙烯酸般於同一分子中含有羥基及羧基之不飽和丙烯酸酯類等。 Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, butenoic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; cis-butyl Adipic acid, fumaric acid, methyl maleic acid, methyl fumaric acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3, 4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid, etc. Saturated dicarboxylic acids Ene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methyl Dicyclo [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 -Ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, methyl maleic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride Unsaturated dicarboxylic anhydrides such as acid anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] heptan-2-ene anhydride; succinate mono [2- (methyl) Unsaturated mono [(meth) acryloxyalkyl groups of polyvalent carboxylic acids such as propylene ethoxyethyl] and phthalic acid mono [2- (meth) acryl ethoxyethyl] ] Esters; unsaturated acrylic esters containing hydroxyl and carboxyl groups in the same molecule, such as α- (hydroxymethyl) acrylic acid.
該等中,就共聚合反應性之方面或所獲得之樹脂於鹼性水溶液中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, etc. are preferable in terms of copolymerization reactivity or the solubility of the obtained resin in an alkaline aqueous solution.
(b)例如係指具有碳數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) For example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an ethylene oxide ring, an oxetane ring, and a tetrahydrofuran ring) and ethylenic unsaturation Bondable polymerizable compound. (b) A monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acrylic fluorenyloxy group is preferred.
再者,於本說明書中,所謂「(甲基)丙烯酸」表示選自由丙烯酸及甲基丙烯酸所組成之群中之至少一種。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等記法亦具有同樣之含義。 In addition, in this specification, "(meth) acrylic acid" means at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. Notations such as "(meth) acrylfluorenyl" and "(meth) acrylate" have the same meaning.
作為(b),例如可列舉:具有環氧乙烷基與乙烯性不飽和鍵之單體(a1)(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。 Examples of (b) include a monomer (a1) (hereinafter sometimes referred to as "(b1)") having an ethylene oxide group and an ethylenically unsaturated bond, and an oxetanyl group and an ethylenically unsaturated bond. A monomer (b2) of a saturated bond (hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), and the like.
作為(b1),例如可列舉:具有直鏈狀或支鏈狀之脂肪族不飽和烴被環氧化之結構之單體(b1-1)(以下有時稱為「(b1-1)」)、具有脂環式不飽和烴被環氧化之結構之單體(b1-2)(以下有時稱為「(b1-2)」)。 Examples of (b1) include a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)") A monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").
作為(b1-1),可列舉:(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸β-甲基縮水甘油酯、(甲基)丙烯酸β-乙基縮水甘油酯、縮水甘油基乙烯醚、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、α-甲基鄰乙烯基苄基縮水甘油醚、α-甲基間乙烯基苄基縮水甘油醚、α-甲基對乙烯基苄基縮水甘油醚、2,3-雙(縮水甘油氧基甲基)苯乙烯、2,4-雙(縮水甘油氧基甲基)苯乙烯、2,5-雙(縮水甘油氧基甲基)苯乙烯、2,6-雙(縮水甘油氧基甲基)苯乙烯、2,3,4-三(縮水甘油氧基甲基)苯乙烯、2,3,5-三(縮水甘油氧基甲基)苯乙烯、2,3,6-三(縮水甘油氧基甲基)苯乙烯、3,4,5-三(縮水甘油氧基甲基)苯乙烯、2,4,6-三(縮水甘油氧基甲基)苯乙烯等。 Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and glycidyl vinyl ether. , O-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl o-vinyl benzyl glycidyl ether, α-methyl m-vinyl benzyl Glycidyl ether, α-methyl p-vinyl benzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2 , 5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2 , 3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) Styrene, 2,4,6-tris (glycidyloxymethyl) styrene, etc.
作為(b1-2),可列舉:一氧化乙烯基環己烯、1,2-環氧-4-乙烯基環己烷(例如,Celloxide 2000,Daicel股份有限公司製造)、(甲基)丙烯酸3,4-環氧環己基甲酯(例如,Cyclomer A400,Daicel股份有限公司製造)、(甲基)丙烯酸3,4-環氧環己基甲酯(例如,Cyclomer M100,Daicel股份有限公司製造)、式(I)所表示之化合物及式(II)所表示之化合物等。 Examples of (b1-2) include vinyl cyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000, manufactured by Daicel Co., Ltd.), and (meth) acrylic acid 3,4-epoxycyclohexyl methyl ester (for example, Cyclomer A400, manufactured by Daicel Co., Ltd.), 3,4-epoxy cyclohexyl methyl (meth) acrylate (for example, Cyclomer M100, manufactured by Daicel Co., Ltd.) A compound represented by formula (I), a compound represented by formula (II), and the like.
[式(I)及式(II)中,Ra及Rb表示氫原子、或碳數1~4之烷基,該烷基所含之氫原子可經羥基取代;Xa及Xb表示單鍵、*-Rc-、*-Rc-O-、*-Rc-S-或*-Rc-NH-;Rc表示碳數1~6之烷二基;*表示與O之鍵結鍵] [In formula (I) and formula (II), R a and R b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group; X a and X b represent a single bond, * - R c -, * - R c -O -, * - R c -S- or * -R c -NH-; R c represents an alkanediyl group having a carbon number of 1 to 6; and * denotes O Key-to-key]
作為碳數1~4之烷基,可列舉:甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基等。 Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, and third butyl.
作為氫原子經羥基取代之烷基,可列舉:羥甲基、1-羥基乙基、2-羥基乙基、1-羥基丙基、2-羥基丙基、3-羥基丙基、1-羥基-1-甲基乙基、2-羥基-1-甲基乙基、1-羥基丁基、2-羥基丁基、3-羥基丁基、4-羥基丁基等。 Examples of the alkyl group having a hydrogen atom substituted with a hydroxyl group include methylol, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, and 1-hydroxyl. 1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.
作為Ra及Rb,較佳可列舉氫原子、甲基、羥甲基、1-羥基乙基、2-羥基乙基,更佳可列舉氫原子、甲基。 Examples of R a and R b include a hydrogen atom, a methyl group, a methylol group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.
作為烷二基,可列舉:亞甲基、伸乙基、丙烷-1,2-二基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基等。 Examples of the alkanediyl group include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane-1,5. -Diyl, hexane-1,6-diyl and the like.
作為Xa及Xb,較佳可列舉單鍵、亞甲基、伸乙基、*-CH2-O-及*-CH2CH2-O-,更佳可列舉單鍵、*-CH2CH2-O-(*表示與O之鍵結鍵)。 As X a and X b , a single bond, methylene, ethylidene, * -CH 2 -O- and * -CH 2 CH 2 -O- are preferred, and a single bond, * -CH is more preferred. 2 CH 2 -O- (* indicates a bond with O).
作為式(I)所表示之化合物,可列舉式(I-1)~式(I-15)所表示之化合物等。較佳可列舉式(I-1)、式(I-3)、式(I-5)、式(I-7)、式(I-9)或式(I-11)~式(I-15)所表示之化合物。更佳可列舉式(I-1)、式(I-7)、式(I-9)或式(I-15)所表示之化合物。 Examples of the compound represented by the formula (I) include compounds represented by the formulae (I-1) to (I-15). Preferred examples include formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), or formula (I-11) to formula (I- 15) The compound represented by More preferred examples include compounds represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).
作為式(II)所表示之化合物,可列舉式(II-1)~式(II-15)所表示之化合物等。較佳可列舉式(II-1)、式(II-3)、式(II-5)、式(II-7)、式(II-9)或式(II-11)~式(II-15)所表示之化合物。更佳可列舉式(II-1)、式(II-7)、式(II-9)或式(II-15)所表示之化合物。 Examples of the compound represented by formula (II) include compounds represented by formula (II-1) to formula (II-15). Preferred examples include formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), or formula (II-11) to formula (II- 15) The compound represented by More preferred examples include compounds represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15).
式(I)所表示之化合物及式(II)所表示之化合物可分別單獨使用。又,該等可以任意比率混合。於混合之情形時,其混合比率以莫耳比計,較佳為式(I):式(II)為5:95~95:5,更佳為10:90~90:10,進而較佳為20:80~80:20。 The compound represented by formula (I) and the compound represented by formula (II) can be used individually. These may be mixed at any ratio. In the case of mixing, the mixing ratio is measured in mole ratio, preferably formula (I): formula (II) is 5:95 to 95: 5, more preferably 10:90 to 90:10, and further preferably It is 20: 80 ~ 80: 20.
作為(b2),更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 more preferable. Examples of (b2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3- Ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-propenemethyloxetane, 3-methyl-3-methacryloxy Ethylethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3- Ethyl-3-methacryloxyethyloxetane, 3-ethyl-3-propenyloxyethyloxetane, and the like.
作為(b3),更佳為具有四氫呋喃基與(甲基)丙烯醯氧基之單體。作為(b3),具體而言,可列舉丙烯酸四氫糠酯(例如,Viscoat V # 150,大阪有機化學工業股份有限公司製造)、甲基丙烯酸四氫糠酯等。 As (b3), a monomer having a tetrahydrofuranyl group and a (meth) acryloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.
作為(b),就可進一步提高所獲得之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)。進而,就著色硬化性樹脂組合物之保存穩定性優異之方面而言,更佳為(b1-2)。 As (b), (b1) is preferable in terms of further improving the reliability such as heat resistance and chemical resistance of the obtained color filter. Furthermore, (b1-2) is more preferable at the point which is excellent in the storage stability of a coloring curable resin composition.
作為(c),例如可列舉:(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]癸烷-8-酯(於該技術領域中,作為慣用名而稱為「(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-酯(於該技術領域中,作為慣用名而稱為「(甲基)丙烯酸二環戊烯酯」)、(甲基)丙烯酸二環戊氧基乙酯、(甲基)丙烯酸異基酯、(甲基)丙烯酸金剛烷基酯、(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)丙烯酸酯類;(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)丙烯酸酯類;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類;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類;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 Tributyl, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic ring Amyl ester, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decane-8-ester (in this technology In the field, it is called "dicyclopentyl (meth) acrylate" as a common name; it is sometimes called "tricyclodecyl (meth) acrylate"), and tricyclic (meth) acrylate [5.2. 1.0 2,6 ] decene-8-ester (known in the technical field as "dicyclopentenyl (meth) acrylate"), dicyclopentyloxyethyl (meth) acrylate (Meth) acrylic acid Ester, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (meth) ) (Meth) acrylates such as benzyl acrylate; 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate (meth) acrylates containing hydroxyl; maleic acid Dicarboxylic acid diesters such as diethyl acid diethyl fumarate, diethyl fumarate, diethyl iconate; bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] heptane -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] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5 , 6-bis (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethyl Oxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] heptane- 2-ene, 5-hydroxymethyl-5- Methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2 -Ene, 5-phenoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5,6-bis (third butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6- Bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and other bicyclic unsaturated compounds; N-phenylcis-butene difluorene imine, N-cyclohexyl-cis butene difluorene imine, N-benzyl cis-butene difluorene imine, N-butyridinyl imino-3-methylene imine benzoate, N-butyridinyl imino-4-maleimide Succinimide butyrate, N-succinimide imino-6-cis butene succinimide hexanoate, N-succinimide imino-3-succinimide imidate propionate , N- (9-acridyl) maleimide derivatives such as dibutylene imine; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, ethylene Toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene Diene, 2,3-dimethyl-1,3-butadiene, etc.
該等中,就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、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-烯等。 Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyltoluene, N-phenylcis butylenediimide, and N-cyclohexylcisbutenediimide are preferred. , N-benzylcis-butenedifluoreneimine, bicyclic [2.2.1] hept-2-ene, and the like.
於樹脂[K1]中,較佳為源自各物質之結構單元之比率於構成樹脂[K1]之全部結構單元中,源自(a)之結構單元:2~60莫耳%,源自(b)之結構單元:40~98莫耳%; 更佳為源自(a)之結構單元:10~50莫耳%,源自(b)之結構單元:50~90莫耳%。 In the resin [K1], the ratio of the structural units derived from each substance is preferred. Among all the structural units constituting the resin [K1], the structural units derived from (a): 2 to 60 mol%, derived from ( b) Structural unit: 40 ~ 98 mole%; More preferably, the structural unit derived from (a): 10-50 mol%, and the structural unit derived from (b): 50-90 mol%.
若樹脂[K1]之結構單元之比率處於上述範圍,則有著色硬化性樹脂組合物之保存穩定性、形成著色圖案時之顯影性、及所獲得之彩色濾光片之耐溶劑性優異之傾向。 When the ratio of the structural unit of the resin [K1] is in the above range, there is a tendency that the storage stability of the colored curable resin composition, the developability when a colored pattern is formed, and the solvent resistance of the obtained color filter are excellent. .
樹脂[K1]例如可以文獻「高分子合成之實驗法」(大津隆行著,發行所化學同人(股),第1版第1次印刷,1972年3月1日發行)中記載之方法及該文獻中記載之引用文獻為參考進行製造。 The resin [K1] can be, for example, the method described in the document "Experimental Method of Polymer Synthesis" (by Otsu Takayuki, Issu Chemical Co., Ltd., 1st edition, first printing, March 1, 1972) and the method The citations described in the literature are used as reference for production.
具體而言,可列舉如下方法:將特定量之(a)及(b)、聚合起始劑及溶劑等加入至反應容器中,例如藉由氮氣置換氧氣,藉此製成脫氧環境,一面攪拌,一面加熱及保溫。再者,此處所使用之聚合起始劑及溶劑等並無特別限定,可使用該領域通常使用者。例如,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,只要為溶解各單體者即可,可列舉下文所述之溶劑等作為本發明之著色硬化性樹脂組合物之溶劑(E)。 Specifically, the following methods can be enumerated: a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are added to a reaction container, and for example, nitrogen is substituted for oxygen to prepare a deoxidizing environment, while stirring , While heating and holding. The polymerization initiator, solvent, and the like used herein are not particularly limited, and can be used by ordinary users in the field. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or organic compounds. As a solvent, any oxide (such as benzamidine peroxide) may be used as long as it dissolves each monomer. The solvent (E) described below is used as the solvent for the colored curable resin composition of the present invention.
再者,所獲得之共聚物可直接使用反應後之溶液,亦可使用經濃縮或稀釋之溶液,亦可使用藉由再沈澱等方法以固體(粉體)之形式取出者。尤其是於該聚合時,藉由使用本發明之著色硬化性樹脂組合物所含之溶劑作為溶劑,而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,因此可簡化本發明之著色硬化性樹脂組合物之製造步驟。 Furthermore, the obtained copolymer may be directly used as a solution after the reaction, a concentrated or diluted solution may also be used, or a solid (powder) may be taken out by a method such as reprecipitation. In particular, during the polymerization, by using the solvent contained in the colored curable resin composition of the present invention as a solvent, the solution after the reaction can be directly used for the preparation of the colored curable resin composition of the present invention. The manufacturing steps of the colored curable resin composition of the present invention are simplified.
於樹脂[K2]中,較佳為源自各物質之結構單元之比率於構成樹脂[K2]之全部結構單元中,源自(a)之結構單元:2~45莫耳%, 源自(b)之結構單元:2~95莫耳%,源自(c)之結構單元:1~65莫耳%;更佳為源自(a)之結構單元:5~40莫耳%,源自(b)之結構單元:5~80莫耳%,源自(c)之結構單元:5~60莫耳%。 In the resin [K2], the ratio of the structural unit derived from each substance is preferred. Among all the structural units constituting the resin [K2], the structural unit derived from (a): 2 to 45 mole%, Structural unit derived from (b): 2 ~ 95 mole%, structural unit derived from (c): 1 ~ 65 mole%; more preferably structural unit derived from (a): 5 ~ 40 mole% , Structural unit derived from (b): 5 ~ 80 mole%, Structural unit derived from (c): 5 ~ 60 mole%.
若樹脂[K2]之結構單元之比率處於上述範圍,則有著色硬化性樹脂組合物之保存穩定性、形成著色圖案時之顯影性、以及所獲得之彩色濾光片之耐溶劑性、耐熱性及機械強度優異之傾向。 When the ratio of the structural unit of the resin [K2] is in the above range, there are storage stability of the colored curable resin composition, developability when a colored pattern is formed, and solvent resistance and heat resistance of the obtained color filter And tends to be excellent in mechanical strength.
樹脂[K2]例如可與作為樹脂[K1]之製造方法而記載之方法同樣地製造。 The resin [K2] can be produced in the same manner as the method described as the method for producing the resin [K1], for example.
於樹脂[K3]中,較佳為源自各物質之結構單元之比率於構成樹脂[K3]之全部結構單元中,源自(a)之結構單元:2~60莫耳%,源自(c)之結構單元:40~98莫耳%;更佳為源自(a)之結構單元:10~50莫耳%,源自(c)之結構單元:50~90莫耳%。 In the resin [K3], the ratio of the structural unit derived from each substance is preferred. Among all the structural units constituting the resin [K3], the structural unit derived from (a): 2 to 60 mol%, derived from ( The structural unit of c): 40 ~ 98 mol%; more preferably, the structural unit derived from (a): 10 ~ 50 mol%, and the structural unit derived from (c): 50 ~ 90 mol%.
樹脂[K3]例如可與作為樹脂[K1]之製造方法而記載之方法同樣地製造。 The resin [K3] can be produced in the same manner as the method described as the method for producing the resin [K1], for example.
樹脂[K4]可藉由獲得(a)與(c)之共聚物,並對(a)所具有之羧酸及/或羧酸酐加成(b)所具有之碳數2~4之環狀醚而製造。 The resin [K4] can obtain a copolymer of (a) and (c), and add a cyclic carbon number of 2 to 4 to the carboxylic acid and / or carboxylic anhydride added in (a) Ether.
首先,與作為樹脂[K1]之製造方法而記載之方法同樣地製造(a)與(c)之共聚物。於該情形時,源自各物質之結構單元之比率較佳為與樹脂[K3]中所列舉者相同之比率。 First, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of the resin [K1]. In this case, the ratio of the structural unit derived from each substance is preferably the same as that listed in the resin [K3].
其次,使上述共聚物中源自(a)之羧酸及/或羧酸酐之一部分與(b) 所具有之碳數2~4之環狀醚反應。 Next, a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the above-mentioned copolymer and (b) It has a cyclic ether with 2 to 4 carbon atoms.
於製造(a)與(c)之共聚物後,將燒瓶內環境由氮氣置換為空氣,於燒瓶內加入(b)、羧酸或羧酸酐及環狀醚之反應觸媒(例如三(二甲胺基甲基)苯酚等)及聚合抑制劑(例如對苯二酚等)等,例如於60~130℃下反應1~10小時,藉此可製造樹脂[K4]。 After manufacturing the copolymer of (a) and (c), the environment in the flask is replaced by nitrogen to air, and (b), a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, three (two) Methylaminomethyl) phenol, etc.) and polymerization inhibitors (such as hydroquinone, etc.), for example, can be produced by reacting at 60 to 130 ° C for 1 to 10 hours, [K4].
(b)之使用量相對於(a)100莫耳,較佳為5~80莫耳,更佳為10~75莫耳。藉由設為該範圍,有著色硬化性樹脂組合物之保存穩定性、形成圖案時之顯影性、以及所獲得之圖案之耐溶劑性、耐熱性、機械強度及感度之平衡變得良好之傾向。就環狀醚之反應性較高、不易殘存未反應之(b)之方面而言,作為用於樹脂[K4]之(b),較佳為(b1),進而較佳為(b1-1)。 The amount of (b) used is preferably 5 to 80 mols, and more preferably 10 to 75 mols relative to (a) 100 mols. By setting it as this range, there exists a tendency for the balance of the storage stability of a coloring curable resin composition, the developability at the time of pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern to become favorable. . In terms of the high reactivity of the cyclic ether and the difficulty of remaining unreacted (b), the (b) used for the resin [K4] is preferably (b1), and more preferably (b1-1) ).
上述反應觸媒之使用量相對於(a)、(b)及(c)之合計量100質量份,較佳為0.001~5質量份。上述聚合抑制劑之使用量相對於(a)、(b)及(c)之合計量100質量份,較佳為0.001~5質量份。 The used amount of the reaction catalyst is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b), and (c). The used amount of the polymerization inhibitor is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b), and (c).
加入方法、反應溫度及時間等反應條件可考慮製造設備或聚合產生之放熱量等而適當調整。再者,與聚合條件同樣地,可考慮製造設備或聚合產生之放熱量等而適當調整加入方法或反應溫度。 The reaction conditions such as the addition method, reaction temperature, and time can be appropriately adjusted in consideration of the exothermic heat generated by the manufacturing equipment or polymerization. In addition, similarly to the polymerization conditions, the addition method or reaction temperature can be appropriately adjusted in consideration of the exothermic heat generated by the manufacturing equipment or polymerization.
樹脂[K5]於第一階段,以與上述之樹脂[K1]之製造方法同樣之方式,獲得(b)與(c)之共聚物。與上述同樣地,所獲得之共聚物可直接使用反應後之溶液,亦可使用經濃縮或稀釋之溶液,亦可使用藉由再沈澱等方法以固體(粉體)之形式取出者。 Resin [K5] In the first stage, a copolymer of (b) and (c) was obtained in the same manner as the method for producing the resin [K1] described above. In the same manner as above, the obtained copolymer may be used directly after the reaction, a concentrated or diluted solution may be used, or a solid (powder) may be taken out by a method such as reprecipitation.
源自(b)及(c)之結構單元之比率相對於構成上述共聚物之全部結構單元之合計莫耳數,較佳為分別為:源自(b)之結構單元:5~95莫耳%,源自(c)之結構單元:5~95莫耳%;更佳為分別為: 源自(b)之結構單元:10~90莫耳%,源自(c)之結構單元:10~90莫耳%。 The ratio of the structural units derived from (b) and (c) to the total number of moles of all the structural units constituting the above copolymer is preferably: structural units derived from (b): 5 to 95 moles %, The structural unit derived from (c): 5 ~ 95 mole%; more preferably, they are: Structural unit derived from (b): 10 ~ 90 mole%, structural unit derived from (c): 10 ~ 90 mole%.
進而,於與樹脂[K4]之製造方法同樣之條件下,使(b)與(c)之共聚物所具有之源自(b)之環狀醚與(a)所具有之羧酸或羧酸酐反應,藉此可獲得樹脂[K5]。 Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) and the carboxylic acid or carboxylic acid possessed from (a) which the copolymer of (b) and (c) have The acid anhydride is reacted to obtain a resin [K5].
與上述共聚物反應之(a)之使用量相對於(b)100莫耳,較佳為5~80莫耳。就環狀醚之反應性較高、不易殘存未反應之(b)之方面而言,作為用於樹脂[K5]之(b),較佳為(b1),進而較佳為(b1-1)。 The amount of (a) used in the reaction with the copolymer is preferably 5 to 80 moles relative to (b) 100 moles. In terms of high reactivity of the cyclic ether and the difficulty of remaining unreacted (b), the (b) used for the resin [K5] is preferably (b1), and more preferably (b1-1) ).
樹脂[K6]係使樹脂[K5]進一步與羧酸酐反應而得之樹脂。使藉由環狀醚與羧酸或羧酸酐之反應產生之羥基與羧酸酐反應。 The resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic anhydride. The hydroxy group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride is reacted with a carboxylic acid anhydride.
作為羧酸酐,可列舉: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(雙環庚烯二甲酸酐)等。羧酸酐之使用量相對於(a)之使用量1莫耳,較佳為0.5~1莫耳。 Examples of the carboxylic acid anhydride include maleic anhydride, methyl maleic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5 , 6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] Hept-2-enoic anhydride (bicycloheptene dicarboxylic anhydride) and the like. The amount of carboxylic acid anhydride used is 1 mole, preferably 0.5 to 1 mole, relative to the amount of (a).
作為樹脂(B),具體而言,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、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、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、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)丙烯酸共聚物等樹脂[K3];對(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物加成(甲基)丙烯酸縮水甘油酯而成之樹脂、對(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸共聚物加成(甲基)丙烯酸縮水甘油酯而成之樹脂、對(甲基)丙烯酸三環癸酯/(甲基)丙烯 酸苄酯/(甲基)丙烯酸共聚物加成(甲基)丙烯酸縮水甘油酯而成之樹脂等樹脂[K4];使(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)丙烯酸反應而得之樹脂、使(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)丙烯酸反應而得之樹脂等樹脂[K5];使(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,使所獲得之樹脂進一步與四氫鄰苯二甲酸酐反應而得之樹脂等樹脂[K6]等。 Specific examples of the resin (B) include 3,4-epoxycyclohexyl methyl (meth) acrylate / (meth) acrylic acid copolymer, and 3,4-epoxy tricycloacrylic acid [5.2.1.0 2,6 ] resins such as decyl ester / (meth) acrylic copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, (meth) acrylic acid Glycidyl ester / styrene / (meth) acrylic acid copolymer, 3,4-epoxy tricyclo [5.2.1.0 2,6 ] decyl ester / (meth) acrylic acid / N-cyclohexyl maleic acid Resins such as imine copolymer, 3-methyl-3- (meth) acryloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate Ester / (meth) acrylic copolymer, styrene / (meth) acrylic copolymer and other resins [K3]; benzyl (meth) acrylate / (meth) acrylic copolymer addition (meth) acrylic acid shrinks Glyceryl ester resin, Tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer added with glycidyl (meth) acrylate, Tri (decyl) (meth) acrylic acid Cyclodecyl ester / benzyl (meth) acrylate / (meth) acrylic acid copolymer Resin and other resins [K4] obtained by adding glycidyl (meth) acrylate; reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid Resin and other resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate with (meth) acrylic acid [K5]; ) Tricyclodecyl acrylate / glycidyl (meth) acrylate copolymer reacts with (meth) acrylic acid to make the obtained resin further react with tetrahydrophthalic anhydride and other resins [K6] Wait.
其中,作為樹脂(B),較佳為樹脂[K1]及樹脂[K2]。 Among them, the resin (B) is preferably resin [K1] and resin [K2].
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5,000~35,000、5,000~30,000。若分子量處於上述範圍,則有如下傾向:塗膜硬度提高,殘膜率亦較高,未曝光部相對於顯影液之溶解性良好,著色圖案之解像度提高。 The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 35,000 and 5,000 to 30,000. When the molecular weight is in the above range, the coating film hardness is increased, the residual film ratio is also high, the solubility of the unexposed portion with respect to the developing solution is good, and the resolution of the colored pattern is improved.
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 1.1 to 6, more preferably 1.2 to 4.
樹脂(B)之固形物成分酸值較佳為50~170mg-KOH/g,更佳為60~150,進而較佳為70~135mg-KOH/g。此處,酸值係作為中和樹脂(B)1g所必需之氫氧化鉀之量(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出。 The acid value of the solid content of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150, and even more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be obtained by, for example, 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%。 The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass with respect to the total amount of the solid components.
聚合性化合物(C)係可藉由自聚合起始劑(D)中產生之活性自由基及/或酸而聚合之化合物,例如,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 that can be polymerized by living radicals and / or acids generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and the like. A (meth) acrylate compound is preferable.
其中,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。 Among them, the polymerizable compound (C) is preferably one having three or more ethylenically unsaturated bonds. Polymerizable compound. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylic acid. Ester, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nine (meth) acrylate Ester, tris (2- (meth) acryloxyethyl isocyanurate), ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, Propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified pentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (methyl) ) Acrylate, etc.
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 preferred.
聚合性化合物(C)之重量平均分子量較佳為150以上且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, and 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%。若聚合性化合物(C)之含量處於上述範圍內,則有形成著色圖案時之殘膜率及彩色濾光片之耐化學品性提高之傾向。 The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass with respect to the total amount of the solid components. When the content of the polymerizable compound (C) is within the above range, the residual film rate at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.
聚合起始劑(D)只要為藉由光或熱之作用產生活性自由基、酸等而可使聚合開始之化合物,則無特別限定,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 that can initiate polymerization by 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),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 polymerization initiator of at least one of the group consisting of a compound, a fluorenylphosphine oxide compound, an O-fluorenyl oxime compound, and a biimidazole compound, more preferably a polymerization initiator containing an O-fluorenyl oxime compound.
作為O-醯基肟化合物,例如可列舉: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 OXE01、OXE02(以上為BASF公司製造)、N-1919(ADEKA公司製造)等市售品。O-醯基肟化合物較佳為選自由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。若為該等O-醯基肟化合物,則有獲得高亮度之彩色濾光片之傾向。 Examples of the O-fluorenyl oxime compound include N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine and N-benzyloxy 1- (4-phenylthiophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylthiophenyl) -3-ring Amylpropane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl] Ethane-1-imine, N-ethoxyl-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxane Amylmethyloxy) benzamidine} -9H-carbazol-3-yl] ethane-1-imine, N-acetamyloxy-1- [9-ethyl-6- (2- Methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzyloxy-1- [9-ethyl-6- (2 -Methylbenzylidene) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (the above are manufactured by BASF), and N-1919 (made by ADEKA) can also be used. The O-fluorenyl oxime compound is preferably selected from the group consisting of N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, and N-benzyloxy 1- (4-phenylthiophenyl) octane-1-one-2-imine and N-benzyloxy-1- (4-phenylthiophenyl) -3-cyclopentane At least one of the group consisting of propylpropane-1-one-2-imine, more preferably N-benzyloxy-1- (4-phenylthiophenyl) octan-1-one- 2-imine. In the case of these O-fluorenyl oxime compounds, a color filter with high brightness tends to be obtained.
上述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、2-二甲胺基-1-(4-啉基苯基)-2-苄基丁烷-1-酮、2-(二甲胺基)-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-酮之低聚物、α,α-二乙氧基苯乙酮、苯偶醯二甲基縮酮等。亦可使用Irgacure 369、907、379(以上為BASF公司製造)等市售品。 Examples of the alkyl phenone compound include 2-methyl-2- Phenyl-1- (4-methylthiophenyl) propane-1-one, 2-dimethylamino-1- (4- Phenylphenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4- Phenyl) phenyl] butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxy Ethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one oligomer Compounds, α, α-diethoxyacetophenone, benzophenone dimethyl ketal, etc. Commercial products such as Irgacure 369, 907, and 379 (above manufactured by BASF) can also be used.
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 Compounds include: 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-tri , 2,4-bis (trichloromethyl) -6-sunfloweryl-1,3,5-tri , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris 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。亦可使用Irgacure(註冊商標)819(BASF公司製造)等市售品。 Examples of the fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide and the like. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF) can also be used.
作為聯咪唑化合物,例如可列舉: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(例如參照日本專利特開平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(例如參照日本專利特公昭48-38403號公報、日本專利特開昭62-174204號公報等)、4,4'5,5'-位之苯基被取代為烷氧羰基之咪唑化合物(例如參照日本專利特開平7-10913號公報等)等。 Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2, 2' -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'- Tetrakis (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 (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204 and the like), an imidazole compound in which a 4,4-'5,5'-phenyl group is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Laid-Open No. 7-10913).
進而,作為聚合起始劑(D),可列舉:安息香、安息香甲醚、安息香乙醚、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'-甲基二苯基硫醚、3,3',4,4'-四(第三丁基過氧基羰基)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、苄基、苯基乙醛酸甲酯、二茂鈦化合物等。較佳為將該等與下文所述之聚合起始助劑(D1)(尤其是胺類)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 benzophenethylbenzoate , 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) di Benzophenone compounds such as benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10-butyl-2 -Chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound and the like. These are preferably used in combination with the polymerization initiation aid (D1) (especially amines) described below.
作為酸產生劑,例如可列舉:4-羥基苯基二甲基鋶對甲苯磺酸鹽、4-羥基苯基二甲基鋶六氟銻酸鹽、4-乙醯氧基苯基二甲基鋶對甲苯磺酸鹽、4-乙醯氧基苯基甲基苄基鋶六氟銻酸鹽、三苯基鋶對甲苯 磺酸鹽、三苯基鋶六氟銻酸鹽、二苯基錪對甲苯磺酸鹽、二苯基錪六氟銻酸鹽等鎓鹽類;或硝基苄基甲苯磺酸酯類、安息香甲苯磺酸酯類等。 Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethoxyphenylphenyldimethyl.鋶 P-toluenesulfonate, 4-Ethyloxyphenylmethylbenzyl hexafluoroantimonate, Triphenyl 鋶 P-toluene Onium salts such as sulfonate, triphenylsulfonium hexafluoroantimonate, diphenylsulfonium p-toluenesulfonate, diphenylsulfonium hexafluoroantimonate; or nitrobenzyltoluenesulfonate, benzoin Tosylate and the like.
聚合起始劑(D)之含量相對於樹脂(B)及聚合性化合物(C)之合計量100質量份,較佳為0.1~30質量份,更佳為1~20質量份。若聚合起始劑(D)之含量處於上述範圍內,則有高感度化而縮短曝光時間之傾向,因此彩色濾光片之生產性提高。 The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, there is a tendency that the sensitivity is increased and the exposure time is shortened, so the productivity of the color filter is improved.
聚合起始助劑(D1)係用以促進藉由聚合起始劑開始聚合之聚合性化合物之聚合的化合物、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 that promotes the polymerization of a polymerizable compound that is polymerized by a polymerization initiator. When a polymerization initiator (D1) is contained, it is usually used in combination with a 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 aid (D1) include amine compounds, alkoxyanthracene compounds, and 9-oxosulfur. Compounds and carboxylic acid compounds.
作為胺化合物,可列舉:三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲胺基苯甲酸甲酯、4-二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸異戊酯、苯甲酸2-二甲胺基乙酯、4-二甲胺基苯甲酸2-乙基己酯、N,N-二甲基對甲苯胺、4,4'-雙(二甲胺基)二苯甲酮(通稱米其勒酮)、4,4'-雙(二乙胺基)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(二乙胺基)二苯甲酮。亦可使用EAB-F(保土穀化學工業股份有限公司製造)等市售品。 Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzene Isoamyl formate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl-p-toluidine, 4,4'-bis (di (Methylamino) benzophenone (commonly known as Michelin), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone Ketones and the like, among them, 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。 Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 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。 As 9-oxysulfur Compounds, including: 2-isopropyl-9-oxysulfur 4-isopropyl-9-oxysulfur , 2,4-diethyl-9-oxysulfur , 2,4-dichloro-9-oxysulfur , 1-chloro-4-propoxy-9-oxysulfur 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 methyl formaldehyde. Oxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio Acetic acid, N-naphthyl glycine, naphthyloxyacetic acid, and the like.
於使用聚合起始助劑(D1)之情形時,其含量相對於樹脂(B)及聚合性化合物(C)之合計量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)之量處於該範圍內,則可進一步以高感度形成著色圖案,而有彩色濾光片之生產性提高之傾向。 When using a polymerization initiator (D1), its content is 100 parts by mass with respect to the total amount of the resin (B) and the polymerizable compound (C), preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be further formed with high sensitivity, and the productivity of the color filter tends to be improved.
溶劑(E)並無特別限定,可使用該領域通常使用之溶劑。例如可列舉: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 solvents commonly used in this field can be used. Examples include: ester solvents (solvents containing -COO- and -O- free in the molecule), ether solvents (solvents containing -O- and -COO- free in the molecule), and ether ester solvents (molecule containing- COO- and -O- solvents), ketone solvents (solvents containing -CO- and no -COO- in the molecule), alcohol solvents (molecules containing OH and no -O-, -CO- and -COO- Solvents), aromatic hydrocarbon solvents, amidine solvents, dimethyl sulfene 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、環己醇乙酸酯及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, cyclamate Hexanol acetate and γ-butyrolactone.
作為醚溶劑,可列舉:乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單乙醚、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、二乙二醇二乙醚、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、苯乙醚及甲基苯甲醚等。 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 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-di 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 and Methyl anisole and so on.
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、乙酸3-甲氧基丁酯、乙酸3-甲基-3-甲氧基丁酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二乙二醇單乙醚乙酸酯及二乙二醇單丁醚乙酸酯等。 Examples of the ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 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, 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、環己酮及異佛爾酮等。 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 and isophorone.
作為醇溶劑,可列舉:甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇及甘油等。 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、二甲苯及均三甲苯等。 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-二甲基乙醯胺及N-甲基吡咯啶酮等。 Examples of the amidine solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
上述溶劑中,就塗佈性、乾燥性之方面而言,較佳為1atm下之沸點為120℃以上且180℃以下之有機溶劑。作為溶劑,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、二乙二醇單甲醚、二乙二醇單乙醚、4-羥基-4-甲基-2-戊酮及N,N-二甲基甲醯胺,更佳為丙二醇單甲醚乙酸酯、丙二醇單甲醚、乳酸乙酯及3-乙氧基丙酸乙酯。 Among the above solvents, an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm in terms of coatability and drying properties is preferred. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethyl ether are preferred. Diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and Ethyl 3-ethoxypropionate.
溶劑(E)之含量相對於本發明之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之總量較佳為5~30質量%,更佳為8~25質量%。若溶劑(E)之含量處於上述範圍內,則塗佈時之平坦性變得良好,且由於形成彩色濾光片時色濃度不會不足,因此有顯示特性變得良好之傾向。 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 of the present invention. In other words, the total amount of solid components of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating will be good, and the color density will not be insufficient when forming a color filter, so the display characteristics tend to be good.
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 polysiloxane-based surfactant, a fluorine-based surfactant, and a polysiloxane-based surfactant having a fluorine atom. These may have a polymerizable group in a 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。具體而言,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,Dow Corning Toray股份有限公司製造)、KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業股份有限公司製造)、TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF4446、TSF4452及TSF4460(Momentive Performance Materials Japan有限公司製造)等。 Examples of the polysiloxane-based surfactant include a surfactant having a siloxane bond in the molecule. Specifically, 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 names, manufactured by Dow Corning Toray Co., Ltd.) , KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan Co., Ltd.) Wait.
作為上述氟系界面活性劑,可列舉分子內具有氟碳鏈之界面活性劑等。具體而言,可列舉:Fluorad(註冊商標)FC430、Fluorad FC431(Sumitomo 3M股份有限公司製造)、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股份有限公司製造)、Eftop(註冊商標)EF301、Eftop EF303、Eftop EF351、Eftop EF352(Mitsubishi Materials Electronic Chemicals股份有限公司製造)、Surflon(註冊商標)S381、Surflon S382、Surflon SC101、Surflon SC105(旭硝子股份有限公司製造)及E5844(大金精密化學研究所股份有限公司製造)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 Co., Ltd.), 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 Corporation), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Precision Chemical Research Institute Co., Ltd.).
作為上述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。具體而言,可列舉:Megafac(註冊商標)R08、Megafac BL20、Megafac F475、Megafac F477及Megafac F443(DIC股份有限公司製造)等。 Examples of the polysiloxane-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC Corporation).
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%以上且0.2質量%以下,較佳為0.002質量%以上且0.1質量%以下,更佳為0.01質量%以上且0.05質量%以下。若調平劑(F)之含量處於上述範圍,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 mass% or more and 0.2 mass% or less, more preferably 0.002 mass% or more and 0.1 mass% or less, and more preferably 0.01 relative to the total amount of the coloring curable resin composition. Above mass% and below 0.05 mass%. When the content of the leveling agent (F) is in the above range, the flatness of the color filter can be made good.
本發明之著色硬化性樹脂組合物可視需要含有填充劑、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公知之添加劑。 The colored curable resin composition of the present invention may contain additives known in the technical field, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, if necessary.
本發明之著色硬化性樹脂組合物例如可藉由將著色劑(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)及其他成分加以混合而製備。 The coloring curable resin composition of the present invention can be prepared by, for example, coloring agent (A), resin (B), polymerizable compound (C), polymerization initiator (D), and solvent (E) as needed, A leveling agent (F), a polymerization initiation aid (D1), and other components are prepared by mixing.
染料(A2)及視需要使用之染料(Ac)可預先分別溶解於溶劑(E)之一部分或全部中而製備溶液。較佳為藉由孔徑0.01~1μm左右之過濾器對該溶液進行過濾。 The dye (A2) and the dye (Ac) used as necessary can be separately dissolved in a part or all of the solvent (E) to prepare a solution. The solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.
藍色顏料(A1)較佳為預先與溶劑(E)之一部分或全部混合,使用珠磨機等使其分散直至顏料之平均粒徑成為0.2μm以下左右為止。此時,可視需要調配顏料分散劑、樹脂(B)之一部分或全部。 The blue pigment (A1) is preferably partially or fully mixed with the solvent (E) in advance, and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. In this case, a part or all of the pigment dispersant and the resin (B) may be blended as necessary.
作為上述顏料分散劑,可使用市售之界面活性劑,可列舉:聚 矽氧系、氟系、酯系、陽離子系、陰離子系、非離子系、兩性、聚酯系、聚胺系、丙烯酸系等界面活性劑等。作為上述界面活性劑,除了聚氧伸乙基烷基醚類、聚氧伸乙基烷基苯基醚類、聚乙二醇二酯類、山梨醇酐脂肪酸酯類、脂肪酸改性聚酯類、三級胺改性聚胺基甲酸酯類、聚伸乙基亞胺類等以外,以商品名之形式可列舉KP(信越化學工業股份有限公司製造)、Flowlen(共榮社化學股份有限公司製造)、Solsperse(Zeneca股份有限公司製造)、EFKA(BASF Japan股份有限公司製造)、Ajisper(註冊商標)(Ajinomoto Fine-Techno股份有限公司製造)、Disperbyk(BYK-Chemie公司製造)等,該等可分別單獨使用,亦可組合兩種以上而使用。 As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include poly Surfactants such as silicone, fluorine, ester, cationic, anionic, non-ionic, amphoteric, polyester, polyamine, and acrylic. As the above-mentioned surfactants, in addition to polyoxyethylene alkyl ethers, polyoxyethyl alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, and fatty acid modified polyesters In addition to tertiary amine modified polyurethanes, polyethylenimines, etc., KP (Shin-Etsu Chemical Industry Co., Ltd.), Flowlen (Kyoeisha Chemical Co., Ltd.) can be listed as trade names. (Manufactured), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Japan Co., Ltd.), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie), etc. They can be used individually or in combination of two or more.
藉由以成為特定濃度之方式將殘餘之成分混合於以上述方式獲得之顏料分散液中,可製備目標之著色硬化性樹脂組合物。 By mixing the remaining components in the pigment dispersion liquid obtained in the above-mentioned manner so as to become a specific concentration, a target coloring curable resin composition can be prepared.
較佳為藉由孔徑0.01~10μm左右之過濾器過濾混合後之著色硬化性樹脂組合物。 The colored hardening resin composition is preferably filtered and mixed by a filter having a pore size of about 0.01 to 10 μm.
根據本發明之著色硬化性樹脂組合物,可製作尤其是耐熱性優異之彩色濾光片。該彩色濾光片作為顯示裝置(例如液晶顯示裝置、有機EL(Electroluminescence,電致發光)裝置、電子紙等)及固體拍攝元件所使用之彩色濾光片有用。 According to the colored curable resin composition of the present invention, a color filter having excellent heat resistance can be produced. This color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL (Electroluminescence) devices, electronic paper, etc.) and solid-state imaging elements.
以下,藉由實施例對本發明之著色硬化性樹脂組合物進行更詳細地說明。只要無特別說明,則例中之「%」及「份」為質量%及質量份。 Hereinafter, the colored curable resin composition of the present invention will be described in more detail with reference to examples. Unless otherwise specified, "%" and "part" in the examples are mass% and mass parts.
於以下之合成例中,化合物係藉由質譜分析(LC,Agilent製造之1200型;MASS,Agilent製造之LC/MSD型)或元素分析(VARIO-EL(Elementar股份有限公司製造))進行鑑定。 In the following synthesis examples, the compounds were identified by mass spectrometry (LC, model 1200 manufactured by Agilent; LC / MSD model manufactured by Agilent) or elemental analysis (VARIO-EL (manufactured by Elementar Corporation)).
於遮光條件下將式(1x)所表示之化合物20份與N-乙基鄰甲苯胺(和光純藥工業股份有限公司製造)200份加以混合,於110℃下將所獲得之溶液攪拌6小時。將所獲得之反應液冷卻至室溫後,添加至水800份、35%鹽酸50份之混合液中,於室溫下攪拌1小時,結果析出結晶。以抽氣過濾之殘渣之形式獲得所析出之結晶後加以乾燥,而獲得式(1-24)所表示之化合物(以下稱為「染料1」)24份。產率為80%。 Under light-shielding conditions, 20 parts of the compound represented by the formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, and the obtained solution was stirred at 110 ° C for 6 hours. . After the obtained reaction solution was cooled to room temperature, it was added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour. As a result, crystals were precipitated. The precipitated crystals are obtained in the form of a residue filtered by suction and then dried to obtain a compound represented by the formula (1-24) (hereinafter referred to as " Dye 1 ") 24 parts. The yield was 80%.
式(1-24)所表示之化合物之鑑定:(質譜分析)離子化模式=ESI+:m/z=[M+H]+603.4 Exact Mass(準確質量):602.2 Identification of the compound represented by formula (1-24): (mass spectrometry) ionization mode = ESI +: m / z = [M + H] + 603.4 Exact Mass: 602.2
於具備冷凝管及攪拌裝置之燒瓶中投入式(A0-1)所表示之化合物及式(A0-2)所表示之化合物之混合物(商品名Chugai Aminol Fast Pink R,中外化成製造)15份、氯仿150份及N,N-二甲基甲醯胺8.9份,一面於攪拌下維持為20℃以下,一面滴加亞硫醯氯10.9份。結束滴加後,升溫至50℃,於該溫度下維持5小時而進行反應,其後冷卻為20℃。一面於攪拌下將冷卻後之反應溶液維持為20℃以下,一面滴加2-乙基己基胺12.5份及三乙胺22.1份之混合液。其後,於該溫度下攪拌5小時 而進行反應。繼而,藉由旋轉蒸發器將所獲得之反應混合物之溶劑蒸餾去除後,添加少量甲醇並遽烈攪拌。一面攪拌一面將該混合物添加至離子交換水375份之混合液中,而使結晶析出。將所析出之結晶過濾分離,藉由離子交換水充分洗淨,於60℃下進行減壓乾燥,而獲得染料2(式(Aa-1-1)~式(Aa-1-8)所表示之化合物之混合物)11.3份。 15 parts of a mixture of the compound represented by formula (A0-1) and the compound represented by formula (A0-2) (trade name Chugai Aminol Fast Pink R, manufactured by Sinochem Corporation) were placed in a flask equipped with a condenser and a stirring device. 150 parts of chloroform and 8.9 parts of N, N-dimethylformamidine were added dropwise while maintaining 10.9 parts of thionyl chloride while maintaining the temperature below 20 ° C under stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C, and the reaction was carried out while maintaining the temperature for 5 hours, and then cooled to 20 ° C. While maintaining the cooled reaction solution below 20 ° C with stirring, a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Then, it stirred at this temperature for 5 hours, and performed reaction. Then, after the solvent of the obtained reaction mixture was distilled off by a rotary evaporator, a small amount of methanol was added and vigorously stirred. This mixture was added to a mixed solution of 375 parts of ion-exchanged water while stirring, and crystals were precipitated. The precipitated crystals were separated by filtration, sufficiently washed with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 11.3 parts of dye 2 (mixture of compounds represented by formula (Aa-1-1) to formula (Aa-1-8)).
以下反應係於氮氣環境下進行。於具備冷凝管及攪拌裝置之燒瓶中投入硫氰酸鉀36.3份及丙酮160.0份後,於室溫下攪拌30分鐘。繼而,歷經10分鐘滴加苯甲醯氯(東京化成股份有限公司製造)50.0份。結束滴加後,進一步於室溫下攪拌2小時。繼而,將反應混合物冰浴冷卻後,滴加N-乙基鄰甲苯胺(東京化成股份有限公司製造)45.7份。結束滴加後,進一步於室溫下攪拌30分鐘。繼而,將反應混合物冰浴冷卻後,滴加30%氫氧化鈉水溶液34.2份。結束滴加後,進一步於室溫下攪拌30分鐘。繼而,於室溫下滴加氯乙酸35.3份。結束滴加後,於加熱回流下攪拌7小時。繼而,將反應混合物放置冷卻至室溫後,將反應溶液注入至自來水120.0份中,其後,添加甲苯200份並攪拌30分鐘。繼而停止攪拌,靜置30分鐘,結果分離為有機層與水層。藉由分液操作將水層廢棄後,對有機層藉由一當量濃度鹽酸200份進行洗淨,繼而藉由自來水200份進行洗淨,最後藉由飽和鹽水200份進行洗淨。向有機層添加適量之芒硝並攪拌30分鐘後進行過濾,獲得經乾燥之有機層。藉由蒸發器將所獲得之有機層之溶劑蒸餾去除,而獲得淡黃色液體。藉由管柱層析法精製所獲得之淡黃色液體。於減壓下以60℃乾燥經精製之淡黃色液體,而獲得式(B-I-1)所表示之化合物52.0份。產率為50%。 The following reactions were performed under a nitrogen atmosphere. After putting 36.3 parts of potassium thiocyanate and 160.0 parts of acetone into a flask equipped with a condenser and a stirring device, the mixture was stirred at room temperature for 30 minutes. Then, 50.0 parts of benzamidine chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Then, after cooling the reaction mixture in an ice bath, 45.7 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Then, after cooling the reaction mixture in an ice bath, 34.2 parts of a 30% sodium hydroxide aqueous solution was added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Then, 35.3 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred under reflux for 7 hours. Next, after the reaction mixture was left to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and then 200 parts of toluene was added and stirred for 30 minutes. The stirring was stopped, and the mixture was left to stand for 30 minutes. As a result, the organic layer and the aqueous layer were separated. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of one equivalent concentration of hydrochloric acid, then washed with 200 parts of tap water, and finally washed with 200 parts of saturated saline. An appropriate amount of thenardite was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent of the obtained organic layer was distilled off by an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 52.0 parts of a compound represented by the formula (B-I-1). The yield is 50%.
以下反應係於氮氣環境下進行。於具備冷凝管及攪拌裝置之燒瓶中投入式(B-I-1)所表示之化合物9.3份、4,4'-雙(二乙胺基)二苯甲酮(東京化成股份有限公司製造)10.0份及甲苯20.0份後,繼而,添加磷醯氯14.8份,於95~100℃下攪拌3小時。繼而,將反應混合物冷卻為室溫後,藉由異丙醇170.0份加以稀釋。繼而,將經稀釋之反應溶液注入至飽和鹽水300.0份中後,添加甲苯100份並攪拌30分鐘。繼而停止攪拌,靜置30分鐘,結果分離為有機層與水層。藉由分液操作將水層廢棄後,對有機層藉由飽和鹽水300份進行洗淨。向有機層添加適量之芒硝並攪拌30分鐘後進行過濾,獲得經乾燥之有機層。藉由蒸發器將所獲得之有機層之溶劑蒸餾去除,而獲得藍紫色固體。進而於減壓下以60℃乾燥藍紫色固體,而獲得式(A-I-a1)所表示之化合物19.8份。產率為100%。 The following reactions were performed under a nitrogen atmosphere. 9.3 parts of the compound represented by formula (BI-1) and 10.0 parts of 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) were put into a flask equipped with a condenser and a stirring device. After adding 20.0 parts of toluene, 14.8 parts of phosphoric acid chloride was added, followed by stirring at 95 to 100 ° C for 3 hours. After the reaction mixture was cooled to room temperature, it was diluted with 170.0 parts of isopropanol. Next, after the diluted reaction solution was poured into 300.0 parts of saturated saline, 100 parts of toluene was added and stirred for 30 minutes. The stirring was stopped, and the mixture was left to stand for 30 minutes. As a result, the organic layer and the aqueous layer were separated. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of thenardite was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent of the obtained organic layer was distilled off by an evaporator to obtain a blue-violet solid. Furthermore, a blue-violet solid was dried under reduced pressure at 60 ° C to obtain 19.8 parts of a compound represented by the formula (A-I-a1). The yield is 100%.
式(A-I-a1)所表示之化合物之鑑定(質譜分析)離子化模式=ESI+:m/z=601.3[M-Cl]+ Exact Mass:636.3 Identification (mass spectrometry) of compound represented by formula (AI-a1) Ionization mode = ESI +: m / z = 601.3 [M-Cl] + Exact Mass: 636.3
以下反應係於氮氣環境下進行。於具備冷凝管及攪拌裝置之燒瓶中投入式(A-I-a1)所表示之化合物10.0份、雙(三氟甲磺醯基)醯亞胺鋰(東京化成股份有限公司製造)4.5份、及N,N-二甲基甲醯胺100.0份 後,於50~60℃下攪拌3小時。繼而,將反應混合物冷卻為室溫後,一面攪拌1小時一面滴加至自來水2000.0份中,而獲得暗藍色懸浮液。將所獲得之懸浮液過濾,而獲得藍綠色固體。進而於減壓下以60℃乾燥藍綠色固體,而獲得式(A-I-a9)所表示之化合物11.3份。產率為82%。 The following reactions were performed under a nitrogen atmosphere. 10.0 parts of a compound represented by the formula (AI-a1), 4.5 parts of lithium bis (trifluoromethanesulfonyl) fluorenimide (manufactured by Tokyo Chemical Industry Co., Ltd.) were put into a flask equipped with a condenser tube and a stirring device, and 100.0 parts of N-dimethylformamide Then, it stirred at 50-60 degreeC for 3 hours. Then, the reaction mixture was cooled to room temperature, and then added dropwise to 2000.0 parts of tap water while stirring for 1 hour, thereby obtaining a dark blue suspension. The obtained suspension was filtered to obtain a blue-green solid. The blue-green solid was further dried at 60 ° C. under reduced pressure to obtain 11.3 parts of a compound represented by the formula (A-I-a9). The yield was 82%.
以0.02L/min向具備回流冷卻器、滴液漏斗及攪拌機之燒瓶內流入氮氣而製成氮氣環境,添加乳酸乙酯305份,一面攪拌一面加熱至70℃。繼而,將丙烯酸46份及丙烯酸3,4-環氧三環[5.2.1.02,6]癸酯(將式(I-1)所表示之化合物及式(II-1)所表示之化合物以莫耳比為50:50加以混合)240份溶解於乳酸乙酯185份中而製備溶液,使用滴液漏斗,歷經4小時而將該溶解液滴加至保溫為70℃之燒瓶內。 Nitrogen was introduced into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer at 0.02 L / min to prepare a nitrogen atmosphere. 305 parts of ethyl lactate was added, and heated to 70 ° C while stirring. Then, 46 parts of acrylic acid and 3,4-epoxytricyclo [5.2.1.0 2,6 ] decyl acrylic acid (the compound represented by formula (I-1) and the compound represented by formula (II-1) were Molar ratio was 50:50 and mixed) 240 parts were dissolved in 185 parts of ethyl lactate to prepare a solution. Using a dropping funnel, the dissolved solution was dropped into a flask held at 70 ° C. over 4 hours.
另一方面,將聚合起始劑2,2'-偶氮雙(2,4-二甲基戊腈)30份溶解 於乳酸乙酯225份中,使用另一滴液漏斗,歷經4小時將所獲得之溶液滴加至燒瓶內。結束滴加聚合起始劑之溶液後,於70℃下保持4小時,其後冷卻至室溫,而獲得重量平均分子量(Mw)為9.1×103、分子量分佈為2.1、固形物成分26質量%、固形物成分酸值120mg-KOH/g之樹脂B1溶液。樹脂B1具有如下述所示之結構單元。 On the other hand, 30 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts of ethyl lactate, and another dropping funnel was used to dissolve all The obtained solution was dropped into the flask. After the completion of the dropwise addition of the solution of the polymerization initiator, it was held at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight (Mw) of 9.1 × 10 3 , a molecular weight distribution of 2.1, and a solid content of 26 masses. %, Solution of resin B1 with solid content acid value 120mg-KOH / g. The resin B1 has a structural unit as shown below.
於具備攪拌機、溫度計、回流冷凝管、滴液漏斗及氮氣導入管之燒瓶中導入丙二醇單甲醚乙酸酯182份,將燒瓶內環境由空氣設為氮氣後,升溫至100℃,其後,滴加於包含甲基丙烯酸苄酯70.5份、甲基丙烯酸43.0份、三環癸烷骨架之單甲基丙烯酸酯(日立化成股份有限公司製造之FA-513M)22.0份及丙二醇單甲醚乙酸酯136份之混合物中添加2,2'-偶氮二異丁腈3.6份而成之溶液,進而於100℃繼續攪拌。 Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, 182 parts of propylene glycol monomethyl ether acetate was introduced. After the atmosphere in the flask was set to nitrogen, the temperature was increased to 100 ° C. Dropwise added to 22.0 parts of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) containing 70.5 parts of benzyl methacrylate, 43.0 parts of methacrylic acid, and tricyclodecane skeleton, and propylene glycol monomethyl ether acetic acid A solution obtained by adding 3.6 parts of 2,2'-azobisisobutyronitrile to a mixture of 136 parts of the ester was further stirred at 100 ° C.
繼而,將燒瓶內環境由氮氣設為空氣,向燒瓶內投入甲基丙烯酸縮水甘油酯35.5份[0.25莫耳(相對於本反應所使用之甲基丙烯酸之羧基為50莫耳%)]、三(二甲胺基甲基)苯酚0.9份及對苯二酚0.145份,於110℃下繼續反應,而獲得固形物成分29%、固形物成分酸值為79mgKOH/g之樹脂B2溶液。藉由GPC(Gel Permeation Chromatography,凝膠滲透層析法)測定而得之聚苯乙烯換算之重量平均分子量為30,000。 Next, the atmosphere in the flask was set to air with nitrogen, and 35.5 parts of glycidyl methacrylate [0.25 mol (50 mol% with respect to the carboxyl group of methacrylic acid used in the reaction)] was charged into the flask. 0.9 parts of (dimethylaminomethyl) phenol and 0.145 part of hydroquinone were further reacted at 110 ° C to obtain a resin B2 solution having a solid content of 29% and a solid content acid value of 79 mgKOH / g. The weight average molecular weight in terms of polystyrene obtained by GPC (Gel Permeation Chromatography, gel permeation chromatography) measurement was 30,000.
合成例中獲得之樹脂之重量平均分子量(Mw)及數量平均分子量(Mn)之測定係使用GPC法,於以下條件下進行。 The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured using the GPC method under the following conditions.
裝置:K2479(島津製作所股份有限公司製造) Device: K2479 (made by Shimadzu Corporation)
管柱:SHIMADZU Shim-pack GPC-80M Column: SHIMADZU Shim-pack GPC-80M
管柱溫度:40℃ Column temperature: 40 ℃
溶劑:THF(四氫呋喃) Solvent: THF (tetrahydrofuran)
流速:1.0mL/min Flow rate: 1.0mL / min
檢測器:RI(Refractive Index,折射率) Detector: RI (Refractive Index, refractive index)
校正用標準物質:TSK STANDARD POLYSTYRENE F-40、F-4、F-288、A-2500、A-500(Tosoh股份有限公司製造) Calibration reference materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
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 number-average molecular weight in terms of polystyrene obtained above was defined as the molecular weight distribution.
於雙(N-乙基-N-羥基乙基胺基)二苯甲酮28.52份、三乙胺17.80份中添加二氯甲烷50mL並攪拌溶解。其後,添加甲基丙烯酸酐13.56份,升溫為40℃並加以維持。反應結束後,冷卻至室溫,其後添加水並進行層分離,追加飽和氯化鈉溶液20mL並攪拌30分鐘。層分離後,將有機層蒸餾去除,將殘留之固體減壓乾燥,而獲得式(aa2)所表示之化合物21.4份。 50 mL of dichloromethane was added to 28.52 parts of bis (N-ethyl-N-hydroxyethylamino) benzophenone and 17.80 parts of triethylamine, and the mixture was dissolved by stirring. Thereafter, 13.56 parts of methacrylic anhydride was added, and the temperature was raised to 40 ° C and maintained. After completion of the reaction, the mixture was cooled to room temperature, water was added to separate the layers, and 20 mL of a saturated sodium chloride solution was added and stirred for 30 minutes. After the layers were separated, the organic layer was distilled off, and the remaining solid was dried under reduced pressure to obtain 21.4 parts of a compound represented by the formula (aa2).
將式(aa2)所表示之化合物21.4份添加至氯仿500mL中並加以攪 拌。其後,追加磷醯氯49.08份並攪拌15分鐘。追加N-苯基-1-萘基胺14.56份後,使其回流。反應結束後,冷卻至室溫,其後添加水並加以攪拌。攪拌後,靜置而使其層分離,將有機層蒸餾去除,將殘留之固體減壓乾燥,加以精製而獲得式(aa3)所表示之化合物20.3份。 21.4 parts of the compound represented by formula (aa2) was added to 500 mL of chloroform and stirred mix. Thereafter, 49.08 parts of phosphoric acid chloride was added and stirred for 15 minutes. After adding 14.56 parts of N-phenyl-1-naphthylamine, it was made to reflux. After completion of the reaction, the mixture was cooled to room temperature, and water was added thereto, followed by stirring. After stirring, it was allowed to stand to separate the layers, the organic layer was distilled off, the remaining solid was dried under reduced pressure, and purified to obtain 20.3 parts of a compound represented by the formula (aa3).
將式(aa3)所表示之化合物10.00份添加至甲醇100mL中並溶解後,添加三氟甲磺酸鈉2.50份而將鹽置換。過濾後,以水洗淨所獲得之化合物,將殘留之固體減壓乾燥,而獲得式(aa4)所表示之化合物5.5份。 After 10.00 parts of the compound represented by formula (aa3) was added to 100 mL of methanol and dissolved, 2.50 parts of sodium trifluoromethanesulfonate was added to replace the salt. After filtration, the obtained compound was washed with water, and the remaining solid was dried under reduced pressure to obtain 5.5 parts of a compound represented by formula (aa4).
將式(aa3)所表示之化合物10.00份添加至甲醇100mL中並溶解後,添加雙(三氟甲磺醯亞胺)鋰2.09份而將鹽置換。過濾後,以水洗淨所獲得之化合物,進行減壓乾燥而獲得式(aa5)所表示之化合物7.5份。 After 10.00 parts of the compound represented by formula (aa3) was added to 100 mL of methanol and dissolved, 2.09 parts of lithium bis (trifluoromethanesulfenimide) was added to replace the salt. After filtration, the obtained compound was washed with water and dried under reduced pressure to obtain 7.5 parts of a compound represented by formula (aa5).
於氮氣環境下,添加甲基乙基酮30份後,升溫為70℃。將式(aa4)所表示之化合物2.54份與2,2'-偶氮二異丁腈0.16份溶解於甲基乙基酮20份中,投入至反應器中3小時並維持為70℃。投入結束後,於70℃下維持8小時,將甲基乙基酮濃縮一部分後,將反應液投入至己烷中,使結晶析出後加以過濾,藉由己烷洗淨殘留之固體後,進行減壓乾燥,而獲得聚合物化合物(aa4)1.80份。 After adding 30 parts of methyl ethyl ketone under a nitrogen atmosphere, the temperature was raised to 70 ° C. 2.54 parts of the compound represented by the formula (aa4) and 0.16 parts of 2,2'-azobisisobutyronitrile were dissolved in 20 parts of methyl ethyl ketone, put into the reactor for 3 hours and maintained at 70 ° C. After the completion of the addition, it was maintained at 70 ° C for 8 hours. After concentrating a part of methyl ethyl ketone, the reaction solution was poured into hexane, and crystals were precipitated and then filtered. The remaining solids were washed with hexane and then reduced. It was pressure-dried to obtain 1.80 parts of a polymer compound (aa4).
於氮氣環境下,添加甲基乙基酮30份後,升溫為70℃。將式(aa4)所表示之化合物2.54份與2,2'-偶氮二異丁腈0.25份、甲基丙烯酸苄酯0.51份、甲基丙烯酸0.51份、N-苯基順丁烯二醯亞胺0.42份溶解於甲基乙基酮50份中,投入至反應器中3小時並維持為70℃。投入結束後,於70℃下維持8小時,將甲基乙基酮濃縮一部分後,將反應液投入至己烷中,使結晶析出後加以過濾,藉由己烷洗淨殘留之固體後,進行減壓乾燥,而獲得聚合物化合物(aa4')2.35份。 After adding 30 parts of methyl ethyl ketone under a nitrogen atmosphere, the temperature was raised to 70 ° C. 2.54 parts of the compound represented by the formula (aa4) and 0.25 parts of 2,2'-azobisisobutyronitrile, 0.51 parts of benzyl methacrylate, 0.51 parts of methacrylic acid, and N-phenylmaleic acid 0.42 part of amine was dissolved in 50 parts of methyl ethyl ketone, and it was put into the reactor for 3 hours and maintained at 70 ° C. After the completion of the addition, it was maintained at 70 ° C for 8 hours. After concentrating a part of methyl ethyl ketone, the reaction solution was poured into hexane, and crystals were precipitated and then filtered. The remaining solids were washed with hexane and then reduced. It was pressure-dried to obtain 2.35 parts of a polymer compound (aa4 ').
於氮氣環境下,添加甲基乙基酮30份後,升溫為70℃。將式(aa5)所表示之化合物2.54份與2,2'-偶氮二異丁腈0.16份溶解於甲基乙基酮20份中,投入至反應器中3小時並維持為70℃。投入結束後,於 70℃下維持8小時,將甲基乙基酮濃縮一部分後,將反應液投入至己烷中,使結晶析出後加以過濾,藉由己烷洗淨殘留之固體後,進行減壓乾燥,而獲得聚合物化合物(aa5)1.63份。 After adding 30 parts of methyl ethyl ketone under a nitrogen atmosphere, the temperature was raised to 70 ° C. 2.54 parts of the compound represented by the formula (aa5) and 0.16 parts of 2,2'-azobisisobutyronitrile were dissolved in 20 parts of methyl ethyl ketone, put into the reactor for 3 hours and maintained at 70 ° C. After the investment is completed, at It was maintained at 70 ° C for 8 hours. After concentrating a part of methyl ethyl ketone, the reaction solution was poured into hexane, and crystals were precipitated and then filtered. The remaining solid was washed with hexane and then dried under reduced pressure to obtain Polymer compound (aa5) 1.63 parts.
於氮氣環境下,添加甲基乙基酮30份後,升溫為70℃。將式(aa5)所表示之化合物2.54份與2,2'-偶氮二異丁腈0.25份、甲基丙烯酸苄酯0.51份、甲基丙烯酸0.51份、N-苯基順丁烯二醯亞胺0.42份溶解於甲基乙基酮50份中,投入至反應器中3小時並維持為70℃。投入結束後,於70℃下維持15小時,將甲基乙基酮濃縮一部分後,將反應液投入至己烷中,使結晶析出後加以過濾,將殘留之固體減壓乾燥,而獲得聚合物化合物(aa5')3.80份。 After adding 30 parts of methyl ethyl ketone under a nitrogen atmosphere, the temperature was raised to 70 ° C. 2.54 parts of the compound represented by the formula (aa5) and 0.25 parts of 2,2'-azobisisobutyronitrile, 0.51 parts of benzyl methacrylate, 0.51 parts of methacrylic acid, and N-phenyl maleic acid 0.42 part of amine was dissolved in 50 parts of methyl ethyl ketone, and it was put into the reactor for 3 hours and maintained at 70 ° C. After the completion of the addition, the solution was maintained at 70 ° C for 15 hours. After concentrating methyl ethyl ketone, the reaction solution was poured into hexane to precipitate crystals and then filtered. The remaining solid was dried under reduced pressure to obtain a polymer. Compound (aa5 ') 3.80 parts.
將式(aa3)所表示之化合物5.00份加入至甲醇50mL中並溶解後,添加對甲苯磺酸鈉鹽1.46份而將鹽置換。過濾後,以水洗淨所獲得之化合物,進行減壓乾燥,而獲得式(aa6)所表示之化合物2.84份。 5.00 parts of the compound represented by formula (aa3) was added to 50 mL of methanol and dissolved, and then 1.46 parts of p-toluenesulfonic acid sodium salt was added to replace the salt. After filtration, the obtained compound was washed with water and dried under reduced pressure to obtain 2.84 parts of a compound represented by formula (aa6).
將5.00份之C.I.鹼性藍26加入至甲醇50mL中並溶解後,添加對甲苯磺酸鈉鹽2.10份而將鹽置換。過濾後,以水洗淨所獲得之化合物,進行減壓乾燥,而獲得式(aa7)所表示之化合物2.71份。 After 5.00 parts of C.I. Basic Blue 26 was added to 50 mL of methanol and dissolved, 2.10 parts of p-toluenesulfonic acid sodium salt was added to replace the salt. After filtration, the obtained compound was washed with water and dried under reduced pressure to obtain 2.71 parts of a compound represented by formula (aa7).
按照下述表1所記載之重量比於具備冷凝管與攪拌機之燒瓶中投入式(aa5)所表示之化合物(以下有時稱為染料Dy)、甲基丙烯酸苄酯、甲基丙烯酸、甲基丙烯酸甲酯及N-苄基順丁烯二醯亞胺,相對於上述化合物之總量100重量份而添加2,2'-偶氮雙(2,4-二甲基戊腈)(起始劑)6重量份。繼而,相對於上述起始劑與化合物之總量100重量份而投入丙二醇單甲醚乙酸酯300重量份後,於氮氣環境下開始緩慢攪拌。將反應溶液升溫至90℃,並攪拌10小時,而獲得共聚物溶液。 The compound represented by formula (aa5) (hereinafter sometimes referred to as dye Dy), benzyl methacrylate, methacrylic acid, and methyl group were charged into a flask equipped with a condenser tube and a stirrer at a weight ratio shown in Table 1 below. 2,2'-Azobis (2,4-dimethylvaleronitrile) was added to methyl acrylate and N-benzyl maleimide diimide based on 100 parts by weight of the total amount of the above compounds (starting Agent) 6 parts by weight. Then, 300 parts by weight of propylene glycol monomethyl ether acetate was added to 100 parts by weight of the total amount of the initiator and the compound, and then slowly stirred in a nitrogen atmosphere. The reaction solution was heated to 90 ° C. and stirred for 10 hours to obtain a copolymer solution.
分別按照下述表2所記載之重量於具備冷凝管與攪拌機之燒瓶中投入式(aa8)所表示之化合物、甲基丙烯酸苄酯、甲基丙烯酸、甲基丙烯酸甲酯及N-苄基順丁烯二醯亞胺,相對於上述化合物之總量100重 量份而添加6重量份之2,2'-偶氮雙(2,4-二甲基戊腈)(2,2'-azobis(2,4-dimethylvaleronitrile))作為起始劑。繼而,相對於上述起始劑及上述化合物之總量100重量份,投入作為溶劑之丙二醇單甲醚乙酸酯(PGMEA)300重量份後,於氮氣環境下開始緩慢攪拌。將反應溶液升溫至90℃,並攪拌10小時,而獲得共聚物溶液。 The compound represented by formula (aa8), benzyl methacrylate, methacrylic acid, methyl methacrylate, and N-benzyl cis were put into a flask equipped with a condenser and a stirrer according to the weights shown in Table 2 below Butene difluorene imide, 100 weight based on the total amount of the above compounds As a starter, 6 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) (2,2'-azobis (2,4-dimethylvaleronitrile)) was added in parts by weight. Next, 300 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added as a solvent with respect to 100 parts by weight of the total amount of the initiator and the compound, and then slowly stirred in a nitrogen atmosphere. The reaction solution was heated to 90 ° C. and stirred for 10 hours to obtain a copolymer solution.
使用式(aa9)所表示之化合物代替式(aa8)所表示之化合物,除此以外,分別藉由與上述合成例19-22相同之方法而獲得共聚物溶液。 A copolymer solution was obtained by the same method as in Synthesis Examples 19-22 above except that the compound represented by formula (aa9) was used instead of the compound represented by formula (aa8).
使用式(aa10)所表示之化合物代替式(aa8)所表示之化合物,除此以外,分別藉由與上述合成例19-22相同之方法而獲得共聚物溶液。 A copolymer solution was obtained by the same method as in Synthesis Example 19-22 except that the compound represented by formula (aa10) was used instead of the compound represented by formula (aa8).
將上述合成例19-30中所製造之各共聚物溶液3.5重量%、C.I.顏料藍顏料15:6(BASF公司)12重量%、分散劑(BYK,Diperbyk 6919)6重量%及丙二醇單甲醚乙酸酯78.5重量%加以混合,使用塗料振盪器分散24小時,而製造各共聚物分散液1~12。 3.5% by weight of each copolymer solution produced in the above Synthesis Examples 19-30, 12% by weight of CI Pigment Blue Pigment 15: 6 (BASF), 6% by weight of dispersant (BYK, Diperbyk 6919), and propylene glycol monomethyl ether The acetate was mixed at 78.5% by weight, and dispersed using a paint shaker for 24 hours to prepare each copolymer dispersion 1-12.
於反應器中投入氯化副玫瑰色素(pararosaniline)25份及乙醇500份,於200℃下攪拌8小時。繼而,將上述溶液之溫度降低至25℃,歷經5小時於上述溶液中緩慢滴加2-甲基-2-丙烯酸羧氧基乙酯(2-methyl-2-propenoic-carboxyoxy ethyl ester)174份。繼而,將上述溶液之溫度升溫至70℃後攪拌24小時。反應結束後,藉由乙醇使其緩慢地再結晶,而獲得式(aa11)所表示之化合物54.5份。 25 parts of pararosaniline chlorinated and 500 parts of ethanol were put into the reactor, and stirred at 200 ° C. for 8 hours. Then, the temperature of the above solution was lowered to 25 ° C, and 174 parts of 2-methyl-2-propenoic-carboxyoxy ethyl ester were slowly added dropwise to the above solution over 5 hours. . Then, the temperature of the solution was raised to 70 ° C. and then stirred for 24 hours. After the reaction was completed, ethanol was slowly recrystallized to obtain 54.5 parts of a compound represented by the formula (aa11).
於反應器中氯化副玫瑰色素25份及乙醇500份,於200℃下攪拌8小時。 In the reactor, 25 parts of chlorinated para-rose pigment and 500 parts of ethanol were stirred at 200 ° C. for 8 hours.
繼而,將上述溫度降低至25℃,歷經5小時於上述溶液中緩慢滴加2-甲基-2-丙烯酸磺酸胺基乙酯(2-methyl-2-propenoic-sulfamino ethyl ester)209份。繼而,將上述溶液之溫度升溫至70℃後攪拌24小時。反應結束後,藉由乙醇使其緩慢地再結晶,而獲得式(aa12)所表示之化合物58.2份。 Then, the temperature was lowered to 25 ° C, and 209 parts of 2-methyl-2-propenoic-sulfamino ethyl ester (2-methyl-2-propenoic-sulfamino ethyl ester) was slowly added dropwise to the solution over 5 hours. Then, the temperature of the solution was raised to 70 ° C. and then stirred for 24 hours. After completion of the reaction, ethanol was used to recrystallize slowly to obtain 58.2 parts of a compound represented by formula (aa12).
於合成例6中,使用式(B-I-1)所表示之化合物代替N-苯基-1-萘基胺,除此以外,以與合成例6同樣之方式合成,而獲得式(aa13)所表示之化合物。 In Synthesis Example 6, a compound represented by formula (BI-1) was used in place of N-phenyl-1-naphthylamine, except that a compound represented by formula (aa13) was synthesized in the same manner as in Synthesis Example 6. Represented compounds.
使用式(aa13)所表示之化合物代替式(aa8)所表示之化合物,除此以外,分別藉由與上述合成例19-22相同之方法而獲得共聚物溶液。 A copolymer solution was obtained by the same method as in Synthesis Example 19-22 except that the compound represented by formula (aa13) was used instead of the compound represented by formula (aa8).
將上述合成例46-49中所製造之各共聚物溶液3.5重量%、C.I.顏料藍顏料15:6(BASF公司)12重量%、分散劑(BYK,Diperbyk 6919)6重量%及丙二醇單甲醚乙酸酯78.5重量%加以混合,使用塗料振盪器分散24小時,而製造各共聚物分散液50~53。 3.5% by weight of each copolymer solution produced in the above Synthesis Examples 46-49, CI Pigment Blue Pigment 15: 6 (BASF) 12% by weight, dispersant (BYK, Diperbyk 6919) 6% by weight, and propylene glycol monomethyl ether The acetate was mixed at 78.5% by weight, and dispersed using a paint shaker for 24 hours to produce 50 to 53 dispersions of each copolymer.
於120度下將4-甲醯基苯-1,3-二磺酸二鈉22.14份、N,N-二丁基-3-胺基苯酚15.6份及對甲苯磺酸鈉2.2份攪拌12小時。冷卻後,將所獲得之混合物添加至乙醇之50%水100份中並過濾,而獲得式(I-2)所表示之化合物。 Stir 22.14 parts of 4-methylfluorenylbenzene-1,3-disulfonic acid disodium, 15.6 parts of N, N-dibutyl-3-aminophenol and 2.2 parts of sodium p-toluenesulfonate at 120 degrees for 12 hours . After cooling, the obtained mixture was added to 100 parts of 50% water in ethanol and filtered to obtain a compound represented by the formula (I-2).
混合: mixing:
(A)著色劑(A1):C.I.顏料藍15:6(顏料) 20份 (A) Colorant (A1): C.I. Pigment Blue 15: 6 (Pigment) 20 parts
丙烯酸系顏料分散劑 3.9份 Acrylic pigment dispersant 3.9 parts
丙二醇單甲醚乙酸酯 130份 Propylene glycol monomethyl ether acetate 130 parts
並使用珠磨機使顏料充分分散,繼而,混合: And use a bead mill to fully disperse the pigment, and then, mix:
(A)著色劑(A3):染料1 2.2份 (A) Colorant (A3): Dye 1 2.2 parts
(A)著色劑:式(I-2)所表示之化合物 1.5份 (A) Colorant: 1.5 parts of the compound represented by formula (I-2)
(B)樹脂:樹脂B1(固形物成分換算) 50份 (B) Resin: Resin B1 (solid content conversion) 50 parts
(C)聚合性化合物:二季戊四醇六丙烯酸酯(Kayarad(註冊商標)DPHA,日本化藥股份有限公司製造) 50份 (C) Polymerizable compound: 50 parts of dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)
(D)聚合起始劑: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) 10份 (D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01, BASF Corporation Made) 10 servings
(E)溶劑:乳酸乙酯 556份 (E) Solvent: 556 parts of ethyl lactate
(E)溶劑:丙二醇單甲醚乙酸酯 8份 (E) Solvent: 8 parts of propylene glycol monomethyl ether acetate
(F)調平劑:聚醚改性聚矽氧油(Toray Silicone SH8400,Dow Corning Toray股份有限公司製造) 0.1份 (F) Leveling agent: Polyether modified polysiloxane (Toray Silicone SH8400, manufactured by Dow Corning Toray Co., Ltd.) 0.1 part
獲得著色硬化性樹脂組合物。 A colored curable resin composition was obtained.
混合: mixing:
(A)著色劑(A1):C.I.顏料藍15:6(顏料) 20份 (A) Colorant (A1): C.I. Pigment Blue 15: 6 (Pigment) 20 parts
丙烯酸系顏料分散劑 3.9份 Acrylic pigment dispersant 3.9 parts
丙二醇單甲醚乙酸酯 130份 Propylene glycol monomethyl ether acetate 130 parts
並使用珠磨機使顏料充分分散,繼而,混合: And use a bead mill to fully disperse the pigment, and then, mix:
(A)著色劑(A3):染料2 1.3份 (A) Colorant (A3): Dye 2 1.3 parts
(A)著色劑:式(I-2)所表示之化合物 1.3份 (A) Colorant: 1.3 parts of the compound represented by formula (I-2)
(B)樹脂:樹脂B1(固形物成分換算) 50份 (B) Resin: Resin B1 (solid content conversion) 50 parts
(C)聚合性化合物:二季戊四醇六丙烯酸酯(Kayarad(註冊商 標)DPHA,日本化藥股份有限公司製造) 50份 (C) Polymerizable compound: dipentaerythritol hexaacrylate (Kayarad (registrar (Subject) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 50 copies
(D)聚合起始劑: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) 10份 (D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01, BASF Corporation Made) 10 servings
(E)溶劑:乳酸乙酯 556份 (E) Solvent: 556 parts of ethyl lactate
(E)溶劑:丙二醇單甲醚乙酸酯 8份 (E) Solvent: 8 parts of propylene glycol monomethyl ether acetate
(F)調平劑:聚醚改性聚矽氧油(Toray Silicone SH8400,Dow Corning Toray股份有限公司製造) 0.1份 (F) Leveling agent: Polyether modified polysiloxane (Toray Silicone SH8400, manufactured by Dow Corning Toray Co., Ltd.) 0.1 part
獲得著色硬化性樹脂組合物。 A colored curable resin composition was obtained.
混合: mixing:
(A)著色劑(A1):C.I.顏料藍15:6(顏料) 20份 (A) Colorant (A1): C.I. Pigment Blue 15: 6 (Pigment) 20 parts
丙烯酸系顏料分散劑 3.9份 Acrylic pigment dispersant 3.9 parts
丙二醇單甲醚乙酸酯 130份 Propylene glycol monomethyl ether acetate 130 parts
並使用珠磨機使顏料充分分散,繼而,混合: And use a bead mill to fully disperse the pigment, and then, mix:
(A)著色劑(A4):鹼性藍7 1.3份 (A) Colorant (A4): 1.3 parts of Basic Blue 7
(A)著色劑:式(I-2)所表示之化合物 0.3份 (A) Colorant: 0.3 part of the compound represented by formula (I-2)
(B)樹脂:樹脂B1(固形物成分換算) 50份 (B) Resin: Resin B1 (solid content conversion) 50 parts
(C)聚合性化合物:二季戊四醇六丙烯酸酯(Kayarad(註冊商標)DPHA,日本化藥股份有限公司製造) 50份 (C) Polymerizable compound: 50 parts of dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)
(D)聚合起始劑: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) 10份 (D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01, BASF Corporation Made) 10 servings
(E)溶劑:乳酸乙酯 556份 (E) Solvent: 556 parts of ethyl lactate
(E)溶劑:丙二醇單甲醚乙酸酯 8份 (E) Solvent: 8 parts of propylene glycol monomethyl ether acetate
(F)調平劑:聚醚改性聚矽氧油(Toray Silicone SH8400,Dow Corning Toray股份有限公司製造) 0.1份 (F) Leveling agent: Polyether modified polysiloxane (Toray Silicone SH8400, manufactured by Dow Corning Toray Co., Ltd.) 0.1 part
獲得著色硬化性樹脂組合物。 A colored curable resin composition was obtained.
混合: mixing:
(A)著色劑(A1):C.I.顏料藍15:6(顏料) 20份 (A) Colorant (A1): C.I. Pigment Blue 15: 6 (Pigment) 20 parts
丙烯酸系顏料分散劑 3.9份 Acrylic pigment dispersant 3.9 parts
丙二醇單甲醚乙酸酯 130份 Propylene glycol monomethyl ether acetate 130 parts
並使用珠磨機使顏料充分分散,繼而,混合: And use a bead mill to fully disperse the pigment, and then, mix:
(A)著色劑(A5):式(2-29)所表示之化合物 1.3份 (A) Colorant (A5): 1.3 parts of the compound represented by formula (2-29)
(A)著色劑:式(I-2)所表示之化合物 0.8份 (A) Colorant: 0.8 part of the compound represented by formula (I-2)
(B)樹脂:樹脂B1(固形物成分換算) 50份 (B) Resin: Resin B1 (solid content conversion) 50 parts
(C)聚合性化合物:二季戊四醇六丙烯酸酯(Kayarad(註冊商標)DPHA,日本化藥股份有限公司製造) 50份 (C) Polymerizable compound: 50 parts of dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)
(D)聚合起始劑: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) 10份 (D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01, BASF Corporation Made) 10 servings
(E)溶劑:乳酸乙酯 556份 (E) Solvent: 556 parts of ethyl lactate
(E)溶劑:丙二醇單甲醚乙酸酯 8份 (E) Solvent: 8 parts of propylene glycol monomethyl ether acetate
(F)調平劑:聚醚改性聚矽氧油(Toray Silicone SH8400,Dow Corning Toray股份有限公司製造) 0.1份 (F) Leveling agent: Polyether modified polysiloxane (Toray Silicone SH8400, manufactured by Dow Corning Toray Co., Ltd.) 0.1 part
獲得著色硬化性樹脂組合物。 A colored curable resin composition was obtained.
混合: mixing:
(A)著色劑(A1):C.I.顏料藍15:6(顏料) 20份 (A) Colorant (A1): C.I. Pigment Blue 15: 6 (Pigment) 20 parts
丙烯酸系顏料分散劑 3.9份 Acrylic pigment dispersant 3.9 parts
丙二醇單甲醚乙酸酯 130份 Propylene glycol monomethyl ether acetate 130 parts
並使用珠磨機使顏料充分分散,繼而,混合: And use a bead mill to fully disperse the pigment, and then, mix:
(A)著色劑(A6):式(3-11)所表示之化合物 1.3份 (A) Colorant (A6): 1.3 parts of the compound represented by formula (3-11)
(A)著色劑:式(I-2)所表示之化合物 1.1份 (A) Colorant: 1.1 parts of the compound represented by formula (I-2)
(B)樹脂:樹脂B1(固形物成分換算) 50份 (B) Resin: Resin B1 (solid content conversion) 50 parts
(C)聚合性化合物:二季戊四醇六丙烯酸酯(Kayarad(註冊商標)DPHA,日本化藥股份有限公司製造) 50份 (C) Polymerizable compound: 50 parts of dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)
(D)聚合起始劑: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) 10份 (D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01, BASF Corporation Made) 10 servings
(E)溶劑:乳酸乙酯 556份 (E) Solvent: 556 parts of ethyl lactate
(E)溶劑:丙二醇單甲醚乙酸酯 8份 (E) Solvent: 8 parts of propylene glycol monomethyl ether acetate
(F)調平劑:聚醚改性聚矽氧油(Toray Silicone SH8400,Dow Corning Toray股份有限公司製造) 0.1份 (F) Leveling agent: Polyether modified polysiloxane (Toray Silicone SH8400, manufactured by Dow Corning Toray Co., Ltd.) 0.1 part
獲得著色硬化性樹脂組合物。 A colored curable resin composition was obtained.
混合: mixing:
(A)著色劑(A1):C.I.顏料藍15:6(顏料) 20份 (A) Colorant (A1): C.I. Pigment Blue 15: 6 (Pigment) 20 parts
丙烯酸系顏料分散劑 3.9份 Acrylic pigment dispersant 3.9 parts
丙二醇單甲醚乙酸酯 130份 Propylene glycol monomethyl ether acetate 130 parts
並使用珠磨機使顏料充分分散,繼而,混合: And use a bead mill to fully disperse the pigment, and then, mix:
(A)著色劑(A7):式(A-I-a9)所表示之化合物 1.8份 (A) Colorant (A7): 1.8 parts of the compound represented by formula (A-I-a9)
(A)著色劑:式(I-2)所表示之化合物 0.3份 (A) Colorant: 0.3 part of the compound represented by formula (I-2)
(B)樹脂:樹脂B1(固形物成分換算) 50份 (B) Resin: Resin B1 (solid content conversion) 50 parts
(C)聚合性化合物:二季戊四醇六丙烯酸酯(Kayarad(註冊商標)DPHA,日本化藥股份有限公司製造) 50份 (C) Polymerizable compound: 50 parts of dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)
(D)聚合起始劑: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) 10份 (D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01, BASF Corporation Made) 10 servings
(E)溶劑:乳酸乙酯 556份 (E) Solvent: 556 parts of ethyl lactate
(E)溶劑:丙二醇單甲醚乙酸酯 8份 (E) Solvent: 8 parts of propylene glycol monomethyl ether acetate
(F)調平劑:聚醚改性聚矽氧油(Toray Silicone SH8400,Dow Corning Toray股份有限公司製造) 0.1份 (F) Leveling agent: Polyether modified polysiloxane (Toray Silicone SH8400, manufactured by Dow Corning Toray Co., Ltd.) 0.1 part
獲得著色硬化性樹脂組合物。 A colored curable resin composition was obtained.
混合: mixing:
(A)著色劑(A1):C.I.顏料藍15:6(顏料) 20份 (A) Colorant (A1): C.I. Pigment Blue 15: 6 (Pigment) 20 parts
丙烯酸系顏料分散劑 3.9份 Acrylic pigment dispersant 3.9 parts
丙二醇單甲醚乙酸酯 130份 Propylene glycol monomethyl ether acetate 130 parts
並使用珠磨機使顏料充分分散,繼而,混合: And use a bead mill to fully disperse the pigment, and then, mix:
(A)著色劑(A3):染料2 2.2份 (A) Colorant (A3): Dye 2 2.2 parts
(B)樹脂:樹脂B1(固形物成分換算) 50份 (B) Resin: Resin B1 (solid content conversion) 50 parts
(C)聚合性化合物:二季戊四醇六丙烯酸酯(Kayarad(註冊商標)DPHA,日本化藥股份有限公司製造) 50份 (C) Polymerizable compound: 50 parts of dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)
(D)聚合起始劑: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) 10份 (D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01, BASF Corporation Made) 10 servings
(E)溶劑:乳酸乙酯 556份 (E) Solvent: 556 parts of ethyl lactate
(E)溶劑:丙二醇單甲醚乙酸酯 8份 (E) Solvent: 8 parts of propylene glycol monomethyl ether acetate
(F)調平劑:聚醚改性聚矽氧油(Toray Silicone SH8400,Dow Corning Toray股份有限公司製造) 0.1份 (F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400, manufactured by Dow Corning Toray Co., Ltd.) 0.1 part
獲得著色硬化性樹脂組合物。 A colored curable resin composition was obtained.
藉由旋轉塗佈法於5cm見方之玻璃基板(Eagle 2000,Corning公司製造)上塗佈著色硬化性樹脂組合物後,於100℃下預烘烤3分鐘而獲得著色層。放置冷卻後,將形成有著色層之基板與石英玻璃製光罩之間隔設為100μm,使用曝光機(TME-150RSK,Topcon股份有限公司製造),於大氣環境下以150mJ/cm2之曝光量(365nm基準)進行光照射。使用形成有100μm線與間隙圖案者作為光罩。於24℃下將光照射後之著色層於含有非離子系界面活性劑0.12%與氫氧化鉀0.04%之水系顯影液中浸漬顯影60秒,水洗後,於烘箱中於200℃下後烘烤30分鐘,而獲得著色圖案。 A 5 cm square glass substrate (Eagle 2000, manufactured by Corning) was coated with a coloring curable resin composition by a spin coating method, and then pre-baked at 100 ° C for 3 minutes to obtain a colored layer. After leaving to cool, the interval between the substrate on which the colored layer was formed and the mask made of quartz glass was set to 100 μm, and an exposure machine (TME-150RSK, manufactured by Topcon Co., Ltd.) was used at an exposure of 150 mJ / cm 2 in the atmospheric environment (365nm standard) Light irradiation was performed. As the photomask, a pattern having a 100 μm line and gap pattern was used. The colored layer after light irradiation was immersed and developed in an aqueous developing solution containing 0.12% of non-ionic surfactant and 0.04% of potassium hydroxide at 24 ° C for 60 seconds. After washing, it was post-baked in an oven at 200 ° C 30 minutes while obtaining a colored pattern.
對於所獲得之著色圖案,使用膜厚測定裝置(DEKTAK3,日本真空技術股份有限公司製造)測定膜厚。 With respect to the obtained colored pattern, the film thickness was measured using a film thickness measuring device (DEKTAK3, manufactured by Japan Vacuum Technology Co., Ltd.).
對於所獲得之著色圖案,使用測色機(OSP-SP-200,Olympus股份有限公司製造)測定分光,使用C光源之特性函數測定CIE(International Commission on Illumination,國際照明委員會)之XYZ表色系中之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6及表7。 For the obtained coloring pattern, a spectrometer (OSP-SP-200, manufactured by Olympus Co., Ltd.) was used to measure the spectrometer, and a characteristic function of the C light source was used to measure the XYZ color system of the CIE (International Commission on Illumination) The xy chromaticity coordinates (x, y) and the tristimulus value Y in. The larger the value of Y, the higher the brightness. The results are shown in Tables 6 and 7.
於230℃下將所獲得之著色硬化性樹脂組合物之塗佈膜加熱20分鐘,使用測色機(OSP-SP-200,OLYMPUS公司製造)測定塗佈膜之加熱前後之色差(△Eab*)。對所獲得之塗佈膜實施以上之耐熱性評估,結果將色差(△Eab*)示於表6及表7。△Eab*越小,表示加熱前後之顏色變化越小,耐熱性越優異。 The coated film of the colored hardening resin composition obtained was heated at 230 ° C for 20 minutes, and the color difference (△ Eab *) before and after the heating of the coated film was measured using a color measuring machine (OSP-SP-200, manufactured by OLYMPUS) ). The obtained coating film was subjected to the above-mentioned heat resistance evaluation. As a result, the color difference (ΔEab *) is shown in Tables 6 and 7. The smaller ΔEab *, the smaller the color change before and after heating, and the better the heat resistance.
使用合成例7中獲得之式(aa4)所表示之化合物代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 Instead of using the compound represented by formula (aa4) obtained in Synthesis Example 7, A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例8中獲得之式(aa5)所表示之化合物代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 Instead of using the compound represented by formula (aa5) obtained in Synthesis Example 8, A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例9中獲得之聚合物化合物(aa4)代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 The polymer compound (aa4) obtained in Synthesis Example 9 was used instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例10中獲得之聚合物化合物(aa4')代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 Instead of using the polymer compound (aa4 ') obtained in Synthesis Example 10 A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例11中獲得之聚合物化合物(aa5)代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 The polymer compound (aa5) obtained in Synthesis Example 11 was used instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例12中獲得之聚合物化合物(aa5')代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 The polymer compound (aa5 ') obtained in Synthesis Example 12 was used instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例13中獲得之式(aa6)所表示之化合物代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 Instead of using the compound represented by formula (aa6) obtained in Synthesis Example 13, A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例14中獲得之式(aa7)所表示之化合物代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 Instead of using the compound represented by formula (aa7) obtained in Synthesis Example 14, A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
混合: mixing:
(A)著色劑(A1):C.I.顏料藍15:6(顏料) 2份 (A) Colorant (A1): C.I. Pigment Blue 15: 6 (Pigment) 2 parts
丙烯酸系顏料分散劑 0.5份 Acrylic pigment dispersant 0.5 part
丙二醇單甲醚乙酸酯 30份 Propylene glycol monomethyl ether acetate 30 parts
並使用珠磨機使顏料充分分散,繼而,混合: And use a bead mill to fully disperse the pigment, and then, mix:
(A)著色劑(A3):合成例15中獲得之共聚物溶液 3.2份 (A) Colorant (A3): 3.2 parts of the copolymer solution obtained in Synthesis Example 15
(A)著色劑:式(I-2)所表示之化合物 0.1份 (A) Colorant: 0.1 part of the compound represented by formula (I-2)
(B)樹脂:樹脂B1(固形物成分換算) 50份 (B) Resin: Resin B1 (solid content conversion) 50 parts
(C)聚合性化合物:二季戊四醇六丙烯酸酯(Kayarad(註冊商標)DPHA,日本化藥股份有限公司製造) 50份 (C) Polymerizable compound: 50 parts of dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)
(D)聚合起始劑: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) 10份 (D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01, BASF Corporation Made) 10 servings
(E)溶劑:乳酸乙酯 556份 (E) Solvent: 556 parts of ethyl lactate
(E)溶劑:丙二醇單甲醚乙酸酯 8份 (E) Solvent: 8 parts of propylene glycol monomethyl ether acetate
(F)調平劑:聚醚改性聚矽氧油(Toray Silicone SH8400,Dow Corning Toray股份有限公司製造) 0.1份 (F) Leveling agent: Polyether modified polysiloxane (Toray Silicone SH8400, manufactured by Dow Corning Toray Co., Ltd.) 0.1 part
獲得著色硬化性樹脂組合物。 A colored curable resin composition was obtained.
混合: mixing:
(A)著色劑(A1):C.I.顏料藍15:6(顏料) 2份 (A) Colorant (A1): C.I. Pigment Blue 15: 6 (Pigment) 2 parts
丙烯酸系顏料分散劑 0.5份 Acrylic pigment dispersant 0.5 part
丙二醇單甲醚乙酸酯 30份 Propylene glycol monomethyl ether acetate 30 parts
並使用珠磨機使顏料充分分散,繼而,混合: And use a bead mill to fully disperse the pigment, and then, mix:
(A)著色劑(A3):合成例16中獲得之共聚物溶液 3.3份 (A) Colorant (A3): 3.3 parts of the copolymer solution obtained in Synthesis Example 16
(A)著色劑:式(I-2)所表示之化合物 0.1份 (A) Colorant: 0.1 part of the compound represented by formula (I-2)
(B)樹脂:樹脂B1(固形物成分換算) 50份 (B) Resin: Resin B1 (solid content conversion) 50 parts
(C)聚合性化合物:二季戊四醇六丙烯酸酯(Kayarad(註冊商標)DPHA,日本化藥股份有限公司製造) 50份 (C) Polymerizable compound: 50 parts of dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)
(D)聚合起始劑: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) 10份 (D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01, BASF Corporation Made) 10 servings
(E)溶劑:乳酸乙酯 556份 (E) Solvent: 556 parts of ethyl lactate
(E)溶劑:丙二醇單甲醚乙酸酯 8份 (E) Solvent: 8 parts of propylene glycol monomethyl ether acetate
(F)調平劑:聚醚改性聚矽氧油(Toray Silicone SH8400,Dow Corning Toray股份有限公司製造) 0.1份 (F) Leveling agent: Polyether modified polysiloxane (Toray Silicone SH8400, manufactured by Dow Corning Toray Co., Ltd.) 0.1 part
獲得著色硬化性樹脂組合物。 A colored curable resin composition was obtained.
混合: mixing:
(A)著色劑(A1):C.I.顏料藍15:6(顏料) 2份 (A) Colorant (A1): C.I. Pigment Blue 15: 6 (Pigment) 2 parts
丙烯酸系顏料分散劑 0.5份 Acrylic pigment dispersant 0.5 part
丙二醇單甲醚乙酸酯 30份 Propylene glycol monomethyl ether acetate 30 parts
並使用珠磨機使顏料充分分散,繼而,混合: And use a bead mill to fully disperse the pigment, and then, mix:
(A)著色劑(A3):合成例17中獲得之共聚物溶液 3.0份 (A) Colorant (A3): 3.0 parts of the copolymer solution obtained in Synthesis Example 17
(A)著色劑:式(I-2)所表示之化合物 0.08份 (A) Colorant: 0.08 part of the compound represented by formula (I-2)
(B)樹脂:樹脂B1(固形物成分換算) 50份 (B) Resin: Resin B1 (solid content conversion) 50 parts
(C)聚合性化合物:二季戊四醇六丙烯酸酯(Kayarad(註冊商標)DPHA,日本化藥股份有限公司製造) 50份 (C) Polymerizable compound: 50 parts of dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)
(D)聚合起始劑: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) 10份 (D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01, BASF Corporation Made) 10 servings
(E)溶劑:乳酸乙酯 556份 (E) Solvent: 556 parts of ethyl lactate
(E)溶劑:丙二醇單甲醚乙酸酯 8份 (E) Solvent: 8 parts of propylene glycol monomethyl ether acetate
(F)調平劑:聚醚改性聚矽氧油(Toray Silicone SH8400,Dow Corning Toray股份有限公司製造) 0.1份 (F) Leveling agent: Polyether modified polysiloxane (Toray Silicone SH8400, manufactured by Dow Corning Toray Co., Ltd.) 0.1 part
獲得著色硬化性樹脂組合物。 A colored curable resin composition was obtained.
混合: mixing:
(A)著色劑(A1):C.I.顏料藍15:6(顏料) 2份 (A) Colorant (A1): C.I. Pigment Blue 15: 6 (Pigment) 2 parts
丙烯酸系顏料分散劑 0.5份 Acrylic pigment dispersant 0.5 part
丙二醇單甲醚乙酸酯 30份 Propylene glycol monomethyl ether acetate 30 parts
並使用珠磨機使顏料充分分散,繼而,混合: And use a bead mill to fully disperse the pigment, and then, mix:
(A)著色劑(A3):合成例18中獲得之共聚物溶液 3.1份 (A) Colorant (A3): 3.1 parts of the copolymer solution obtained in Synthesis Example 18
(A)著色劑:式(I-2)所表示之化合物 0.1份 (A) Colorant: 0.1 part of the compound represented by formula (I-2)
(B)樹脂:樹脂B1(固形物成分換算) 50份 (B) Resin: Resin B1 (solid content conversion) 50 parts
(C)聚合性化合物:二季戊四醇六丙烯酸酯(Kayarad(註冊商標)DPHA,日本化藥股份有限公司製造) 50份 (C) Polymerizable compound: 50 parts of dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)
(D)聚合起始劑: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) 10份 (D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01, BASF Corporation Made) 10 servings
(E)溶劑:乳酸乙酯 556份 (E) Solvent: 556 parts of ethyl lactate
(E)溶劑:丙二醇單甲醚乙酸酯 8份 (E) Solvent: 8 parts of propylene glycol monomethyl ether acetate
(F)調平劑:聚醚改性聚矽氧油(Toray Silicone SH8400,Dow Corning Toray股份有限公司製造) 0.1份 (F) Leveling agent: Polyether modified polysiloxane (Toray Silicone SH8400, manufactured by Dow Corning Toray Co., Ltd.) 0.1 part
獲得著色硬化性樹脂組合物。 A colored curable resin composition was obtained.
與實施例1~5同樣地對實施例15~實施例18中獲得之各著色硬化性樹脂組合物進行色度評估及耐熱性評估。將結果示於表8。Y之值越大,表示亮度越高,△Eab*越小,表示加熱前後之顏色變化越小,耐熱性越優異。 Each of the colored curable resin compositions obtained in Examples 15 to 18 was subjected to colorimetric evaluation and heat resistance evaluation in the same manner as in Examples 1 to 5. The results are shown in Table 8. The larger the value of Y, the higher the brightness, and the smaller ΔEab *, the smaller the color change before and after heating, and the better the heat resistance.
使用合成例31中獲得之共聚物分散液代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 The copolymer dispersion obtained in Synthesis Example 31 was used instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例32中獲得之共聚物分散液代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 The copolymer dispersion obtained in Synthesis Example 32 was used instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例33中獲得之共聚物分散液代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 The copolymer dispersion obtained in Synthesis Example 33 was used instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例34中獲得之共聚物分散液代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 The copolymer dispersion obtained in Synthesis Example 34 was used instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例35中獲得之共聚物分散液代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 The copolymer dispersion obtained in Synthesis Example 35 was used instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例36中獲得之共聚物分散液代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 The copolymer dispersion obtained in Synthesis Example 36 was used instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例37中獲得之共聚物分散液代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 The copolymer dispersion obtained in Synthesis Example 37 was used instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例38中獲得之共聚物分散液代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 The copolymer dispersion obtained in Synthesis Example 38 was used instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例39中獲得之共聚物分散液代替染料1,除此以 外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 The copolymer dispersion obtained in Synthesis Example 39 was used instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例40中獲得之共聚物分散液代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 The copolymer dispersion obtained in Synthesis Example 40 was used instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例41中獲得之共聚物分散液代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 The copolymer dispersion obtained in Synthesis Example 41 was used instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例42中獲得之共聚物分散液代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 Use the copolymer dispersion obtained in Synthesis Example 42 instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例43中獲得之式(aa11)所表示之化合物代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 Use the compound represented by the formula (aa11) obtained in Synthesis Example 43 instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例44中獲得之式(aa12)所表示之化合物代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 Use the compound represented by formula (aa12) obtained in Synthesis Example 44 instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例45中獲得之式(aa13)所表示之化合物代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 Instead of using the compound represented by formula (aa13) obtained in Synthesis Example 45, A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
將如下物質加以混合,使用珠磨機使顏料充分分散: The following materials are mixed and the pigment is fully dispersed using a bead mill:
(A)著色劑(A1):C.I.顏料藍15:6(顏料) 0.8份 (A) Colorant (A1): C.I. Pigment Blue 15: 6 (Pigment) 0.8 parts
丙烯酸系顏料分散劑 0.2份 Acrylic pigment dispersant 0.2 parts
丙二醇單甲醚乙酸酯 30份 Propylene glycol monomethyl ether acetate 30 parts
繼而,混合如下物質而獲得著色硬化性樹脂組合物: Then, the following were mixed to obtain a colored curable resin composition:
(A)著色劑(A3):合成例46中獲得之共聚物溶液 3.0份 (A) Colorant (A3): 3.0 parts of the copolymer solution obtained in Synthesis Example 46
(A)著色劑:式(I-2)所表示之化合物 0.03份 (A) Colorant: 0.03 part of the compound represented by formula (I-2)
(B)樹脂:樹脂B1(固形物成分換算) 50份 (B) Resin: Resin B1 (solid content conversion) 50 parts
(C)聚合性化合物:二季戊四醇六丙烯酸酯(Kayarad(註冊商標)DPHA,日本化藥股份有限公司製造) 50份 (C) Polymerizable compound: 50 parts of dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)
(D)聚合起始劑: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) 10份 (D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01, BASF Corporation Made) 10 servings
(E)溶劑:乳酸乙酯 556份 (E) Solvent: 556 parts of ethyl lactate
(E)溶劑:丙二醇單甲醚乙酸酯 8份 (E) Solvent: 8 parts of propylene glycol monomethyl ether acetate
(F)調平劑:聚醚改性聚矽氧油(Toray Silicone SH8400,Dow Corning Toray股份有限公司製造) 0.1份 (F) Leveling agent: Polyether modified polysiloxane (Toray Silicone SH8400, manufactured by Dow Corning Toray Co., Ltd.) 0.1 part
混合: mixing:
(A)著色劑(A1):C.I.顏料藍15:6(顏料) 0.8份 (A) Colorant (A1): C.I. Pigment Blue 15: 6 (Pigment) 0.8 parts
丙烯酸系顏料分散劑 0.2份 Acrylic pigment dispersant 0.2 parts
丙二醇單甲醚乙酸酯 30份 Propylene glycol monomethyl ether acetate 30 parts
並使用珠磨機使顏料充分分散,繼而,混合: And use a bead mill to fully disperse the pigment, and then, mix:
(A)著色劑(A3):合成例47中獲得之共聚物溶液 3.0份 (A) Colorant (A3): 3.0 parts of the copolymer solution obtained in Synthesis Example 47
(A)著色劑:式(I-2)所表示之化合物 0.04份 (A) Colorant: 0.04 part of the compound represented by formula (I-2)
(B)樹脂:樹脂B1(固形物成分換算) 50份 (B) Resin: Resin B1 (solid content conversion) 50 parts
(C)聚合性化合物:二季戊四醇六丙烯酸酯(Kayarad(註冊商標)DPHA,日本化藥股份有限公司製造) 50份 (C) Polymerizable compound: 50 parts of dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)
(D)聚合起始劑: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) 10份 (D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01, BASF Corporation Made) 10 servings
(E)溶劑:乳酸乙酯 556份 (E) Solvent: 556 parts of ethyl lactate
(E)溶劑:丙二醇單甲醚乙酸酯 8份 (E) Solvent: 8 parts of propylene glycol monomethyl ether acetate
(F)調平劑:聚醚改性聚矽氧油(Toray Silicone SH8400,Dow Corning Toray股份有限公司製造) 0.1份 (F) Leveling agent: polyether modified silicone oil (Toray Silicone SH8400, Dow Corning Toray Co., Ltd.) 0.1 copies
獲得著色硬化性樹脂組合物。 A colored curable resin composition was obtained.
混合: mixing:
(A)著色劑(A1):C.I.顏料藍15:6(顏料) 0.8份 (A) Colorant (A1): C.I. Pigment Blue 15: 6 (Pigment) 0.8 parts
丙烯酸系顏料分散劑 0.2份 Acrylic pigment dispersant 0.2 parts
丙二醇單甲醚乙酸酯 30份 Propylene glycol monomethyl ether acetate 30 parts
並使用珠磨機使顏料充分分散,繼而,混合: And use a bead mill to fully disperse the pigment, and then, mix:
(A)著色劑(A3):合成例48中獲得之共聚物溶液 2.9份 (A) Colorant (A3): 2.9 parts of the copolymer solution obtained in Synthesis Example 48
(A)著色劑:式(I-2)所表示之化合物 0.04份 (A) Colorant: 0.04 part of the compound represented by formula (I-2)
(B)樹脂:樹脂B1(固形物成分換算) 50份 (B) Resin: Resin B1 (solid content conversion) 50 parts
(C)聚合性化合物:二季戊四醇六丙烯酸酯(Kayarad(註冊商標)DPHA,日本化藥股份有限公司製造) 50份 (C) Polymerizable compound: 50 parts of dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)
(D)聚合起始劑: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) 10份 (D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01, BASF Corporation Made) 10 servings
(E)溶劑:乳酸乙酯 556份 (E) Solvent: 556 parts of ethyl lactate
(E)溶劑:丙二醇單甲醚乙酸酯 8份 (E) Solvent: 8 parts of propylene glycol monomethyl ether acetate
(F)調平劑:聚醚改性聚矽氧油(Toray Silicone SH8400,Dow Corning Toray股份有限公司製造) 0.1份 (F) Leveling agent: Polyether modified polysiloxane (Toray Silicone SH8400, manufactured by Dow Corning Toray Co., Ltd.) 0.1 part
獲得著色硬化性樹脂組合物。 A colored curable resin composition was obtained.
混合: mixing:
(A)著色劑(A1):C.I.顏料藍15:6(顏料) 0.8份 (A) Colorant (A1): C.I. Pigment Blue 15: 6 (Pigment) 0.8 parts
丙烯酸系顏料分散劑 0.2份 Acrylic pigment dispersant 0.2 parts
丙二醇單甲醚乙酸酯 30份 Propylene glycol monomethyl ether acetate 30 parts
並使用珠磨機使顏料充分分散,繼而,混合: And use a bead mill to fully disperse the pigment, and then, mix:
(A)著色劑(A3):合成例49中獲得之共聚物溶液 3.1份 (A) Colorant (A3): 3.1 parts of the copolymer solution obtained in Synthesis Example 49
(A)著色劑:式(I-2)所表示之化合物 0.05份 (A) Colorant: 0.05 part of the compound represented by formula (I-2)
(B)樹脂:樹脂B1(固形物成分換算) 50份 (B) Resin: Resin B1 (solid content conversion) 50 parts
(C)聚合性化合物:二季戊四醇六丙烯酸酯(Kayarad(註冊商標)DPHA,日本化藥股份有限公司製造) 50份 (C) Polymerizable compound: 50 parts of dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)
(D)聚合起始劑: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) 10份 (D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01, BASF Corporation Made) 10 servings
(E)溶劑:乳酸乙酯 556份 (E) Solvent: 556 parts of ethyl lactate
(E)溶劑:丙二醇單甲醚乙酸酯 8份 (E) Solvent: 8 parts of propylene glycol monomethyl ether acetate
(F)調平劑:聚醚改性聚矽氧油(Toray Silicone SH8400,Dow Corning Toray股份有限公司製造) 0.1份 (F) Leveling agent: Polyether modified polysiloxane (Toray Silicone SH8400, manufactured by Dow Corning Toray Co., Ltd.) 0.1 part
獲得著色硬化性樹脂組合物。 A colored curable resin composition was obtained.
與實施例1~5同樣地對實施例34~實施例37中獲得之各著色硬化性樹脂組合物進行色度評估及耐熱性評估。將結果示於表9。Y之值越大,表示亮度越高,△Eab*越小,表示加熱前後之顏色變化越小,耐熱性越優異。 Each of the colored curable resin compositions obtained in Examples 34 to 37 was subjected to colorimetric evaluation and heat resistance evaluation in the same manner as in Examples 1 to 5. The results are shown in Table 9. The larger the value of Y, the higher the brightness, and the smaller ΔEab *, the smaller the color change before and after heating, and the better the heat resistance.
使用合成例50中獲得之共聚物分散液代替染料1,除此以 外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 The copolymer dispersion obtained in Synthesis Example 50 was used instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例51中獲得之共聚物分散液代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 The copolymer dispersion obtained in Synthesis Example 51 was used instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例52中獲得之共聚物分散液代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 Use the copolymer dispersion obtained in Synthesis Example 52 instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用合成例53中獲得之共聚物分散液代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 The copolymer dispersion obtained in Synthesis Example 53 was used instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用溶劑藍(Solvent Blue)38(Orient Corp.,Valifast blue1605)代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 Use Solvent Blue 38 (Orient Corp., Valifast blue1605) instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用溶劑藍(Solvent Blue)129(Orient Corp.,Valifast blue100)代替染料1,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 Use Solvent Blue 129 (Orient Corp., Valifast blue 100) instead A colored curable resin composition was obtained in the same manner as in Example 1 except for the dye 1.
使用式(4-9)所表示之化合物代替染料1,進而含有C.I.顏料紫23,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 Use a compound represented by formula (4-9) instead A colored curable resin composition was obtained in the same manner as in Example 1 except that the dye 1 further contained CI Pigment Violet 23.
使用式(1-44)所表示之化合物代替染料1,進而含有C.I.顏料紫23,除此以外,以與實施例1同樣之方式獲得著色硬化性樹脂組合物。 Use a compound represented by formula (1-44) instead A colored curable resin composition was obtained in the same manner as in Example 1 except that the dye 1 further contained CI Pigment Violet 23.
由本發明之著色硬化性樹脂組合物所形成之著色塗膜或著色圖案具有良好之耐熱性與良好之亮度。由本發明之著色硬化性樹脂組合物所形成之彩色濾光片有用,可知包含該彩色濾光片之液晶顯示裝置之顯示特性良好。 The colored coating film or colored pattern formed from the colored hardening resin composition of the present invention has good heat resistance and good brightness. The color filter formed from the coloring curable resin composition of the present invention is useful, and it is found that the liquid crystal display device including the color filter has good display characteristics.
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JP2012083652A (en) * | 2010-10-14 | 2012-04-26 | Nippon Kayaku Co Ltd | Colored resin composition |
KR20140001731A (en) * | 2010-10-21 | 2014-01-07 | 니폰 가야꾸 가부시끼가이샤 | Colored resin composition for use in color filter, color filter, display device, and solid-state imaging element |
JP5962042B2 (en) * | 2011-02-28 | 2016-08-03 | 住友化学株式会社 | Colored curable resin composition |
JP6461453B2 (en) * | 2011-12-09 | 2019-01-30 | 住友化学株式会社 | Red colored curable resin composition |
JP5953754B2 (en) | 2012-01-13 | 2016-07-20 | 住友化学株式会社 | Colored curable resin composition |
JP6115281B2 (en) * | 2012-06-07 | 2017-04-19 | Jsr株式会社 | Coloring composition, color filter and display element |
TW201423272A (en) * | 2012-11-27 | 2014-06-16 | Jsr Corp | Photosensitive composition, colorant dispersion solution, light filter and light sensor |
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JP2016094593A (en) | 2016-05-26 |
KR20160051625A (en) | 2016-05-11 |
TW201623482A (en) | 2016-07-01 |
CN105573055B (en) | 2020-11-17 |
CN105573055A (en) | 2016-05-11 |
KR102402498B1 (en) | 2022-05-27 |
JP6672701B2 (en) | 2020-03-25 |
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