TWI739971B - Compound, colored resin composition, color filter, display device, and solid-state imaging element - Google Patents

Abstract

本發明係關於一種化合物、著色樹脂組合物、濾色器、顯示裝置及固體攝像元件。能夠充分地滿足由本發明的著色樹脂組合物形成的濾色器的對比度。 The present invention relates to a compound, a colored resin composition, a color filter, a display device, and a solid-state imaging element. The contrast of the color filter formed from the colored resin composition of the present invention can be sufficiently satisfied.

Description

化合物、著色樹脂組合物、濾色器、顯示裝置及固體攝像元件 Compound, colored resin composition, color filter, display device, and solid-state imaging element

本發明係關於一種化合物、著色樹脂組合物、濾色器、顯示裝置及固體攝像元件。 The present invention relates to a compound, a colored resin composition, a color filter, a display device, and a solid-state imaging element.

在液晶顯示裝置、電致發光顯示裝置及電漿顯示器等顯示裝置、與CCD、CMOS感測器等固體攝像元件中所使用的濾色器係由著色樹脂組合物所製造。作為這樣的著色樹脂組合物，已知有包含部分溴化酞菁鋅顏料作為著色劑的組合物(專利文獻1)。 Color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, plasma displays, and solid-state imaging devices such as CCD and CMOS sensors are made of colored resin compositions. As such a colored resin composition, a composition containing a partially brominated zinc phthalocyanine pigment as a colorant is known (Patent Document 1).

先前技術文獻 Prior art literature

專利文獻 Patent literature

專利文獻1：日本專利特開第2004-70342號公報 Patent Document 1: Japanese Patent Laid-Open No. 2004-70342

由以往已知的上述著色樹脂組合物所形成的濾色器係有時不能充分地滿足對比度。 The color filter system formed from the aforementioned colored resin composition known in the past may not sufficiently satisfy the contrast.

本發明包含以下的發明。 The present invention includes the following inventions.

[1]著色樹脂組合物，其包含著色劑及樹脂，上述著色劑包含由式(Ia)表示的化合物。 [1] A colored resin composition containing a colorant and a resin, and the colorant contains a compound represented by formula (Ia).

[式(Ia)中，R¹至R⁴各自獨立地表示可具有取代基的碳數6至20的芳香族烴基或者可具有取代基的碳數3至19的芳香族雜環基。R⁵至R¹²各自獨立地表示氫原子、鹵素原子、氰基、硝基、可具有取代基的碳數1至20的飽和烴基、可具有取代基的碳數6至20的芳香族烴基或者可具有取代基的碳數3至19的芳香族雜環基。R⁵與R⁶、R⁷與R⁸、R⁹與R¹⁰以及R¹¹與R¹²可各自相互結合而形成可具有取代基的芳香族烴環。M表示2價的金屬原子或者具有取代基的3價或4價的金屬原子。] [In formula (Ia), R ¹ to R ⁴ each independently represent an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms or an optionally substituted aromatic heterocyclic group having 3 to 19 carbon atoms. R ⁵ to R ¹² each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an optionally substituted saturated hydrocarbon group having 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbons, or An optionally substituted aromatic heterocyclic group having 3 to 19 carbon atoms. R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁹ and R ^10, and R ¹¹ and R ¹² may each be combined with each other to form an aromatic hydrocarbon ring that may have a substituent. M represents a divalent metal atom or a trivalent or tetravalent metal atom having a substituent. ]

[2]上述[1]所述的著色樹脂組合物，其還包含聚合性化合物及聚合引發劑。 [2] The colored resin composition described in [1] above, which further contains a polymerizable compound and a polymerization initiator.

[3]由上述[1]或[2]所述的著色樹脂組合物形成的濾色器。 [3] A color filter formed from the coloring resin composition described in [1] or [2] above.

[4]顯示裝置，其包含上述[3]所述的濾色器。 [4] A display device including the color filter described in [3] above.

[5]固體攝像元件，其包含上述[3]所述的濾色器。 [5] A solid-state imaging element including the color filter described in [3] above.

[6]由式(Ib')表示的化合物。 [6] The compound represented by the formula (Ib').

[式(Ib')中，環A¹至A⁴各自獨立地表示可具有取代基的芳香族烴環。不過，環A¹至A⁴中至少一個為具有取代基的芳香族烴環。R¹至R⁴各自獨立地表示可具有取代基的碳數6至20的芳香族烴基或者可具有取代基的碳數3至19的芳香族雜環基。M表示2價的金屬原子或者具有取代基的3價或4價的金屬原子。] [In formula (Ib'), rings A ¹ to A ⁴ each independently represent an aromatic hydrocarbon ring which may have a substituent. However, ^{at least one of the rings A 1} to A ⁴ is an aromatic hydrocarbon ring having a substituent. R ¹ to R ⁴ each independently represent an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms or an optionally substituted aromatic heterocyclic group having 3 to 19 carbon atoms. M represents a divalent metal atom or a trivalent or tetravalent metal atom having a substituent. ]

採用本發明的著色樹脂組合物，能夠製造對比度高的濾色器。 With the colored resin composition of the present invention, a color filter with high contrast can be manufactured.

本發明的著色樹脂組合物包含著色劑及樹脂。以下，有時將著色劑稱為「著色劑(A)」，有時將樹脂稱為「樹脂(B)」。 The colored resin composition of the present invention contains a colorant and a resin. Hereinafter, the coloring agent may be referred to as "coloring agent (A)", and the resin may be referred to as "resin (B)".

<著色劑(A)> <Colorant (A)>

上述著色劑(A)包含由式(Ia)表示的化合物。以下，有時將由式(Ia)表示的化合物稱為「化合物(Ia)」。 The above-mentioned coloring agent (A) contains a compound represented by formula (Ia). Hereinafter, the compound represented by formula (Ia) may be referred to as "compound (Ia)".

[式(Ia)中，R¹至R⁴各自獨立地表示可具有取代基的碳數6至20的芳香族烴基或者可具有取代基的碳數3至19的芳香族雜環基。R⁵至R¹²各自獨立地表示氫原子、鹵素原子、氰基、硝基、可具有取代基的碳數1至20的飽和烴基、可具有取代基的碳數6至20的芳香族烴基或者可具有取代基的碳數3至19的芳香族雜環基。R⁵與R⁶、R⁷與R⁸、R⁹與R¹⁰以及R¹¹與R¹²可各自相互結合而形成可具有取代基的芳香族烴環。M表示2價的金屬原子或者具有取代基的3價或4價的金屬原子。] [In formula (Ia), R ¹ to R ⁴ each independently represent an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms or an optionally substituted aromatic heterocyclic group having 3 to 19 carbon atoms. R ⁵ to R ¹² each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an optionally substituted saturated hydrocarbon group having 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbons, or An optionally substituted aromatic heterocyclic group having 3 to 19 carbon atoms. R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁹ and R ^10, and R ¹¹ and R ¹² may each be combined with each other to form an aromatic hydrocarbon ring that may have a substituent. M represents a divalent metal atom or a trivalent or tetravalent metal atom having a substituent. ]

由R¹至R⁴及R⁵至R¹²表示的芳香族烴基的碳數較佳為6至15，更佳為6至12。作為該芳香族烴基，可列舉出苯基、鄰-甲苯基、間-甲苯基、對-甲苯基、二甲苯基、4-正-丁基苯基、4-三級-丁基苯基、萘基、蒽基、菲基、聯苯基、三聯苯基等，較佳為苯基、鄰-甲苯基、間-甲苯基、對-甲苯基、4-正-丁基苯基、4-三級- 丁基苯基，特別佳為4-正-丁基苯基、苯基。 The carbon number of the aromatic hydrocarbon group represented by R ¹ to R ⁴ and R ⁵ to R ^{12 is preferably 6-15, more preferably 6-12.} Examples of the aromatic hydrocarbon group include phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, 4-n-butylphenyl, 4-tertiary-butylphenyl, Naphthyl, anthracenyl, phenanthryl, biphenyl, terphenyl, etc., preferably phenyl, o-tolyl, m-tolyl, p-tolyl, 4-n-butylphenyl, 4- Tertiary-butylphenyl, particularly preferably 4-n-butylphenyl and phenyl.

由R¹至R⁴及R⁵至R¹²表示的上述芳香族烴基可具有一個或二個以上的取代基。作為該取代基，可列舉出氟原子、氯原子、碘原子、溴原子等鹵素原子；氯甲基、三氟甲基等碳數1至6的鹵代烷基；甲氧基、乙氧基等碳數1至6的烷氧基；羥基；甲磺醯基等碳數1至6的烷烴磺醯基；甲氧基羰基、乙氧基羰基等碳數1至6的烷氧基羰基等。作為具有取代基的芳香族烴基，例如可列舉出2-氟苯基、2-氯苯基、2-溴苯基、2-碘苯基、3-氟苯基、3-氯苯基、3-溴苯基、3-碘苯基、4-氟苯基、4-氯苯基、4-溴苯基、4-碘苯基、2,3-二氯苯基、2,4-二氯苯基、2,5-二氯苯基、2,6-二氯苯基、3,5-二氯苯基、2,6-二氟苯基、1,3,5-三氯苯基、2,3,4,5-四氯苯基、4-氯甲基苯基、2-三氟甲基、2-甲氧基苯基、3-甲氧基苯基、4-甲氧基苯基、2-羥基苯基、3-羥基苯基、4-羥基苯基、4-胺磺醯基苯基、2-甲磺醯基苯基等，較佳為2-甲氧基苯基、3-甲氧基苯基、4-甲氧基苯基。 The above-mentioned aromatic hydrocarbon groups represented by R ¹ to R ⁴ and R ⁵ to R ¹² may have one or two or more substituents. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; halogenated alkyl groups having 1 to 6 carbon atoms such as chloromethyl group and trifluoromethyl group; carbon atoms such as methoxy group and ethoxy group. Alkoxy groups having 1 to 6; hydroxyl groups; alkanesulfonyl groups having 1 to 6 carbon atoms such as methanesulfonyl groups; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl groups. Examples of the substituted aromatic hydrocarbon group include 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-iodophenyl, 3-fluorophenyl, 3-chlorophenyl, 3 -Bromophenyl, 3-iodophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 2,3-dichlorophenyl, 2,4-dichloro Phenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 3,5-dichlorophenyl, 2,6-difluorophenyl, 1,3,5-trichlorophenyl, 2,3,4,5-tetrachlorophenyl, 4-chloromethylphenyl, 2-trifluoromethyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxybenzene Group, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 4-sulfamoylphenyl, 2-methanesulfonylphenyl, etc., preferably 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl.

由R¹至R⁴及R⁵至R¹²表示的芳香族雜環基的碳數較佳為3至12，更佳為3至8。作為該芳香族雜環基，可列舉出噻吩基、甲基噻吩基、呋喃基、吡咯基、咪唑基、吡唑基、噻唑基、異噻唑基、吡啶基、吲哚基、異吲哚基、吲唑基等。 The carbon number of the aromatic heterocyclic group represented by R ¹ to R ⁴ and R ⁵ to R ^{12 is preferably 3-12, more preferably 3-8.} Examples of the aromatic heterocyclic group include thienyl, methylthienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, pyridyl, indolyl, and isoindolyl. , Indazolyl and so on.

由R¹至R⁴及R⁵至R¹²表示的上述芳香族雜環基可具有一個或二個以上的取代基。作為該取代基，可列舉出氟原子、氯原子、碘原子、溴原子等鹵素原子；氯甲基、三氟甲基等碳數1至 6的鹵代烷基；甲氧基、乙氧基等碳數1至6的烷氧基；羥基；甲磺醯基等碳數1至6的烷烴磺醯基；甲氧基羰基、乙氧基羰基等碳數1至6的烷氧基羰基等。作為具有取代基的芳香族雜環基，可列舉出噻吩基、呋喃基、吡咯基、噻唑基、噁唑基等。 The above-mentioned aromatic heterocyclic group represented by R ¹ to R ⁴ and R ⁵ to R ¹² may have one or two or more substituents. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; halogenated alkyl groups having 1 to 6 carbon atoms such as chloromethyl group and trifluoromethyl group; carbon atoms such as methoxy group and ethoxy group. Alkoxy groups having 1 to 6; hydroxyl groups; alkanesulfonyl groups having 1 to 6 carbon atoms such as methanesulfonyl groups; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl groups. As a substituted aromatic heterocyclic group, a thienyl group, a furyl group, a pyrrolyl group, a thiazolyl group, an oxazolyl group, etc. are mentioned.

由R⁵至R¹²表示的飽和烴基可為直鏈狀、分支鏈狀及環狀的任一種。作為直鏈狀、分支鏈狀或環狀的飽和烴基，可列舉出甲基、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、正二十烷基等直鏈狀烷基；異丙基、異丁基、異戊基、新戊基、2-乙基己基等分支鏈狀烷基等；環己基等環烷基等。該飽和烴基的碳數較佳為1至10，更佳為1至8，進一步更佳為1至6。 The saturated hydrocarbon group represented by R ⁵ to R ¹² may be any of linear, branched, and cyclic. Examples of linear, branched, or cyclic saturated hydrocarbon groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and n-nonyl. , N-decyl, n-dodecyl, n-hexadecyl, n-eicosyl and other linear alkyl groups; isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl Such as branched chain alkyl, etc.; cyclohexyl and other cycloalkyl, etc. The carbon number of the saturated hydrocarbon group is preferably from 1 to 10, more preferably from 1 to 8, and still more preferably from 1 to 6.

由R⁵至R¹²表示的上述飽和烴基可具有一個或二個以上的取代基。作為該取代基，可列舉出氟原子、氯原子、碘原子、溴原子等鹵素原子；甲氧基、乙氧基等碳數1至6的烷氧基；羥基；氰基；乙醯基等醯基；甲磺醯基等碳數1至6的烷烴磺醯基；甲氧基羰基、乙氧基羰基等碳數1至6的烷氧基羰基等。作為具有取代基的飽和烴基，可列舉出氯甲基、三氟甲基、羥基乙基、乙氧基乙基、氰基丙基、乙醯基丙基等。 The aforementioned saturated hydrocarbon group represented by R ⁵ to R ¹² may have one or two or more substituents. Examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a cyano group; an acetyl group, etc. Alkylsulfonyl groups having 1 to 6 carbon atoms such as methanesulfonyl group; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group. Examples of the saturated hydrocarbon group having a substituent include chloromethyl, trifluoromethyl, hydroxyethyl, ethoxyethyl, cyanopropyl, and acetoxypropyl.

作為由R⁵至R¹²表示的鹵素原子，可列舉出氟原子、氯原子、溴原子、碘原子等，較佳為溴原子。 Examples of the halogen atom represented by R ⁵ to R ¹² include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a bromine atom is preferred.

R⁵與R⁶、R⁷與R⁸、R⁹與R¹⁰或者R¹¹與R¹²可各自相互結合而形成芳香族烴環。作為該芳香族烴環，可列舉出苯。在該 苯上進一步稠合或結合碳數6至20的芳香族烴環而成的結構也包含在該芳香族烴環中。作為在苯上稠合或結合芳香族烴環而成的結構，可列舉出萘、蒽、菲、聯苯、三聯苯等。另外，在芳香族烴環上結合了碳數1至20的飽和烴基的結構也包含在芳香族烴環中。作為芳香族烴環，較佳為苯。 R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁹ and R ^10, or R ¹¹ and R ¹² may be combined with each other to form an aromatic hydrocarbon ring. As the aromatic hydrocarbon ring, benzene can be cited. A structure in which an aromatic hydrocarbon ring having 6 to 20 carbon atoms is further condensed or bonded to the benzene is also included in the aromatic hydrocarbon ring. Examples of the structure formed by condensing or bonding an aromatic hydrocarbon ring to benzene include naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, and the like. In addition, a structure in which a saturated hydrocarbon group having 1 to 20 carbon atoms is bonded to an aromatic hydrocarbon ring is also included in the aromatic hydrocarbon ring. As the aromatic hydrocarbon ring, benzene is preferred.

R⁵與R⁶、R⁷與R⁸、R⁹與R¹⁰或者R¹¹與R¹²形成的芳香族烴環可具有一個或二個以上的取代基。作為該取代基，可列舉出氟原子、氯原子、碘原子、溴原子等鹵素原子；氯甲基、三氟甲基等碳數1至6的鹵代烷基；甲氧基、乙氧基等碳數1至6的烷氧基；羥基；甲磺醯基等碳數1至6的烷烴磺醯基；乙醯基等碳數2至6的醯基；羥基羰基；甲氧基羰基、乙氧基羰基等碳數1至6的烷氧基羰基等。作為具有取代基的芳香族烴環，例如可列舉出一氟苯、二氟苯、三氟苯、四氟苯、一氯苯、二氯苯、三氯苯、四氯苯、一溴苯、二溴苯、三溴苯、四溴苯、甲氧基苯、乙氧基苯、羥基苯、甲磺醯基苯、乙醯基苯、羥基羰基苯、甲氧基羰基苯、乙氧基羰基苯等，較佳為乙醯基苯、羥基羰基苯、乙氧基羰基苯、一氟苯、一氯苯、一溴苯、二氟苯、二氯苯、二溴苯，特別佳為一氯苯。 The aromatic hydrocarbon ring formed by R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁹ and R ¹⁰ or R ¹¹ and R ¹² may have one or two or more substituents. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; halogenated alkyl groups having 1 to 6 carbon atoms such as chloromethyl group and trifluoromethyl group; carbon atoms such as methoxy group and ethoxy group. Alkoxy groups with numbers from 1 to 6; hydroxyl groups; alkanesulfonyl groups with carbon numbers from 1 to 6 such as methanesulfonyl groups; acetyl groups with carbon numbers from 2 to 6 such as acetyl groups; hydroxycarbonyl groups; Alkoxycarbonyl groups having 1 to 6 carbon atoms such as carbonyl groups and the like. As the aromatic hydrocarbon ring having a substituent, for example, monofluorobenzene, difluorobenzene, trifluorobenzene, tetrafluorobenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, monobromobenzene, Dibromobenzene, tribromobenzene, tetrabromobenzene, methoxybenzene, ethoxybenzene, hydroxybenzene, methanesulfonylbenzene, acetylbenzene, hydroxycarbonylbenzene, methoxycarbonylbenzene, ethoxycarbonyl Benzene, etc., preferably acetylbenzene, hydroxycarbonylbenzene, ethoxycarbonylbenzene, monofluorobenzene, monochlorobenzene, monobromobenzene, difluorobenzene, dichlorobenzene, dibromobenzene, and particularly preferably monochlorobenzene benzene.

作為由上述M表示的2價至4價的金屬原子，可列舉出根據IUPAC 1990年規則的長週期型週期表中分類為第2族至第15族的金屬原子。在這些中，作為金屬元素，較佳為Mg、Ti、Zr、V、Nb、Ta、Cr、Mo、W、Mn、Fe、Co、Ni、Ru、Rh、Pd、Os、 Ir、Pt、Cu、Ag、Au、Zn、Cd、Hg、Al、Ga、In、Si、Ge、Sn、Pb、Sb、Bi等，更佳為Ti、Zr、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Hg、Al、Ga、Si、Ge、Sn等，進一步更佳為Ni、Zn、Hg，最佳為Zn。 As the divalent to tetravalent metal atom represented by the above-mentioned M, metal atoms classified into groups 2 to 15 in the long-period periodic table according to the IUPAC 1990 rules can be cited. Among these, the metal element is preferably Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu , Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, etc., more preferably Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu , Zn, Hg, Al, Ga, Si, Ge, Sn, etc., more preferably Ni, Zn, Hg, and most preferably Zn.

上述金屬原子中3價或4價的金屬原子具有取代基。較佳為具有取代基的3價或4價的金屬原子係藉由與二個氮原子形成二個N-M鍵，從而使用二個原子價，用剩餘的原子價與取代基結合。作為3價或4價的金屬原子具有的取代基，可列舉出氯原子等鹵素原子；側氧基；羥基；乙醯氧基等醯氧基；甲磺醯氧基等烷烴磺醯氧基等。 Among the above-mentioned metal atoms, the trivalent or tetravalent metal atom has a substituent. Preferably, a trivalent or tetravalent metal atom having a substituent forms two N-M bonds with two nitrogen atoms, so that two valences are used, and the remaining valences are bonded to the substituent. Examples of the substituents possessed by the trivalent or tetravalent metal atom include halogen atoms such as chlorine atoms; pendant oxy groups; hydroxyl groups; acyloxy groups such as acetoxy groups; alkanesulfonyloxy groups such as methanesulfonyloxy groups. .

作為具有鹵素原子的3價或4價的金屬原子，可列舉出AlCl、SiCl₂、VCl、VCl₂、VOCl、FeCl、GaCl、ZrCl等。 Examples of trivalent or tetravalent metal atoms having halogen atoms include AlCl, SiCl ₂ , VCl, VCl ₂ , VOCl, FeCl, GaCl, ZrCl, and the like.

作為具有側氧基的3價或4價的金屬原子，可列舉出VO、GeO等。 Examples of trivalent or tetravalent metal atoms having pendant oxygen groups include VO, GeO, and the like.

作為具有羥基的3價或4價的金屬原子，可列舉出Si(OH)₂、Cr(OH)₂、Sn(OH)₂等。 Examples of the trivalent or tetravalent metal atom having a hydroxyl group include Si(OH) ₂ , Cr(OH) ₂ , Sn(OH) ₂ and the like.

化合物(Ia)較佳係R⁵至R¹²的至少一個為碳數6至20的芳香族烴基或碳數3至19的芳香族雜環基，或者R⁵與R⁶、R⁷與R⁸、R⁹與R¹⁰、或R¹¹與R¹²相互結合而形成了芳香族烴環，進一步更佳為由式(Ib)表示的化合物。以下，有時將由式(Ib)表示的化合物稱為「化合物(Ib)」。 Compound (Ia) is preferably ^{that at least one of R 5} to R ¹² is an aromatic hydrocarbon group having 6 to 20 carbons or an aromatic heterocyclic group having 3 to 19 carbons, or R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , or R ¹¹ and R ¹² combine with each other to form an aromatic hydrocarbon ring, and it is more preferably a compound represented by formula (Ib). Hereinafter, the compound represented by formula (Ib) may be referred to as "compound (Ib)".

[式(Ib)中，環A¹至A⁴各自獨立地表示可具有取代基的芳香族烴環。R¹至R⁴及M與上述相同。] [In formula (Ib), rings A ¹ to A ⁴ each independently represent an aromatic hydrocarbon ring that may have a substituent. R ¹ to R ⁴ and M are the same as described above. ]

再有，由A¹至A⁴表示的芳香族烴環的至少一個可為具有取代基的芳香族烴環。在化合物(Ib)中，有時將由A¹至A⁴表示的芳香族烴環的至少一個為具有取代基的芳香族烴環的化合物稱為「化合物(Ib')」。 Furthermore, ^{at least one of the aromatic hydrocarbon rings represented by A 1} to A ⁴ may be an aromatic hydrocarbon ring having a substituent. Among the compounds (Ib), a compound in which ^{at least one of the aromatic hydrocarbon rings represented by A 1} to A ⁴ is an aromatic hydrocarbon ring having a substituent is sometimes referred to as "compound (Ib')".

作為由A¹至A⁴表示的芳香族烴環，可列舉出苯。在該苯上進一步稠合或結合了碳數6至20的芳香族烴環的結構也包含於上述芳香族烴環中。作為在苯上稠合或結合了芳香族烴環的結構，可列舉出萘、蒽、菲、聯苯、三聯苯等。另外，在芳香族烴環上結合了碳數1至20的飽和烴基的結構也包含在芳香族烴環中。作為芳香族烴環，較佳為苯。 As the aromatic hydrocarbon ring represented by A ¹ to A ⁴ , benzene can be cited. A structure in which an aromatic hydrocarbon ring having 6 to 20 carbon atoms is further condensed or bonded to this benzene is also included in the above-mentioned aromatic hydrocarbon ring. As the structure in which an aromatic hydrocarbon ring is condensed or bonded to benzene, naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, and the like can be cited. In addition, a structure in which a saturated hydrocarbon group having 1 to 20 carbon atoms is bonded to an aromatic hydrocarbon ring is also included in the aromatic hydrocarbon ring. As the aromatic hydrocarbon ring, benzene is preferred.

由A¹至A⁴表示的上述芳香族烴環可具有一個或二個以上的取代基。作為該取代基，可列舉出碳數1至20的飽和烴基；碳數6至20的芳香族烴基；氟原子、氯原子、碘原子、溴原子等鹵素原子；氯甲基、三氟甲基等碳數1至6的鹵代烷基；甲氧基、乙氧基等碳數1至6的烷氧基；羥基；甲磺醯基等碳數1至6的烷烴磺 醯基；乙醯基等碳數2至6的醯基；羥基羰基；甲氧基羰基、乙氧基羰基等碳數1至6的烷氧基羰基等。作為具有取代基的芳香族烴環，例如可列舉出一氟苯、二氟苯、三氟苯、四氟苯、一氯苯、二氯苯、三氯苯、四氯苯、一溴苯、二溴苯、三溴苯、四溴苯、甲氧基苯、乙氧基苯、羥基苯、甲磺醯基苯、乙醯基苯、羥基羰基苯、甲氧基羰基苯、乙氧基羰基苯等，較佳為乙醯基苯、羥基羰基苯、乙氧基羰基苯、一氟苯、一氯苯、一溴苯、二氟苯、二氯苯、二溴苯，特別佳為一氯苯。 The above-mentioned aromatic hydrocarbon ring represented by A ¹ to A ⁴ may have one or two or more substituents. Examples of the substituent include saturated hydrocarbon groups having 1 to 20 carbon atoms; aromatic hydrocarbon groups having 6 to 20 carbon atoms; halogen atoms such as fluorine, chlorine, iodine, and bromine atoms; chloromethyl and trifluoromethyl Alkyl groups with carbon numbers from 1 to 6 such as methoxy and ethoxy groups; hydroxyl groups; alkanesulfonyl groups with carbon numbers from 1 to 6 such as methanesulfonyl groups; acetyl groups, etc. An acyl group having 2 to 6 carbons; a hydroxycarbonyl group; an alkoxycarbonyl group having 1 to 6 carbons such as a methoxycarbonyl group and an ethoxycarbonyl group. As the aromatic hydrocarbon ring having a substituent, for example, monofluorobenzene, difluorobenzene, trifluorobenzene, tetrafluorobenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, monobromobenzene, Dibromobenzene, tribromobenzene, tetrabromobenzene, methoxybenzene, ethoxybenzene, hydroxybenzene, methanesulfonylbenzene, acetylbenzene, hydroxycarbonylbenzene, methoxycarbonylbenzene, ethoxycarbonyl Benzene, etc., preferably acetylbenzene, hydroxycarbonylbenzene, ethoxycarbonylbenzene, monofluorobenzene, monochlorobenzene, monobromobenzene, difluorobenzene, dichlorobenzene, dibromobenzene, and particularly preferably monochlorobenzene benzene.

作為化合物(Ib)，較佳為由式(Ic)表示的化合物。以下，有時將由式(Ic)表示的化合物稱為「化合物(Ic)」。 As the compound (Ib), a compound represented by formula (Ic) is preferred. Hereinafter, the compound represented by formula (Ic) may be referred to as "compound (Ic)".

[式(Ic)中，R²¹至R³⁶各自獨立地表示氫原子、可具有取代基的碳數1至20的飽和烴基、可具有取代基的碳數6至20的芳香族烴基、鹵素原子、碳數1至6的鹵代烷基、碳數1至6的烷氧基、羥基、碳數1至6的烷烴磺醯基、碳數2至6的醯基、羥基羰基或碳數1至6的烷氧基羰基。R¹至R⁴及M與上述相同。] [In formula (Ic), R ²¹ to R ³⁶ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbons which may have a substituent, a halogen atom , Haloalkyl with 1 to 6 carbons, alkoxy with 1 to 6 carbons, hydroxy, alkanesulfonyl with 1 to 6 carbons, acyl with 2 to 6 carbons, hydroxycarbonyl or 1 to 6 carbons的alkoxycarbonyl. R ¹ to R ⁴ and M are the same as described above. ]

再有，R²¹至R³⁶中的至少一個可為可具有取代基的碳數1至20的飽和烴基、可具有取代基的碳數6至20的芳香族烴基、鹵素原子、碳數1至6的鹵代烷基、碳數1至6的烷氧基、羥基、碳數1至6的烷烴磺醯基、碳數2至6的醯基、羥基羰基或碳數1至6的烷氧基羰基。 In addition, ^{at least one of R 21} to R ³⁶ may be a saturated hydrocarbon group having 1 to 20 carbons that may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbons that may have a substituent, a halogen atom, and a carbon number of 1 to 20. 6 halogenated alkyl group, carbon number 1 to 6 alkoxy group, hydroxyl group, carbon number 1 to 6 alkanesulfonyl group, carbon number 2 to 6 acyl group, hydroxycarbonyl group or carbon number 1 to 6 alkoxycarbonyl group .

由R²¹至R³⁶表示的可具有取代基的飽和烴基係與由R⁵至R¹²表示的可具有取代基的飽和烴基相同。 The saturated hydrocarbon group that may have a substituent represented by R ²¹ to R ³⁶ is the same as the saturated hydrocarbon group that may have a substituent represented ^{by R 5} to R ^12.

由R²¹至R³⁶表示的可具有取代基的芳香族烴基係與由R¹至R⁴及R⁵至R¹²表示的可具有取代基的芳香族烴基相同。 The aromatic hydrocarbon group that may have a substituent represented by R ²¹ to R ³⁶ is the same as the aromatic hydrocarbon group that may have a substituent represented ^{by R 1} to R ⁴ and R ⁵ to R ^12.

作為由R²¹至R³⁶表示的鹵素原子，可列舉出氟原子、氯原子、碘原子、溴原子等，作為由R²¹至R³⁶表示的鹵代烷基，可列舉出氯甲基、三氟甲基等，作為由R²¹至R³⁶表示的烷氧基，可列舉出甲氧基、乙氧基等，作為由R²¹至R³⁶表示的烷烴磺醯基，可列舉出甲磺醯基等，作為由R²¹至R³⁶表示的烷氧基羰基，可列舉出甲氧基羰基、乙氧基羰基等。 Examples of the halogen atom represented by R ²¹ to R ³⁶ include a fluorine atom, a chlorine atom, an iodine atom, a bromine atom, etc., and examples of the halogenated alkyl group represented ^{by R 21} to R ^{36 include chloromethyl and trifluoromethyl.} Examples of the alkoxy group represented by R ²¹ to R ³⁶ include a methoxy group, ethoxy group, etc., and examples of the alkanesulfonyl group represented by R ²¹ to R ³⁶ include methanesulfonyl group, etc. As the alkoxycarbonyl group represented by R ²¹ to R ³⁶ , a methoxycarbonyl group, an ethoxycarbonyl group, and the like can be cited.

作為化合物(Ic)，較佳係由R²¹至R³⁶表示的基團中的一個至八個為氯原子或溴原子、剩餘為氫原子的化合物以及由R²¹至R³⁶表示的基團都為氫原子的化合物。更佳地，可列舉出由式(I-1)至(I-23)表示的化合物，特別佳地，可列舉出由式(I-1)至(I-6)表示的化合物。 As the compound (Ic), it is preferable ^{that one to eight of the groups represented by R 21} to R ³⁶ are a chlorine atom or a bromine atom, the remainder are a hydrogen atom, and the groups represented ^{by R 21} to R ^{36 are all} It is a compound of hydrogen atom. More preferably, compounds represented by formulas (I-1) to (I-23) can be cited, and particularly preferably, compounds represented by formulas (I-1) to (I-6) can be cited.

化合物(Ia)例如能夠藉由使由式(II)表示的化合物與由式(III)表示的化合物反應，接下來與甲醯胺反應而合成由式(IV)表示的化合物，使該由式(IV)表示的化合物與由式(V)表示的化合物反應而製造。 Compound (Ia) can be synthesized by, for example, reacting a compound represented by formula (II) with a compound represented by formula (III) and then reacting with foramidine to synthesize a compound represented by formula (IV), and making the compound represented by formula (IV) The compound represented by (IV) is produced by reacting the compound represented by formula (V).

[式中，R¹至R¹²及M與上述相同。X表示鹵素原子。 Z^n-表示n價的陰離子，a、b表示自然數。不過，a×n與b×2相等。] [In the formula, R ¹ to R ¹² and M are the same as described above. X represents a halogen atom. Z ^n- represents an n-valent anion, and a and b represent natural numbers. However, a×n is equal to b×2. ]

就化合物(Ia)的含有率而言，在著色劑(A)的總量中，例如，為1至100質量%，較佳為50至100質量%，更佳為80至100質量%，最佳為90至100質量%。 With regard to the content of the compound (Ia), in the total amount of the colorant (A), for example, it is 1 to 100% by mass, preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and most Preferably, it is 90 to 100% by mass.

著色劑(A)可包含染料或顏料作為化合物(Ia)以外的著色劑。作為染料，可列舉出溶劑染料、酸性染料、直接染料、媒染染料等，例如可列舉出在色指數(The Society of Dyers and Colourists出版)中在色料(pigment)以外分類為具有色調的物質的化合物、以及染色筆記(色染社)中記載的習知的染料。作為顏料，並無特別限定，能夠使用習知的顏料，例如可列舉出在色指數(The Society of Dyers and Colourists出版)中分類為色料的顏料。 The coloring agent (A) may contain a dye or a pigment as a coloring agent other than the compound (Ia). Examples of dyes include solvent dyes, acid dyes, direct dyes, mordant dyes, and the like. Examples include those classified as substances having hue in the Color Index (published by The Society of Dyers and Colourists) other than pigments. Compounds, and conventional dyes described in the dyeing notes (Seiransha). The pigment is not particularly limited, and conventional pigments can be used. For example, pigments classified as colorants in the color index (published by The Society of Dyers and Colourists) can be cited.

例如可列舉出：C.I.色料黃1(以下省略C.I.色料黃的記載，只記載序號)、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、137、138、139、147、148、150、153、154、166、173、194、214等黃色顏料；C.I.色料橙13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等橙色顏料；C.I.色料紅9、97、105、122、123、144、149、166、168、175、176、177、180、192、209、215、216、224、242、254、255、264、265等紅色顏料； C.I.色料藍15、15：3、15：4、15：6、60、80等青色顏料；C.I.色料紫1、19、23、29、32、36、38等紫色顏料；C.I.色料綠7、36、58等綠色顏料等。 Examples include: CI Color Yellow 1 (hereinafter the description of CI Color Yellow is omitted, and only the serial number is described), 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86 , 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168 , 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments; CI pigment blue 15, 15: 3, 15: 4, 15: 6, Cyan pigments such as 60 and 80; purple pigments such as CI color purple 1, 19, 23, 29, 32, 36, 38; CI color green 7, 36, 58 and other green pigments.

作為可使用的染料，可列舉出：C.I.溶劑黃4、14、15、23、24、38、62、63、68、82、94、98、99、162；C.I.溶劑紅45、49、125、130；C.I.溶劑橙2、7、11、15、26、56；C.I.溶劑藍4、5、37、67、70、90；C.I.溶劑綠1、4、5、7、34、35等C.I.溶劑染料，C.I.酸性黃1、3、7、9、11、17、23、25、29、34、36、38、40、42、54、65、72、73、76、79、98、99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、212、214、220、221、228、230、232、235、238、240、242、243、251；C.I.酸性紅1、4、8、14、17、18、26、27、29、31、34、35、37、42、44、50、57、66、73、88、91、97、103、111、114、129、133、134、138、143、145、150、151、158、176、182、183、195、198、206、211、215、216、217、227、228、249、252、257、258、260、261、266、268、270、274、277、280、281、308、312、315、316、339、341、345、346、349、382、383、394、401、412、417、 418、422、426；C.I.酸性橙6、7、8、10、12、26、50、51、52、56、62、63、64、74、75、94、95、107、108、169、173；C.I.酸性紫6B、7、17、19；C.I.酸性藍1、7、9、15、18、22、29、42、59、60、62、70、72、74、82、83、86、87、90、92、93、100、102、103、104、113、117、120、126、130、131、142、147、151、154、158、161、166、167、168、170、171、184、187、192、199、210、229、234、236、242、243、256、259、267、285、296、315、335；C.I.酸性綠1、3、5、9、16、50、58、63、65、80、104、105、106、109等C.I.酸性染料，C.I.直接黃2、33、34、35、38、39、43、47、50、54、58、68、69、70、71、86、93、94、95、98、102、108、109、129、136、138、141；C.I.直接紅79、82、83、84、91、92、96、97、98、99、105、106、107、172、173、176、177、179、181、182、184、204、207、211、213、218、220、221、222、232、233、234、241、243、246、250；C.I.直接橙26、34、39、41、46、50、52、56、57、61、64、65、68、70、96、97、106、107；C.I.直接紫47、52、54、59、60、65、66、79、80、81、82、84、89、90、93、95、96、103、104； C.I.直接藍1、2、6、8、15、22、25、41、57、71、76、78、80、81、84、85、86、90、93、94、95、97、98、99、100、101、106、107、108、109、113、114、115、117、119、120、137、149、150、153、155、156、158、159、160、161、162、163、164、165、166、167、168、170、171、172、173、188、189、190、192、193、194、195、196、198、199、200、201、202、203、207、209、210、212、213、214、222、225、226、228、229、236、237、238、242、243、244、245、246、247、248、249、250、251、252、256、257、259、260、268、274、275、293；C.I.直接綠25、27、31、32、34、37、63、65、66、67、68、69、72、77、79、82等C.I.直接染料，C.I.分散黃54、76等C.I.分散染料，C.I.鹼性藍1、3、5、7、9、19、24、25、26、28、29、40、41、54、58、59、64、65、66、67、68；C.I.鹼性綠1等C.I.鹼性染料，C.I.反應性黃2、76、116；C.I.反應性橙16等C.I.反應性染料，C.I.媒染黃5、8、10、16、20、26、30、31、33、42、43、45、56、61、62、65；C.I.媒染紅1、2、4、9、12、14、17、18、19、22、23、24、25、26、30、32、33、36、37、38、39、41、43、45、46、48、53、56、63、71、74、85、86、88、90、94、95； C.I.媒染橙3、4、5、8、12、13、14、20、21、23、24、28、29、32、34、35、36、37、42、43、47、48；C.I.媒染紫1、2、4、5、7、14、22、24、30、31、32、37、40、41、44、45、47、48、53、58；C.I.媒染藍1、2、3、7、9、12、13、15、16、19、20、21、22、26、30、31、39、40、41、43、44、49、53、61、74、77、83、84；C.I.媒染綠1、3、4、5、10、15、26、29、33、34、35、41、43、53等C.I.媒染染料，C.I.還原綠1等C.I.還原染料等。 Examples of usable dyes include: CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; CI Solvent Red 45, 49, 125, 130; CI solvent orange 2, 7, 11, 15, 26, 56; CI solvent blue 4, 5, 37, 67, 70, 90; CI solvent green 1, 4, 5, 7, 34, 35 and other CI solvent dyes , CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 57, 66, 73, 88, 91, 97, 103, 111, 114 , 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258 , 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418 , 422, 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet 6B, 7, 17, 19; CI Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335; CI acid green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109 and other CI acid dyes, CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184 , 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI direct purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90 , 93, 95, 96, 103, 104; CI direct blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72 CI direct dyes such as, 77, 79, 82, CI disperse dyes such as CI Disperse Yellow 54, 76, CI Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68; CI .CI basic dyes such as basic green 1, CI reactive yellow 2, 76, 116; CI reactive dyes such as CI reactive orange 16, CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31 , 33, 42, 43, 45, 56, 61, 62, 65; CI mordant red 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CI Mordant Orange 3, 4 , 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI Mordant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; CI mordant blue 1, 2, 3, 7, 9, 12, 13 , 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61, 74, 77, 83, 84; CI mordant green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53 and other CI mordant dyes, CI vat green 1 and other CI vat dyes, etc.

就著色劑(A)的含量而言，相對於樹脂(B)100質量份，較佳為0.1至100質量份，更佳為1至50質量份，進一步更佳為5至30質量份。 The content of the coloring agent (A) is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and still more preferably 5 to 30 parts by mass relative to 100 parts by mass of the resin (B).

<樹脂(B)> <Resin (B)>

對樹脂(B)並無特別限定，較佳為鹼可溶性樹脂，更佳為具有來自從不飽和羧酸及不飽和羧酸酐所組成之群組中選擇的至少一種(a)(以下有時稱為「(a)」)的結構單元的樹脂。樹脂(B)較佳還具有從來自具有碳數2至4的環狀醚結構及烯屬不飽和鍵的單體(b)(以下有時稱為「(b)」)的結構單元、來自可與(a)共聚的單體(c)(不過，與(a)及(b)不同)(以下有時稱為「(c)」)的結構單元以及側鏈具有烯屬不飽和鍵的結構單元所組成之群組中選擇的至少一種結構單元。 The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably has at least one (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter sometimes referred to as It is the resin of the structural unit of "(a)"). The resin (B) preferably also has structural units derived from monomers (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure with carbon number 2 to 4 and ethylenically unsaturated bonds, derived from Monomers (c) copolymerizable with (a) (but different from (a) and (b)) (hereinafter sometimes referred to as "(c)") structural units and side chains with ethylenically unsaturated bonds At least one structural unit selected from the group consisting of structural units.

作為(a)，具體地，例如可列舉出丙烯酸、甲基丙烯酸、馬來酸酐、伊康酸酐、3,4,5,6-四氫鄰苯二甲酸酐、琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯等，較佳為丙烯酸、甲基丙烯酸、馬來酸酐。 Specific examples of (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and succinic acid mono[2-(formaldehyde). (Yl)acryloyloxyethyl]ester, etc., preferably acrylic acid, methacrylic acid, and maleic anhydride.

(b)較佳為具有碳數2至4的環狀醚結構(例如選自環氧乙烷環、氧呾環及四氫呋喃環所組成之群組中的至少一種)及(甲基)丙烯醯氧基的單體。 (b) Preferably, it has a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an ethylene oxide ring, an oxygen ring, and a tetrahydrofuran ring) and (meth)acrylic acid The monomer of the oxy group.

應予說明，本說明書中，「(甲基)丙烯酸」表示選自丙烯酸及甲基丙烯酸所組成之群組中的至少一種。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等的表記也具有同樣的含義。 In addition, in this specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

作為(b)，例如可列舉出(甲基)丙烯酸縮水甘油酯、乙烯基苄基縮水甘油基醚、(甲基)丙烯酸3,4-環氧三環[5.2.1.0^2,6]癸酯、3-乙基-3-(甲基)丙烯醯氧基甲基氧呾、(甲基)丙烯酸四氫糠酯等，較佳為(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧三環[5.2.1.0^2,6]癸酯、3-乙基-3-(甲基)丙烯醯氧基甲基氧呾。 Examples of (b) include glycidyl (meth)acrylate, vinyl benzyl glycidyl ether, and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate , 3-ethyl-3-(meth)acryloyloxymethyloxy, tetrahydrofurfuryl (meth)acrylate, etc., preferably glycidyl (meth)acrylate, (meth)acrylic acid 3 ,4-Epoxy tricyclo [5.2.1.0 ^2,6 ] decyl ester, 3-ethyl-3-(meth)propenyloxymethyloxy group.

作為(c)，例如可列舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(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[5.2.1.0^2,6]癸烷-8-基酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-羥基乙酯、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、苯乙烯、乙烯基甲苯等，較佳為苯乙烯、乙烯基甲苯、N-苯基馬來醯亞胺、N-環己基 馬來醯亞胺、N-苄基馬來醯亞胺等。 As (c), for example, methyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, (methyl) ) Tricyclo [5.2.1.0 ^2,6 ]decane-8-yl acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N -Cyclohexyl maleimide, N-benzyl maleimide, styrene, vinyl toluene, etc., preferably styrene, vinyl toluene, N-phenyl maleimide, N-ring Hexylmaleimide, N-benzylmaleimide, etc.

具有在側鏈具有烯屬不飽和鍵的結構單元的樹脂能夠藉由使(b)加成於(a)與(c)的共聚物，或者使(a)加成於(b)與(c)的共聚物而製造。該樹脂可以是使(a)加成於(b)與(c)的共聚物、進而使羧酸酐反應而成的樹脂。 A resin having a structural unit having an ethylenically unsaturated bond in the side chain can be added to the copolymer of (a) and (c) by (b), or (a) is added to (b) and (c) ) Copolymers. The resin may be a resin obtained by adding (a) to the copolymer of (b) and (c), and further reacting carboxylic anhydride.

樹脂(B)的聚苯乙烯換算的重量平均分子量較佳為3,000至100,000，更佳為5,000至50,000，進一步更佳為5,000至30,000。 The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000.

樹脂(B)的分散度[重量平均分子量(Mw)/數量平均分子量(Mn)]較佳為1.1至6，更佳為1.2至4。 The degree of dispersion [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

樹脂(B)的酸值以固體成分換算計，較佳為50至170毫克-KOH/公克，更佳為60至150毫克-KOH/公克，進一步更佳為70至135毫克-KOH/公克。在此，酸值是作為將樹脂(B)1公克中和所需的氫氧化鉀的量(毫克)而被測定的值，例如能夠藉由使用氫氧化鉀水溶液進行滴定而求出。 The acid value of the resin (B) in terms of solid content is preferably 50 to 170 mg-KOH/g, more preferably 60 to 150 mg-KOH/g, and still more preferably 70 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 gram of the resin (B), and it can be determined, for example, by titration using an aqueous potassium hydroxide solution.

就樹脂(B)的含有率而言，相對於固體成分的總量，較佳為7至65質量%，更佳為13至60質量%，進一步更佳為17至55質量%。 The content rate 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 relative to the total solid content.

在此，本說明書中的「固體成分的總量」是指從著色樹脂組合物的總量中去除了溶劑的含量後的量。固體成分的總量及相對於其的各成分的含量係例如能夠採用液相色譜或氣相色譜等習知的分析手段來測定。 Here, the "total amount of solid content" in this specification refers to the amount after excluding the solvent content from the total amount of the colored resin composition. The total amount of solid content and the content of each component relative to it can be measured by conventional analysis means such as liquid chromatography or gas chromatography, for example.

本發明的著色樹脂組合物可包含聚合性化合物及/或聚合引發劑。以下，有時將包含聚合性化合物及聚合引發劑的著色樹脂組合物稱為「著色固化性樹脂組合物」。另外以下，有時將聚合性化合物稱為「聚合性化合物(C)」，有時將聚合引發劑稱為「聚合引發劑(D)」。 The colored resin composition of the present invention may contain a polymerizable compound and/or a polymerization initiator. Hereinafter, the colored resin composition containing a polymerizable compound and a polymerization initiator may be referred to as a "colored curable resin composition". In addition, hereinafter, the polymerizable compound is sometimes referred to as "polymerizable compound (C)", and the polymerization initiator is sometimes referred to as "polymerization initiator (D)".

<聚合性化合物(C)> <Polymerizable compound (C)>

聚合性化合物(C)是可利用由聚合引發劑(D)產生的活性自由基及/或酸進行聚合的化合物，例如可列舉出具有聚合性的烯屬不飽和鍵的化合物等，較佳為(甲基)丙烯酸酯化合物。 The polymerizable compound (C) is a compound that can be polymerized using living radicals and/or acid generated by the polymerization initiator (D). For example, a compound having a polymerizable ethylenic unsaturated bond, etc., is preferred. (Meth)acrylate compound.

其中，聚合性化合物(C)較佳為具有三個以上烯屬不飽和鍵的聚合性化合物。作為這樣的聚合性化合物，例如可列舉出三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等。 Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dixin Pentaerythritol penta(meth)acrylate, dineopentaerythritol hexa(meth)acrylate, etc.

聚合性化合物(C)的重量平均分子量較佳為150以上且2,900以下，更佳為250以上且1,500以下。 The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less.

在包含聚合性化合物(C)的情況下，就聚合性化合物(C)的含有率而言，相對於固體成分的總量，較佳為7至65質量%，更佳為13至60質量%，進一步更佳為17至55質量%。 When the polymerizable compound (C) is contained, the content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass relative to the total solid content. , Still more preferably 17 to 55% by mass.

<聚合引發劑(D)> <Polymerization initiator (D)>

聚合引發劑(D)只要是在光、熱的作用下產生活性 自由基、酸等且可引發聚合的化合物，則並無特別限定，能夠使用習知的聚合引發劑。作為產生活性自由基的聚合引發劑，例如可列舉出N-苯甲醯氧基-1-(4-苯基氫硫基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基氫硫基苯基)辛烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基氫硫基苯基)-3-環戊基丙烷-1-酮-2-亞胺、2-甲基-2-嗎福啉基-1-(4-甲基氫硫基苯基)丙烷-1-酮、2-二甲基胺基-1-(4-嗎福啉基苯基)-2-苄基丁烷-1-酮、1-羥基環己基苯基酮、2,4-雙(三氯甲基)-6-向日葵基-1,3,5-三嗪、2,4,6-三甲基苯甲醯基二苯基氧化膦、2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑等。 The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating living radicals, acids, etc. under the action of light and heat, and conventional polymerization initiators can be used. Examples of polymerization initiators that generate living radicals include N-benzyloxy-1-(4-phenylhydrothiophenyl)butan-1-one-2-imine, N-benzene Formyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl) )-3-cyclopentylpropane-1-one-2-imine, 2-methyl-2-morpholinyl-1-(4-methylhydrothiophenyl)propane-1-one, 2 -Dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,4-bis(trichloromethyl )-6-Sunflower-1,3,5-triazine, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2,2'-bis(2-chlorophenyl)-4 ,4',5,5'-tetraphenylbiimidazole and so on.

在包含聚合引發劑(D)的情況下，就聚合引發劑(D)的含量而言，相對於樹脂(B)及聚合性化合物(C)的合計量100質量份，較佳為0.1至30質量份，更佳為1至20質量份。如果聚合引發劑(D)的含量在上述的範圍內，則具有高感度化、使曝光時間縮短的傾向，因此濾色器的生產率提高。 When the polymerization initiator (D) is included, the content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) Parts by mass, more preferably 1 to 20 parts by mass. If the content of the polymerization initiator (D) is within the above-mentioned range, there is a tendency to increase sensitivity and shorten the exposure time, so the productivity of the color filter improves.

本發明的著色樹脂組合物可包含聚合引發助劑。以下，有時將聚合引發助劑稱為「聚合引發助劑(D1)」。 The coloring resin composition of the present invention may contain a polymerization initiation assistant. Hereinafter, the polymerization initiation aid may be referred to as "polymerization initiation aid (D1)".

<聚合引發助劑(D1)> <Polymerization initiator (D1)>

聚合引發助劑(D1)為用於促進由聚合引發劑引發了聚合的聚合性化合物的聚合的化合物或者增感劑。在包含聚合引發助劑(D1)的情況下，通常與聚合引發劑(D)組合使用。 The polymerization initiation adjuvant (D1) is a compound or a sensitizer for accelerating the polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).

作為聚合引發助劑(D1)，可列舉出4,4'-雙(二甲 基胺基)二苯甲酮(通稱米其勒酮)、4,4'-雙(二乙基胺基)二苯甲酮、9,10-二甲氧基蒽、2,4-二乙基噻噸酮、N-苯基甘胺酸等。 As the polymerization initiator (D1), 4,4'-bis(dimethylamino)benzophenone (commonly known as Michlerone), 4,4'-bis(diethylamino) Benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, N-phenylglycine, etc.

在使用這些聚合引發助劑(D1)的情況下，相對於樹脂(B)及聚合性化合物(C)的合計量100質量份，其含量較佳為0.1至30質量份，更佳為1至20質量份。如果聚合引發助劑(D1)的量在該範圍內，則能夠進一步以高感度形成著色圖案，濾色器的生產率有提高的傾向。 In the case of using these polymerization initiation aids (D1), the content is preferably 0.1 to 30 parts by mass, more preferably 1 to 100 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and polymerizable compound (C) 20 parts by mass. If the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

本發明的著色樹脂組合物較佳包含溶劑。以下，有時將溶劑稱為「溶劑(E)」。 The colored resin composition of the present invention preferably contains a solvent. Hereinafter, the solvent may be referred to as "solvent (E)".

<溶劑(E)> <Solvent (E)>

對溶劑(E)並無特別限定，能夠使用該領域中通常使用的溶劑。例如可列舉出酯溶劑(分子內含-COO-且不含-O-的溶劑)、醚溶劑(分子內含-O-且不含-COO-的溶劑)、醚酯溶劑(分子內含-COO-及-O-的溶劑)、酮溶劑(分子內含-CO-且不含-COO-的溶劑)、醇溶劑(分子內含OH且不含-O-、-CO-及-COO-的溶劑)、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 generally used in this field can be used. For example, ester solvents (solvents containing -COO- and no -O- in the molecule), ether solvents (solvents containing -O- and no -COO- in the molecule), ether ester solvents (solvents that contain- COO- and -O- solvents), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (containing OH in the molecule and not containing -O-, -CO- and -COO- Solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfide, etc.

作為溶劑，可列舉出乳酸乙酯、乳酸丁酯、2-羥基異丁酸甲酯、醋酸正丁酯、丁酸乙酯、丁酸丁酯、丙酮酸乙酯、乙醯乙酸甲酯、環己醇乙酸酯及γ-丁內酯等酯溶劑(分子內含-COO-且不含-O-的溶劑)；乙二醇單丁基醚、二乙二醇單甲基醚、丙二醇單甲基醚、3-甲氧基-1-丁醇、二乙二醇二甲基醚、二乙二醇甲基乙基醚等醚溶劑(分子內含-O-且不含-COO-的溶劑)；3- 甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸3-甲氧基丁酯、丙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙二醇單乙基醚乙酸酯等醚酯溶劑(分子內含-COO-及-O-的溶劑)；4-羥基-4-甲基-2-戊酮、庚酮、4-甲基-2-戊酮、環己酮等酮溶劑(分子內含-CO-且不含-COO-的溶劑)；丁醇、環己醇、丙二醇等醇溶劑(分子內含OH且不含-O-、-CO-及-COO-的溶劑)；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基吡咯烷酮等醯胺溶劑等。 Examples of solvents include ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetylacetate, cyclic Ester solvents such as hexanol acetate and γ-butyrolactone (solvents containing -COO- and no -O- in the molecule); ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol mono Methyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and other ether solvents (with -O- and no -COO- in the molecule) Solvent); Methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetic acid Ester, diethylene glycol monoethyl ether acetate and other ether ester solvents (solvents containing -COO- and -O- in the molecule); 4-hydroxy-4-methyl-2-pentanone, heptanone, 4 -Methyl-2-pentanone, cyclohexanone and other ketone solvents (solvents containing -CO- and no -COO- in the molecule); alcohol solvents such as butanol, cyclohexanol, and propylene glycol (containing OH in the molecule and no Solvents containing -O-, -CO- and -COO-); N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and other amide solvents.

作為溶劑，更佳為丙二醇單甲基醚乙酸酯、丙二醇單甲基醚、乳酸乙酯、N-甲基吡咯烷酮及3-乙氧基丙酸乙酯。 As the solvent, more preferred are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, N-methylpyrrolidone, and ethyl 3-ethoxypropionate.

在包含溶劑(E)的情況下，就溶劑(E)的含有率而言，相對於本發明的著色樹脂組合物的總量，較佳為70至95質量%，更佳為75至92質量%。換言之，著色樹脂組合物的固體成分的總量較佳為5至30質量%，更佳為8至25質量%。如果溶劑(E)的含量在上述的範圍內，則塗布時的平坦性變得良好，另外在形成了濾色器時色濃度沒有不足，因此具有顯示特性變得良好的傾向。 When the solvent (E) is included, the content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass relative to the total amount of the coloring resin composition of the present invention %. In other words, the total solid content of the colored resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. If the content of the solvent (E) is within the above-mentioned range, the flatness at the time of application becomes good, and the color density is not insufficient when the color filter is formed, so there is a tendency for the display characteristics to become good.

<其他成分> <Other ingredients>

本發明的著色樹脂組合物根據需要可包含流平劑、填充劑、其他高分子化合物、密合促進劑、抗氧化劑、光穩定劑、鏈轉移劑等該技術領域中習知的添加劑。 The colored resin composition of the present invention may contain leveling agents, fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and other additives known in the art as needed.

<著色樹脂組合物的製造方法> <Manufacturing Method of Colored Resin Composition>

本發明的著色樹脂組合物能夠藉由將著色劑(A)、 樹脂(B)、以及根據需要使用的聚合性化合物(C)、聚合引發劑(D)、溶劑(E)及其他成分混合而製備。 The colored resin composition of the present invention can be obtained by mixing the colorant (A), the resin (B), and the polymerizable compound (C), the polymerization initiator (D), the solvent (E), and other components used as needed. preparation.

<濾色器的製造方法> <Method of Manufacturing Color Filter>

作為由本發明的著色樹脂組合物製造著色圖案的方法，可列舉出光刻法、噴墨法、印刷法等。其中，較佳為光刻法。 As a method of producing a colored pattern from the colored resin composition of the present invention, a photolithography method, an inkjet method, a printing method, and the like can be cited. Among them, photolithography is preferred.

採用本發明的著色樹脂組合物，能夠製作對比度高的濾色器。該濾色器可用作在液晶顯示裝置、有機EL裝置、電子紙等顯示裝置及固體攝像元件中使用的濾色器。 With the colored resin composition of the present invention, a color filter with high contrast can be produced. This color filter can be used as a color filter used in display devices such as liquid crystal display devices, organic EL devices, electronic paper, and solid-state imaging elements.

實施例 Example

以下藉由實施例對本發明更詳細地說明，但本發明並不受這些實施例限定。例中，表示含量或使用量的%及份，只要無特別說明，則為質量基準。 The following examples illustrate the present invention in more detail, but the present invention is not limited by these examples. In the examples, it represents the content or the used amount in% and parts, and unless otherwise specified, it is a quality standard.

以下，化合物的結構係經由質量分析(LC：Agilent製1200型，MAS：Agilent製LC/MSD型)而確認。 Hereinafter, the structure of the compound was confirmed by mass analysis (LC: Agilent 1200 model, MAS: Agilent LC/MSD model).

(合成例1) (Synthesis example 1)

使鄰苯二甲腈(東京化成股份有限公司製造)5.0份溶解於脫水二***(關東化學股份有限公司製造)40份中，冷卻到-20℃，將苯基溴化鎂的1M四氫呋喃溶液(關東化學股份有限公司製造)42.6份滴入。滴入後，升溫到室溫，攪拌了3小時。將得到的反應液濃縮後，加入預先加入硫酸鎂經脫水的甲醯胺(東京化成股份有限公司製造)280份，在140℃下攪拌了3小時。反應結束後冷卻到室溫，將析出的固體過濾。將得到的過濾物用甲醇/ 水混合液700份洗淨後，在60℃下減壓乾燥一晚，得到了由式(IV-1)表示的化合物1.7份。收率為22%。 Dissolve 5.0 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) in 40 parts of dehydrated diethyl ether (manufactured by Kanto Chemical Co., Ltd.), and cool to -20°C, and add a 1M phenylmagnesium bromide solution in tetrahydrofuran ( Kanto Chemical Co., Ltd.) 42.6 parts are dropped. After dropping, the temperature was raised to room temperature and stirred for 3 hours. After concentrating the obtained reaction liquid, 280 parts of formamide (manufactured by Tokyo Chemical Industry Co., Ltd.) to which magnesium sulfate was added and dehydrated in advance was added, and the mixture was stirred at 140°C for 3 hours. After the reaction was completed, it was cooled to room temperature, and the precipitated solid was filtered. After washing the obtained filtrate with 700 parts of methanol/water mixed liquid, it dried under reduced pressure at 60 degreeC overnight, and obtained 1.7 parts of compounds represented by Formula (IV-1). The yield was 22%.

鑒定：(質量分析)離子化模式=ESI+：m/z=[M+H]⁺398.5 Identification: (mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 398.5

確切質量：397.2 Exact quality: 397.2

(合成例2) (Synthesis example 2)

接下來，加入由式(IV-1)表示的化合物0.5份、醋酸鋅(和光純藥工業股份有限公司製造)0.3份、二異丙基乙基胺(東京化成股份有限公司製造)0.325份、1-丁醇(和光純藥工業股份有限公司製造)10份，在110℃下進行了加熱回流6小時。反應結束後冷卻到室溫，將析出的固體過濾。將得到的固體用氯仿50份邊加熱邊洗淨後，在60℃下減壓乾燥一晚，得到了由式(I-1)表示的化合物0.4份。收率為76%。 Next, 0.5 part of the compound represented by formula (IV-1), 0.3 part of zinc acetate (manufactured by Wako Pure Chemical Industries, Ltd.), 0.325 part of diisopropylethylamine (manufactured by Tokyo Kasei Co., Ltd.), 10 parts of 1-butanol (manufactured by Wako Pure Chemical Industries, Ltd.) was heated and refluxed at 110°C for 6 hours. After the reaction was completed, it was cooled to room temperature, and the precipitated solid was filtered. The obtained solid was washed with 50 parts of chloroform while heating, and then dried under reduced pressure at 60° C. overnight to obtain 0.4 part of the compound represented by formula (I-1). The yield was 76%.

鑒定：(質量分析)離子化模式=ESI+：m/z=[M+H]⁺857.0 Identification: (Quality Analysis) Ionization Mode=ESI+: m/z=[M+H] ⁺ 857.0

確切質量：856.23 Exact quality: 856.23

(合成例3) (Synthesis example 3)

使3-氯鄰苯二甲腈(和光純藥工業股份有限公司製造)2.0份溶解於脫水二***(關東化學股份有限公司製造)28份中，冷卻到-20℃，將苯基溴化鎂的1M四氫呋喃溶液(關東化學股份有限公司製造)13.2份滴入。滴入後，升溫到室溫，攪拌了3小時。將得到的反應液濃縮後，加入預先加入硫酸鎂經脫水的甲醯胺(東京化成股份有限公司製造)75份，在140℃下攪拌了30分鐘。反應結束後冷卻到室溫，將析出的固體過濾。將得到的過濾物用甲醇/水混合液375份洗淨後，在60℃下減壓乾燥一晚，得到了由式(IV-2)表示的化合物1.2份。收率為43%。 Dissolve 2.0 parts of 3-chlorophthalonitrile (manufactured by Wako Pure Chemical Industries Co., Ltd.) in 28 parts of dehydrated diethyl ether (manufactured by Kanto Chemical Co., Ltd.), and cool to -20°C. 13.2 parts of 1M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.) After dropping, the temperature was raised to room temperature and stirred for 3 hours. After concentrating the obtained reaction liquid, 75 parts of formamide (manufactured by Tokyo Chemical Industry Co., Ltd.) which was dehydrated by adding magnesium sulfate in advance was added, and the mixture was stirred at 140°C for 30 minutes. After the reaction was completed, it was cooled to room temperature, and the precipitated solid was filtered. After washing the obtained filtrate with 375 parts of a methanol/water mixed solution, it was dried under reduced pressure at 60° C. overnight to obtain 1.2 parts of a compound represented by formula (IV-2). The yield was 43%.

鑒定：(質量分析)離子化模式=ESI+：m/z=[M+H]⁺466.5 Identification: (mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 466.5

確切質量：465.1 Exact quality: 465.1

(合成例4) (Synthesis example 4)

接下來，加入由式(IV-2)表示的化合物4.0份、醋酸鋅(和光純藥工業股份有限公司製造)1.8份、二異丙基乙基胺 (東京化成股份有限公司製造)2.0份、1-丁醇(和光純藥工業股份有限公司製造)120份，在110℃下進行了3小時加熱回流。反應結束後冷卻到室溫，將析出的固體過濾。將得到的固體用氯仿、四氫呋喃加熱洗淨後，在60℃下減壓乾燥一晚，得到了由式(I-4)表示的化合物2.2份。收率為55%。 Next, 4.0 parts of the compound represented by the formula (IV-2), 1.8 parts of zinc acetate (manufactured by Wako Pure Chemical Industries, Ltd.), 2.0 parts of diisopropylethylamine (manufactured by Tokyo Kasei Co., Ltd.), 120 parts of 1-butanol (manufactured by Wako Pure Chemical Industries Co., Ltd.) was heated and refluxed at 110°C for 3 hours. After the reaction was completed, it was cooled to room temperature, and the precipitated solid was filtered. After the obtained solid was heated and washed with chloroform and tetrahydrofuran, it was dried under reduced pressure at 60° C. overnight to obtain 2.2 parts of the compound represented by formula (I-4). The yield was 55%.

鑒定：(質量分析)離子化模式=ESI+：m/z=[M+H]⁺994.8 Identification: (mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 994.8

確切質量：992.07 Exact quality: 992.07

(合成例5) (Synthesis example 5)

在具有回流冷凝器、滴液漏斗及攪拌機的燒瓶內使適量的氮氣流入而置換為氮氣氣氛，裝入乙酸1-甲氧基-2-丙酯371份，邊攪拌邊加熱至85℃。接下來，在該燒瓶內歷時4小時滴入丙烯酸54份、丙烯酸3,4-環氧三環[5.2.1.0^2,6]癸烷-8-基酯及丙烯酸3,4-環氧三環[5.2.1.0^2,6]癸烷-9-基酯的混合物(商品名「E-DCPA」、大賽璐股份有限公司製造)225份、乙烯基甲苯(異構體混合物)81份、乙酸1-甲氧基-2-丙酯80份的混合溶液。另一方面，歷時5小時滴入將聚合引發劑2,2-偶氮二(2,4-二甲基戊腈)30份溶解於乙 酸1-甲氧基-2-丙酯160份而成的溶液。引發劑溶液的滴入結束後，在相同溫度下保持了4小時後，冷卻到室溫，用B型黏度計(23℃)測定的黏度為246毫帕(mPas)。樹脂(B-1)溶液的固體成分為37.5%，固體成分換算的酸值為115毫克-KOH/公克。生成的共聚物的重量平均分子量Mw為10600，分散度[Mw/Mn]為2.01。樹脂(B-1)具有以下的結構單元。 In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was introduced to replace the nitrogen atmosphere, 371 parts of 1-methoxy-2-propyl acetate was charged, and the mixture was heated to 85°C while stirring. Next, 54 parts of acrylic acid, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate and 3,4-epoxy tricyclic acrylate were dropped into the flask over 4 hours. [5.2.1.0 ^2,6 ] Decane-9-yl ester mixture (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) 225 parts, vinyl toluene (isomer mixture) 81 parts, acetic acid 1 -A mixed solution of 80 parts of methoxy-2-propyl ester. On the other hand, 30 parts of polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 160 parts of 1-methoxy-2-propyl acetate by dripping over 5 hours. The solution. After the dripping of the initiator solution was completed, it was kept at the same temperature for 4 hours and then cooled to room temperature. The viscosity measured with a B-type viscometer (23°C) was 246 milliPascals (mPas). The solid content of the resin (B-1) solution was 37.5%, and the acid value in terms of solid content was 115 mg-KOH/g. The weight average molecular weight Mw of the resulting copolymer was 10600, and the degree of dispersion [Mw/Mn] was 2.01. The resin (B-1) has the following structural units.

樹脂的聚苯乙烯換算的重量平均分子量(Mw)及數量平均分子量(Mn)的測定係使用GPC法、在以下的條件下進行。 The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin in terms of polystyrene was performed under the following conditions using the GPC method.

裝置：HLC-8120GPC(東曹股份有限公司製造) Device: HLC-8120GPC (manufactured by Tosoh Corporation)

柱：TSK-GELG2000HXL Column: TSK-GELG2000HXL

柱溫度：40℃ Column temperature: 40℃

溶劑：THF Solvent: THF

流速：1.0毫升/分鐘(mL/min) Flow rate: 1.0 ml/min (mL/min)

被檢測液固體成分濃度；0.001至0.01質量% The concentration of the solid content of the tested liquid; 0.001 to 0.01% by mass

注入量：50微升 Injection volume: 50 microliters

檢測器：RI Detector: RI

校正用標準物質：TSK標準聚苯乙烯(TSK STANDARD POLYSTYRENE) Standard material for calibration: TSK Standard Polystyrene (TSK STANDARD POLYSTYRENE)

F-40、F-4、F-288、A-2500、A-500(東曹股份有限公司製造) F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

將上述得到的聚苯乙烯換算的重量平均分子量及數量平均分子量之比(Mw/Mn)作為分散度。 The ratio (Mw/Mn) of the weight average molecular weight in terms of polystyrene obtained above and the number average molecular weight (Mw/Mn) was taken as the degree of dispersion.

[實施例1至2、比較例1] [Examples 1 to 2, Comparative Example 1]

[著色樹脂組合物的製備] [Preparation of Colored Resin Composition]

按表1中所示的份數將各成分混合，得到了著色樹脂組合物。 Each component was mixed in the number of parts shown in Table 1, and the colored resin composition was obtained.

註1： Note 1:

註2：將表中的右邊成分混合，使用珠磨機使顏料充分地分散而成的液體 Note 2: Mix the ingredients on the right in the table and use a bead mill to fully disperse the pigments.

註3：固體成分換算量 Note 3: Conversion amount of solid content

註4：在顏料分散液以外使用的溶劑 Note 4: Solvents used other than pigment dispersion

註5：採用日本專利特開第2004-70342號公報的合成實施例1中記載的方法製造 Note 5: Manufactured using the method described in Synthesis Example 1 of Japanese Patent Laid-Open No. 2004-70342

[著色圖案的製作] [Making of Coloring Pattern]

在5公分見方的玻璃基板(EAGLE 2000；康寧公司製造)上採用旋塗法塗布著色樹脂組合物後，在100℃下預烘焙3分鐘，得到了著色組合物層。放冷後，使形成有著色組合物層的基板與石英玻璃製光遮罩的間隔為100微米，使用曝光機(TME-150RSK；拓普康(TOPCON)股份有限公司製造)，在大氣氣氛下，用150毫焦耳/平方公分(mJ/cm²)的曝光量(365奈米基準)進行光照射。作為光遮罩，使用了形成有100微米線及間隙圖案的光遮罩。將光照射後的著色組合物層在包含非離子系表面活性劑0.12%及氫氧化鉀0.04%的水系顯影液中在24℃下浸漬顯影60秒，水洗後，在烘箱中、150℃下進行20分鐘後烘焙，得到了著色圖案。 The colored resin composition was applied on a 5 cm square glass substrate (EAGLE 2000; manufactured by Corning Incorporated) by spin coating, and then pre-baked at 100°C for 3 minutes to obtain a colored composition layer. After leaving to cool, the space between the substrate on which the coloring composition layer was formed and the quartz glass photomask was 100 microns, and an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) was used in an atmospheric atmosphere. , The light is irradiated with an exposure of 150 millijoules/cm² (mJ/cm ^{2) (365nm standard).} As the light mask, a light mask in which a pattern of 100-micron lines and gaps was formed was used. The light-irradiated coloring composition layer was immersed and developed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24°C for 60 seconds. After washing with water, it was carried out in an oven at 150°C. Bake after 20 minutes to obtain a colored pattern.

用光學顯微鏡觀察由實施例1及2的著色樹脂組合物得到的著色圖案，結果確認分辨出100微米線及間隙。 The colored patterns obtained from the colored resin compositions of Examples 1 and 2 were observed with an optical microscope, and as a result, it was confirmed that 100-micron lines and gaps were distinguished.

[膜厚測定] [Film thickness measurement]

使用膜厚測定裝置(DEKTAK(註冊商標)3；日本真空技術股份有限公司製造)測定了得到的著色圖案的膜厚。將 結果示於表2中。 The film thickness of the obtained colored pattern was measured using a film thickness measuring device (DEKTAK (registered trademark) 3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 2.

[著色塗膜的製作] [Production of Colored Coating Film]

在5公分見方的玻璃基板(EAGLE 2000；康寧公司製造)上，採用旋塗法塗布著色樹脂組合物使得後烘焙後的膜厚成為與上述著色圖案相同的膜厚後，在100℃下預烘焙3分鐘。放冷後，使用曝光機(TME-150RSK；拓普康股份有限公司製造)，在大氣氣氛下、用150毫焦耳/平方公分的曝光量(365奈米基準)進行光照射。光照射後，在烘箱中、150℃下進行20分鐘後烘焙，得到了著色塗膜。 On a 5 cm square glass substrate (EAGLE 2000; manufactured by Corning Incorporated), spin coating is used to coat the colored resin composition so that the film thickness after post-baking becomes the same as the above-mentioned colored pattern, and then pre-baked at 100°C 3 minutes. After being allowed to cool, an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used to irradiate light with an exposure amount of 150 millijoules/cm² (365 nm standard) in an atmospheric atmosphere. After light irradiation, post-baking was performed in an oven at 150°C for 20 minutes to obtain a colored coating film.

[對比度評價] [Contrast Evaluation]

對於得到的著色塗膜，使用對比度計(CT-1；壺坂電機股份有限公司製造、色彩色差計BM-5A；拓普康股份有限公司製造、光源；F-10、偏光膜；壺坂電機股份有限公司製造)測定對比度。應予說明，測定時的空白值為30000。將結果示於表2中。 For the obtained colored coating film, a contrast meter (CT-1; manufactured by Kosaka Electric Co., Ltd., color and color difference meter BM-5A; manufactured by Topcon Co., Ltd., light source; F-10, polarizing film; Kosaka Electric Co., Ltd.) The contrast was measured. It should be noted that the blank value at the time of measurement is 30000. The results are shown in Table 2.

以上確認了採用實施例的著色樹脂組合物得到的著 色塗膜的對比度高。由此可知，由本發明的著色樹脂組合物得到的著色塗膜、著色圖案作為濾色器是有用的，包含該濾色器的顯示裝置的顯示特性優異，包含該濾色器的固體攝像元件的攝像特性優異。 As mentioned above, it was confirmed that the colored coating film obtained by using the colored resin composition of the example had a high contrast. From this, it can be seen that the colored coating film and colored pattern obtained from the colored resin composition of the present invention are useful as color filters, the display device including the color filter has excellent display characteristics, and the solid-state imaging element including the color filter The imaging characteristics are excellent.

產業上的可利用性 Industrial availability

採用本發明的著色固化性樹脂組合物，能夠形成對比度高的濾色器。 The coloring curable resin composition of the present invention can form a high-contrast color filter.

Claims (6)

一種著色樹脂組合物，其包含著色劑及樹脂，該著色劑包含由式(I-1)至(I-23)所表示的化合物中之至少一者，且該樹脂包含(甲基)丙烯酸3,4-環氧三環[5.2.1.0^2,6]癸酯，

。 A coloring resin composition comprising a coloring agent and a resin, the coloring agent comprising at least one of the compounds represented by formulas (I-1) to (I-23), and the resin comprising (meth)acrylic acid 3 ,4-Epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester,

. 如請求項1所述的著色樹脂組合物，其更包含聚合性化合物及聚合引發劑。 The colored resin composition according to claim 1, which further contains a polymerizable compound and a polymerization initiator. 一種由如請求項1或2所述的著色樹脂組合物形成的濾色器。 A color filter formed of the colored resin composition as described in claim 1 or 2. 一種顯示裝置，其包含如請求項3所述的濾色器。 A display device including the color filter according to claim 3. 一種固體攝像元件，其包含如請求項3所述的濾色器。 A solid-state imaging element including the color filter according to claim 3. 一種由式(I-1)至(I-23)之任一者所表示的化合物使用於濾色器之用途：

。 The use of a compound represented by any one of formula (I-1) to (I-23) in a color filter:

.