TWI734946B

TWI734946B - Red curable resin composition, color filter and display device

Info

Publication number: TWI734946B
Application number: TW107146637A
Authority: TW
Inventors: 髙石悠; 中山智博
Original assignee: 南韓商東友精細化工有限公司
Priority date: 2017-12-27
Filing date: 2018-12-22
Publication date: 2021-08-01
Also published as: KR102508777B1; CN111512232A; TW201927917A; JP2019116544A; KR20200093524A; JP7077012B2; WO2019132328A1

Abstract

[課題] 由先前已知的紅色硬化性樹脂組成物所形成之彩色濾光片及顯示裝置存在有無法充分滿足深色（高彩度）區域中之薄膜化的情況。 [解決方式] 本發明提供一種紅色硬化性樹脂組成物，其包含著色劑、樹脂、聚合性化合物及聚合起始劑，其中著色劑包含四氮雜卟啉化合物與紅色色素。[Subject] The color filters and display devices formed from the previously known red curable resin composition may not sufficiently satisfy the thinning in the dark (high chroma) region. [Solution] The present invention provides a red curable resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant includes a porphyrazine compound and a red pigment.

Description

紅色硬化性樹脂組成物、彩色濾光片及顯示裝置Red curable resin composition, color filter and display device

本發明係關於一種紅色硬化性樹脂組成物、彩色濾光片及顯示裝置。The present invention relates to a red curable resin composition, color filter and display device.

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或CCD（Charge-Coupled Device，電荷耦合裝置）或CMOS（Complementary Metal-Oxide-Semiconductor，互補金氧半導體）感測器等固體攝像元件中所使用之彩色濾光片係由著色硬化性樹脂組成物製造。作為此種著色硬化性樹脂組成物，已知有包含C.I.顏料紅177作為著色劑之組成物（專利文獻1）。 [先前技術文獻] [專利文獻]In liquid crystal display devices, electroluminescence display devices, plasma displays and other display devices or CCD (Charge-Coupled Device) or CMOS (Complementary Metal-Oxide-Semiconductor, complementary metal oxide semiconductor) sensors and other solid-state imaging The color filter used in the element is made of a colored curable resin composition. As such a colored curable resin composition, a composition containing C.I. Pigment Red 177 as a coloring agent is known (Patent Document 1). [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本專利申請特開2004-341245號[Patent Document 1] Japanese Patent Application Laid-Open No. 2004-341245

[發明所欲解決之課題][The problem to be solved by the invention]

近年來，在顯示裝置等中進行有擴大色域之研究，進一步要求該等中所使用之彩色濾光片為深色（高彩度）。若增厚彩色濾光片之膜厚則彩色濾光片變成深色（高彩度），但對於彩色濾光片而言，於要求深色（高彩度）化之同時亦要求薄膜化。惟由先前已知之上述著色硬化性樹脂組成物所形成之彩色濾光片並非可滿足深色（高彩度）區域中之薄膜化者。 [解決課題之手段]In recent years, research on expanding the color gamut has been conducted in display devices and the like, and the color filters used in these are further required to be dark (high chroma). If the film thickness of the color filter is increased, the color filter becomes dark (high chroma), but for color filters, it is required to be thinner (high chroma) at the same time as the color filter is required. However, the color filter formed by the previously known colored curable resin composition is not one that can satisfy the thin film in the dark (high chroma) area. [Means to solve the problem]

[1] 一種紅色硬化性樹脂組成物，其包含：著色劑、樹脂、聚合性化合物及聚合起始劑，其中著色劑包含四氮雜卟啉（tetraazaporphyrin）化合物與紅色色素。[1] A red curable resin composition comprising: a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein The coloring agent contains a tetraazaporphyrin compound and a red pigment.

[2] 一種彩色濾光片，其係由如[1]所述之紅色硬化性樹脂組成物所形成。[2] A color filter formed of the red curable resin composition as described in [1].

[3] 一種顯示裝置，其包含如[2]所述之彩色濾光片。 [發明之效果][3] A display device including the color filter as described in [2]. [Effects of Invention]

根據本發明之紅色硬化性樹脂組成物，可形成深色（高彩度）且薄膜之彩色濾光片。According to the red curable resin composition of the present invention, a dark color (high chroma) and thin film color filter can be formed.

本發明之紅色硬化性樹脂組成物包含著色劑（以下，存在有稱為著色劑（A）之情況）、樹脂（以下，存在有稱為樹脂（B）之情況）、聚合性化合物（以下，存在有稱為聚合性化合物（C）之情況）、以及聚合起始劑（以下，存在有稱為聚合起始劑（D）之情況）。The red curable resin composition of the present invention contains a colorant (hereinafter, sometimes referred to as colorant (A)), resin (hereinafter, sometimes referred to as resin (B)), and a polymerizable compound (hereinafter, It may be called a polymerizable compound (C)) and a polymerization initiator (hereinafter, it may be called a polymerization initiator (D)).

本發明之紅色硬化性樹脂組成物較佳進一步包含溶劑（以下，存在有稱為溶劑（E）之情況）。The red curable resin composition of the present invention preferably further contains a solvent (hereinafter, it may be referred to as a solvent (E)).

本發明之紅色硬化性樹脂組成物亦可進一步包含調平劑。The red curable resin composition of the present invention may further include a leveling agent.

於本說明書中，作為各成分而例示之化合物，只要無特別說明，則可單獨使用或將多種組合而使用。In this specification, the compound exemplified as each component can be used alone or in combination of multiple types unless otherwise specified.

＜著色劑（A）＞＜Colorant (A)＞

著色劑（A）包含四氮雜卟啉化合物及紅色色素。四氮雜卟啉化合物係於分子內具有四氮雜卟啉骨架之化合物。另外，於四氮雜卟啉化合物為鹽之情況下，亦可與任意之陽離子或陰離子形成鹽。The coloring agent (A) contains a porphyrazine compound and a red pigment. The porphyrazine compound is a compound having a porphyrazine skeleton in the molecule. In addition, when the porphyrazine compound is a salt, it may form a salt with any cation or anion.

作為四氮雜卟啉化合物，較佳為由式（1）所表示之化合物（以下，存在有稱為化合物（1）之情況）。 [化1]

（於式（1）中，R^1a 至R^1d 及R^2a 至R² ^d 分別獨立地表示可具有取代基之飽和烴基或可具有取代基之芳基； x表示1或2；當x為1時，M1表示二價金屬原子、取代金屬原子或氧化金屬原子；當x為2時，M1表示氫原子或一價金屬原子）The porphyrazine compound is preferably a compound represented by formula (1) (hereinafter, it may be referred to as compound (1)). [化1]

(In formula (1), R ^1a to R ^1d and R ^2a to R ² ^d each independently represent a saturated hydrocarbon group that may have a substituent or an aryl group that may have a substituent; x represents 1 or 2; when x is 1 When, M1 represents a divalent metal atom, a substituted metal atom or an oxidized metal atom; when x is 2, M1 represents a hydrogen atom or a monovalent metal atom)

於式（1）中，R^1a 至R^1d 及R^2a 至R² ^d 係鍵結於四氮雜卟啉骨架之基團。In the formula (1), R ^1a to R ^1d and R ^2a to R ² ^d are groups bonded to the porphyrazine skeleton.

R^1a 至R^1d 可分別相同，亦可不同，較佳為相同；另外，R^2a 至R² ^d 可分別相同，亦可不同，較佳為相同。更佳為R^1a 至R^1d 相同，且R^2a 至R² ^d 相同。R ^1a to R ^1d may be the same or different, and are preferably the same; in addition, R ^2a to R ² ^d may be the same or different, and are preferably the same. More preferably, R ^1a to R ^{1d are the} same, and R ^2a to R ² ^{d are the} same.

作為表示R^1a 至R^1d 及R^2a 至R² ^d 之飽和烴基，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、正十一基、正十二基、正十三基、正十四基、正十五基等直鏈狀烷基；異丙基、異丁基、二級丁基、三級丁基、2-甲基丁基、1-甲基丁基、新戊基、1,2-二甲基丙基、1,1-二甲基丙基、4-甲基戊基、3-甲基戊基、2-甲基戊基、1-甲基戊基、3,3-二甲基丁基、2,3-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、1,2-二甲基丁基、1,1-二甲基丁基、3-乙基丁基、2-乙基丁基、1-乙基丁基、1,1,2-三甲基丙基、1-乙基-2-甲基丙基、2-甲基己基、3-甲基己基、4-甲基己基、5-甲基己基、1-乙基戊基、2,4-二甲基戊基、2-乙基己基、2,5-二甲基己基、2,5,5-三甲基戊基、2,4-二甲基己基、2,2,4-三甲基戊基、1,1-二甲基己基、3,5,5-三甲基己基、4-乙基辛基、4-乙基-4,5-二甲基己基、1,3,5,7-四甲基辛基、4-丁基辛基、6,6-二乙基辛基、6-甲基-4-丁基辛基、3,5-二甲基十七基、2,6-二甲基十七基、2,4-二甲基十七基、2,2,5,5-四甲基己基等分支鏈狀烷基；環戊基、環己基、1-環戊基-2,2-二甲基丙基、1-環己基-2,2-二甲基丙基等環烷基。Examples of saturated hydrocarbon groups representing R ^1a to R ^1d and R ^2a to R ² ^d include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, N-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl and other linear alkyl groups; isopropyl, isobutyl, 2-butyl Base, tertiary butyl, 2-methylbutyl, 1-methylbutyl, neopentyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 4-methylpentyl Base, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethyl Butyl, 2,2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-dimethylbutyl, 3-ethylbutyl, 2-ethylbutyl, 1-ethyl Butyl, 1,1,2-trimethylpropyl, 1-ethyl-2-methylpropyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methyl Hexyl, 1-ethylpentyl, 2,4-dimethylpentyl, 2-ethylhexyl, 2,5-dimethylhexyl, 2,5,5-trimethylpentyl, 2,4- Dimethylhexyl, 2,2,4-trimethylpentyl, 1,1-dimethylhexyl, 3,5,5-trimethylhexyl, 4-ethyloctyl, 4-ethyl-4 ,5-Dimethylhexyl, 1,3,5,7-tetramethyloctyl, 4-butyloctyl, 6,6-diethyloctyl, 6-methyl-4-butyloctyl , 3,5-dimethyl heptadecyl, 2,6-dimethyl heptadecyl, 2,4-dimethyl heptadecyl, 2,2,5,5-tetramethylhexyl and other branched chains Alkyl; Cycloalkyl groups such as cyclopentyl, cyclohexyl, 1-cyclopentyl-2,2-dimethylpropyl, 1-cyclohexyl-2,2-dimethylpropyl, etc.

飽和烴基之碳數較佳為1至20，更佳為1至15，進一步佳為1至10，進一步更佳為1至5。The carbon number of the saturated hydrocarbon group is preferably from 1 to 20, more preferably from 1 to 15, further preferably from 1 to 10, and still more preferably from 1 to 5.

該等中，較佳為碳數1至10之烷基，更佳為碳數1至5之烷基。Among them, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred.

作為該飽和烴基可具有之取代基，較佳為鹵素原子。作為具有鹵素原子之飽和烴基，可列舉：氯甲基、二氯甲基、氟甲基、三氟甲基、五氟乙基、九氟丁基、全氟環丁基、全氟環戊基等。As the substituent which this saturated hydrocarbon group may have, a halogen atom is preferable. Examples of saturated hydrocarbon groups having halogen atoms include: chloromethyl, dichloromethyl, fluoromethyl, trifluoromethyl, pentafluoroethyl, nonafluorobutyl, perfluorocyclobutyl, perfluorocyclopentyl Wait.

作為表示R^1a 至R^1d 及R^2a 至R^2d 之芳基，可列舉：苯基、甲基苯基、二甲基苯基、三甲基苯基、萘基、甲基萘基等。Examples of the aryl group representing R ^1a to R ^1d and R ^2a to R ^2d include phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, naphthyl, methylnaphthyl, and the like.

作為該芳基可具有之取代基，可列舉：硝基、氰基、鹵素原子（較佳為氟原子、氯原子、溴原子）、羥基、羧基、碳數1至8之烷氧基、可經碳數1至8之烷基取代之胺基等。Examples of substituents that the aryl group may have include nitro groups, cyano groups, halogen atoms (preferably fluorine atoms, chlorine atoms, and bromine atoms), hydroxyl groups, carboxyl groups, alkoxy groups having 1 to 8 carbon atoms, and Amino groups substituted by alkyl groups having 1 to 8 carbon atoms, etc.

作為具有取代基之芳基，可列舉：氟苯基、二氟苯基、三氟苯基、四氟苯基、五氟苯基、氯苯基、二氯苯基、三氯苯基、四氯苯基、五氯苯基、溴苯基、二溴苯基、三溴苯基、四溴苯基、五溴苯基、三氟甲基苯基、雙-三氟甲基苯基、參-三氟甲基苯基、肆-三氟甲基苯基、伍-氟甲基苯基、氟萘基、氯萘基、溴萘基、三氟甲基萘基等經鹵素原子取代之芳基；硝基苯基、硝基萘基；氰基苯基、氰基萘基；羥基苯基、羥基萘基；羧基苯基；甲氧基苯基、乙氧基苯基；N,N-二甲基胺基苯基等。Examples of the substituted aryl group include: fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, tetrafluorophenyl Chlorophenyl, pentachlorophenyl, bromophenyl, dibromophenyl, tribromophenyl, tetrabromophenyl, pentabromophenyl, trifluoromethylphenyl, bis-trifluoromethylphenyl, ginseng -Trifluoromethylphenyl, 4-trifluoromethylphenyl, fluoromethylphenyl, fluoronaphthyl, chloronaphthyl, bromonaphthyl, trifluoromethylnaphthyl and other aromatics substituted by halogen atoms Group; nitrophenyl, nitronaphthyl; cyanophenyl, cyanonaphthyl; hydroxyphenyl, hydroxynaphthyl; carboxyphenyl; methoxyphenyl, ethoxyphenyl; N,N- Dimethylaminophenyl and so on.

芳基之碳數例如為6至20，較佳為6至18，更佳為6至15，進一步佳為6至10。The carbon number of the aryl group is, for example, 6-20, preferably 6-18, more preferably 6-15, and still more preferably 6-10.

作為可具有取代基之芳基，較佳為未經取代之芳基或經鹵素原子取代之芳基。As the aryl group which may have a substituent, an unsubstituted aryl group or an aryl group substituted with a halogen atom is preferable.

R^1a 至R^1d 較佳係分別獨立地為可具有取代基之碳數1至10之飽和烴基，更佳係分別獨立地為可具有取代基之碳數1至10之直鏈狀烷基或分支鏈狀烷基，進一步佳係分別獨立地為可具有取代基之碳數1至5之直鏈狀烷基或分支鏈狀烷基。R^1a 至R^1d 特佳係均為三級丁基。Preferably, R ^1a to R ^1d are each independently a saturated hydrocarbon group of 1 to 10 carbons which may have a substituent, and more preferably each independently are a linear alkyl group of 1 to 10 carbons which may have a substituent or The branched chain alkyl group is more preferably each independently a linear alkyl group having 1 to 5 carbon atoms or a branched chain alkyl group which may have a substituent. R ^1a to R ^{1d are} particularly preferably tertiary butyl groups.

R^2a 至R^2d 較佳係分別獨立地為可具有取代基之碳數6至20之芳基，更佳係分別獨立地為具有取代基之碳數6至20之芳基，進一步佳係分別獨立地為經鹵素原子取代之碳數6至20之芳基，尤佳係分別獨立地為經氟原子取代之碳數6至20之芳基。R^2a 至R^2d 特佳為2-氟苯基。Preferably, R ^2a to R ^2d are each independently an aryl group having 6 to 20 carbon atoms that may have a substituent, more preferably each independently an aryl group having 6 to 20 carbon atoms that may have a substituent, and more preferably each independently Each independently is an aryl group having 6 to 20 carbons substituted by a halogen atom, and more preferably is an aryl group having 6 to 20 carbon atoms substituted by a fluorine atom. R ^2a to R ^{2d are} particularly preferably 2-fluorophenyl.

作為當x為2時表示M1之一價金屬原子，可列舉Na、K及Li等鹼金屬原子。在該情況下，式（1）中之＞N—、—N＜並不橋接而是與各個一價金屬原子鍵結而存在。When x is 2, it represents an M1 monovalent metal atom, and examples include alkali metal atoms such as Na, K, and Li. In this case, >N—, —N< in formula (1) does not bridge but is bonded to each monovalent metal atom.

作為當x為1時表示M1之二價金屬原子，可列舉：Cu、Zn、Fe、Co、Ni、Ru、Rh、Pd、Pt、Mn、Mg、Ti、Be、Ca、Ba、Cd、Hg、Pb及Sn等。As the divalent metal atom that represents M1 when x is 1, examples include: Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg , Pb and Sn etc.

作為取代金屬原子，可列舉：Al-Cl、Ga-Br、Ga-I、In-Cl、Al-C₆ H₅ 、In-C₆ H₅ 、Mn(OH)、Mn[OSi(CH₃ )₃ ]及Fe-Cl等。Examples of the substituted metal atom include: Al-Cl, Ga-Br, Ga-I, In-Cl, Al-C ₆ H ₅ , In-C ₆ H ₅ , Mn(OH), Mn[OSi(CH ₃ ) ₃ ] and Fe-Cl and so on.

作為氧化金屬原子，可列舉：V(=O)、Mn(=O)及Ti(=O)等。Examples of oxidized metal atoms include V (=O), Mn (=O), Ti (=O), and the like.

M1較佳為二價金屬原子或氧化金屬原子，更佳為Cu、Zn、Fe、Co、Ni、Pd、Mn、Mg、V(=O)或Ti(=O)，進一步佳為Cu、Zn、Ni、Pd或V(=O)，尤佳為Cu、Pd或V(=O)。M1 is preferably a divalent metal atom or an oxide metal atom, more preferably Cu, Zn, Fe, Co, Ni, Pd, Mn, Mg, V(=O) or Ti(=O), and further preferably Cu, Zn , Ni, Pd or V(=O), particularly preferably Cu, Pd or V(=O).

較佳為於化合物（1）中，x為1、M1為二價金屬原子或氧化金屬原子之化合物。Preferably, in compound (1), x is 1 and M1 is a compound in which a divalent metal atom or an oxidized metal atom is used.

作為化合物（1）之具體例，可列舉由式（2-1）至式（2-38）所表示之化合物等。 [化2]

[化3]

[化4]

[化5]

[化6]

As specific examples of the compound (1), compounds represented by formula (2-1) to formula (2-38) and the like can be cited. [化2]

[化3]

[化4]

[化5]

[化6]

作為其他具體例，可列舉由式（2-39）至式（2-45）所表示之化合物等。 [化7]

[化8]

[化9]

[化10]

As other specific examples, compounds represented by formula (2-39) to formula (2-45) and the like can be cited. [化7]

[化8]

[化9]

[化10]

其中，特佳為由式（2-29）、式（2-38）、式（2-39）至式（2-45）所表示之化合物。Among them, particularly preferred are compounds represented by formula (2-29), formula (2-38), formula (2-39) to formula (2-45).

化合物（1）通常為吸收590奈米附近示出橙色之光之化合物，且其吸收極大波長（λmax）較佳為570奈米以上且620奈米以下，更佳為575奈米以上且615奈米以下。Compound (1) is usually a compound that absorbs orange light near 590 nm, and its absorption maximum wavelength (λmax) is preferably 570 nm or more and 620 nm or less, more preferably 575 nm or more and 615 nm Below meters.

著色劑（A）包含紅色色素。作為紅色色素，可列舉：紅色顏料及紅色染料。The coloring agent (A) contains a red pigment. Examples of red pigments include red pigments and red dyes.

作為紅色顏料，可使用習知之顏料，例如可列舉在染料索引（Colour Index）（英國染料及色彩師學會（The Society of Dyers and Colourists）出版）中被分類為顏料之顏料中、被分類為紅色者。亦可將二種以上組合。但，化合物（1）除外。As red pigments, conventional pigments can be used, for example, the pigments classified as pigments in the Colour Index (published by The Society of Dyers and Colourists), are classified as red By. Two or more types can also be combined. However, the compound (1) is excluded.

具體而言，可列舉：C.I.顏料紅9、97、105、122、123、144、149、166、168、176、177、179、180、192、202、208、209、215、216、224、242、254、255、264、265、266、268、269、273等。Specifically, include: CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 202, 208, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273, etc.

在紅色顏料中，較佳為蒽醌顏料、偶氮顏料、喹吖啶酮顏料、苝顏料、二酮基吡咯并吡咯顏料；較佳為C.I.顏料紅177、179、202、208、242、254、269、溴化二酮基吡咯并吡咯顏料；更佳為C.I.顏料紅177、254、溴化二酮基吡咯并吡咯顏料。Among the red pigments, anthraquinone pigments, azo pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments are preferred; CI Pigment Red 177, 179, 202, 208, 242, 254 are preferred , 269, brominated diketopyrrolopyrrole pigment; more preferably CI Pigment Red 177, 254, brominated diketopyrrolopyrrole pigment.

作為紅色染料，可列舉油溶性染料、酸性染料、鹼性染料、直接染料、媒染染料、酸性染料之胺鹽或酸性染料之磺醯胺衍生物等染料，例如可列舉在染料索引（英國染料及色彩師學會出版）中被分類為染料、即顏料以外之化合物；或在染色筆記（色染公司）中所記載之習知之染料。另外，根據化學結構，可列舉偶氮染料、蒽醌染料、二苯并哌喃（xanthene）染料、花青染料、萘醌染料、醌亞胺染料、次甲基染料、偶氮次甲基染料及吖啶染料等。該等中，較佳為有機溶劑可溶性染料。該等染料亦可併用二種以上。Examples of red dyes include dyes such as oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes or sulfonamide derivatives of acid dyes. Published by the Society of Colorists) are classified as dyes, that is, compounds other than pigments; or the conventional dyes recorded in the dyeing notes (color dyeing company). In addition, according to the chemical structure, azo dyes, anthraquinone dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azomethine dyes can be cited And acridine dyes and so on. Among them, organic solvent-soluble dyes are preferred. Two or more of these dyes may be used in combination.

具體而言，可列舉：C.I.溶劑紅24、49、90、91、111、118、119、122、124、125、127、130、132、143、145、146、150、151、155、160、168、169、172、175、181、207、218、222、227、230、245、247； C.I.酸性紅73、80、91、92、97、138、151、211、274、289等。Specifically, examples include: CI Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; C.I. Acid Red 73, 80, 91, 92, 97, 138, 151, 211, 274, 289, etc.

本發明之紅色硬化性樹脂組成物可包含化合物（1）及紅色色素、以及化合物（1）以外之著色劑（以下，存在有稱為著色劑（A1）之情況）作為著色劑（A）。The red curable resin composition of the present invention may contain the compound (1) and the red pigment, and a coloring agent other than the compound (1) (hereinafter, it may be referred to as a coloring agent (A1)) as the coloring agent (A).

著色劑（A1）可為染料亦可為顏料。作為染料，可列舉在染料索引（英國染料及色彩師學會出版）及染色筆記（色染公司）中所記載之習知之染料（但紅色染料除外）。另外，根據化學結構，可列舉：偶氮染料、蒽醌染料、三苯基甲烷染料、二苯并哌喃染料、花青染料、萘醌染料、醌亞胺染料、次甲基染料、偶氮次甲基染料、方酸菁（squarylium）染料、吖啶染料、苯乙烯基染料、香豆素染料、喹啉染料、硝基染料及酞菁染料等。該等中，較佳為有機溶劑可溶性染料。該等染料亦可併用二種以上。The colorant (A1) may be a dye or a pigment. Examples of dyes include conventional dyes (except for red dyes) described in the Dye Index (published by the British Society of Dyestuffs and Colorists) and Dyeing Notes (Color Dyeing Company). In addition, according to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, dibenzopyran dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azo Methylene dyes, square acid cyanine (squarylium) dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes and phthalocyanine dyes, etc. Among them, organic solvent-soluble dyes are preferred. Two or more of these dyes may be used in combination.

具體而言，可列舉如下染料索引（C.I.）編號之染料。 C.I.溶劑黃14、15、23、24、25、38、62、63、68、79、81、82、83、89、94、98、99、162； 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.活性黃2、76、116； C.I.直接黃2、4、28、33、34、35、38、39、43、44、47、50、54、58、68、69、70、71、86、93、94、95、98、102、108、109、129、132、136、138、141； C.I.分散黃51、54、76； C.I.溶劑橙2、7、11、15、26、41、54、56、99； C.I.酸性橙6、7、8、10、12、26、50、51、52、56、62、63、64、74、75、94、95、107、108、149、162、169、173； C.I.活性橙16； 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.酸性紫34、102； C.I.分散紫26、27； C.I.溶劑紫11、13、14、26、31、36、37、38、45、47、48、51、59、60； C.I.溶劑藍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.酸性藍25、27、40、45、78、80、112； C.I.直接藍40； C.I.分散藍1、14、56、60； C.I.溶劑綠1、3、5、28、29、32、33； C.I.酸性綠3、5、9、25、27、28、41； C.I.鹼性綠1； C.I.還原綠1等｡Specifically, the dyes with the following dye index (C.I.) numbers can be listed. C.I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; 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; C.I. Reactive Yellow 2, 76, 116; CI Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102 , 108, 109, 129, 132, 136, 138, 141; C.I. Disperse Yellow 51, 54, 76; C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99; C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; C.I. Reactive Orange 16; C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Acid Violet 34, 102; C.I. Disperse Violet 26, 27; C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI solvent blue 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. Acid Blue 25, 27, 40, 45, 78, 80, 112; C.I. Direct Blue 40; C.I. Disperse Blue 1, 14, 56, 60; C.I. Solvent Green 1, 3, 5, 28, 29, 32, 33; C.I. Acid Green 3, 5, 9, 25, 27, 28, 41; C.I. Basic Green 1; C.I. Vat Green 1 etc.

作為顏料，可使用習知之顏料，例如可列舉在染料索引（英國染料及色彩師學會出版）中被分類為顏料之顏料。亦可將二種以上組合。As the pigment, conventional pigments can be used, for example, pigments classified as pigments in the Dyestuff Index (published by the British Society of Dyestuffs and Colorists). Two or more types can also be combined.

具體而言，可列舉：C.I.顏料黃1、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、129、137、138、139、147、148、150、153、154、166、173、185、194、214等黃色顏料； C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等橙色顏料； C.I.顏料藍15、15：3、15：4、15：6、60等藍色顏料； C.I.顏料紫1、19、23、29、32、36、38等紫色顏料； C.I.顏料綠7、36、58、59等綠色顏料。Specifically, include: CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other yellow pigments; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; C.I. Purple pigments such as pigment violet 1, 19, 23, 29, 32, 36, 38; C.I. Pigment Green 7, 36, 58, 59 and other green pigments.

其中，著色劑（A1）較佳為黃色色素及橙色色素之一或二者，更佳為黃色色素。亦即，著色劑（A）進一步佳為在包含四氮雜卟啉化合物、紅色色素之外，亦進一步包含黃色色素。Among them, the coloring agent (A1) is preferably one or both of a yellow pigment and an orange pigment, and more preferably a yellow pigment. That is, the coloring agent (A) further preferably contains a yellow pigment in addition to the porphyrazine compound and the red pigment.

作為著色劑（A1）之顏料較佳為黃色顏料及／或橙色顏料，更佳為黃色顏料。The pigment as the colorant (A1) is preferably a yellow pigment and/or an orange pigment, and more preferably a yellow pigment.

紅色顏料及作為著色劑（A1）之顏料（存在有總稱為顏料之情況）視需要亦可實施有松香處理、使用導入有酸性基或鹼性基之著色劑衍生物等表面處理、利用高分子化合物等對顏料等表面之接枝處理、利用硫酸微粒化法等微粒化處理、用以去除雜質之利用有機溶劑或水等清洗處理、利用離子性雜質之離子交換法等去除處理等。顏料等之粒徑較佳為各自大致均勻。顏料可藉由含有分散劑並進行分散處理而成為於分散液中均勻地分散之狀態。Red pigments and pigments as colorants (A1) (sometimes referred to as pigments) may be treated with rosin, surface treatments such as coloring agent derivatives with acidic or basic groups introduced, and polymer Grafting treatment of the surface of pigments with compounds, etc., micronization treatment using sulfuric acid micronization method, cleaning treatment using organic solvent or water to remove impurities, ion exchange method using ionic impurities, etc. removal treatment, etc. The particle diameters of the pigments and the like are preferably each substantially uniform. The pigment can be uniformly dispersed in the dispersion liquid by containing a dispersant and performing a dispersion treatment.

作為分散劑，可列舉界面活性劑等，可為陽離子系、陰離子系、非離子系及兩性之任一種界面活性劑。具體而言，可列舉聚酯系、多胺系及丙烯酸系等界面活性劑等。作為其他分散劑，亦可使用後述之樹脂（B）。該等分散劑可單獨使用或將二種以上組合使用。作為分散劑，若以商品名來表示，則可列舉：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（註冊商標）（捷利康股份有限公司製造）、EFKA（註冊商標）（巴斯夫（BASF）公司製造）、Ajisper（註冊商標）（味之素精密科技股份有限公司製造）及Disperbyk（註冊商標）（畢克化學公司製造）、BYK（註冊商標）（畢克化學公司製造）等。As a dispersing agent, surfactant etc. are mentioned, and it may be any of a cationic, anionic, nonionic, and amphoteric surfactant. Specifically, surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants, etc., can be cited. As other dispersants, the resin (B) described later can also be used. These dispersants can be used alone or in combination of two or more kinds. As a dispersant, if it is expressed by a trade name, it can include: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zelikon Co., Ltd.) ), EFKA (registered trademark) (manufactured by BASF), Ajisper (registered trademark) (manufactured by Ajinomoto Precision Technology Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK Chemie), BYK (registered trademark) ) (Manufactured by BYK Chemical Company) and so on.

於使用分散劑之情況下，相對於顏料100質量份，分散劑之使用量較佳為100質量份以下，更佳為5質量份以上且50質量份以下。若分散劑之使用量處於前述範圍，則存在有可獲得更均勻之分散狀態之顏料分散液的傾向。In the case of using a dispersant, relative to 100 parts by mass of the pigment, the amount of the dispersant used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less. If the amount of dispersant used is in the aforementioned range, there is a tendency to obtain a pigment dispersion in a more uniform dispersion state.

相對於固體成分總量，化合物（1）之含有率較佳為0.2質量%以上且20質量%以下，更佳為0.5質量%以上且15質量%以下，進一步佳為1質量%以上且12質量%以下。Relative to the total solid content, the content of the compound (1) is preferably 0.2% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less, and still more preferably 1% by mass or more and 12% by mass %the following.

在著色劑100質量%中，紅色色素之含有率較佳為45質量%至80質量%，更佳為47質量%至75質量%，進一步佳為50質量%至70質量%。In 100% by mass of the coloring agent, the content of the red pigment is preferably from 45% by mass to 80% by mass, more preferably from 47% by mass to 75% by mass, and still more preferably from 50% by mass to 70% by mass.

相對於固體成分總量，紅色色素之含有率較佳為1質量%以上且50質量%以下，更佳為5質量%以上且45質量%以下，進一步佳為10質量%以上且40質量%以下。Relative to the total solid content, the content of the red pigment is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 45% by mass or less, and still more preferably 10% by mass or more and 40% by mass or less .

相對於紅色色素100質量份，化合物（1）之含量較佳為0.1質量份以上且200質量份以下，更佳為1質量份以上且100質量份以下，進一步佳為1質量份以上且70質量份以下。With respect to 100 parts by mass of the red pigment, the content of the compound (1) is preferably 0.1 part by mass or more and 200 parts by mass or less, more preferably 1 part by mass or more and 100 parts by mass or less, and still more preferably 1 part by mass or more and 70 parts by mass The following.

相對於固體成分總量，著色劑（A1）（較佳為黃色色素）之含有率通常為0質量%以上且50質量%以下，較佳為0質量%以上且40質量%以下，更佳為0質量%以上且30質量%以下。Relative to the total solid content, the content of the colorant (A1) (preferably yellow pigment) is usually 0% by mass or more and 50% by mass or less, preferably 0% by mass or more and 40% by mass or less, more preferably 0% by mass or more and 30% by mass or less.

於包含黃色色素之情況下，在著色劑中，紅色色素及黃色色素之合計含有率較佳為65質量%以上且97質量%以下，更佳為70質量%以上且95質量%以下，進一步佳為75質量%以上且93質量%以下。When a yellow pigment is included, the total content of the red pigment and the yellow pigment in the colorant is preferably 65% by mass or more and 97% by mass or less, more preferably 70% by mass or more and 95% by mass or less, and more preferably It is 75% by mass or more and 93% by mass or less.

相對於固體成分總量，著色劑（A）之含有率較佳為5質量%以上且60質量%以下，更佳為8質量%以上且55質量%以下，進一步佳為10質量%以上且50質量%以下。Relative to the total solid content, the content of the colorant (A) is preferably 5% by mass or more and 60% by mass or less, more preferably 8% by mass or more and 55% by mass or less, and still more preferably 10% by mass or more and 50% by mass. Less than mass%.

此處，本說明書中之「固體成分總量」是指自紅色硬化性樹脂組成物總量去除溶劑之含量後而成的量。固體成分總量及相對於其之各成分之含量例如可利用液相層析法或氣相層析法等習知之分析手段來測定。Here, the "total solid content" in this specification refers to the amount obtained by subtracting the solvent content from the total amount of the red curable resin composition. The total solid content and the content of each component relative to it can be measured, for example, by conventional analytical means such as liquid chromatography or gas chromatography.

＜樹脂（B）＞＜Resin (B)＞

樹脂（B）並無特別限定，較佳為鹼可溶性樹脂，更佳為具有源自從不飽和羧酸及不飽和羧酸酐所組成之群組中所選之至少一種單體（a）（以下存在有稱為「（a）」之情況）的結構單元的樹脂。樹脂（B）進一步較佳為具有從以下結構單元所組成之群組中所選之至少一種結構單元：源自具有碳數2至4之環狀醚結構與乙烯性不飽和鍵之單體（b）（以下存在有稱為「（b）」之情況）之結構單元、源自可與（a）共聚之單體（c）（但，與（a）及（b）不同）（以下存在有稱為「（c）」之情況）之結構單元、以及於側鏈具有乙烯性不飽和鍵之結構單元。The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably has at least one monomer (a) derived from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter There is a resin with a structural unit called "(a)"). The resin (B) further preferably has at least one structural unit selected from the group consisting of the following structural units: a monomer derived from a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond ( b) (Hereinafter, there are cases called "(b)") structural units derived from monomers (c) that can be copolymerized with (a) (but, different from (a) and (b)) (below There are structural units called "(c)") and structural units having ethylenically unsaturated bonds in the side chain.

作為（a），具體而言，例如可列舉丙烯酸、甲基丙烯酸、馬來酸酐、伊康酸酐、3,4,5,6-四氫酞酸酐、琥珀酸單[2-（甲基）丙烯醯基氧基乙基]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-(meth)propylene Acrylic oxyethyl] ester and the like are preferably acrylic acid, methacrylic acid, and maleic anhydride.

再者，於本說明書中，「（甲基）丙烯酸」係表示從丙烯酸及甲基丙烯酸所組成之群組中所選之至少一種。「（甲基）丙烯醯基」及「（甲基）丙烯酸酯」等表述亦具有相同之含義。Furthermore, in this specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

（b）較佳為具有碳數2至4之環狀醚結構（例如，從環氧乙烷環、氧呾環及四氫呋喃環所組成之群組中所選之至少一種）與（甲基）丙烯醯基氧基之單體。(B) Preferably, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxygen ring, and a tetrahydrofuran ring) and (methyl) The monomer of acryloxy group.

作為（b），例如可列舉（甲基）丙烯酸縮水甘油酯、乙烯基苄基縮水甘油醚、（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）丙烯醯基氧基甲基氧呾、（甲基）丙烯酸四氫糠基酯等；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）丙烯醯基氧基甲基氧呾。Examples of (b) include glycidyl (meth)acrylate, vinyl benzyl glycidyl ether, 3,4-epoxy tricyclo[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)acryloyloxymethyloxy group.

作為（c），例如可列舉（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）丙烯酸苄基酯、（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；較佳以苯乙烯、乙烯基甲苯、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺等為宜。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-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyl toluene, etc.; preferably styrene, vinyl toluene, N-phenylmaleimide, N -Cyclohexyl maleimide, N-benzyl maleimide, etc. are suitable.

具有於側鏈帶有乙烯性不飽和鍵之結構單元的樹脂可藉由對（a）與（c）之共聚物加成（b）、或對（b）與（c）之共聚物加成（a）來製造。該樹脂亦可為對（b）與（c）之共聚物加成（a）並進一步使羧酸酐反應而成之樹脂。Resins having structural units with ethylenically unsaturated bonds in the side chain can be added to the copolymer of (a) and (c) (b), or to the copolymer of (b) and (c) (A) Come to manufacture. The resin may also be a resin obtained by adding (a) to the copolymer of (b) and (c) and further reacting carboxylic anhydride.

樹脂（B）之聚苯乙烯換算之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）之分子量分布[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 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.

以固體成分換算計，樹脂（B）之酸價較佳為50 mg-KOH/g（毫克-KOH／公克）至170 mg-KOH/g，更佳為60 mg-KOH/g至150 mg-KOH/g，進一步佳為70 mg-KOH/g至135 mg-KOH/g。此處，酸價係作為中和樹脂（B）1公克所需之氫氧化鉀之量（毫克）而測定之值，例如可藉由使用氫氧化鉀水溶液進行滴定來求出。In terms of solid content, the acid value of resin (B) is preferably 50 mg-KOH/g (mg-KOH/gram) to 170 mg-KOH/g, more preferably 60 mg-KOH/g to 150 mg- KOH/g is more preferably 70 mg-KOH/g 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.

相對於固體成分總量，樹脂（B）之含有率較佳為10質量%至70質量%，更佳為15質量%至65質量%，進一步佳為20質量%至60質量%。The content of the resin (B) is preferably 10% by mass to 70% by mass relative to the total solid content, more preferably 15% by mass to 65% by mass, and still more preferably 20% by mass to 60% by mass.

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

聚合性化合物（C）係可藉由自聚合起始劑（D）產生之活性自由基及／或酸而進行聚合之化合物，例如可列舉聚合性之具有乙烯性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 by living radicals and/or acid generated from the polymerization initiator (D). For example, a polymerizable compound having an ethylenically unsaturated bond can be cited. It is preferably a (meth)acrylate compound.

其中，聚合性化合物（C）較佳為具有三個以上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、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. As such a polymerizable compound, for example, trimethylolpropane tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, neopentaerythritol tetra(meth)acrylate, dixin Pentaerythritol penta(meth)acrylate, dineopentaerythritol hexa(meth)acrylate, etc.

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.

相對於固體成分總量，聚合性化合物（C）之含有率較佳為3質量%至60質量%，更佳為5質量%至50質量%，進一步佳為11質量%至40質量%。The content of the polymerizable compound (C) relative to the total solid content is preferably 3% by mass to 60% by mass, more preferably 5% by mass to 50% by mass, and still more preferably 11% by mass to 40% by mass.

＜聚合起始劑（D）＞＜Polymerization initiator (D)＞

聚合起始劑（D）若為可藉由光或熱之作用而產生活性自由基、酸等並使聚合開始的化合物，則並無特別限定，可使用習知之聚合起始劑。作為產生活性自由基之聚合起始劑，例如可列舉：N-苯甲醯基氧基-1-（4-苯基氫硫基苯基）丁烷-1-酮-2-亞胺、N-苯甲醯基氧基-1-（4-苯基氫硫基苯基）辛烷-1-酮-2-亞胺、N-苯甲醯基氧基-1-（4-苯基氫硫基苯基）-3-環戊基丙烷-1-酮-2-亞胺、2-甲基-2-嗎福林基-1-（4-甲基氫硫基苯基）丙烷-1-酮、2-二甲基胺基-1-（4-嗎福林基苯基）-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膦氧化物、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 that can generate active radicals, acids, etc. by the action of light or heat and initiate polymerization, and conventional polymerization initiators can be used. As a polymerization initiator that generates living radicals, for example, N-benzyloxy-1-(4-phenylhydrothiophenyl)butan-1-one-2-imine, N -Benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylhydro) Thiophenyl)-3-cyclopentylpropane-1-one-2-imine, 2-methyl-2-morpholinyl-1-(4-methylhydrosulfanylphenyl)propane-1 -Ketone, 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-chloro Phenyl) -4,4',5,5'-tetraphenylbiimidazole and the like.

聚合起始劑較佳為包含從三嗪化合物、醯基膦氧化物化合物、苯烷基酮化合物、O-醯基肟化合物及聯咪唑化合物所組成之群組中所選之至少一種的聚合起始劑，更佳為包含O-醯基肟化合物之聚合起始劑。The polymerization initiator preferably includes polymerization of at least one selected from the group consisting of a triazine compound, an phosphine oxide compound, a phenalkyl ketone compound, an O-acyl oxime compound, and a biimidazole compound. The initiator is more preferably a polymerization initiator containing an O-acetoxime compound.

相對於樹脂（B）及聚合性化合物（C）之合計量100質量份，聚合起始劑（D）之含量較佳為0.1質量份至30質量份，更佳為1質量份至20質量份。若聚合起始劑（D）之含量處於前述範圍內，則存在有高感度化而曝光時間縮短之傾向，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, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and polymerizable compound (C) . If the content of the polymerization initiator (D) is within the aforementioned range, the sensitivity tends to be increased and the exposure time is shortened, so the productivity of the color filter is improved.

相對於聚合起始劑（D）之總量，O-醯基肟化合物之含有率較佳為50質量%以上，更佳為80質量%以上，進一步佳為90質量%以上，特佳為95質量%以上。若O-醯基肟化合物之含有率在前述範圍內，則存在有即便於形成著色圖案時之感度或顯影性、著色劑含有率高之情況下亦可製作高亮度之彩色濾光片的傾向。With respect to the total amount of the polymerization initiator (D), the content of the O-acetoxime compound is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95 Above mass%. If the content of the O-acetoxime compound is within the aforementioned range, there is a tendency to produce a high-brightness color filter even when the sensitivity or developability at the time of forming a colored pattern and the content of the coloring agent are high. .

本發明之紅色硬化性樹脂組成物亦可包含聚合起始助劑。The red curable resin composition of the present invention may also contain a polymerization initiation assistant.

＜聚合起始助劑（D1）＞＜Polymerization initiator (D1)＞

聚合起始助劑（D1）係用以促進藉由聚合起始劑而開始聚合之聚合性化合物之聚合的化合物、或增感劑。於包含聚合起始助劑（D1）之情況下，通常係與聚合起始劑（D）組合而使用。The polymerization initiator (D1) is a compound or a sensitizer for accelerating the polymerization of a polymerizable compound that starts polymerization by a polymerization initiator. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D).

作為聚合起始助劑（D1），可列舉：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、2,4-二乙基硫雜蒽酮、N-苯基甘胺酸等。Examples of the polymerization initiation aid (D1) include: 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler ketone), 4,4'-bis(diethylamino) ) Benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, N-phenylglycine, etc.

於使用該等聚合起始助劑（D1）之情況下，相對於樹脂（B）及聚合性化合物（C）之合計量100質量份，聚合起始助劑（D1）的含量較佳為0.1質量份至30質量份，更佳為1質量份至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，存在有彩色濾光片之生產性提高的傾向。In the case of using the polymerization initiation aid (D1), the content of the polymerization initiation aid (D1) is preferably 0.1 relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) Parts by mass to 30 parts by mass, more preferably 1 part by mass to 20 parts by mass. If the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be further formed with high sensitivity, and there is a tendency for the productivity of the color filter to improve.

本發明之紅色硬化性樹脂組成物較佳為包含溶劑。The red curable resin composition of the present invention preferably contains a solvent.

＜溶劑（E）＞＜Solvent (E)＞

溶劑（E）並無特別限定，可使用在該領域中通常所使用之溶劑。例如可列舉：酯溶劑（分子內包含-COO-且不包含-O-之溶劑）、醚溶劑（分子內包含-O-且不包含-COO-之溶劑）、醚酯溶劑（分子內包含-COO-與-O-之溶劑）、酮溶劑（分子內包含-CO-且不包含-COO-之溶劑）、醇溶劑（分子內包含OH且不包含-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 not containing -O- in the molecule), ether solvents (solvents containing -O- and not containing -COO- in the molecule), ether ester solvents (containing-in the molecule) COO- and -O- solvents), ketone solvents (solvents containing -CO- and not containing -COO- in the molecule), 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：乳酸乙酯、乳酸丁酯、2-羥基異丁酸甲酯、乙酸正丁酯、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；乙二醇單丁醚、二乙二醇單甲醚、丙二醇單甲醚、3-甲氧基-1-丁醇、二乙二醇二甲醚、二乙二醇甲基***等醚溶劑； 3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲氧基丁基乙酸酯、丙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單***乙酸酯等醚酯溶劑； 4-羥基-4-甲基-2-戊酮、庚酮、4-甲基-2-戊酮、環己酮等酮溶劑；丁醇、環己醇、丙二醇等醇溶劑；甲苯、二甲苯等芳香族烴溶劑； N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基吡咯啶酮等醯胺溶劑等。As the solvent, one can cite: Ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetylacetate, cyclohexanol acetate and Ester solvents such as γ-butyrolactone; Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and other ether solvents; Methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethyl Ether ester solvents such as glycol monoethyl ether acetate; Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone and cyclohexanone; Alcohol solvents such as butanol, cyclohexanol and propylene glycol; Aromatic hydrocarbon solvents such as toluene and xylene; Amine solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

作為溶劑，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。As the solvent, more preferred are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and ethyl 3-ethoxypropionate.

於包含溶劑（E）之情況下，相對於本發明之紅色硬化性樹脂組成物之總量，溶劑（E）之含有率較佳為70質量%至95質量%，更佳為75質量%至92質量%。換言之，紅色硬化性樹脂組成物之固體成分之總量較佳為5質量%至30質量%，更佳為8質量%至25質量%。若溶劑（E）之含量處於前述範圍內，則塗布時之平坦性變得良好，另外，形成彩色濾光片時顏色濃度不會不足，因此存在有顯示特性變得良好之傾向。When the solvent (E) is included, the content of the solvent (E) is preferably 70% to 95% by mass, and more preferably 75% to 95% by mass relative to the total amount of the red curable resin composition of the present invention 92% by mass. In other words, the total solid content of the red curable 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 aforementioned range, the flatness at the time of coating 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＞

本發明之紅色硬化性樹脂組成物視需要亦可包含調平劑、填充劑、其他高分子化合物、密接促進劑、抗氧化劑、光穩定劑、鏈轉移劑等該技術領域中習知之添加劑。The red curable 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.

＜紅色硬化性樹脂組成物之製造方法＞＜Manufacturing method of red curable resin composition＞

本發明之紅色硬化性樹脂組成物可藉由將著色劑（A）、樹脂（B）、聚合性化合物（C）、聚合起始劑（D）、視需要之溶劑（E）及其他成分混合而製備。The red curable resin composition of the present invention can be prepared by mixing colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E) and other components as needed And preparation.

＜彩色濾光片之製造方法＞＜Manufacturing method of color filter＞

作為由本發明之紅色硬化性樹脂組成物製造著色圖案之方法，可列舉光刻法、噴墨法、印刷法等。其中，較佳為光刻法。於光刻法中，藉由在曝光時不使用光罩、及／或不進行顯影而可形成作為上述著色樹脂組成物層之硬化物的著色塗膜。如此形成之著色圖案或著色塗膜即為本發明之彩色濾光片。As a method of producing a colored pattern from the red curable resin composition of the present invention, a photolithography method, an inkjet method, a printing method, etc. can be cited. Among them, photolithography is preferred. In the photolithography method, a colored coating film that is a hardened product of the colored resin composition layer can be formed by not using a photomask during exposure and/or not performing development. The colored pattern or colored coating film thus formed is the color filter of the present invention.

根據本發明之紅色硬化性樹脂組成物，可製作深色（高彩度）且薄膜之彩色濾光片。該彩色濾光片可作為顯示裝置（例如，液晶顯示裝置、有機EL（electroluminescence，電致發光）裝置、電子紙等）及固體攝像元件中所使用之彩色濾光片而有用。According to the red curable resin composition of the present invention, a dark color (high chroma) and thin film color filter can be produced. The color filter can be useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL (electroluminescence, electroluminescence) devices, electronic paper, etc.) and solid-state imaging devices.

[實施例][Example]

以下，藉由實施例來對本發明之紅色硬化性樹脂組成物更詳細地進行說明。例中之「%」及「份」只要無特別記載，則為質量%及質量份。Hereinafter, the red curable resin composition of the present invention will be described in more detail with examples. The "%" and "parts" in the examples are mass% and parts by mass unless otherwise stated.

〔合成例1〕[Synthesis Example 1]

（二氰基乙烯衍生物之合成）(Synthesis of dicyanoethylene derivatives)

利用日本專利第3961078號公報中所記載之合成法來分別獲得由式（x）所表示之化合物及由式（y）所表示之化合物。 [化11]

The compound represented by the formula (x) and the compound represented by the formula (y) were respectively obtained by the synthesis method described in Japanese Patent No. 3961078. [化11]

（二亞胺基異吡咯衍生物之合成）(Synthesis of diimino isopyrrole derivatives)

與日本專利申請特開平02-000665號公報中所記載之合成法同樣地進行，從由式（x）所表示之化合物獲得由式（z）所表示之化合物。 [化12]

It is performed in the same manner as the synthesis method described in Japanese Patent Application Laid-Open No. 02-000665, and the compound represented by the formula (z) is obtained from the compound represented by the formula (x). [化12]

（四氮雜卟啉化合物之合成）(Synthesis of porphyrazine compounds)

利用日本專利第3961078號公報中所記載之合成法，從由式（x）所表示之化合物獲得由式（a-1）所表示之化合物。 [化13]

The compound represented by the formula (a-1) is obtained from the compound represented by the formula (x) by the synthesis method described in Japanese Patent No. 3961078. [化13]

再者，由式（a-1）所表示之化合物係表示由式（a-1-1）至式（a-1-4）所表示之化合物，且利用上述合成法獲得之產物係該等結構異構體之混合物。 [化14]

Furthermore, the compound represented by the formula (a-1) means the compound represented by the formula (a-1-1) to the formula (a-1-4), and the products obtained by the above-mentioned synthesis method are these A mixture of structural isomers. [化14]

〔合成例2〕[Synthesis Example 2]

於安裝有冷卻管、溫度計、攪拌機之反應器中，投入由式（x）所表示之化合物（4.6公克）、戊醇（20毫升）、二氮雜雙環十一烯（4.6公克），並於120°C下添加氯化鋅（0.82公克）。攪拌4小時後，排出至甲醇-水混合液中並對析出固體進行過濾分離而獲得1.1公克之由式（a-2）所表示之化合物。 [化15]

Put the compound represented by formula (x) (4.6 g), pentanol (20 ml), and diazabicycloundecene (4.6 g) into a reactor equipped with a cooling tube, a thermometer, and a stirrer. Add zinc chloride (0.82 g) at 120°C. After stirring for 4 hours, it was discharged into a methanol-water mixed liquid and the precipitated solid was separated by filtration to obtain 1.1 g of the compound represented by the formula (a-2). [化15]

〔合成例3〕[Synthesis Example 3]

除了將由式（a-2）所表示之化合物之合成（合成例2）中的氯化鋅變更為氯化鎳以外，同樣地進行而獲得0.7公克之由式（a-3）所表示之化合物。 [化16]

Except for changing the zinc chloride in the synthesis of the compound represented by the formula (a-2) (Synthesis Example 2) to nickel chloride, the same procedure was performed to obtain 0.7 g of the compound represented by the formula (a-3) . [化16]

〔合成例4〕[Synthesis Example 4]

除了將由式（a-2）所表示之化合物之合成（合成例2）中的氯化鋅變更為氯化鈀以外，同樣地進行而獲得0.6公克之由式（a-4）所表示之化合物。 [化17]

Except that the zinc chloride in the synthesis of the compound represented by the formula (a-2) (Synthesis Example 2) was changed to palladium chloride, the same procedure was performed to obtain 0.6 g of the compound represented by the formula (a-4) . [化17]

〔合成例5〕除了將由式（a-2）所表示之化合物之合成（合成例2）中的由式（x）所表示之化合物變更為由式（y）所表示之化合物、且將氯化鋅變更為氯化釩(III)以外，同樣地進行而獲得1.5公克之由式（a-5）所表示之化合物。 [化18]

[Synthesis Example 5] Except that the compound represented by the formula (x) in the synthesis of the compound represented by the formula (a-2) (synthesis example 2) was changed to the compound represented by the formula (y), and the chlorine Except for changing the zinc chloride to vanadium (III) chloride, the same procedure was performed to obtain 1.5 g of the compound represented by the formula (a-5). [化18]

〔合成例6〕[Synthesis Example 6]

利用日本專利申請特開2016-27075號公報中記載之合成法來獲得由式（S-1）所表示之化合物。 [化19]

The compound represented by formula (S-1) is obtained by the synthesis method described in Japanese Patent Application Laid-Open No. 2016-27075. [化19]

〔合成例7〕[Synthesis Example 7]

於具備回流冷卻器、滴加漏斗及攪拌機之燒瓶內流通適量氮氣而置換為氮氣氣氛，加入乳酸乙酯141份、丙二醇單甲醚乙酸酯178份，一邊攪拌一邊加熱至85°C為止。接著，歷時5小時滴加以下之混合溶液：丙烯酸38份、丙烯酸-3,4-環氧三環[5.2.1.0^2,6 ]癸-8-基酯與丙烯酸-3,4-環氧三環[5.2.1.0^2,6 ]癸-9-基酯之混合物（含有率1：1）25份、環己基馬來醯亞胺137份、甲基丙烯酸-2-羥基乙酯50份、丙二醇單甲醚乙酸酯338份。另一方面，歷時6小時滴加使2,2-偶氮雙異丁腈5份溶解於丙二醇單甲醚乙酸酯88份中而成之混合溶液。滴加結束後，於該溫度下保持4小時，之後冷卻至室溫為止，獲得B型黏度（23°C）為23毫帕．秒（mPa·s）、固體成分為25.6%之共聚物（樹脂（B-1））溶液。所生成之共聚物之重量平均分子量Mw為8000，固體成分酸價為111 mg-KOH/g，分散度為2.1。樹脂（B-1）具有下述結構單元。 [化20]

A suitable amount of nitrogen was circulated in a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to replace it with a nitrogen atmosphere. 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added and heated to 85°C while stirring. Then, the following mixed solution was added dropwise over 5 hours: 38 parts of acrylic acid, acrylic acid-3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] dec-8-yl ester and acrylic acid-3,4-epoxy tricyclo [5.2.1.0 2,6] 25 parts of cyclo[5.2.1.0 ^2,6 ]dec-9-yl ester mixture (content ratio 1:1), 137 parts of cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, propylene glycol 338 parts of monomethyl ether acetate. On the other hand, a mixed solution obtained by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropping, keep it at this temperature for 4 hours, then cool to room temperature, and obtain a type B viscosity (23°C) of 23 mPa. Second (mPa·s), 25.6% solid content copolymer (resin (B-1)) solution. The resulting copolymer has a weight average molecular weight Mw of 8000, a solid acid value of 111 mg-KOH/g, and a dispersion degree of 2.1. The resin (B-1) has the following structural unit. [化20]

樹脂之聚苯乙烯換算之重量平均分子量（Mw）及數量平均分子量（Mn）之測定係利用GPC（Gel Permeation Chromatography，凝膠滲透層析法）在以下條件下進行。裝置：HLC-8120GPC（東曹股份有限公司製造）管柱：TSK-GELG2000HXL 管柱溫度：40°C 溶媒： THF（tetrahydrofuran，四氫呋喃）流速：1.0毫升／分鐘（mL/min）被檢測液體固體成分濃度：0.001質量%至0.01質量% 注入量：50 微升（μL）檢測器：RI 校正用標準物質：TSK STANDARD POLYSTYRENE（標準聚苯乙烯）F-40、F-4、F-288、A-2500、A-500（東曹股份有限公司製造）The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin in terms of polystyrene is carried out under the following conditions using GPC (Gel Permeation Chromatography). Device: HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSK-GELG2000HXL Column temperature: 40°C Solvent: THF (tetrahydrofuran, tetrahydrofuran) Flow rate: 1.0 ml/min (mL/min) Detected liquid solid content concentration: 0.001% to 0.01% by mass Injection volume: 50 microliters (μL) Detector: RI Standard materials for calibration: TSK STANDARD POLYSTYRENE (standard polystyrene) F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

將上述所得之聚苯乙烯換算之重量平均分子量及數量平均分子量的比（Mw/Mn）設為分散度。The ratio (Mw/Mn) of the weight average molecular weight in terms of polystyrene obtained above and the number average molecular weight (Mw/Mn) is defined as the degree of dispersion.

＜著色樹脂組成物之製作＞＜Production of colored resin composition＞

〔分散液1之製作〕〔Production of Dispersion 1〕

將C.I.顏料紅177（顏料）13份、丙烯酸系顏料分散劑（固體成分換算）3.3份、作為樹脂之樹脂（B-1）（固體成分換算）5.2份、丙二醇單甲醚乙酸酯76份、乳酸乙酯3.0份混合，使用珠磨機使顏料充分分散而製作分散液1。13 parts of CI Pigment Red 177 (pigment), 3.3 parts of acrylic pigment dispersant (in terms of solid content), resin as resin (B-1) (in terms of solid content) 5.2 parts, and 76 parts of propylene glycol monomethyl ether acetate , 3.0 parts of ethyl lactate were mixed, and the pigment was sufficiently dispersed using a bead mill to prepare a dispersion liquid 1.

〔分散液2之製作〕〔Production of Dispersion 2〕

將C.I.顏料紅254（顏料）14份、丙烯酸系顏料分散劑（固體成分換算）4.9份、作為樹脂之樹脂（B-1）（固體成分換算）4.2份、丙二醇單甲醚乙酸酯74份、乳酸乙酯2.5份混合，使用珠磨機使顏料充分分散而製作分散液2。14 parts of CI Pigment Red 254 (pigment), 4.9 parts of acrylic pigment dispersant (in terms of solid content), resin as resin (B-1) (in terms of solid content) 4.2 parts, and 74 parts of propylene glycol monomethyl ether acetate , 2.5 parts of ethyl lactate are mixed, and the pigment is fully dispersed using a bead mill to prepare a dispersion liquid 2.

〔分散液3之製作〕〔Production of Dispersion 3〕

將C.I.顏料黃139（顏料）12份、丙烯酸系顏料分散劑（固體成分換算）4.2份、作為樹脂之樹脂（B-1）（固體成分換算）4.2份、丙二醇單甲醚乙酸酯77份、乳酸乙酯2.4份混合，使用珠磨機使顏料充分分散而製作分散液3。12 parts of CI Pigment Yellow 139 (pigment), 4.2 parts of acrylic pigment dispersant (in terms of solid content), 4.2 parts of resin as resin (B-1) (in terms of solid content), and 77 parts of propylene glycol monomethyl ether acetate , 2.4 parts of ethyl lactate were mixed, and the pigment was sufficiently dispersed using a bead mill to prepare a dispersion liquid 3.

〔分散液4之製作〕〔Production of Dispersion 4〕

將C.I.顏料黃185（顏料）5份、丙烯酸系顏料分散劑（固體成分換算）3.5份、作為樹脂之樹脂（B-1）（固體成分換算）3.5份、丙二醇單甲醚乙酸酯86份、乳酸乙酯2.0份混合，使用珠磨機使顏料充分分散而製作分散液4。5 parts of CI Pigment Yellow 185 (pigment), 3.5 parts of acrylic pigment dispersant (in terms of solid content), 3.5 parts of resin (B-1) (in terms of solid content), and 86 parts of propylene glycol monomethyl ether acetate , 2.0 parts of ethyl lactate were mixed, and the pigment was sufficiently dispersed using a bead mill to prepare dispersion 4.

＜紅色硬化性樹脂組成物之製作＞＜Production of red curable resin composition＞

〔實施例1〕[Example 1]

藉由將下述成分混合而獲得紅色硬化性樹脂組成物。四氮雜卟啉：由式（a-1）所表示之化合物 17份紅色顏料：分散液1 435份黃色顏料：分散液3 309份樹脂（B）：樹脂（B-1）（固體成分換算） 29份聚合性化合物（C）：二新戊四醇六丙烯酸酯（KAYARAD（註冊商標）DPHA；日本化藥股份有限公司製造） 35份聚合起始劑（D）：N-苯甲醯基氧基-1-（4-苯基氫硫基苯基）辛烷-1-酮-2-亞胺（Irgacure（註冊商標）OXE01；巴斯夫公司製造；O-醯基肟化合物） 7.0份溶劑（E）：丙二醇單甲醚乙酸酯 510份乳酸乙酯 17份調平劑：聚醚改質矽油（固體成分換算）（Toray silicone SH8400；東麗道康寧股份有限公司製造） 0.10份The red curable resin composition is obtained by mixing the following components. Porphyrazine: 17 parts of compound represented by formula (a-1) Red pigment: 1,435 parts of dispersion Yellow pigment: 3 309 parts of dispersion Resin (B): Resin (B-1) (calculated as solid content) 29 parts Polymerizable compound (C): 35 parts of dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; BASF Manufactured by the company; O-acetoxime compound) 7.0 parts Solvent (E): 510 parts of propylene glycol monomethyl ether acetate 17 parts of ethyl lactate Leveling agent: polyether modified silicone oil (conversion of solid content) (Toray silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.10 parts

〔實施例2〕[Example 2]

除了代替由式（a-1）所表示之化合物而使用由式（a-2）所表示之化合物以外，與實施例1同樣地進行而獲得紅色硬化性樹脂組成物。Except having used the compound represented by formula (a-2) instead of the compound represented by formula (a-1), it carried out similarly to Example 1, and obtained the red curable resin composition.

〔實施例3〕[Example 3]

除了代替由式（a-1）所表示之化合物而使用由式（a-3）所表示之化合物以外，與實施例1同樣地進行而獲得紅色硬化性樹脂組成物。Except having used the compound represented by formula (a-3) instead of the compound represented by formula (a-1), it carried out similarly to Example 1, and obtained the red curable resin composition.

〔實施例4〕[Example 4]

除了代替由式（a-1）所表示之化合物而使用由式（a-4）所表示之化合物以外，與實施例1同樣地進行而獲得紅色硬化性樹脂組成物。Except having used the compound represented by formula (a-4) instead of the compound represented by formula (a-1), it carried out similarly to Example 1, and obtained the red curable resin composition.

〔實施例5〕[Example 5]

除了代替由式（a-1）所表示之化合物而使用由式（a-5）所表示之化合物以外，與實施例1同樣地進行而獲得紅色硬化性樹脂組成物。Except having used the compound represented by formula (a-5) instead of the compound represented by formula (a-1), it carried out similarly to Example 1, and obtained the red curable resin composition.

〔實施例6〕[Example 6]

藉由將下述成分混合而獲得紅色硬化性樹脂組成物。四氮雜卟啉：由式（a-1）所表示之化合物 11份紅色染料：由式（S-1）所表示之化合物 16份紅色顏料：分散液1 293份黃色顏料：分散液3 357份樹脂（B）：樹脂（B-1）（固體成分換算） 35份聚合性化合物（C）：二新戊四醇六丙烯酸酯（KAYARAD（註冊商標）DPHA；日本化藥股份有限公司製造） 35份聚合起始劑（D）：N-苯甲醯基氧基-1-（4-苯基氫硫基苯基）辛烷-1-酮-2-亞胺（Irgacure（註冊商標）OXE01；巴斯夫公司製造；O-醯基肟化合物） 7.0份溶劑（E）：丙二醇單甲醚乙酸酯 251份二丙酮醇 308份乳酸乙酯 20份調平劑：聚醚改質矽油（固體成分換算）（Toray silicone SH8400；東麗道康寧股份有限公司製造） 0.10份The red curable resin composition is obtained by mixing the following components. Porphyrazine: 11 parts of compound represented by formula (a-1) Red dye: 16 parts of compound represented by formula (S-1) Red pigment: 1,293 parts of dispersion Yellow pigment: 3,357 parts of dispersion Resin (B): Resin (B-1) (in terms of solid content) 35 parts Polymerizable compound (C): 35 parts of dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; BASF Manufactured by the company; O-acetoxime compound) 7.0 parts Solvent (E): 251 parts of propylene glycol monomethyl ether acetate Diacetone alcohol 308 parts 20 parts of ethyl lactate Leveling agent: polyether modified silicone oil (conversion of solid content) (Toray silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.10 parts

〔實施例7〕[Example 7]

藉由將下述成分混合而獲得紅色硬化性樹脂組成物。四氮雜卟啉：由式（a-1）所表示之化合物 17份紅色顏料：分散液1 354份紅色顏料：分散液2 80份黃色顏料：分散液3 312份樹脂（B）：樹脂（B-1）（固體成分換算） 30份聚合性化合物（C）：二新戊四醇六丙烯酸酯（KAYARAD（註冊商標）DPHA；日本化藥股份有限公司製造） 35份聚合起始劑（D）：N-苯甲醯基氧基-1-（4-苯基氫硫基苯基）辛烷-1-酮-2-亞胺（Irgacure（註冊商標）OXE01；巴斯夫公司製造；O-醯基肟化合物） 7.0份溶劑（E）：丙二醇單甲醚乙酸酯 521份乳酸乙酯 25份調平劑：聚醚改質矽油（固體成分換算）（Toray silicone SH8400；東麗道康寧股份有限公司製造） 0.10份The red curable resin composition is obtained by mixing the following components. Porphyrazine: 17 parts of compound represented by formula (a-1) Red pigment: 1,354 parts of dispersion Red pigment: 2 80 parts of dispersion Yellow pigment: 3 312 parts of dispersion Resin (B): Resin (B-1) (calculated as solid content) 30 parts Polymerizable compound (C): 35 parts of dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; BASF Manufactured by the company; O-acetoxime compound) 7.0 parts Solvent (E): 521 parts of propylene glycol monomethyl ether acetate 25 parts of ethyl lactate Leveling agent: polyether modified silicone oil (conversion of solid content) (Toray silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.10 parts

〔實施例8〕[Example 8]

藉由將下述成分混合而獲得紅色硬化性樹脂組成物。四氮雜卟啉：由式（a-1）所表示之化合物 19份紅色顏料：分散液1 496份黃色顏料：分散液4 854份樹脂（B）：樹脂（B-1）（固體成分換算） 9份聚合性化合物（C）：二新戊四醇六丙烯酸酯（KAYARAD（註冊商標）DPHA；日本化藥股份有限公司製造） 35份聚合起始劑（D）：N-苯甲醯基氧基-1-（4-苯基氫硫基苯基）辛烷-1-酮-2-亞胺（Irgacure（註冊商標）OXE01；巴斯夫公司製造；O-醯基肟化合物） 7.0份溶劑（E）：丙二醇單甲醚乙酸酯 124份乳酸乙酯 5份調平劑：聚醚改質矽油（固體成分換算）（Toray silicone SH8400；東麗道康寧股份有限公司製造） 0.10份The red curable resin composition is obtained by mixing the following components. Porphyrazine: 19 parts of compound represented by formula (a-1) Red pigment: 1,496 parts of dispersion Yellow pigment: 4,854 parts of dispersion Resin (B): Resin (B-1) (calculated as solid content) 9 parts Polymerizable compound (C): 35 parts of dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; BASF Manufactured by the company; O-acetoxime compound) 7.0 parts Solvent (E): 124 parts of propylene glycol monomethyl ether acetate 5 parts of ethyl lactate Leveling agent: polyether modified silicone oil (conversion of solid content) (Toray silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.10 parts

〔比較例1〕[Comparative Example 1]

藉由將下述成分混合而獲得紅色硬化性樹脂組成物。紅色顏料：分散液1 859份樹脂（B）：樹脂（B-1）（固體成分換算） 20份聚合性化合物（C）：二新戊四醇六丙烯酸酯（KAYARAD（註冊商標）DPHA；日本化藥股份有限公司製造） 35份聚合起始劑（D）：N-苯甲醯基氧基-1-（4-苯基氫硫基苯基）辛烷-1-酮-2-亞胺（Irgacure（註冊商標）OXE01；巴斯夫公司製造；O-醯基肟化合物） 7.0份溶劑（E）：丙二醇單甲醚乙酸酯 435份乳酸乙酯 12份調平劑：聚醚改質矽油（固體成分換算）（Toray silicone SH8400；東麗道康寧股份有限公司製造） 0.10份The red curable resin composition is obtained by mixing the following components. Red pigment: 1,859 parts of dispersion Resin (B): Resin (B-1) (calculated as solid content) 20 parts Polymerizable compound (C): 35 parts of dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; BASF Manufactured by the company; O-acetoxime compound) 7.0 parts Solvent (E): 435 parts of propylene glycol monomethyl ether acetate 12 parts of ethyl lactate Leveling agent: polyether modified silicone oil (conversion of solid content) (Toray silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.10 parts

＜彩色濾光片之製作＞＜Production of color filter＞

於5公分見方之玻璃基板（Eagle 2000；康寧公司製造）上，利用旋塗法塗布紅色硬化性樹脂組成物後，於100°C下預烘烤3分鐘而形成著色樹脂組成物層。放置冷卻後，使用曝光機（TME-150RSK；拓普康股份有限公司製造）於大氣氣氛下以60毫焦耳／平方公分（mJ/cm² ）之曝光量（365奈米基準）進行光照射。其後，於烘箱中，在230°C下進行20分鐘的後烘烤，獲得彩色濾光片。On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated), the red curable resin composition was applied by spin coating, and then pre-baked at 100°C for 3 minutes to form a colored resin composition layer. After being left to cool, use an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) to irradiate light with an exposure amount of ^{60 millijoules/cm² (mJ/cm 2) (365nm standard) in an atmospheric atmosphere.} Thereafter, in an oven, post-baking was performed at 230°C for 20 minutes to obtain a color filter.

＜膜厚測定＞＜Measurement of film thickness＞

關於所獲得之彩色濾光片，使用膜厚測定裝置（DEKTAK 3；日本真空技術股份有限公司製造）來測定膜厚。將結果示於表1中。Regarding the obtained color filter, a film thickness measuring device (DEKTAK 3; manufactured by Nippon Vacuum Technology Co., Ltd.) was used to measure the film thickness. The results are shown in Table 1.

＜色度評價＞＜Chromaticity evaluation＞

關於所獲得之彩色濾光片，使用測色機（OSP-SP-200；奧林巴斯股份有限公司製造）來測定分光，並使用C光源之特性函數測定在CIE（International Commission on Illumination，國際照明委員會）1931表色系統中之xy色度座標（x，y）。將結果示於表1中。當以相同之x進行比較時之膜厚越薄，越可謂其係深色（高彩度）且薄膜之彩色濾光片。Regarding the obtained color filter, a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.) was used to measure the spectroscopy, and the characteristic function of the C light source was measured in CIE (International Commission on Illumination, International Commission on Illumination). Illumination Committee) xy chromaticity coordinates (x, y) in the 1931 color system. The results are shown in Table 1. When comparing with the same x, the thinner the film thickness, the more it can be said to be a dark color (high chroma) and thin film color filter.

[表1]

[Table 1]

x成為0.688時係深色（高彩度）之紅色區域。由本發明之紅色硬化性樹脂組成物形成之彩色濾光片的膜厚為3微米以下，可謂其係深色（高彩度）且薄膜之彩色濾光片。另一方面，由比較例之紅色硬化性樹脂組成物形成之彩色濾光片雖可再現深色（高彩度）之紅色，但無法達成薄膜化。When x becomes 0.688, it is a dark (high chroma) red area. The color filter formed from the red curable resin composition of the present invention has a film thickness of 3 microns or less, which can be said to be a dark color (high chroma) and thin film color filter. On the other hand, although the color filter formed of the red curable resin composition of the comparative example can reproduce dark (high chroma) red, it cannot achieve thinning.

無none

無。none.

Claims

一種紅色硬化性樹脂組成物，其包含：以紅色硬化性樹脂組成物之固體成分總量計，5質量%至60質量%之著色劑(A)、10質量%至70質量%之鹼可溶性樹脂(B)、及3質量%至60質量%之聚合性化合物(C)；以及聚合起始劑(D)，其中相對於鹼可溶性樹脂(B)與聚合性化合物(C)之合計量100質量份，聚合起始劑(D)的含量為0.1質量份至30質量份，其中著色劑包含四氮雜卟啉(tetraazaporphyrin)化合物與紅色色素，且其中當由該紅色硬化性樹脂組成物所形成之彩色濾光片係藉由CIE 1931中的C光源之特性函數來測定時，x=0.688、0.298

y

0.310，且彩色濾光片的膜厚為3微米或更低。 A red curable resin composition comprising: based on the total solid content of the red curable resin composition, 5 to 60% by mass of coloring agent (A), and 10 to 70% by mass of alkali-soluble resin (B), and 3% to 60% by mass of the polymerizable compound (C); and polymerization initiator (D), wherein the total amount of the alkali-soluble resin (B) and the polymerizable compound (C) is 100 mass The content of the polymerization initiator (D) is 0.1 to 30 parts by mass, wherein the colorant contains a tetraazaporphyrin (tetraazaporphyrin) compound and a red pigment, and when it is formed from the red curable resin composition When the color filter is measured by the characteristic function of C light source in CIE 1931, x=0.688, 0.298

y

0.310, and the film thickness of the color filter is 3 microns or less.

一種彩色濾光片，其係由如請求項1所述之紅色硬化性樹脂組成物所形成。 A color filter which is formed of the red curable resin composition as described in claim 1.

一種顯示裝置，其包含如請求項2所述之彩色濾光片。 A display device comprising the color filter according to claim 2.