TWI648353B - Colored composition, manufacturing method and application thereof, colored cured film and display element - Google Patents

Abstract

An object of the present invention is to provide a coloring composition suitable for forming a coloring cured film exhibiting excellent heat resistance.

The solution of the present invention is a coloring composition, which is a coloring composition containing (A) a colorant and (B) a polymerizable compound, and further containing (C ² ) having the following formula (2), (3) Any one or more of the polymers of the structural unit represented by (4) or (5).

In the formulae (2) to (5), R ¹ , R ¹¹ , R ²¹ and R ³¹ each independently represent a methyl group, a trifluoromethyl group or a hydrogen atom, and R ¹² and R ¹³ each independently represent a hydrogen atom or a substituent. Or unsubstituted aliphatic hydrocarbon group, R _f represents a hydrogen atom, a halogen group, or a substituted or unsubstituted hydrocarbon group, at least one R _f is a fluorine atom or an alkyl group having a fluorine atom, and Y represents a divalent group or a single bond D represents a divalent organic group, and W represents a monovalent group having a halogen group, a halogenated hydrocarbon group, or a bonding group containing an atom other than a carbon atom, a hydrogen atom, or a halogen atom between the CC bonds of the halogenated hydrocarbon group. , A represents a divalent group or a single bond, G represents a divalent organic group or a single bond containing a fluorine atom, Ar represents a substituted arylene group having at least one halogen group, and E represents a divalent group or single bond X ^{m +} represents a proton, an onium cation, or a metal ion, m represents a natural number of 1 to 3, n represents an integer of 0 to 3, and p represents an integer of 1 to 8.

Description

Colored composition, manufacturing method and application thereof, colored cured film and display element

The present invention relates to a colored composition, a colored hardened film, and a display element. More specifically, the present invention relates to formation for use in a transmissive or reflective color liquid crystal display element, solid-state imaging element, organic EL display element, electronic paper, and the like. A colored composition of a colored cured film, a colored cured film formed using the colored composition, and a display element including the colored cured film.

Regarding the production of a color filter using a colored radiation-sensitive composition, a method is known in which a pigment-dispersed colored radiation-sensitive composition is coated on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern ( Hereinafter, it is referred to as "exposure"), and development is performed to obtain pixels of each color (for example, refer to Patent Documents 1 to 2). A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed is also known (for example, refer to Patent Document 3). Further, a method of obtaining pixels of each color by an inkjet method using a pigment-dispersed colored resin composition is also known (for example, refer to Patent Document 4).

In recent years, high-contrast liquid crystal display elements and high-definition solid-state imaging elements are urgently required. In order to realize these demands, technologies using dyes as colorants have been studied. In many cases, the dye has low heat resistance.

Under such a background, as a dye-containing coloring composition capable of forming a pixel having excellent heat resistance, for example, Patent Document 5 proposes the use of a triarylmethane-based dye having an alkylsulfonimide anion.

Prior art literature Patent literature

Patent Document 1 Japanese Unexamined Patent Publication No. 2-144502

Patent Document 2 Japanese Unexamined Patent Publication No. 3-52201

Patent Document 3 Japanese Patent Laid-Open No. 6-35188

Patent Document 4 Japanese Patent Laid-Open No. 2000-310706

Patent Document 5 Japanese Patent Application Publication No. 2012-83652

However, in reality, the heat resistance of the dye of Patent Document 5 is not sufficient. Therefore, an object of the present invention is to provide a coloring composition suitable for forming a coloring cured film exhibiting excellent heat resistance. Another object of the present invention is to provide a colored cured film formed using the colored composition and a display element including the colored cured film.

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by using a compound having a specific structure together with a coloring agent.

That is, the present invention provides a coloring composition which is a coloring composition containing (A) a coloring agent and (B) a polymerizable compound, further containing (C ² ) having a formula represented by the following formulae (2), (3), Any one or more of the polymers of the structural unit represented by (4) or (5).

[In the formulae (2) to (5), R ¹ , R ¹¹ , R ^21, and R ³¹ each independently represent a methyl group, a trifluoromethyl group, or a hydrogen atom, and R ¹² and R ¹³ each independently represent a hydrogen atom, or A substituted or unsubstituted aliphatic hydrocarbon group, R _f represents a hydrogen atom, a halogen group, or a substituted or unsubstituted hydrocarbon group, at least one R _f is a fluorine atom or an alkyl group having a fluorine atom, and Y represents a divalent group or a monovalent group. Bond, D represents a divalent organic group, and W represents a monovalent group having a halogen group, a halogenated hydrocarbon group, or a bonding group containing an atom other than a carbon atom, a hydrogen atom, or a halogen atom between the CC bonds of the halogenated hydrocarbon group. Group, A represents a divalent group or a single bond, G represents a divalent organic group or a single bond containing a fluorine atom, Ar represents a substituted arylene group having at least one halogen group, and E represents a divalent group or Single bond, X ^{m +} represents a proton, onium cation, or metal ion, m represents a natural number from 1 to 3, n represents an integer from 0 to 3, and p represents an integer from 1 to 8. ]

The present invention also provides a coloring composition containing (A) a colorant, (B) a polymerizable compound, (C ¹ ) a compound represented by the following formula (1), and (D) a binder resin.

X ⁺ (Z _a R ⁰ _b M) ^- (1)

[In the formula (1), X ⁺ represents a proton, an onium cation or an alkali metal ion, Z represents an electron withdrawing group, R ⁰ represents an alkyl group, an aryl group, a cycloalkyl group or an alkaryl group, and M represents a nitrogen atom, a phosphorus atom, For a boron atom, an arsenic atom, or an antimony atom, a represents an integer of 1 to 6, and b represents an integer of 0 to 5.

Among them, a + b is 2, 4, or 6, and when there are multiple Z and R ⁰ , they may be the same or different. ]

The present invention also provides a colored cured film formed using the colored composition and a display element including the colored cured film. Here, the "colored cured film" refers to pixels of each color, a black matrix, a black spacer, and the like used in a display element and a solid-state imaging element.

By using the coloring composition of the present invention, a coloring cured film exhibiting excellent heat resistance can be formed. In particular, when a dye is used as a colorant, a colored hardened film exhibiting particularly excellent heat resistance can be formed.

Therefore, the coloring composition of the present invention is extremely suitable for use in the production of color liquid crystal display elements, organic EL display elements, display elements such as electronic paper, and solid-state imaging elements such as CMOS image sensors.

Hereinafter, the present invention will be described in detail.

Coloring composition

Hereinafter, the constituent components of the coloring composition of the present invention will be described in detail.

-(A) Colorant-

The colorant can be used without particular limitation as long as it has colorability, and colors and materials can be appropriately selected according to the use of the coloring composition. For example, when the coloring composition of the present invention is used to form a color-hardened film of a color filter, the color filter is required to have high color purity, brightness, and contrast. Therefore, as the colorant, it is preferably selected from pigments and At least one kind of dye is preferable, and at least one kind selected from an organic pigment and an organic dye is especially preferable. Among these, when an organic dye is contained, it is easy to obtain the desired effect of this invention, and it is preferable.

As the dye, acid dyes, basic dyes, and nonionic dyes can be preferably used. These can be used singly or in combination of two or more kinds. When two or more kinds are used in combination, any combination can be used. Herein, the "acid dye" in this specification means an ionic dye whose anion part becomes a chromophore, and an ionic dye which forms a salt with this anion part also serves as an acid dye. In addition, the "basic dye" in this specification means an ionic dye whose cation part becomes a chromophore, and an ionic dye which forms a salt with this cationic part also serves as a basic dye. "Nonionic dye" means dyes other than acid dyes and basic dyes.

Among dyes, a basic dye is preferred from the viewpoint of further improving heat resistance. The basic dye is an ionic dye having a cation group as a chromophore, and is not particularly limited as long as it has a cationic chromophore, and examples thereof include an azo-based basic dye, a triarylmethane-based basic dye, Basic dyes, quinone imine-based basic dyes, cyanine-based basic dyes, and the like. These can be used singly or in combination of two or more kinds. When two or more kinds are used in combination, any combination can be used. Among them, triarylmethane-based basic dyes, Department of basic dyes.

The triarylmethane-based basic dye preferably has a cationic chromophore represented by the following formula (6-1) or (6-2). In addition, various resonance structures exist in the cationic chromophore represented by the following formulae (6-1) and (6-2), but in this specification, when there are resonance structures in the chromophore represented by each formula Is the same as the chromophore represented by the formula (6-1) or (6-2).

[In the formulae (6-1) and (6-2), R ⁵¹ to R ⁵⁶ and R ⁶¹ to R ⁶⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or An unsubstituted cycloalkyl group having 3 to 8 carbon atoms, or a substituted or unsubstituted aryl group, R ⁵⁷ to R ⁵⁹ and R ⁶⁷ to R ⁶⁹ each independently represent an alkyl group having 1 to 8 carbon atoms or a chlorine atom , C, d, f, g, and h each independently represent an integer from 0 to 4, and e represents an integer from 0 to 6. ]

Examples of the alkyl group having 1 to 8 carbon atoms related to R ⁵¹ to R ⁵⁹ and R ⁶¹ to R ⁶⁹ include methyl, ethyl, propyl, isopropyl, butyl, second butyl, and third butyl. Group, isobutyl, pentyl, third pentyl, hexyl, heptyl, octyl, isooctyl, third octyl, 2-ethylhexyl, and the like. Among them, an alkyl group having 1 to 4 carbon atoms is preferred, and a methyl group or an ethyl group is particularly preferred.

In addition, the alkyl group in this specification may be linear or branched.

Examples of the cycloalkyl group having 3 to 8 carbon atoms related to R ⁵¹ to R ⁵⁶ and R ⁶¹ to R ⁶⁶ include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Among them, a cycloalkyl group having 4 to 6 carbon atoms is preferred, and cyclohexyl is particularly preferred.

The aryl groups related to R ⁵¹ to R ⁵⁶ and R ⁶¹ to R ^{66 are} preferably aryl groups having 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. As a specific example, a phenyl group, a naphthyl group, and an anthryl group are preferable, and a phenyl group is especially preferable.

Examples of the substituents of the alkyl group, cycloalkyl group, and aryl group in R ⁵¹ to R ⁵⁶ and R ⁶¹ to R ⁶⁶ include an alkoxy group having 1 to 6 carbon atoms, a halogen group, and a trifluoromethyl group. , Cyano, and the like, and the cycloalkyl group and the aryl group may be substituted with an alkyl group having 1 to 6 carbon atoms. Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, third butoxy, and second butoxy , N-pentyloxy, isopentyloxy, n-hexyloxy, methoxymethoxy, ethoxyethoxy, 3- (isopropoxy) propoxy and the like. In addition, the alkoxy group in this specification may be linear or branched. Examples of the halogen group include a fluoro group, a chloro group, a bromo group, and an iodo group. Specific examples of the alkyl group having 1 to 6 carbon atoms include the same groups as described above. The position and number of the substituents are arbitrary, and when there are two or more substituents, the substituents may be the same or different.

R ⁵⁷ to R ⁵⁹ and R ⁶⁷ to R ^{69 are} preferably an alkyl group having 1 to 4 carbon atoms or a chlorine atom, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group. .

In formula (6-1), c and d are preferably integers of 0 to 2, and e is preferably 0 or 1. Among them, the combination of c, d, and e is preferably a combination of c = 0, d = 0, and e = 0, a combination of c = 1, d = 0, and e = 0, c = 0, d = 0, e = 1 combination, c = 2, d = 0, e = 0 combination, c = 1, d = 1, e = 0 combination, c = 1, d = 1, e = 1 group Combination, more preferably a combination of c = 0, d = 0, e = 0, a combination of c = 1, d = 0, e = 0, a combination of c = 0, d = 0, e = 1, c = 1 , D = 1, e = 0.

In formula (6-2), f is preferably an integer of 0 to 2, and g and h are preferably 0 or 1. Among them, the combination of f, g, and h is preferably a combination of f = 0, g = 0, and h = 0, a combination of f = 1, g = 0, and h = 0, f = 2, g = 0, The combination of h = 0, the combination of f = 1, g = 1, h = 0, the combination of f = 1, g = 1, h = 1, especially more preferably f = 1, g = 0, h = 0 Combination of f = 1, g = 1, h = 0.

Examples of the chromophore represented by the formula (6-1) or the chromophore represented by the formula (6-2) include a chromophore represented by the following compound group a and compound group b, where , Preferably chromophores a1, a2, a3, a4, a5, a6, b1, b2, b3, b4, b6, more preferably a3, a4, a5, a6, b3, b4.

In addition to the above, examples of the cationic chromophore represented by the formula (6-1) include a chromophore described in Japanese Patent Application Laid-Open No. 2012-17425.

Examples of the azo dye include compounds having a cationic chromophore as described in paragraphs [0066] to [0067] of Japanese Patent Application Laid-Open No. 2012-108469.

As The basic dye is preferably a cationic chromophore represented by the following formula (8).

[In formula (8), R ¹⁰¹ , R ¹⁰² , R ^103, and R ¹⁰⁴ each independently represent a hydrogen atom, —R ^108, or an aromatic hydrocarbon group having 6 to 10 carbon atoms (wherein the aromatic hydrocarbon group may be a halogen group) Group, -R ¹⁰⁸ , -OH, -OR ¹⁰⁸ , -SO ₃ H, -SO ₃ M ¹ , -CO ₂ H, -CO ₂ R ¹⁰⁸ , -SO ₃ R ¹⁰⁸ , -SO ₂ NHR ^109, or -SO ₂ NR ¹⁰⁹ R ^{110 is} substituted); R ¹⁰⁵ and R ¹⁰⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; R ¹⁰⁷ represents -SO ₃ H, -SO ₃ M ¹ , -CO ₂ H, -CO ₂ R ¹⁰⁸ , -SO ₃ R ¹⁰⁸ , -SO ₂ NHR ^109, or -SO ₂ NR ¹⁰⁹ R ¹¹⁰ ; K represents an integer of 0 to 5, and when k is an integer of 2 or more, multiple R ¹⁰⁷ may be the same or different; R ¹⁰⁸ represents a saturated hydrocarbon group having 1 to 10 carbon atoms (wherein the saturated hydrocarbon group may be substituted with a halogen group, and an oxygen atom, a carbonyl group, or -NR ^108- ) may be present between CC bonds of the saturated hydrocarbon group; R ¹⁰⁹ and R ¹¹⁰ each independently represent a chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms or -L, or the number of carbon atoms formed by combining R ¹⁰⁹ and R ¹¹⁰ with each other 1 to 10 substituted or unsubstituted heterocyclic groups. Wherein, the alkyl group and the cycloalkyl group may be substituted with a hydroxyl group, a halogen group, -L, -CH = CH ₂ or -CH = CHR ¹⁰⁸ , and the CC bond between the alkyl group and the cycloalkyl group may have Oxygen atom, carbonyl group or -NR ^108- , the hydrogen atom contained in the heterocyclic group may be substituted by -R ¹⁰⁸ , -OH or -L; M ¹ represents a sodium atom or a potassium atom; L represents a carbon atom number of 6 to 10 Is an aromatic hydrocarbon group or an aromatic heterocyclic group having 5 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group may be -OH, -R ¹⁰⁸ , -OR ¹⁰⁸ , -NO ₂ , -CH = CH ₂ , -CH = CHR ¹⁰⁸ or a halogen group. To replace. ]

When the number of carbon atoms of the saturated hydrocarbon group related to R ¹⁰⁸ is 1 to 10, it may be any of linear, branched, and cyclic, or it may have a bridge structure. For example, in addition to the above-mentioned alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 3 to 8 carbon atoms, nonyl, decyl, tricyclodecyl, norbornyl, norbornyl, and adamantane may be mentioned. Base, bicyclic octyl, etc. Examples of the group having an oxygen atom between the CC bonds of the saturated hydrocarbon group include methoxypropyl, ethoxypropyl, 2-ethylhexyloxypropyl, and methoxyhexyl.

^Examples of the substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms formed by bonding R ¹⁰⁹ and R ^{110 to} each other include pyrrolidinyl, pyrazolinyl, morpholinyl, thiomorpholinyl, Piperidinyl, N-hexahydropyridyl, piperidino Base Radical, tetrahydropyrimidinyl, 1,3-dioxopentacyclo-2-yl, pyridyl, pyridine Base, pyrimidinyl, Quinolyl, isoquinolyl, phthaloyl Quinine Phosphono, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, benzothiazolyl, Oxazolyl, indolyl, indazolyl, benzimidazolyl, phthalimide and the like. Examples of the substituent in the heterocyclic group include a halogen group, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an amine group, and an alkyl group having 1 to 8 carbon atoms.

Examples of the aromatic heterocyclic group having 5 to 10 carbon atoms according to L include furyl, thienyl, pyridyl, pyrrolyl, Oxazolyl, iso Oxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, pyrimidinyl and the like.

Examples of the aromatic hydrocarbon group in R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and L include a phenyl group and a naphthyl group.

Examples of -SO ₃ R ¹⁰⁸ among R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ^104, and R ¹⁰⁷ include methylsulfonyl, ethylsulfonyl, hexanesulfonyl, and decylsulfonyl. Examples of -CO ₂ R ¹⁰⁸ include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, cyclohexyloxycarbonyl, and methoxypropyloxycarbonyl. Wait. The R ¹⁰⁹ and R ^{110 of} -SO ₂ NHR ¹⁰⁹ and -SO ₂ NR ¹⁰⁹ R ¹¹⁰ are preferably a branched alkyl group having 6 to 8 carbon atoms and a cycloalkane having 5 to 7 carbon atoms. Group, allyl group, aralkyl group having 8 to 10 carbon atoms, hydroxyl-containing alkyl group having 2 to 8 carbon atoms, alkoxy-containing alkyl group having 2 to 8 carbon atoms, and 6 to 6 carbon atoms 10 aryl.

Examples of the quinone imine-based basic dye include a compound having a cationic chromophore described in paragraph [0078] of Japanese Patent Application Laid-Open No. 2012-108469.

Examples of the cyanine-based basic dye include compounds having a cationic chromophore as described in paragraphs [0064] to [0065] of Japanese Patent Application Laid-Open No. 2012-212089.

Examples of the anion capable of forming a salt with the cationic chromophore include a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, and a methylate anion.

Examples of the halogen ion include fluoride ion, chloride ion, bromide ion, and iodide ion.

As boron anion, and examples thereof include BF ₄ ^- and organic boron ^{_{anion; (CF 3) 4 B -}} , (CF 3) 3 BF -, (CF 3) 2 BF 2 -, (CF 3) BF 3 -, ( ^{_{C 2 F 5) 4 B -}} , (C 2 F 5) 3 BF -, (C 2 F 5) BF 3 -, (C 2 F 5) 2 BF 2 -, (CF 3) (C 2 F 5) ^{_{2 BF -, (C 6 F}} 5) 4 B -, [(CF 3) 2 C 6 H 3] 4 B -, (CF 3 C 6 H 4) 4 B -, (C 6 F 5) 2 BF 2 ^{_{-, (C 6 F 5)}} BF 3 -, (C 6 H 3 F 2) 4 B -, B (CN) 4 -, B (CN) F 3 -, B (CN) 2 F 2 -, B ( ^{_{CN) 3 F -, (CF}} 3) 3 B (CN) -, (CF 3) 2 B (CN) 2 -, (C 2 F 5) 3 B (CN) -, (C 2 F 5) 2 B ^{_{(CN) 2 -, (nC}} 3 F 7) 3 B (CN) -, (nC 4 F 9) 3 B (CN) -, (nC 4 F 9) 2 B (CN) 2 -, (nC 6 F ^{_{13) 3 B (CN) -}} , (CHF 2) 3 B (CN) -, (CHF 2) 2 B (CN) 2 -, (CH 2 CF 3) 3 B (CN) -, (CH 2 CF 3 ^{_{) 2 B (CN) 2 -}} , (CH 2 C 2 F 5) 3 B (CN) -, (CH 2 C 2 F 5) 2 B (CN) 2 -, (CH 2 CH 2 C 3 F 7) ^{_{2 B (CN) 2 -,}} (nC 3 F 7 CH 2) 2 B (CN) 2 -, (C 6 H 5) 3 B (CN) -, tetraphenylborate, tetrakis (monofluorophenyl) Borate, Di (difluorophenyl) borate, Di (trifluorophenyl) boric acid Salt, tetra (tetrafluorophenyl) borate, meta (pentafluorophenyl) borate, meta (tetrafluoromethylphenyl) borate, meta (tolyl) borate, meta (xylyl) borate , (Triphenyl, pentafluorophenyl) borate, [gins (pentafluorophenyl), phenyl] borate, tridecyl-7,8-dicarbon undecylborate (tridecahydride-7,8 -dicarba undecaborate) and other organic boron anions, and Japanese Patent Laid-Open No. 10-195119, Japanese Patent Laid-Open No. 2010-094807, Japanese Patent Laid-Open No. 2006-243594, Japanese Patent Laid-Open No. 2002-341533, and Japanese Patent Laid-Open No. A boron anion described in Japanese Patent Publication No. 8-015521 and the like.

As the phosphate anions, include, for example, _{^{HPO 4 2-, PO 4 3-,}} PF 6 - and inorganic phosphate _{anions; (C 2 F 5) 2} PF 4 -, (C 2 F 5) 3 PF 3 -, _{[(CF 3) 2 CF]} 2 PF 4 -, [(CF 3) 2 CF] 3 PF 3, (nC 3 F 7) 2 PF 4 -, (nC 3 F 7) 3 PF 3 -, (nC 4 ^{_{F 9) 3 PF 3 -,}} (C 2 F 5) (CF 3) 2 PF 3 -, [(CF 3) 2 CFCF 2] 2 PF 4 -, [(CF 3) 2 CFCF 2] 3 PF 3 - _{, (nC 4 F 9) 2} PF 4 -, (nC 4 F 9) 3 PF 3 -, (C 2 F 4 H) (CF 3) 2 PF 3 -, (C 2 F 3 H 2) 3 PF 3 _{^{-, (C 2 F 5)}} (CF 3) 2 PF 3 -, octyl phosphate anion, a dodecyl phosphate anion, an octadecyl phosphate anion, a phenyl phosphate anion, a nonylphenyl phosphate Organophosphate anions such as root anions.

Examples of the carboxylate anion include CH ₃ COO ⁻ , C ₂ H ₅ COO ⁻ , C ₆ H ₅ COO ⁻ , and the like, and the carboxylic acid described in Japanese Patent Application Laid-Open No. 2009-265641 and Japanese Patent Application Laid-Open No. 2008-096680. Acid anion.

Examples of the sulfate anion include a sulfate anion and a sulfite anion.

Examples of the organic sulfonate anion include alkylsulfonate anions such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, and nonafluorobutanesulfonic acid; benzenesulfonic acid, benzenedisulfonic acid ion, and p-toluenesulfonic acid. Acid, p-trifluoromethanesulfonic acid, pentafluorobenzenesulfonic acid, naphthalenesulfonic acid, naphthalenesulfonic acid ion and other aryl sulfonate anions, as well as International Publication No. 2011/037195, Japanese Patent No. 3376221, Japan An organic sulfonate anion described in JP-A-2011-070172.

Examples of the nitrogen anion include [(CN) ₂ N] ^- , [(FSO ₂ ) ₂ N] ^- , [(FSO ₂ ) N (CF ₃ SO ₂ )] ^- , and [(FSO ₂ ) N (CF ₃ CF ₂ SO ₂ )] ^- , [(FSO ₂ ) N {(CF ₃ ) ₂ CFSO ₂ }] ^- , [(FSO ₂ ) N (CF ₃ CF ₂ CF ₂ SO ₂ )] ^- , [(FSO ₂ ) N (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ )] ^- , [(FSO ₂ ) N {(CF ₃ ) ₂ CFCF ₂ SO ₂ }] ^- , [(FSO ₂ ) N {CF ₃ CF ₂ (CF ₃ ) CFSO ₂ }] ^- , [(FSO ₂ ) N {(CF ₃ ) ₃ CSO ₂ }] ^- etc., and Japanese Patent Laid-Open No. 2011-133844, Japanese Patent Laid-Open No. 2011-116803, Japanese Patent Laid-Open No. 2010 The nitrogen anion described in -090341.

As methide anion, and examples thereof include _{(CF 3 SO 2) 3 C} -, (CF 3 CF 2 SO 2) 3 C -, [(CF 3) 2 CFSO 2] 3 C -, (CF 3 CF 2 ^{_{CF 2 SO 2) 3 C -}} , (CF 3 CF 2 CF 2 CF 2 SO 2) 3 C -, [(CF 3) 2 CFCF 2 SO 2] 3 C -, [CF 3 CF 2 (CF 3) CFSO ^{_{2] 3 C -, [(}} CF 3) 3 CSO 2] 3 C -, (FSO 2) 3 C - and the like, and Japanese Unexamined Patent Publication No. 2011-145540, U.S. Patent No. 5,554,664 specification, Japanese Patent Laid-open 2005- Methylate anions described in JP 309408, JP 2004-085657, JP 2010-505787, and the like.

Examples of the acid dye include Japanese Patent Laid-Open No. 2010-191358, Japanese Patent Laid-Open No. 2011-138094, Japanese Patent Laid-Open No. 2011-174987, Japanese Patent Laid-Open No. 2012-008421, and Japanese Patent Laid-Open No. 2012-013757. Acid dyes described in bulletins and the like.

Examples of the organic pigment include compounds classified as pigments in the color index (issued by The Society of Dyers and Colourists). Among them, Japanese Patent Application Laid-Open No. 2001-081348 and Japanese Patent Application Laid-Open No. 2010- 026334, JP 2010-191304, JP 2010-237384, JP 2010-237569, JP 2011-006602, JP 2011-145346, etc. Lake pigments described, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58 , CI Pigment Blue 15: 6, CI Pigment Blue 80, CI Pigment Yellow 83, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Yellow 211, CI Pigment Organic pigments other than lake pigments such as yellow 215, CI pigment orange 38, and CI pigment violet 23. Among the lake pigments, triarylmethane-based lake pigments, Based lake pigments and azo based lake pigments, more preferably triarylmethane based lake pigments and Department of lake pigments. These organic pigments can be used suitably according to the hue of a coloring composition.

In the present invention, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof, and used. In addition, these pigments may be used by modifying the surface of their particles with a resin as necessary. Examples of resins that modify the surface of pigment particles include vehicle resins described in Japanese Patent Application Laid-Open No. 2001-108817, and various commercially available resins for pigment dispersion. As a resin coating method on the surface of carbon black, for example, the methods described in Japanese Patent Application Laid-Open No. 9-71733, Japanese Patent Application Laid-Open No. 9-95625, Japanese Patent Application Laid-Open No. 9-124969, and the like can be used. The organic pigment can be used by miniaturizing the primary particles by a so-called salt milling. As a method of salt milling, the method disclosed in Unexamined-Japanese-Patent No. 8-179111 can be used, for example.

In addition, in the present invention, in addition to the pigment, at least one selected from the group consisting of a known dispersant and a dispersing aid may be further contained. Examples of known dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene alkylphenyl ether-based dispersants, and polyethylene glycol. A glycol diester-based dispersant, a sorbitan fatty acid ester-based dispersant, a polyester-based dispersant, an acrylic-based dispersant, and the like. Examples of the dispersion aid include pigment derivatives.

Such a dispersant is commercially available. Examples of the acrylic dispersant include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (above, manufactured by BYK-Chemie (BYK)). ) And the like, examples of the urethane-based dispersant include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK-Chemie (BYK)) ), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), etc., as the polyethyleneimine dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), etc., and polyester dispersants, such as Adisper PB821, Adisper PB822, Adisper PB880, Adisper PB881 (above, manufactured by Ajinomoto Fine-Techno Co., Ltd.), etc., and BYK-LPN21324 (manufactured by BYK-Chemie (BYK)).

Examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinophthalone.

In this invention, a pigment can be used individually or in mixture of 2 or more types.

From the viewpoint of forming a pixel having high heat resistance and brightness and excellent color purity, or a black matrix and a black spacer having excellent light shielding properties, the content ratio of the (A) colorant is usually 5 to 70 mass in the solid content of the coloring composition. %, Preferably 5 to 60% by mass. The solid content is a component other than the solvent mentioned later.

-(B) polymerizable compound-

In the present invention, the polymerizable compound refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an epoxyethyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth) acrylfluorenyl groups or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth) acrylfluorenyl groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, and modified with caprolactone. Polyfunctional (meth) acrylate, polyfunctional (meth) acrylate modified with alkylene oxide, polyfunctional aminocarboxylic acid obtained by reacting (meth) acrylate having a hydroxyl group with polyfunctional isocyanate Ester (meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride, and the like.

Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; glycerol, trimethylolpropane, pentaerythritol, A trivalent or higher aliphatic polyhydroxy compound such as dipentaerythritol. Examples of the (meth) acrylate having the above-mentioned hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and Pentaerythritol penta (meth) acrylate, glycerol dimethacrylate and the like. Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and the like. Examples of the acid anhydride include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, pyromellitic dianhydride Tetracarboxylic dianhydride such as biphenyltetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride.

Examples of the polyfunctional (meth) acrylate modified with caprolactone include compounds described in paragraphs [0015] to [0018] of Japanese Patent Application Laid-Open No. 11-44955. Examples of the polyfunctional (meth) acrylate modified with the alkylene oxide include bisphenol A di (meth) acrylate modified with at least one selected from the group consisting of ethylene oxide and propylene oxide. Isocyanuric acid tri (meth) acrylate modified with at least one kind selected from ethylene oxide and propylene oxide, and modified with at least one kind selected from ethylene oxide and propylene oxide Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, selected from ethylene oxide and At least one modified pentaerythritol tetra (meth) acrylate in propylene oxide, at least one modified dipentaerythritol penta (meth) acrylate selected from ethylene oxide and propylene oxide, At least one kind of modified dipentaerythritol hexa (meth) acrylate and the like selected from ethylene oxide and propylene oxide.

Examples of the compound having two or more N-alkoxymethylamine groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. In addition, the melamine structure and the benzoguanamine structure mean that one or more Ring or phenyl substituted tri The chemical structure of a ring as a basic skeleton is a concept including melamine, benzoguanamine, or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ', N', N ", N" -hexa (alkoxymethyl) melamine, N, N, N ', N'-tetrakis (alkoxymethyl) benzoguanamine, N, N, N', N'-tetrakis (alkoxymethyl) glycol urea and the like.

Among these polymerizable compounds, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, or a polyfunctional (meth) modified with caprolactone is preferred. Acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate with carboxyl group, N, N, N ', N', N ", N" -hexa (alkoxy) (Meth) melamine, N, N, N ', N'-tetrakis (alkoxymethyl) benzoguanamine. From the viewpoint that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and dirt and film residue are not easily generated on the substrate and the light-shielding layer in the unexposed portion, the aliphatic polyhydric compound having a trivalent or higher valence and ( Among the polyfunctional (meth) acrylates obtained by the reaction of (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly preferred. Among the polyfunctional (meth) acrylates, particularly preferred are compounds obtained by reacting pentaerythritol triacrylate and succinic anhydride, and compounds obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride.

In the present invention, the (B) polymerizable compound can be used alone or in combination of two or more.

The content of the (B) polymerizable compound in the present invention is preferably from 10 to 1,000 parts by mass, more preferably from 20 to 700 parts by mass, and even more preferably from 100 to 600 parts by mass relative to 100 parts by mass of the (A) colorant. . By adopting such an aspect, it is possible to further improve the hardenability and the alkali developability, and to suppress the occurrence of dirt, film residue, and the like on the substrate or the light-shielding layer in the unexposed portion at a high level.

-(C) Specific compounds-

Coloring composition of the present invention contains (C ¹⁾ or the component (C ²⁾ as the component (C) a specific compound. In the following description, the (C ¹ ) and (C ² ) components may be collectively described as “(C) specific compound”.

The specific compound (C) in the present invention is a compound in which the maximum value of the molar absorption coefficient in the visible light region (380 nm to 780 nm) is 10,000 or less, and the maximum value of the molar absorption coefficient in the visible light region is preferably 5,000 or less, further more It is preferably below 3000.

First, the anion portion of the (C ¹ ) component and the (C ² ) component will be described.

The anion part of the (C ¹ ) component is represented by (Z _a R ⁰ _b M) ⁻ .

Z is not particularly limited as long as it is an electron-withdrawing group, and examples thereof include a halogen group, a monovalent organic group having a halogen group, a cyano group, a monovalent organic group having a cyano group, and a monovalent organic group having a nitro group. Groups, halogenated sulfonyl groups, alkylsulfonyl groups which may have a halogen group, and the like.

Examples of the halogen group include the same groups as described above. Among them, a fluorine group is preferred from the viewpoint of heat resistance.

The monovalent organic group having a halogen group is not particularly limited, and examples thereof include a monovalent halogenated hydrocarbon group, and the halogenated hydrocarbon group may have a substituent other than a halogen group. As a hydrocarbon group which is a skeleton of a halogenated hydrocarbon group, an alkyl group, a cycloalkyl group, an aryl group, and an alkaryl group are preferable, and an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, An aryl group having 6 to 14 carbon atoms and an alkylaryl group having 7 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 8 carbon atoms, the cycloalkyl group having 3 to 8 carbon atoms, and the aryl group having 6 to 14 carbon atoms include the same groups as described above. Examples of the alkaryl group include a group in which the above-mentioned alkyl group having 1 to 8 carbon atoms is substituted with an aryl group having 6 to 14 carbon atoms.

As the halogen group in the halogenated hydrocarbon group, a fluorine group is preferable. The halogen group can replace part or all of the hydrogen atoms of the hydrocarbon group, especially the hydrogen atom of the hydrocarbon group is preferably 80 mol% or more, more preferably 90% mol or more, and particularly preferably 100 mol%. To replace. This can further improve heat resistance.

The monovalent organic group having a cyano group is not particularly limited, and examples thereof include a monovalent hydrocarbon group substituted with a cyano group, and the monovalent hydrocarbon group may have a substituent other than a cyano group. The monovalent hydrocarbon group is preferably an aryl group, and particularly preferably a phenyl group.

The monovalent organic group having a nitro group is not particularly limited, and examples thereof include a monovalent hydrocarbon group substituted with a nitro group, and the monovalent hydrocarbon group may have a substituent other than a nitro group. The monovalent hydrocarbon group is preferably an aryl group, and particularly preferably a phenyl group.

The alkylsulfonyl group which may have a halogen group is not particularly limited, and an alkylsulfonyl group or a halogenated alkylsulfonyl group may be appropriately selected. use. The number of carbon atoms of the alkyl group constituting the skeleton of the alkylsulfonyl group and the halogenated alkylsulfonyl group is preferably 1 to 8. Specific examples of the alkyl group include the same groups as described above. The halogen group in the halogenated alkylsulfonyl group is preferably a fluoro group. This halogen group may replace part or all of the hydrogen atoms of the hydrocarbon group. From the viewpoint of heat resistance, it is preferably 80 mol% or more, more preferably 90% mol or more, and particularly preferably 100 mol%. Ear% is substituted with a halogen group.

Examples of the halogenated sulfonyl group include a FSO ₂ group, a ClSO ₂ group, a BrSO ₂ group, and an ISO ₂ group, and a FSO ₂ group is preferable.

As Z, when M is a phosphorus atom, a boron atom, an arsenic atom, or an antimony atom, a halogen group, a monovalent halogenated hydrocarbon group which may have a substituent other than a halogen group, a cyano group, and a fluorine group, particularly preferred Cyano, fluorinated alkyl, fluorinated aryl, or fluorinated alkylaryl. The fluorinated alkyl group is preferably a perfluoroalkyl group, and the number of carbon atoms of the perfluoroalkyl group is preferably 1 to 6, more preferably 1 to 4. Specific examples include CF ₃ group, CF ₃ CF ₂ group, (CF ₃ ) ₂ CF group, CF ₃ CF ₂ CF ₂ group, CF ₃ CF ₂ CF ₂ CF ₂ group, (CF ₃ ) ₂ CFCF ₂ groups, CF ₃ CF ₂ (CF ₃ ) CF group, (CF ₃ ) ₃ C group, and the like. The fluorinated aryl group is preferably a perfluoroaryl group, and the number of carbon atoms of the perfluoroaryl group is preferably 6 to 14, and more preferably 6 to 10. Specific examples include pentafluorophenyl. The fluorinated alkaryl group is preferably a perfluoroalkaryl group, and the number of carbon atoms of the perfluoroalkaryl group is preferably 7-20, more preferably 7-16. Specific examples include a phenyl group substituted with a CF ₃ group.

On the other hand, when M is a nitrogen atom, Z is preferably a cyano group, a halogenated sulfonyl group, or a halogenated alkylsulfonyl group, and particularly preferably a fluorinated alkylsulfonyl group. Specific examples of the fluorinated alkylsulfonyl group include CF ₃ SO ₂ group, CF ₃ CF ₂ SO ₂ group, (CF ₃ ) ₂ CFSO ₂ group, CF ₃ CF ₂ CF ₂ SO ₂ group, CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ group, (CF ₃ ) ₂ CFCF ₂ SO ₂ group, CF ₃ CF ₂ (CF ₃ ) CFSO ₂ group, (CF ₃ ) ₃ CSO ₂ group, and the like.

R ⁰ represents an alkyl group, an aryl group, a cycloalkyl group or an alkaryl group, and is preferably an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a cycloalkyl group having 3 to 8 carbon atoms. Alkyl groups having 7 to 20 carbon atoms. Specific examples include the same groups as described above.

Among nitrogen atoms, phosphorus atoms, boron atoms, arsenic atoms, and antimony atoms, from the viewpoint of safety, M is preferably a nitrogen atom, a phosphorus atom, or a boron atom.

In addition, a + b represents 2, 4, or 6, when M is a nitrogen atom, a + b is 2, M is a boron atom, a + b is 4, and M is a phosphorus atom, arsenic atom, or antimony atom, a + b is 6. When there are a plurality of Z and R ⁰ each, they may be the same as or different from each other.

a represents an integer from 1 to 6, and b represents an integer from 0 to 5. In the present invention, it is preferably b = 0, that is, a is 2, 4, or 6.

In the present invention, preferred as ^{_{(Z a R 0 b M)}} -, anions include any one from the following formula (1a) ~ (1c) indicated one.

[(R ^1a ) ₁ P Hal _6-1 ] ^- (1a)

[In the formula (1a), R ^1a represents a halogenated hydrocarbon group, P represents a phosphorus atom, Hal represents a halogen group, and 1 represents an integer of 0 to 6. When a plurality of R ^1a and Hal are present, they may be the same or different. ]

[(R ^1b ) _q B Hal _4-q ] ^- (1b)

[In the formula (1b), R ^1b each independently represents a halogenated hydrocarbon group, a cyano group, or a phenyl group substituted with a nitro group or a cyano group, B represents a boron atom, Hal represents a halogen group, and q represents an integer of 0 to 4. When a plurality of R ^1b and Hal are present, they may be the same or different. ]

[(EA) ₂ N] ^- (1c)

[In formula (1c), EA each independently represents a cyano group, an FSO ₂ group, or a fluorinated alkylsulfonyl group. Among them, at least one of the two EAs represents a cyano group or an FSO ₂ group. ]

R ^1a represents a halogenated hydrocarbon group, and examples of the halogenated hydrocarbon group include the halogenated hydrocarbon groups listed in the description of Z above. In the present invention, R ^{1a is} preferably a fluorinated alkyl group, and more specifically, it is preferably a fluorinated alkyl group listed in the description of Z above.

R ^1b each independently represents a halogenated hydrocarbon group, a cyano group, or a phenyl group substituted with a nitro group or a cyano group. Examples of the halogenated hydrocarbon group include the halogenated hydrocarbon groups listed in the description of Z above. In the present invention, R ^{1b is} preferably a fluorinated alkyl group, a fluorinated aryl group, a cyano group, or a phenyl group substituted with a trifluoromethyl group or a fluorine atom, and more specifically, it is preferably described in the above description of Z The groups listed in.

As Hal according to Formula (1a) and Formula (1b), a fluorine group is preferable from a heat resistant viewpoint.

EA of formula (1c) represents a cyano group, a FSO ₂ group or a fluorinated alkylsulfonyl group. The fluorinated alkylsulfonyl group is preferably the fluorinated alkylsulfonyl group listed in the description of Z above. In formula (1c), as EA, it is preferable that two of them are both a cyano group or an FSO ₂ group, or one is an FSO ₂ group and the other is a fluorinated alkylsulfonyl group.

As a representative example of the anion represented by the formula (1a), the same anion as that exemplified in the above paragraph [0041] can be mentioned. Wherein, preferably ^{_{PF 6 -, (C 2 F}} 5) 2 PF 4 -, (C 2 F 5) 3 PF 3 -, (nC 3 F 7) 3 PF 3 -, (nC 4 F 9) 3 PF ^{_{3 -, [(CF 3)}} 2 CF] 3 PF 3 -, [(CF 3) 2 CF] 2 PF 4 -, [(CF 3) 2 CFCF 2] 3 PF 3 -, [(CF 3) 2 CFCF _{2] 2} PF ₄ ^-.

As a typical example of the anion represented by Formula (1b), the same anion as the anion illustrated in the said paragraph [0040] is mentioned. Which is preferably ^{_{BF 4 -, B (CN)}} 3 F -, B (CN) 4 -, (CF 3) 4 B -, (C 6 F 5) 4 B -, [(CF 3) 2 C 6 H _{3] 4} B ^-.

Among the anions represented by the formula (1c), preferred anions include the same anions as those exemplified in the above paragraph [0044]. Wherein, preferably ^{_{[(CN) 2 N] -}} .

The anion part according to the (C ² ) component is a structural unit represented by any one of the following formulae (2 ′) to (5 ′).

[Formula (2 ') ~ ^{(5'), R 1, R 11,} R 21 and R ³¹ each independently represent a methyl, trifluoromethyl or a hydrogen atom, R ¹² and R ¹³ each independently represent a hydrogen atom Or a substituted or unsubstituted aliphatic hydrocarbon group, R _f represents a hydrogen atom, a halogen group, or a substituted or unsubstituted hydrocarbon group, at least one R _f is a fluorine atom or an alkyl group having a fluorine atom, and Y represents a divalent group Or a single bond, D represents a divalent organic group, and W represents a halogen group, a halogenated hydrocarbon group, or a bond group having an atom other than a carbon atom, a hydrogen atom, or a halogen atom between CC bonds of the halogenated hydrocarbon group. Valent group, A represents a divalent group or a single bond, G represents a divalent organic group or a single bond containing a fluorine atom, Ar represents a substituted arylene group having at least one halogen group, and E represents a divalent group Group or single bond, m is a natural number from 1 to 3, n is an integer from 0 to 3, and p is an integer from 1 to 8. ]

Among methyl, trifluoromethyl and hydrogen atoms, R ¹ , R ¹¹ , R ²¹ and R ^{31 are} preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

As the halogen group related to W, a fluoro group is preferred.

The hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group according to W is preferably an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an alicyclic hydrocarbon-substituted aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon-substituted aromatic hydrocarbon group, or an aromatic hydrocarbon-substituted fat. Group of hydrocarbon groups.

The aliphatic hydrocarbon group may be linear or branched. In addition, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The unsaturated aliphatic hydrocarbon group may be anywhere in the molecule or at the terminal. Has unsaturated bonds. Among them, the aliphatic hydrocarbon group is preferably an alkyl group, and the number of carbon atoms of the alkyl group is preferably 1 to 20, and more preferably 1 to 8. Specific examples of the alkyl group include the same groups as described above.

The alicyclic hydrocarbon group may be a 2 to 4 ring bridged alicyclic hydrocarbon group. The alicyclic hydrocarbon group is preferably an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. Specific examples include the same groups as the above-mentioned cycloalkyl group and bridged alicyclic hydrocarbon group.

As the alicyclic hydrocarbon-substituted aliphatic hydrocarbon group, an alicyclic saturated hydrocarbon-substituted alkyl group is preferable, and the number of carbon atoms thereof is preferably 4 to 20, and more preferably 6 to 14. Specific examples include cyclopropylmethyl, cyclobutylmethyl, cyclohexylmethyl, cyclohexylpropyl, adamantylmethyl, 1- (1-adamantyl) ethyl, and cyclopentylethyl. Base etc.

The aromatic hydrocarbon group is preferably an aryl group, and the number of carbon atoms of the aryl group is preferably 6 to 14, and more preferably 6 to 10. Specific examples include a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, and an anthryl group. Among them, a phenyl group is preferred.

The aliphatic hydrocarbon-substituted aromatic hydrocarbon group is preferably an alkyl-substituted phenyl group, and the number of carbon atoms of the alkyl-substituted phenyl group is preferably 7 to 30, and more preferably 7 to 20. Specific examples include tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, and hexylphenyl.

The aromatic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an aralkyl group, and the number of carbon atoms of the aralkyl group is preferably 7 to 30, and more preferably 7 to 20. Specific examples include benzyl, phenethyl, α-methylbenzyl, 2-phenylpropane-2-yl, and the like.

Among them, the hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group according to W is preferably an aliphatic hydrocarbon group, an alicyclic hydrocarbon-substituted aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon-substituted aromatic hydrocarbon group, or an aromatic hydrocarbon-substituted aliphatic hydrocarbon group. More preferred are alkyl, alicyclic saturated hydrocarbon-substituted alkyl, phenyl, alkyl-substituted phenyl, and aralkyl, and particularly preferred is alkyl.

The halogen atom in the halogenated hydrocarbon group according to W is preferably a fluorine atom from the viewpoint of the heat resistance of the colorant, and the fluorine atom may replace part or all of the hydrogen atoms of the hydrocarbon group. It is considered that by selecting a fluorine atom as a substituent, a salt having a stronger ionic bonding force can be formed and heat resistance can be improved.

In addition, W may be a monovalent group having a bonding group containing an atom other than a carbon atom, a hydrogen atom, or a halogen atom between the CC bonds of the halogenated hydrocarbon group. Examples of the bonding group containing an atom other than a carbon atom, a hydrogen atom, or a halogen atom include -O-, -S-, -CO-, -COO-, -CONH-, -SO _2- , and the like. In addition, when the bonding group has carbon atoms, the number of carbon atoms of the hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group refers to the total number of carbon atoms other than the carbon atoms constituting the bonding group.

In the present invention, from the viewpoint of the heat resistance of the colorant, W is preferably a halogenated hydrocarbon group or a group having a bonding group containing an atom other than a carbon atom, a hydrogen atom, or a halogen atom between the CC bonds of the halogenated hydrocarbon group. It is more preferably a group represented by the following formula (11) or (12), and particularly preferably a group represented by the following formula (11) that forms a conjugate base of an organic acid having a stronger acidity.

[In formula (11), R ⁴⁰ represents a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, an alicyclic hydrocarbon group, an alkoxy group, a fluorinated alkoxy group, R ⁴¹ COOR ⁴² -or R ⁴³ COOR ⁴⁴ CFH -, R ⁴¹ and R ⁴³ each independently represent an alkyl group, an alicyclic hydrocarbon group, or a substituted or unsubstituted aryl group, R ⁴² and R ⁴⁴ each independently represent an alkanediyl group, and r represents an integer of 1 or more, ""*" Indicates a bond. ]

[In formula (12), R ⁴⁵ to R ⁴⁹ each independently represent a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluorinated alkyl group, or an alkoxy group, and "*" represents a bonding bond.

Among them, at least one of R ⁴⁵ to R ⁴⁹ is a fluorine atom or a fluorinated alkyl group. ]

In the formula (11), the number of carbon atoms of the alkyl group related to R ⁴⁰ is preferably 1 to 20, more preferably 1 to 8, and still more preferably 1 to 4. Specific examples include the same groups as described above.

The number of carbon atoms of the fluorinated alkyl group related to R ⁴⁰ is preferably 1 to 20, more preferably 1 to 8, and even more preferably 1 to 4. The fluorinated alkyl group in this specification may be a straight chain or a branched chain. As a specific example, a group in which a part or all of the hydrogen atoms of the alkyl group is replaced with a fluorine atom is particularly preferred. A perfluoroalkyl group is particularly preferred. .

The alicyclic hydrocarbon group related to R ⁴⁰ may be a 2 to 4 ring bridged alicyclic hydrocarbon group. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 20, and even more preferably 3 to 12. Specific examples include the same groups as described above.

The carbon number of the alkoxy group related to R ⁴⁰ is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 4. Specific examples include the same groups as described above.

The number of carbon atoms of the fluorinated alkoxy group involved in R ⁴⁰ is preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 4. Specific examples include a group in which some or all of the hydrogen atoms of the alkoxy group are substituted with fluorine atoms.

R ⁴⁰ R according to ^{41 COOR 42 -, R 44 CFH-} 43 COOR in, R ⁴¹ and R ⁴³ each independently represents an alkyl group, an alicyclic hydrocarbon group, or a substituted or unsubstituted aryl group. The number of carbon atoms of the alkyl group is preferably from 1 to 12, and even more preferably from 1 to 8. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 20, and even more preferably 3 to 12. The number of carbon atoms of the aryl group is preferably from 6 to 14, and even more preferably from 6 to 10. As these specific examples, the same groups as described above can be mentioned. Examples of the substituent of the aryl group include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen group, or a trifluoromethyl group. In addition, the position and number of the substituents are arbitrary, and when there are two or more substituents, the substituents may be the same or different.

Among them, R ^{40 is} preferably a fluorine atom, a fluorinated alkyl group, an alicyclic hydrocarbon group, a fluorinated alkoxy group, R ⁴¹ COOR ⁴² -or R ⁴³ COOR ⁴⁴ CFH-, particularly preferably a fluorine atom and an alicyclic group. Hydrocarbyl, perfluoroalkoxy, R ⁴¹ COOCH ₂ CH ₂ -or R ⁴³ COOCH ₂ CH ₂ CFH-.

R ⁴² and R ⁴⁴ each independently represent an alkanediyl group. The alkanediyl group may be linear or branched, and the number of carbon atoms is preferably 1 to 10. Specific examples include methylene, ethylidene, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, and propane-1,3- Diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,4-diyl Base, pentane-1,5-diyl, hexane-1,5-diyl, hexane-1,6-diyl, octane-1,8-diyl, decane-1,10-diyl Base etc. Among them, an alkanediyl group having 2 to 6 carbon atoms is preferred, and an alkanediyl group having 2 to 4 carbon atoms is more preferred. From the standpoint of ease of production, ethylene is more preferred.

The upper limit of r is preferably 10, and more preferably 8.

In the formula (12), as the alkyl group, fluorinated alkyl group, and alkoxy group related to R ⁴⁵ to R ⁴⁹ , an alkyl group, fluorinated alkyl group, and alkoxy group related to R ⁴⁰ in the formula (11) can be used. The same structure as the oxy group. Among them, at least one of R ⁴⁵ to R ⁴⁹ is a fluorine atom or a fluorinated alkyl group, and preferably at least three of R ⁴⁵ to R ⁴⁹ are a fluorine atom or a fluorinated alkyl group.

Examples of the divalent organic group related to D and G include a divalent hydrocarbon group, a group obtained by combining a divalent hydrocarbon group with a bonding group containing an atom other than a carbon atom and a hydrogen atom, or these groups. A group in which part of the hydrogen atom is replaced by a halogen atom. Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. The divalent aliphatic hydrocarbon group may have any form of a straight chain or a branched chain, and the divalent aliphatic hydrocarbon group and the divalent alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.

Examples of the divalent aliphatic hydrocarbon group include an alkanediyl group and an alkenyldiyl group. The number of carbon atoms of the alkanediyl group is preferably from 1 to 20, more preferably from 2 to 12, and even more preferably from 2 to 6. In addition, the carbon of alkenyl diyl The number of atoms is preferably 2 to 20, more preferably 2 to 12, and even more preferably 2 to 6. Specific examples of alkenyl diyl include ethylene-1,1-diyl, ethylene-1,2-diyl, propylene-1,2-diyl, propylene-1,3-diyl, and propylene. -2,3-diyl, 1-butene-1,2-diyl, 1-butene-1,3-diyl, 1-butene-1,4-diyl, 2-pentene-1 , 5-diyl, 3-hexene-1,6-diyl and the like. Specific examples of the alkanediyl group include the same groups as described above.

Examples of the divalent alicyclic hydrocarbon group include a cycloalkyl group and a cycloalkenyl group. The number of carbon atoms thereof is preferably 3 to 20, and more preferably 3 to 12. Specific examples include monocyclic hydrocarbon ring groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl, 1, 4-norbornyl group, 2,5-norbornyl group and other subnorbornyl group, 1,5-adamantyl group, 2,6-adamantyl group and other cross-linked cyclic hydrocarbon ring groups.

Examples of the divalent aromatic hydrocarbon group include an arylene group, and the number of carbon atoms thereof is preferably 6 to 20, and more preferably 6 to 10. Specific examples of the arylene group include a phenylene group, a naphthyl group, a phenylene group, and an anthryl group.

The divalent organic group may be an arylene alkanediyl group obtained by combining an arylene group and an alkanediyl group. The number of carbon atoms of the arylene alkanediyl group is preferably 7 to 15, and still more preferably 7 to 13. Specific examples include phenylene methylene, phenylene dimethylene, phenylene trimethylene, phenylene tetramethylene, phenylene pentamethylene, and phenylene hexamethylene Methylene isenylene C _1-6 alkanediyl. In addition, in the arylene alkanediyl group, an ortho, a meta and a para are present, and from the viewpoint of a small steric hindrance, the para is preferred.

Examples of the group obtained by combining a divalent hydrocarbon group with a bonding group containing an atom other than a carbon atom and a hydrogen atom include an alkanediyl group selected from the group consisting of 1 to 10 carbon atoms and / or a carbon atom. At least one of 6 to 20 arylene groups is selected from -O-, -S-,-(CO) O-, -O (CO)-, -CO-, -NR'-, -CONR ' -(R 'represents an alkyl group having 1 to 8 carbon atoms which may have a hydrogen atom or a halogen atom) and at least one of -SO ₂ -are combined, and the like.

G is a group substituted with a fluoro group among these divalent organic groups. The substitution position of the fluoro group is arbitrary, and part of the organic group may be substituted, or all of them may be substituted.

Among them, D is preferably an alkanediyl group and an arylene group, and G is preferably an alkanediyl group having a fluorine atom, and more preferably a fluorine atom is substituted for the entire alkanediyl group.

Examples of the divalent group related to Y, A, and E include a divalent group containing a hetero atom in addition to the aforementioned divalent organic group. Examples of the divalent group containing a hetero atom include -O-, -S-,-(CO) O-, -O (CO)-, -CO-, -NR'-, -CONR '-( R 'represents an alkyl group having 1 to 8 carbon atoms, which may have a hydrogen atom or a halogen atom, or -SO _2- . The divalent organic group may have the same configuration as described above.

Among them, as Y, A, and E, a divalent group containing a hetero atom is preferable, and -O-,-(CO) O-, and -CONH- are more preferable.

The aliphatic hydrocarbon groups involved in R ¹² and R ¹³ may be linear, branched, or cyclic. In addition, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The unsaturated aliphatic hydrocarbon group may be There are unsaturated bonds in both the molecule and the terminal. Examples of the substituent of the aliphatic hydrocarbon group include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, and an amino group. Among them, the aliphatic hydrocarbon group is preferably an alkyl group, and the number of carbon atoms thereof is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. Specific examples include the same groups as described above.

The halogen group related to R _{f is} preferably a fluoro group.

In addition, as the hydrocarbon group related to R _f , the same structure as that of the hydrocarbon group that becomes the skeleton of the halogenated hydrocarbon group according to W may be adopted, and an alkyl group is preferred, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, It is more preferably 1 to 6. Specific examples include the same groups as described above.

Among these, R _{f is} preferably a fluoro group or a perfluoroalkyl group. Specific examples of the perfluoroalkyl group include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, undecylpentyl, tridecylhexyl, pentafluoroheptyl, Heptafluorooctyl, nonafluorononyl, twenty-one fluorodecyl, (1-trifluoromethyl) tetrafluoroethyl, (1-trifluoromethyl) hexafluoropropyl, 1,1-bis Trifluoromethyl-2,2,2-trifluoroethyl and so on.

The number of carbon atoms of the arylene group related to Ar is preferably 6 to 20, and even more preferably 6 to 10. Specific examples of the arylene group include the same groups as described above. The halogen group may replace part or all of the arylene group, and as the halogen group, a fluoro group is preferred.

n represents an integer of 0 to 3, preferably an integer of 0 to 2, and even more preferably 0 or 1.

p represents an integer of 1 to 8, preferably an integer of 1 to 6, and even more preferably an integer of 2 to 6.

The (C ² ) component-containing anion part may have a structural unit (hereinafter also referred to as “other structural unit”) other than the structural unit represented by the formulae (2 ′) to (5 ′). Examples of such a structural unit include, for example, at least one monomer unit selected from the group consisting of unsaturated monomers (d1) and unsaturated monomers (d2), as exemplified in the (D) binder resin item described later. . Among these, from the viewpoint of dispersibility, it is preferable to have an unsaturated monomer (d2) as a monomer unit, and it is more preferable to have a (meth) acrylate as a monomer unit.

When the anion part according to the (C ² ) component has another structural unit, from the viewpoint of dispersibility, the copolymerization ratio of the other structural unit is preferably as follows.

That is, the ratio p of the structural unit represented by the formulae (2 ') to (5') and the ratio r of the other structural units in all the structural units of the anion portion related to the (C ² ) component is preferably the molar ratio. p / r = 5/95 ~ 50/50, more preferably 10/90 ~ 30/70.

The weight average molecular weight (Mw) of the component (C ² ) measured by gel permeation chromatography (hereinafter referred to as GPC) (washing solvent: tetrahydrofuran) in terms of polystyrene is usually 1,000 to 50,000, preferably 3,000 to 20000. With such an aspect, heat resistance, film characteristics, electrical characteristics, pattern shape, and resolution can be made good.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the (C ² ) component in the present invention is preferably 1.0 to 5.0, and more preferably 1.0 to 3.0. The Mn referred to herein is a polystyrene-equivalent number average molecular weight measured by GPC (washing solvent: tetrahydrofuran).

The (C ² ) component can be produced by a known method, and can be produced, for example, by the same method as in the example of Japanese Patent Application Laid-Open No. 2012-194466. The colorant thus obtained is soluble in various organic solvents typified by propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and the like, and has excellent heat resistance.

Next, the cation portion of the (C ¹ ) component and the (C ² ) component will be described.

X ^{m +} represents a proton, an onium cation, or a metal ion. The onium cation is preferably a cation in which the maximum value of the molar absorption coefficient in the visible light region (380 nm to 780 nm) is 10,000 or less, preferably 5,000 or less, and even more preferably 3,000 or less. Specific examples include ammonium cations, sulfonium cations, sulfonium cations, sulfonium cations, and diazonium cations. The ammonium cation is preferably an organic ammonium cation, and examples thereof include tetramethylammonium, tetraethylammonium, monostearyltrimethylammonium, distearyldimethylammonium and tristearylmonomethyl Ammonium, cetyltrimethylammonium, trioctylmethylammonium, dioctyldimethylammonium, monolauryltrimethylammonium, dilauryldimethylammonium, trilaurylmethylammonium, Tripentyl benzyl ammonium, trihexyl benzyl ammonium, trioctyl benzyl ammonium, trilauryl benzyl ammonium, benzyl dimethyl stearyl ammonium, benzyl dimethyl octyl ammonium, dialkyl ( The alkyl group is C14 to C18) dimethyl ammonium and the like. The above sulfonium cation is preferably an organic sulfonium cation, and examples thereof include methyltrioctylfluorene, octyltributylphosphonium, dodecyltributylphosphonium, cetyltributylphosphonium, and dihexyl Tetraalkylfluorene such as dioctylfluorene, aryltrialkylfluorene such as benzyltributylfluorene, dialkyldiarylfluorene such as dibutyldiphenylfluorene, alkyltriphenylfluorene such as butyltriphenylfluorene Tetraarylfluorene and the like such as phenylfluorene and benzyltriphenylfluorene. Examples of the sulfonium cation include the cation described in paragraph [0063] of Japanese Patent Application Laid-Open No. 2009-073871. Examples of the sulfonium cation include the cation described in paragraph [0065] of Japanese Patent Application Laid-Open No. 2009-073871. Examples of the diazonium cation include a cation described in paragraph [0374] of Japanese Patent Application Laid-Open No. 2002-332271.

Examples of the metal ions include monovalent metal cations such as lithium ions, sodium ions, and potassium ions, and divalent metal cations such as magnesium ions and calcium ions.

m represents a natural number of 1 to 3, and is appropriately selected so as to be electrically neutral with the anion part according to the type of the cationic chromophore described later.

In the present invention, the (C) specific compound may be used singly or in combination of two or more kinds, but from the viewpoint of heat resistance and electrical characteristics, it is preferable to contain at least a (C ² ) component. Among the (C ² ) component, a polymer having a structural unit represented by formula (2), (4) or (5) is preferred, and a polymer having a structural unit represented by formula (2) or (4) is more preferred Polymer.

In the present invention, when (C ¹ ) a compound represented by the formula (1) or (C ² ) a polymer having a structural unit represented by the formulas (2) to (5), The content of the (C) specific compound is preferably 10 to 500 parts by mass, more preferably 20 to 300 parts by mass, and still more preferably 30 to 200 parts by mass with respect to 100 parts by mass of the colorant (A). When (C ¹ ) the compound represented by the above formula (1) and (C ² ) any one of the polymers having a structural unit represented by the above formulas (2) to (5) are used in combination, their total contents are relatively In (A) 100 parts by mass of the colorant is preferably 10 to 500 parts by mass, more preferably 15 to 300 parts by mass, and still more preferably 20 to 200 parts by mass. With such an aspect, a colored hardened film having high heat resistance can be obtained.

In particular, when the coloring composition contains a dye as a colorant, the content of the (C) specific compound is preferably as follows.

When only the (C ¹ ) component is contained as the (C) specific compound, the (C ¹ ) component is preferably 1.0 to 10 mol, more preferably 1.5 to 8 mol, and even more preferably 2 to 1 mol of the dye. ~ 7 Mor.

When only the (C ² ) component is contained as the (C) specific compound, the anionic portion in the (C ² ) component is preferably 1.0 to 10 mol, more preferably 1.5 to 8 mol, with respect to 1 mol of the dye. More preferably, it is 2 to 7 moles.

When the (C ¹ ) component and the (C ² ) component are used in combination as the (C) specific compound, the total of the (C ¹ ) component and the (C ² ) component in the anion part is preferably 1.0 to 10 with respect to 1 mole of the dye. Mohr, more preferably 1.2 to 8 moles, and even more preferably 1.5 to 5 moles.

With such an aspect, a colored hardened film having high heat resistance can be obtained.

The molar number of the anion portion in the (C ² ) component can be determined as follows. For example, when the component (C ² ) is a binary copolymer of monomer X and monomer Y, when the structural units represented by formulae (2) to (5) are derived from monomer X, and other structural units are derived from monomer Y, m = W _C / {W _X + (Y _r × W _Y / X _p )}. Wherein, m: (C ²⁾ component in the number of moles of anion W _{C: (C} ²⁾ component mass W _X: the molecular weight of monomer X W _Y: molecular weight monomer Y X _p: from monomer X The ratio (molar number) of the structural unit Y _r : The ratio (molar number) of the structural unit derived from the monomer Y.

-(D) Binder resin-

(D) A binder resin may be contained in the coloring composition of this invention. This can improve alkali solubility and storage stability of the coloring composition. The binder resin (D) is not particularly limited, and a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group is preferred. Among these, a polymer having a carboxyl group (hereinafter also referred to as a "carboxyl-containing polymer") is preferred, and examples thereof include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as "unsaturated monomer ( d1) ") is a copolymer of other copolymerizable ethylenically unsaturated monomers (hereinafter also referred to as" unsaturated monomers (d2) ").

Examples of the unsaturated monomer (d1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinate mono [2- (meth) acryloxyethyl] ester, and ω-carboxyl. Polycaprolactone mono (meth) acrylate, p-vinylbenzoic acid and the like.

These unsaturated monomers (d1) can be used individually or in mixture of 2 or more types.

Examples of the unsaturated monomer (d2) include N-substituted maleimide such as N-phenylmaleimide and N-cyclohexylmaleimide; benzene; Aromatic vinyl compounds such as ethylene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinyl benzyl glycidyl ether, and pinene; (meth) acrylic acid methyl Ester, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate Polyethylene glycol (polymerization degree 2 ~ 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 ~ 10) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 ~ 10) Mono (meth) acrylate, polypropylene glycol (polymerization degree 2 ~ 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclic (meth) acrylate [5.2.1.0 ^2,6 ] Decane-8-yl ester, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, p-isopropyl Ethylene oxide modified (meth) acrylate of phenylphenol, (formaldehyde ) Glycidyl acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, 3-[(meth) acryloxymethyl] oxetane, 3-[(meth) propylene (Methoxymethyl) -3-ethyloxetane (meth) acrylates; cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane Vinyl ethers such as alk-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane; polystyrene, Polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, a macromonomer having a mono (meth) acrylfluorene group at the end of a polymer molecular chain such as polysiloxane, and the like.

These unsaturated monomers (d2) can be used individually or in mixture of 2 or more types.

In the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2), the copolymerization ratio of the unsaturated monomer (d1) in the copolymer is preferably 5 to 50% by mass, and more preferably 10 ~ 40% by mass. By copolymerizing the unsaturated monomer (d1) within such a range, a colored composition having excellent alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2) include, for example, Japanese Patent Application Laid-Open No. 7-140654 Newspaper, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10-31308, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. Copolymers disclosed in 2000-56118, Japanese Patent Application Laid-Open No. 2004-101728, and the like.

In addition, in the present invention, for example, Japanese Patent Laid-Open No. 5-19467, Japanese Patent Laid-Open No. 6-230212, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 9-325494, and Japanese Patent Laid-Open No. As disclosed in Japanese Unexamined Patent Publication No. 11-140144, Japanese Unexamined Patent Publication No. 2008-181095, and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylfluorenyl group in a side chain is used as a binder resin.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter referred to as GPC) (washing solvent: tetrahydrofuran) of the binder resin in the present invention is usually 1000 to 100,000, preferably It is 3000 ~ 50,000. With such an aspect, the residual film rate, pattern shape, heat resistance, electrical characteristics, and resolution of the film can be further improved, and the generation of dry foreign matter at the time of coating can be suppressed at a high level.

In addition, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, and more preferably 1.0 to 3.0. In addition, Mn here means the number average molecular weight in polystyrene conversion measured by GPC (washing solvent: tetrahydrofuran).

The binder resin in the present invention can be produced by a known method. For example, it can also be used in Japanese Patent Application Laid-Open No. 2003-222717, The methods disclosed in Japanese Patent Laid-Open No. 2006-259680, International Publication No. 2007/029871, and the like control the structure, Mw, Mw / Mn.

In this invention, a binder resin can be used individually or in mixture of 2 or more types.

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, and preferably 20 to 500 parts by mass with respect to 100 parts by mass of the colorant (A). With such an aspect, it is possible to further improve the alkali developability, the storage stability of the colored composition, and the chromaticity characteristics.

-Photopolymerization initiator-

The coloring composition of the present invention may contain a photopolymerization initiator. This makes it possible to impart radiation-sensitive linearity to the colored composition. The photopolymerization initiator used in the present invention is a compound that generates active species that can initiate polymerization of the polymerizable compound by exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays.

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, and Compounds, O-fluorenyl oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, diazo compounds, sulfonium sulfinate compounds, and the like.

In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and At least one of a compound and an O-fluorenyl oxime compound.

Among the preferred photopolymerization initiators in the present invention, as specific examples of the thioxanthone compound, thioxanthone, 2-chlorothioxanthone, 2- Methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-bis Ethyl thioxanthone, 2,4-diisopropyl thioxanthone and the like.

Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropane-1-one and 2-benzyl- 2-dimethylamino-1- (4-morpholinylphenyl) butane-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- ( 4-morpholinylphenyl) butane-1-one and the like.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4, 6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

When a biimidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor in combination from the viewpoint of improving the sensitivity. The "hydrogen donor" as used herein refers to a compound capable of supplying a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzo Thiol hydrogen donors such as azoles, amine hydrogen donors such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone. In the present invention, the hydrogen donor may be used alone or in combination of two or more, but from the viewpoint of further improving the sensitivity, it is preferable to combine one or more thiol hydrogen donors and one or more amine hydrogen donors. To use.

In addition, as the above three Specific examples of the compound include 2,4,6-ginseno (trichloromethyl) -symmetric tris , 2-methyl-4,6-bis (trichloromethyl) -symmetric tris , 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -symmetric tri , 2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -symmetric tri , 2- [2- (4-diethylamino-2-methylphenyl) vinyl] -4,6-bis (trichloromethyl) -symmetric tri , 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -symmetric tri , 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -symmetric tri , 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -symmetric tris , 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -symmetric tri Trihalide Compound.

Specific examples of the O-fluorenyl oxime compound include 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzidine oxime), 1 -[9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -ethanone 1- (O-acetamoxime), 1- [9-ethyl- 6- (2-methyl-4-tetrahydrofurylmethoxybenzyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetamoxime), 1- [9-ethyl -6- {2-methyl-4- (2,2-dimethyl-1,3-dioxacycloalkyl) methoxybenzyl} -9H-carbazol-3-yl]- Ethyl ketone 1- (O-acetamoxime) and the like. As commercially available products of O-fluorenyl oxime compounds, NCI-831, NCI-930 (above, manufactured by ADEKA Co., Ltd.), DFI-020, DFI-091 (above, manufactured by Daitochemix Co., Ltd.), and the like can also be used.

In the present invention, when a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination. Examples of such a sensitizer include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, and 4-bis Ethylaminoacetophenone, 4-dimethylaminophenylacetone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5- Bis (4-diethylamino (Benzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzyl) coumarin, 4- (diethylamino) chalcone, and the like.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, and particularly preferably 1 to 100 parts by mass with respect to 100 parts by mass of the polymerizable compound. By setting it as such an aspect, hardenability and film characteristics can be further improved.

-Solvent-

The coloring composition of the present invention contains the above-mentioned components (A) to (C) and other components optionally added, and is usually mixed with a solvent to prepare a liquid composition.

As the solvent, as long as it can disperse or dissolve the components (A) to (C) and other components constituting the coloring composition, and does not react with these components, and has moderate volatility, it can be appropriately selected and used.

Examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Alcohol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether (Poly) alkanediols such as ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether Monoalkyl ethers; alkyl lactates such as methyl lactate and ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethyl (Cyclo) alkyl alcohols such as hexanol and cyclohexanol; keto alcohols such as diacetone alcohol; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether (Poly) alkanediol monoalkyl ether acetates, such as ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate. ; Diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; propylene glycol di Diacetates such as acetate, 1,3-butanediol diacetate, and 1,6-hexanediol diacetate; methyl 3-methoxypropionate, 3-methoxypropionic acid Alkoxycarboxylates such as ethyl ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate Acid esters; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, butyl acetate N-propyl ester, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, acetone Ethyl esters, n-propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, ethyl 2-oxobutanoate and other esters; aromatic hydrocarbons such as toluene and xylene; N, N-di Methylamines, such as methylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone, or lactams.

Among these solvents, from the viewpoints of solubility, pigment dispersibility, and coatability, (poly) alkanediol monoalkyl ethers, alkyl lactate, and (poly) alkanediol monoalkyl ether are preferred. Acetates, other ethers, ketones, diacetates, alkoxycarboxylic acid esters, other esters, particularly preferred Propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether Ether, diethylene glycol methyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate Esters, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, and the like.

In this invention, a solvent can be used individually or in mixture of 2 or more types.

The content of the solvent is not particularly limited, and the total concentration of the components other than the solvent of the coloring composition is preferably an amount of 5 to 50% by mass, and more preferably an amount of 10 to 40% by mass. With such an aspect, a coloring agent dispersion liquid having good dispersibility and stability, and a coloring composition having good coatability and stability can be obtained.

-additive-

The coloring composition of this invention may contain various additives as needed.

Examples of the additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); surfactants such as fluorine surfactants and polysiloxane surfactants; ethylene Trimethoxysilane, vinyltriethoxysilane, vinyl ginseng (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethyl Oxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Adhesion promoters such as mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-ditert-butylphenol, pentaerythritol [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methyl Phenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxa-spiro [5.5] undecane, thiodiethylidenebis [3 -(3,5-Di-tertiarybutyl-4-hydroxyphenyl) propionate] and other antioxidants; 2- (3-tertiary-butyl-5-methyl-2-hydroxyphenyl) -5- UV absorbers such as chlorobenzotriazole and alkoxybenzophenones; coagulation inhibitors such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid , 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1, 2-propanol Residue improving agents such as diol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; mono [2- (meth) propenyloxyethyl] succinate, Developability improvers such as mono [2- (meth) acryloxyethyl] phthalate, ω-carboxy polycaprolactone mono (meth) acrylate, and the like.

Manufacturing method of colored composition

The colored composition of the present invention can be prepared by an appropriate method, and can be produced, for example, by mixing (A) a colorant, (B) a polymerizable compound, and at least one selected from the group consisting of a (C ² ) component and a (C ¹ ) component. . When both a dye and a pigment are used as a colorant, the methods for producing the same include, for example, the methods disclosed in Japanese Patent Application Laid-Open No. 2008-58642, Japanese Patent Application Laid-Open No. 2010-132874, and the like. Specifically, as disclosed in Japanese Patent Application Laid-Open No. 2010-132874, the following method may be adopted: after passing the dye solution through the first filter, mixing the dye solution passed through the first filter with a separately prepared pigment dispersion liquid, The obtained colored composition was prepared by passing it through a second filter. Alternatively, the following method may be used: the dye, the components (B) and (C), and other components used as necessary are dissolved in a solvent, and the obtained solution passes through the first filter, and then passes through the first filter. The solution was mixed with a separately prepared pigment dispersion, and the obtained colored composition was passed through a second filter to prepare it. In addition, the following method can also be adopted: after passing the dye solution through the first filter, mixing and dissolving the dye solution passing through the first filter, the components (B) and (C), and other components used as necessary, The solution was passed through a second filter, and the solution passing through the second filter was mixed with a separately prepared pigment dispersion, and the obtained colored composition was passed through a third filter to prepare the solution.

In the method for producing a colored composition of the present invention, it is preferable to contain an organic dye as the (A) colorant because the desired effect of the present invention is easily obtained.

Colored hardened film and manufacturing method thereof

The coloring cured film of the present invention is formed using the coloring composition of the present invention, and specifically refers to a pixel, a black matrix, a black spacer, and the like of each color used in a color filter.

Hereinafter, a colored hardened film used in a color filter and a forming method thereof will be described.

As a method of producing a color filter, the following method is mentioned first. First, a light-shielding layer (black matrix) is formed on the surface of the substrate so that a portion forming a pixel is divided as necessary. Next, on this substrate, for example, a blue liquid composition of the radiation-sensitive coloring composition of the present invention is applied, and thereafter, pre-baking is performed to evaporate the solvent to form a coating film. Next, after exposing this coating film through a photomask, it develops using an alkaline developing solution, and the unexposed part of a coating film is melt | dissolved and removed. Thereafter, a pixel array in which blue pixel patterns (colored cured films) are arranged in a predetermined arrangement is formed by post-baking.

Next, using each of the green or red radioactive coloring compositions, coating, prebaking, exposure, development, and post-baking of each of the radioactive coloring compositions are performed in the same manner as described above, and green pixels are sequentially formed on the same substrate Array and red pixel array. As a result, a color filter having a pixel array of three primary colors of blue, green, and red arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the order described above.

In addition, the black matrix can be formed by forming a metal thin film such as chromium by sputtering or vapor deposition into a desired pattern by a photo-etching method, or by using a radiation-sensitive coloring composition in which a black pigment is dispersed and forming The above-mentioned pixels are formed in the same manner.

Examples of the substrate used when forming a color filter include glass, silicon, polycarbonate, polyester, aromatic polyamine, polyimide, polyimide, and the like.

In addition, these substrates may be subjected to appropriate pretreatments such as reagent treatment using a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction method, and vacuum evaporation, if necessary.

When applying a radiation-sensitive coloring composition to a substrate, appropriate coatings such as a spray method, a roll coating method, a spin coat method, a slit die coating method (slit coating method), and a rod coating method can be used. The method is particularly preferably a spin coating method or a slit die coating method.

Pre-baking is usually performed by combining reduced pressure drying and heat drying. Drying under reduced pressure is usually performed until it reaches 50 to 200 Pa. The conditions for heating and drying are usually 70 to 110 ° C and about 1 to 10 minutes.

The coating thickness is 0.6 to 8 μm, and preferably 1.2 to 5 μm, based on the film thickness after drying.

Examples of a light source for forming radiation used when at least one selected from a pixel and a black matrix include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, and a medium-pressure mercury lamp , Low-pressure mercury lamp and other lamp light sources or argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser and other laser light sources. As the light source for exposure, an ultraviolet LED may be used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.

The amount of radiation exposure is usually preferably 10 to 10,000 J / m ² . In addition, as the alkaline developing solution, for example, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4. 0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene and other aqueous solutions.

For example, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol, a surfactant, and the like may be added to the alkaline developer. In addition, after alkaline development, water washing is usually performed.

As the development treatment method, a spray development method, a spray development method, a dip development method, a paddle (filled) development method, and the like can be applied. The developing conditions are preferably room temperature and 5 to 300 seconds.

Post-baking conditions are usually 180 to 280 ° C and about 10 to 60 minutes.

The film thickness of the pixel formed in this manner is usually 0.5 to 5 μm, and preferably 1.0 to 3 μm.

In addition, as a second method of manufacturing a color filter, a method of obtaining pixels of each color by an inkjet method disclosed in Japanese Patent Application Laid-Open No. 7-318723, Japanese Patent Application Laid-Open No. 2000-310706, and the like can be used. In this method, first, a partition wall having a light shielding function is formed on the surface of the substrate. Next, a blue liquid composition of the thermosetting coloring composition of the present invention is ejected into the formed partition wall by an inkjet device, and then pre-baking is performed to evaporate the solvent. Next, after exposing this coating film as needed, it hardens by post-baking, and a blue pixel pattern is formed.

Next, a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate in the same manner as described above using each of the green or red thermosetting coloring compositions. Thus, a color filter having pixel patterns of three primary colors of blue, green, and red arranged on the substrate was obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the order described above.

In addition, the partition wall not only performs a light-shielding function, but also functions to prevent the thermosetting coloring composition of each color ejected into the partition from mixing colors. Therefore, the film thickness is thicker than the black matrix used in the first method. Therefore, the partition wall is usually formed using a black radiation-sensitive composition.

The substrate, the light source for radiation, and the methods and conditions for pre-baking and post-baking when forming a color filter are the same as the first method. In this way, the film thickness of the pixels formed by the inkjet method is equal to the height of the partition wall.

After forming a protective film on the pixel pattern thus obtained, a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer may be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, and a spacer (black spacer) having a light-shielding property may be used. In this case, a colored radiation-sensitive composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be applied to the formation of the black spacer.

The coloring composition of the present invention can also be applied to the formation of any colored cured film of each color pixel, black matrix, black spacer, or the like used in the color filter.

The color filter containing the colored hardened film of the present invention thus formed has extremely high brightness and tinting power, and is therefore extremely useful for color liquid crystal display elements, color photographic tube elements, color sensors, organic EL display elements, electronic paper, and the like. . In addition, a display element described later may include at least one coloring cured film formed using the coloring composition of the present invention.

Display element

The display element of the present invention includes the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

The color liquid crystal display element including the colored cured film of the present invention may be a transmissive type or a reflective type, and an appropriate structure may be adopted. For example, a structure in which a color filter is formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween, A structure in which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is arranged and a substrate on which an ITO (tin-doped indium oxide) electrode is formed to face each other with a liquid crystal layer interposed therebetween. The latter structure can significantly improve the aperture ratio, and has the advantage that a bright and high-definition liquid crystal display element can be obtained. In the latter configuration, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed and the substrate side on which the ITO electrode is formed.

The color liquid crystal display element including the colored hardened film of the present invention may include a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp) and a backlight unit using a white LED as a light source. Examples of the white LED include a white LED obtained by combining red LEDs, green LEDs, and blue LEDs to obtain white light by mixing colors; a white LED obtained by combining blue LEDs, red LEDs, and green phosphors to obtain white light by mixing colors; Combination of blue LED, red light-emitting phosphor, and green light-emitting phosphor to obtain white light white LED by color mixing; white color to obtain white light white LED by color mixing of blue LED and YAG phosphor; combination of blue LED, orange Light-emitting phosphors and green light-emitting phosphors, white LEDs with white light obtained by color mixing; combination of ultraviolet LEDs, red light-emitting phosphors, green-light-emitting phosphors, and blue light-emitting phosphors, white color obtained by mixing colors LED, etc.

In a color liquid crystal display element having the colored hardened film of the present invention, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, and IPS (In-Planes) (Switching)) type, VA (Vertical Alignment) type, OCB (Optically Compensated Birefringence) type and other suitable liquid crystal modes.

Moreover, the organic EL display element provided with the colored hardened film of this invention can take an appropriate structure, For example, the structure disclosed by Unexamined-Japanese-Patent No. 11-307242 is mentioned.

Moreover, the electronic paper provided with the colored hardened film of this invention can take an appropriate structure, For example, the structure disclosed by Unexamined-Japanese-Patent No. 2007-41169 is mentioned.

Examples

Hereinafter, examples will be given to explain the embodiments of the present invention in more detail. However, the present invention is not limited to the following examples.

<Synthesis of Dyes>

Synthesis Example 1

Referring to Example 2 of International Publication No. 2010/123071, the following compound was obtained. Let this be a dye A. Dye A is a triarylmethane-based basic dye.

Synthesis Example 2

Referring to Synthesis Example 1 of Japanese Patent Application Laid-Open No. 2012-107192, the following compounds were obtained. Let this be a dye B. Dye B is Department of basic dyes.

<Synthesis of (C ² ) component>

Synthesis Example 3 [Synthesis of monomer (1)]

According to the following mechanism, the monomer (1) was synthesized according to the following steps.

A 300 mL four-necked flask equipped with a stirrer was equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube. 100 g of water, 14 g (0.080 mol) of sodium dithiosulfinate, and 12.1 g of triethylamine (0.12) were added. Mol). Next, a solution of 9.56 g (0.040 mol) of 5-bromo-4,4,5,5-tetrafluoropentane-1-ol dissolved in 80 g of acetonitrile was added dropwise from the dropping funnel over 15 minutes while stirring. . Next, the mixture was heated in an oil bath, and reacted at an internal temperature of 60 ° C. for 5 hours under a nitrogen stream. After the reaction was completed, the reaction solution was cooled to 25 ° C. and left to stand for 15 minutes, and then the reaction solution was separated into two layers. The organic layer was separated, and 100 g of acetonitrile was further added to the aqueous layer. The organic layer was separated, combined with the previous organic layer, and concentrated under reduced pressure. The obtained residue was dried under reduced pressure at 40 ° C to obtain 11.4 g (0.0350 mol, yield: 88%) of a thick oily substance. It was confirmed by ¹ H and ¹⁹ F-NMR spectrum (solvent: deuterated methanol) that the obtained compound was a compound represented by the above formula (1-b).

Next, 80 mL of water, 60 mg of sodium tungstate dihydrate, and 4.5 g of a 30% by mass hydrogen peroxide solution were added to the compound (1-b) obtained above, and the mixture was heated at 60 ° C. for 1 hour. After completion of the reaction, the reaction mixture was cooled to 25 ° C, and sodium sulfite was added to decompose excess hydrogen peroxide, followed by concentration under reduced pressure. The residue was dissolved in methanol to remove insoluble matters by filtration, and the resulting solution was concentrated under reduced pressure. The obtained residue was dried under reduced pressure at 50 ° C to obtain 9.90 g (0.0290 mol, yield: 83%) of a viscous oily substance. It was confirmed by ¹ H and ¹⁹ F-NMR spectrum (solvent: deuterated methanol) that the obtained compound was a compound represented by the above formula (1-c).

A 300 mL three-necked flask was equipped with a stirrer, a thermometer, and a dropping funnel. The compound (1-c) obtained above and 50 mL of dichloromethane were added, and the mixture was cooled to 5 ° C. under a nitrogen stream and stirred. Thereafter, 4.33 g (0.043 mol) of triethylamine was added, and the mixture was stirred for a while, and 3.58 g (0.034 mol) of methacrylic acid chloride was added dropwise over 15 minutes. Thereafter, the internal temperature was heated to 25 ° C and stirred for 6 hours. Thereafter, the reaction mixture was poured into 100 g of water to separate an organic layer, and the aqueous layer was extracted with 100 g of dichloromethane. The organic layers were combined, washed three times with 150 g of water, and concentrated under reduced pressure. The obtained residue was purified by column chromatography to obtain 10.1 g of a viscous oily substance (0.0247 mol, yield: 85%). It was confirmed by ¹ H and ¹⁹ F-NMR spectrum (solvent: deuterated chloroform) that the obtained compound was a compound represented by the above formula. Let this be a monomer (1).

[Synthesis of polymer (1)]

4.50 g of monomer (1), 5.50 g of methyl methacrylate, 0.713 g of α-thioglycerin, and 20 g of cyclohexanone were mixed and uniformly dissolved. This solution was heated to 100 ° C with stirring under a nitrogen stream. At this temperature, a solution in which 0.541 g of α, α'-azobisisobutyronitrile was dissolved in 10.4 g of cyclohexanone was added dropwise with stirring for 30 minutes, and stirring was continued at this temperature for 3 hours after the completion of the dropwise addition. After the reaction solution was cooled to room temperature, 60 g of acetone was added to prepare a homogeneous solution, and the solution was added dropwise to 1.1 L of hexane. The resulting precipitate was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50 ° C to obtain 8.90 g of a polymer represented by the above structural formula. The Mw of the obtained polymer was 7,900 and the Mn was 3600. As a result of measurement by ¹ H-NMR spectrum (solvent: deuterated acetone), it was confirmed that the ratio of x to y was 1 / 4.91 in molar ratio (x / y). Let this be a polymer (1).

10 parts by mass of the polymer (1) and 90 parts by mass of propylene glycol monomethyl ether acetate were mixed to prepare a polymer solution (1).

Synthesis Example 4

[Synthesis of polymer (2)]

In the synthesis of the polymer (1), except that 4.57 g of the following monomer (2) was used instead of the monomer (1), a polymer (2) represented by the above structural formula was obtained in the same manner as in Synthesis Example 1. 7.51g. Mw of the obtained polymer (2) was 8600, and Mn was 3700. Measurement by ¹ H-NMR spectrum (solvent: deuterated acetone) confirmed that the ratio of x to y was 1 / in terms of mole ratio (x / y). 4.30. The monomer (2) was synthesized according to Synthesis Example 1 of Japanese Patent Application Laid-Open No. 2012-194466.

10 parts by mass of the polymer (2) and 90 parts by mass of propylene glycol monomethyl ether were mixed to prepare a polymer solution (2).

Synthesis Example 5

[Synthesis of polymer (3)]

The polymer (1) was synthesized in the same manner as in Synthesis Example 1 except that 2.39 g of vinylsulfonic acid triethylamine salt was used instead of the monomer (1). The polymer (3) ) 7.51g. Mw of the obtained polymer (3) was 8,200 and Mn was 3,800. As a result of measurement by ¹ H-NMR spectrum (solvent: deuterated acetone), it was confirmed that the ratio of x to y was 1 / in terms of mole ratio (x / y). 4.66.

10 parts by mass of the polymer (3) and 90 parts by mass of propylene glycol monomethyl ether acetate were mixed to prepare a polymer solution (3).

<Preparation of colorant solution>

Preparation Example 1

10 parts by mass of Dye A and 90 parts by mass of propylene glycol monomethyl ether acetate were mixed to prepare a dye solution (A-1).

Preparation Example 2

10 parts by mass of C.I. Basic Blue 7 (triarylmethane-based basic dye) and 90 parts by mass of propylene glycol monomethyl ether were mixed to prepare a dye solution (A-2).

Preparation Example 3

10 parts by mass of dye B and 90 parts by mass of propylene glycol monomethyl ether were mixed to prepare a dye solution (B-1).

<Synthesis of Binder Resin>

Synthesis Example 6

100 parts by mass of propylene glycol monomethyl ether acetate was added to a flask equipped with a cooling tube and a stirrer, and nitrogen replacement was performed. Heat to 80 ° C, and add 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, and methacrylic acid 2 at this temperature dropwise over 1 hour at this temperature. -15 parts by mass of hydroxyethyl ester, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, and 15 parts by mass of mono (2-propenyloxyethyl) succinate And 6 parts by mass of a mixed solution of 2,2'-azobis (2,4-dimethylvaleronitrile), and the mixture was polymerized while maintaining the temperature for 2 hours. After that, the temperature of the reaction solution was raised to 100 ° C, and repolymerized. For 1 hour, a binder resin solution (solid content concentration: 33% by mass) was thus obtained. Mw of the obtained binder resin was 12,200 and Mn was 6,500. This adhesive resin is referred to as "adhesive resin (D1)".

<Preparation of Pigment Dispersion>

Preparation Example 4

The following reagents were processed with a bead mill to prepare a pigment dispersion liquid (a-1): CI Pigment Blue 15: 6 / CI Pigment Violet 23 = 80/20 (mass ratio) as a colorant, and 12 parts by mass as a dispersion. 8.3 parts by mass of BYK2001 (Disperbyk: manufactured by BYK-Chemie (BYK), non-volatile content = 46% by mass), Solsperse 12000 as a dispersing aid: 0.8 parts by mass, and propylene glycol monomethyl ether acetate as a solvent 78.9 parts by mass.

<Preparation and Evaluation of Coloring Composition>

Example 1

13.5 parts by mass of a pigment dispersion liquid (a-1) as a colorant and 7.2 parts by mass of a dye solution (A-1), 30.0 parts by mass of a binder resin (D1) solution as (D) binder resin, and (B ) 13.7 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate of a polymerizable compound (manufactured by Nippon Kayaku Co., Ltd. under the trade name KAYARAD DPHA) as a component (C ¹ ) trifluoromethanesulfonamide 0.40 2 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butane-1-one (trade name IRGACURE 369, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator 1.8 parts by mass and 0.1 parts by mass of NCI-930 (manufactured by ADEKA Co., Ltd.), 0.05 parts by mass of MEGAFAC F-554 (manufactured by DIC Co., Ltd.) as a fluorine-based surfactant, and propylene glycol monomethyl ether ethyl as a solvent Acid ester to prepare a colored composition (S-1) having a solid content concentration of 20% by mass.

Evaluation of heat resistance

The coloring composition (S-1) was coated on a soda glass substrate having a SiO ₂ film preventing the elution of sodium ions using a spin coater, and then prebaked with a 90 ° C. hot plate for 2 minutes to form a film thickness of 2.5 μm. Coating.

Next, after cooling the substrate to room temperature, each coating film was exposed to radiation including wavelengths of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp through a photomask at an exposure amount of 400 J / m ² . Thereafter, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was sprayed onto these substrates at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm), and spray development was performed for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and then baked in a clean oven at 200 ° C. for 30 minutes, thereby forming a dot pattern on the substrate.

With respect to the obtained dot pattern, the chromaticity coordinate values (x, y) and the stimulus values (Y) in the CIE color system were measured with a C light source and a 2-degree field of view using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.).

Next, after the substrate was additionally baked at 230 ° C for 90 minutes, the chromaticity coordinate values (x, y) and stimulus values (Y) were measured, and the color change before and after the additional baking was evaluated, that is, ΔE ^* _{ab was} evaluated. As a result, a case where the value of ΔE ^* _ab was less than 2.0 was evaluated as "◎", a case where 2.0 or more and less than 3.0 was evaluated as "○", a case where 3.0 or more and less than 5.0 was evaluated as "△", and 5.0 or more Was evaluated as "×". The evaluation results are shown in Table 1. In addition, it can be said that the smaller the ΔE ^* _ab value, the better the heat resistance.

Examples 2 to 4 and Comparative Examples 1 and 2

A coloring composition was prepared in the same manner as in Example 1 except that the type of the dye solution and / or the content of the (C ¹ ) component were changed as shown in Table 1. Next, heat resistance was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Examples 5 to 8

A coloring composition was prepared in the same manner as in Example 1 except that the (C ² ) component shown in Table 2 was used instead of the (C ¹ ) component. Next, heat resistance was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Claims (8)

A coloring composition comprising (A) a colorant and (B) a polymerizable compound, further containing (C ² ) a compound having the following formula (2), (3), (4), or ( 5) Any one or more of the polymers represented by the structural unit, and (A) the colorant contains a member selected from the group consisting of an azo-based basic dye, a triarylmethane-based basic dye, One or more basic dyes, quinone imine basic dyes, and cyanine basic dyes, In the formulae (2) to (5), R ¹ , R ¹¹ , R ²¹ and R ³¹ each independently represent a methyl group, a trifluoromethyl group or a hydrogen atom, and R ¹² and R ¹³ each independently represent a hydrogen atom or a substituent. Or unsubstituted aliphatic hydrocarbon group, R _f represents a hydrogen atom, a halogen group, or a substituted or unsubstituted hydrocarbon group, at least one R _f is a fluorine atom or an alkyl group having a fluorine atom, and Y represents a divalent group or a single bond D represents a divalent organic group, and W represents a monovalent group having a halogen group, a halogenated hydrocarbon group, or a bonding group containing an atom other than a carbon atom, a hydrogen atom, or a halogen atom between the CC bonds of the halogenated hydrocarbon group. , A represents a divalent group or a single bond, G represents a divalent organic group or a single bond containing a fluorine atom, Ar represents a substituted arylene group having at least one halogen group, and E represents a divalent group or single bond X ^{m +} represents a proton, an onium cation, or a metal ion, m represents a natural number of 1 to 3, n represents an integer of 0 to 3, and p represents an integer of 1 to 8. The colored composition according to claim 1, wherein (C ² ) has a content of a polymer having a structural unit represented by the formula (2), (3), (4), or (5) with respect to (A) the colorant 100 parts by mass is 10 to 500 parts by mass. The coloring composition as claimed in claim 1, wherein (A) the colorant comprises One or more basic dyes and quinone imine basic dyes. For example, the coloring composition of claim 1, wherein the content of (A) the colorant is 5 to 70% by mass of the solid content of the composition. A use of the coloring composition according to any one of claims 1 to 4 for a color filter. A method for producing a coloring composition, which is a mixed (A) colorant, which comprises a azo-based basic dye, a triarylmethane-based basic dye, One or two or more basic dyes, quinone imine-based dyes, and cyanine-based basic dyes; (B) a polymerizable compound; and (C ² ) a component having the following formula (2) Any one or more of the polymers of the structural unit represented by (3), (4), or (5), In the formulae (2) to (5), R ¹ , R ¹¹ , R ²¹ and R ³¹ each independently represent a methyl group, a trifluoromethyl group or a hydrogen atom, and R ¹² and R ¹³ each independently represent a hydrogen atom or a substituent. Or unsubstituted aliphatic hydrocarbon group, R _f represents a hydrogen atom, a halogen group, or a substituted or unsubstituted hydrocarbon group, at least one R _f is a fluorine atom or an alkyl group having a fluorine atom, and Y represents a divalent group or a single bond D represents a divalent organic group, and W represents a monovalent group having a halogen group, a halogenated hydrocarbon group, or a bonding group containing an atom other than a carbon atom, a hydrogen atom, or a halogen atom between the CC bonds of the halogenated hydrocarbon group. , A represents a divalent group or a single bond, G represents a divalent organic group or a single bond containing a fluorine atom, Ar represents a substituted arylene group having at least one halogen group, and E represents a divalent group or single bond X ^{m +} represents a proton, an onium cation, or a metal ion, m represents a natural number of 1 to 3, n represents an integer of 0 to 3, and p represents an integer of 1 to 8. A colored hardened film formed using the colored composition according to any one of claims 1 to 4. A display element having a colored hardened film as claimed in claim 7.