KR20150048044A - Coloring composition, colored cured film and display device - Google Patents

Abstract

In the present invention, provided is a coloring composition which is properly used for forming a colored cured film having a good heat resistance wherein the coloring composition comprises (A) a coloring agent, (B) a polymerizable compound and (C^2) at least one type among polymers having structure units denoted by chemical formula (2),(3),(4) or (5). In chemical formula (2),(3),(4), and (5), R1, R11, R21 and R31 are independently a methyl group, trifluoromethyl group or hydrogen atom and R12 and R13 are independently are hydrogen atom or substituted or unsubstituted aliphatic hydrocarbon group.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored composition, a colored cured film,

The present invention relates to a colored composition, a colored cured film, and a display device, and more particularly to a colored composition, a colored cured film, and a display device used for forming a colored cured film used in a transmission type or reflection type color liquid crystal display device, A colored cured film formed using the colored composition, and a display element comprising the colored cured film.

In the production of a color filter using a coloring and radiation-sensitive composition, a pigment-dispersed coloring and radiation-sensitive composition is applied onto a substrate and dried, and then the dry film is irradiated with a desired pattern (hereinafter, (For example, refer to Patent Documents 1 and 2) are known. Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed (see, for example, Patent Document 3) is known. Further, there is known a method of obtaining pixels of respective colors by an ink jet method using a pigment dispersion type colored resin composition (see, for example, Patent Document 4).

In recent years, high contrast of a liquid crystal display element and high definition of a solid-state image pickup element have been strongly demanded. In order to realize these, application of a dye as a coloring agent has been examined. Generally speaking, when a dye is applied Heat resistance is often low.

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

Japanese Patent Application Laid-Open No. 2-144502 Japanese Patent Laid-Open Publication No. 3-53201 Japanese Patent Application Laid-Open No. 6-35188 Japanese Patent Application Laid-Open No. 2000-310706 Japanese Patent Application Laid-Open No. 8-3652

However, even in the case of the dye of Patent Document 5, the heat resistance is not sufficient. Accordingly, an object of the present invention is to provide a coloring composition suitable for forming a colored cured film exhibiting excellent heat resistance. It is still another object of the present invention to provide a colored cured film formed using the colored composition, and a display device having the colored cured film.

As a result of extensive studies, the present inventors have found that the above problems can be solved by using a compound having a specific structure together with a colorant.

That is, the present invention provides a colored composition comprising (A) a colorant and (B) a polymerizable compound, and (C ² ) a structural unit represented by the following formula (2), (3), (4) And a colorant composition containing at least one of the above-mentioned polymers.

(In the formulas (2) to (5)

R ¹ , R ¹¹ , R ²¹ and R ³¹ independently represent a methyl group, a trifluoromethyl group or a hydrogen atom,

R ¹² and R ¹³ independently represent a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group,

R _f is a hydrogen atom, a halo group, or a substituted or unsubstituted hydrocarbon group, at least one of R _f is an alkyl group having a fluorine atom or a fluorine atom,

Y represents a divalent group or a single bond,

D represents a divalent organic group,

W represents a monovalent group having a linking group containing a carbon atom, a hydrogen atom or an atom other than a halogen atom between C-C bonds of a halo group, a halogenated hydrocarbon group, or a halogenated hydrocarbon group,

A represents a divalent group or a single bond,

G represents a divalent organic group containing a fluorine atom, or a single bond,

Ar represents a substituted arylene group having at least one halo group,

E represents a divalent group or a 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 present invention also provides a coloring composition comprising (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 ^{< + &} gt ^; 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 alkylaryl group,

M represents a nitrogen atom, a phosphorus atom, a boron atom, an arsenic atom or an antimony atom,

a represents an integer of 1 to 6,

b represents an integer of 0 to 5;

Provided that a + b is 2, 4 or 6, and when plural Z and R ⁰ are present, they may be the same or different)

The present invention also provides a colored cured film formed using the colored composition, and a display device comprising the colored cured film. Here, the "colored cured film" means each color pixel, a black matrix, a black spacer, etc. used in a display element or a solid-state image pickup element.

When the coloring composition of the present invention is used, a colored cured film exhibiting excellent heat resistance can be formed. In particular, when a dye is used as a coloring agent, a colored cured film having particularly excellent heat resistance can be formed.

Therefore, the coloring composition of the present invention can be suitably used for the production of solid-state image pickup devices such as color liquid crystal display devices, organic EL display devices, display devices such as electronic paper, and 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 coloring agent can be used without particular limitation as long as it has coloring property, and the color and the material can be appropriately selected depending on the use of the coloring composition. For example, when the coloring composition of the present invention is used for forming a colored cured film of a color filter, a color filter is required to have high color purity, brightness, contrast and the like. Therefore, at least one coloring agent selected from pigments and dyes is preferable , Organic pigments, and organic dyes. Among them, when an organic dye is contained, the desired effect of the present invention is easily obtained, which is preferable.

As the dyes, both acidic dyes, basic dyes and nonionic dyes can be suitably used. These may be used singly or in combination of two or more, and may be arbitrarily combined when two or more are used in combination. In the present specification, the term "acidic dye" means an ionic dye in which the anion portion is a chromophore, and the ionic dye forming a salt with the anion portion is also an acidic dye. In the present specification, the term " basic dye " means an ionic dye in which a cation part is a chromophore, and an ionic dye forming a salt with the cation part is also a basic dye. &Quot; Nonionic dye " means a dye other than an acidic dye and a basic dye.

Among dyes, basic dyes are preferable from the viewpoint of further improving the heat resistance. The basic dye means an ionic dye in which the cation moiety serves as a chromophore and is not particularly limited as long as it has a cationic chromophore. Examples of the basic dye include azo-based basic dyes, triarylmethane-based basic dyes, xanthene-based basic dyes, quinoneimine- Dyes, cyanine-based basic dyes, and the like. These may be used singly or in combination of two or more, and may be arbitrarily combined when two or more are used in combination. Of these, triarylmethane-based basic dyes and xanthene-based basic dyes are preferable.

The triarylmethane-based basic dye preferably has a cationic chromophore represented by the following formula (6-1) or (6-2). There are various resonance structures in the cationic chromophores represented by the following chemical formulas (6-1) and (6-2), but in the present specification, when a resonance structure exists in the chromophore represented by each chemical formula, (6-1) or (6-2).

(In formulas (6-1) and (6-2)

R ⁵¹ to R ⁵⁶ and R ⁶¹ to R ⁶⁶ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, or a substituted or unsubstituted aryl Lt; / RTI >

R ⁵⁷ to R ⁵⁹ and R ⁶⁷ to R ⁶⁹ independently represent an alkyl group or a chlorine atom having 1 to 8 carbon atoms,

c, d, f, g and h independently represent an integer of 0 to 4,

e represents an integer of 0 to 6.]

Examples of the alkyl group having 1 to 8 carbon atoms according to R ⁵¹ to R ⁵⁹ and R ⁶¹ to R ⁶⁹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, A tert-butyl group, an amyl group, a tert-amyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a tert-octyl group and a 2-ethylhexyl group. Among them, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is particularly preferable.

In the present specification, the alkyl group may be linear or branched.

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

The aryl group according to R ⁵¹ to R ⁵⁶ and R ⁶¹ to R ⁶⁶ is preferably an aryl group having 6 to 14 carbon atoms and more preferably 6 to 10 carbon atoms. Specific examples thereof include a phenyl group, a naphthyl group and an anthranyl group, among which a phenyl group is preferable.

Examples of the substituent 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 halo group, a trifluoromethyl group and a cyano group 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, tert- iso-pentyloxy group, n-hexyloxy group, methoxymethoxy group, ethoxyethoxy group, and 3- (isopropyloxy) propyloxy group. In the present specification, the alkoxy group may be linear or branched. Examples of the halo 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 ones as described above. The position and the number of the substituent are arbitrary, and when two or more substituents are present, the substituents may be the same or different.

As R ⁵⁷ to R ⁵⁹ and R ⁶⁷ to R ⁶⁹ , an alkyl group or a chlorine atom having 1 to 4 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable.

In the formula (6-1), c and d are preferably an integer of 0 to 2, and e is preferably 0 or 1. The combination of c = 0, d = 0 and e = 0, c = 1, d = 0 and e = A combination of c = 1, d = 0 and e = 0, a combination of c = 1, d = 1 and e = 0, A combination of c = 1, d = 0, e = 0, a combination of c = 0, d = 0 and e = 1, c = 1, d = 1, e = 0 is more preferable.

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

Examples of the chromophore represented by the formula (6-1) or the chromophore represented by the formula (6-2) include chromophores represented by the following groups a and b, among which chromophore a1, a2, a3, a4, a5, a6, b1, b2, b3, b4 and b6 are preferable, and a3, a4, a5, a6, b3 and b4 are more preferable.

In addition to the above, examples of the cationic chromophore represented by the above formula (6-1) include those described in, for example, Japanese Patent Laid-Open Publication No. 147425/1990.

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

As the xanthene basic dye, it is preferable to have a cationic chromophore represented by the following chemical formula (8).

(In the formula (8)

R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ independently represent a hydrogen atom, -R ^108, or an aromatic hydrocarbon group having 6 to 10 carbon atoms (provided that the aromatic hydrocarbon group is a halo 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 ) ;

R ¹⁰⁵ and R ¹⁰⁶ 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, plural R ¹⁰⁷ may be the same or different;

R ¹⁰⁸ is a saturated hydrocarbon group having 1 to 10 carbon atoms (provided that the saturated hydrocarbon group may be substituted with a halo group and may have an oxygen atom, a carbonyl group or -NR ¹⁰⁸ - between the CC bonds of the saturated hydrocarbon group) Lt; / RTI >

R ¹⁰⁹ and R ¹¹⁰ independently represent a straight chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms or -L, or a substituted or unsubstituted C 1-10 alkyl group formed by bonding R ¹⁰⁹ and R ¹¹⁰ to each other; Represents an unsubstituted heterocyclic group. The alkyl group and the cycloalkyl group may be substituted with a hydroxyl group, a halo group, -L, -CH = CH ₂ or -CH = CHR ¹⁰⁸ , and an oxygen atom, a carbonyl group or an oxygen atom may be interposed between the CC bond of the alkyl group and the cycloalkyl group -NR ¹⁰⁸ -, and the hydrogen atom contained in the heterocyclic group may be substituted with -R ¹⁰⁸ , -OH or -L;

M ¹ represents a sodium atom or a potassium atom;

L represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms. However, the hydrogen atoms contained in the aromatic hydrocarbon group and aromatic heterocyclic group is ^{-OH, -R 108, -OR 108,} -NO 2, -CH = CH 2, may be substituted with a group -CH = CHR ¹⁰⁸ or halo. ]

The saturated hydrocarbon group according to R ¹⁰⁸ has 1 to 10 carbon atoms, and may be any of linear, branched and cyclic, and may have a crosslinked structure. For example, in addition to the above-mentioned alkyl group having 1 to 8 carbon atoms and cycloalkyl group having 3 to 8 carbon atoms, a nonyl group, a decyl group, a tricyclodecanyl group, a norbornyl group, a boronyl group, an adamantyl group, a bicyclooctyl group, . Examples of the group having an oxygen atom between the CC bonds of the saturated hydrocarbon group include a methoxypropyl group, an ethoxypropyl group, a 2-ethylhexyloxypropyl group, and a methoxyhexyl group.

Examples of the substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms formed by bonding R ¹⁰⁹ and R ¹¹⁰ together include a pyrrolidinyl group, a pyrazolinyl group, a morpholinyl group, a deomolpolinyl group, a piperidyl group, , A piperazinyl group, a homopiperazinyl group, a tetrahydropyrimidine group, a 1,3-dioxolan-2-yl group, a pyridyl group, a pyranyl group, a pyrimidyl group, a pyridazinyl group, A thiazolyl group, a benzothiazolyl group, an oxazolyl group, an indolyl group, an indazolyl group, a benzoyl group, an imidazolyl group, an imidazolyl group, an imidazolyl group, a pyrazolyl group, An imidazolyl group, a phthalimide group and the like. Examples of the substituent in the heterocyclic group include a halo group, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an amino 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, isoxazole, thiazolyl, isothiazolyl, Group, a pyrimidyl group, and the like.

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

Examples of -SO ₃ R ^{108 in} R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁷ include a methanesulfonyl group, an ethanesulfonyl group, a hexanesulfonyl group and a decanesulfonyl group. Examples of -CO ₂ R ¹⁰⁸ include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, a butyloxycarbonyl group, a cyclohexyloxycarbonyl group, and a methoxypropyloxycarbonyl group. Examples of R ¹⁰⁹ and R ^{110 in} -SO ₂ NHR ¹⁰⁹ and -SO ₂ NR ¹⁰⁹ R ¹¹⁰ include a branched alkyl group having 6 to 8 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an allyl group, an alkyl group having 8 to 10 carbon atoms An alkyl group having 2 to 8 carbon atoms, a hydroxyl group-containing alkyl group having 2 to 8 carbon atoms, an alkoxy group-containing alkyl group having 2 to 8 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

Examples of the quinone imine basic dyes include compounds having a cationic chromophore as described in paragraph [0078] of JP-A-2008-108469.

Examples of the cyanine-based basic dye include a compound having a cationic chromophore as described in paragraphs [0064] to [0065] of JP-A-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 carboxylic acid anion, a sulfuric acid anion, an organic sulfonic acid anion, a nitrogen anion and a methide anion .

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

Examples of the boron anion include an inorganic boron anion such as BF ₄ ^-

^{_{(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 F1 3) 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) ^- , tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis Phenyl) borate, tetra (Tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetra (tolyl) In addition to organoboron anions such as borate, [tris (pentafluorophenyl) phenyl] borate, and tridecahydride-7,8-dicarbal undecaborate, JP-A 10-195119 Boron anions described in JP-A-2010-094807, JP-A-2006-243594, JP-A-2002-341533 and JP-A-8-015521.

Examples of the phosphate anion include inorganic phosphate anions such as HPO ₄ ^2- , PO ₄ ^3- , PF ₆ ^- and the like;

_{(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 Phosphoric acid anion, phenylphosphoric acid anion, and nonylphenylphosphoric acid anion.

Examples of the carboxylic acid anion include CH ₃ COO ^- , C ₂ H ₅ COO ^- , C ₆ H ₅ COO ^{-, and the like} as disclosed in Japanese Patent Application Laid-Open Nos. 2009-265641 and 2008-096680 And the carboxylic acid anions described.

Examples of the sulfuric acid anion include a sulfuric acid anion and a sulfurous acid anion.

Examples of the organic sulfonic acid anion include alkylsulfonic acid anions such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid and nonafluorobutanesulfonic acid;

In addition to arylsulfonic acid anions such as benzenesulfonic acid, benzene disulfonic acid ion, p-toluenesulfonic acid, p-trifluoromethylsulfonic acid, pentafluorobenzenesulfonic acid, naphthalenesulfonic acid and naphthalenedisulfonic acid ion, Japanese Patent No. 3736221, and Japanese Patent Laid-Open Publication No. 2011-070172.

As the nitrogen anion, for example, ^{_{[(CN) 2 N] -}} , [(FSO 2) 2 N] -, [(FSO 2) N (CF 3 SO 2)] -, [(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 }] ^- and the like are disclosed in Japanese Patent Applications Laid-open No. 2011-133844, Laid-Open Patent Publication No. 2011-116803, Nitrogen negative ions described in JP-A-090341.

As the methide anion, such as _{(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 - , etc. In addition, Japanese Patent Laid-Open No. 2011-145540 discloses, U.S. Patent No. 5,554,664 specification, Japanese Laid-Open Patent Publication No. 2005 - 309408, 2004-085657, and 2010-505787, and the like.

As the acidic dyes, there can be mentioned, for example, Japanese Patent Application Laid-Open Nos. 2010-191358, 2011-138094, 2011-174987, 2012-008421, 2012- 013757, and the like.

As organic pigments, for example, compounds classified as pigments in a color index (CI) (published by The Society of Dyers and Colourists) can be cited. Among them, Japanese Patent Application Laid-Open No. 2001-081348, JP-A-2010-026334, JP-A-2010-191304, JP-A-2010-237384, JP-A-2010-237569, JP-A-2011-006602, JP- 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 Organic pigments other than rake pigments such as yellow 139, C.I. pigment yellow 150, C.I. pigment yellow 185, C.I. pigment yellow 211, C.I. pigment yellow 215, C.I. pigment orange 38 and C.I. pigment violet 23 are preferable. Among the lake pigments, triarylmethane lake pigments, xanthene lake pigments and azo lake pigments are preferable, and triarylmethane lake pigments and xanthane lake pigments are more preferable. These organic pigments can be suitably used in accordance with the color tone of the coloring composition.

In the present invention, the pigment may be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. The pigment may be used by modifying the surface of the particles with a resin, if necessary. As the resin for modifying the particle surface of the pigment, for example, the vehicle resin described in Japanese Patent Application Laid-Open No. 2001-108817 or a commercially available resin for dispersing various pigments may be mentioned. Examples of the resin coating method for the carbon black surface include a method described in Japanese Patent Application Laid-Open Nos. 9-71733, 9-95625, 9-124969, Can be adopted. Further, the organic pigment may be used by finely pulverizing primary particles by so-called salt milling. As the salt milling method, for example, a method disclosed in Japanese Unexamined Patent Application Publication No. 8-179111 can be adopted.

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

Such dispersants are commercially available and include, for example, acrylic dispersants such as Disperbyk-2000, Disperby-2001, BYK-LPN 6919, Vic-LPN21116, Vic-LPN22102 DISPERBY-161, DISPERBY-165, DISPERBY-167, DISPERBIC-170 and DISPERBY-182 (manufactured by BYK) as urethane dispersants, As a polyethylene imine dispersant, such as Solsperse 76500 (manufactured by Lubrizol Corporation), etc., as a polyester dispersant such as Solsperse 24000 (manufactured by Lubrizol Corporation), Agisper PB821, Ajisper PB822, PB880, Ajisper PB881 (manufactured by Ajinomoto Fine Techno Co., Ltd.), and Big-LPN21324 (BYK).

Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.

In the present invention, pigments may be used alone or in combination of two or more.

The content ratio of the (A) coloring agent is usually from 5 to 70% by mass, preferably from 5 to 70% by mass, more preferably from 5 to 70% by mass, in terms of forming a black matrix or black spacer having excellent heat resistance, high brightness, To 60% by mass. Here, the solid content is a component other than the solvent described later.

- (B) Polymerizable compound -

The polymerizable compound in the present invention refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenic unsaturated group, an oxiranyl group, an oxetanyl group and an N-alkoxymethylamino group. In the present invention, as the polymerizable compound, a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferable.

Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, a polyfunctional (meth) acrylate modified with caprolactone, A polyfunctional urethane (meth) acrylate obtained by reacting a (meth) acrylate modified with an alkylene oxide and a polyfunctional (meth) acrylate having a hydroxyl group and a polyfunctional isocyanate, a (meth) acrylate having a hydroxyl group and an acid anhydride And a polyfunctional (meth) acrylate having a carboxyl group obtained by the reaction.

Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol; And tri- or higher aliphatic polyhydroxy compounds such as glycerin, trimethylol propane, pentaerythritol and dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate, and glycerol dimethacrylate. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, anhydrous glutaric acid, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, anhydrous pyromellitic acid, biphenyltetracarboxylic acid dianhydride , Benzophenone tetracarboxylic dianhydride, and the like.

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

Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to chemical structures having one or more triazine rings or phenyl-substituted triazine rings as basic skeletons, and also include melamine, benzoguanamine, or condensates thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ', N', N '', N '' - hexa (alkoxymethyl) N, N ', N'-tetra (alkoxymethyl) glycoluril, and the like.

Among these polymerizable compounds, a polyfunctional (meth) acrylate, a caprolactone modified polyfunctional (meth) acrylate, a polyfunctional urethane (meth) acrylate obtained by reacting a trifunctional or higher aliphatic polyhydroxy compound with (meth) (Meth) acrylate having a carboxyl group, N, N, N ', N', N '', N '' - hexa (alkoxymethyl) ) Benzoguanamine is preferred. Among multifunctional (meth) acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, di Among the polyfunctional (meth) acrylates having a carboxyl group, pentaerythritol hexaacrylate is a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride Compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and the background contamination, film residue and the like on the substrate of the unexposed portion and on the light-shielding layer are hardly generated.

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

The content of the polymerizable compound (B) in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 700 parts by mass, and further preferably 100 to 600 parts by mass based on 100 parts by mass of the (A) colorant. By such a form, the curability and alkali developability are further enhanced, and generation of background contamination, film residue, etc. on the substrate of the unexposed portion or on the light shielding layer can be suppressed to a high level.

- (C) Specific compound -

The coloring composition of the present invention (C) contains, as specific compounds, (C ¹ ) component or (C ² ) component. In the following description, the components (C ¹ ) and (C ² ) may be collectively referred to as "(C) specific compounds".

The specific compound (C) in the present invention is a compound having a maximum molar extinction coefficient in the visible light region (380 nm to 780 nm) of 10,000 or less, and the maximum value of the molar extinction coefficient in the visible light region is preferably 5,000 or less, more preferably 3,000 or less.

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

The negative ion part according to 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 halo group, a cyano group, a monovalent organic group having a cyano group, a monovalent organic group having a nitro group, a halosulfonyl group, An alkylsulfonyl group which may have a group, and the like.

Examples of the halo group include the same groups as described above. Among them, a fluoro group is preferable from the viewpoint of heat resistance.

The monovalent organic group having a halo 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 halo group. The hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group is preferably an alkyl group, a cycloalkyl group, an aryl group or an alkylaryl group, and is preferably 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 more preferably an alkylaryl group having 1 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 are the same as those described above. Examples of the alkylaryl group include groups in which the above-mentioned alkyl group having 1 to 8 carbon atoms is substituted in an aryl group having 6 to 14 carbon atoms.

As the halo group in the halogenated hydrocarbon group, a fluoro group is preferable. The halo group may substitute some or all of the hydrogen atoms of the hydrocarbon group. In particular, the hydrogen atom of the hydrocarbon group is preferably at least 80 mol%, more preferably at least 90 mol%, particularly preferably at least 100 mol %. As a result, the heat resistance can be further increased.

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 a monovalent hydrocarbon group may have a substituent other than a cyano group. As the monovalent hydrocarbon group, an aryl group is preferable, and a phenyl group is particularly preferable.

The monovalent organic group having a nitro group is not particularly limited, and for example, a monovalent hydrocarbon group substituted with a nitro group may be mentioned, and a monovalent hydrocarbon group may have a substituent other than a nitro group. As the monovalent hydrocarbon group, an aryl group is preferable, and a phenyl group is particularly preferable.

The alkylsulfonyl group which may have a halo group is not particularly limited, and an alkylsulfonyl group or a halogenated alkylsulfonyl group can be appropriately selected and used. The alkyl group constituting the skeleton of the alkylsulfonyl group and the halogenated alkylsulfonyl group preferably has 1 to 8 carbon atoms. Specific examples of the alkyl group include the same ones as described above. The halo group in the alkyl halide group is preferably a fluoro group. The halogen group may substitute a part or all of the hydrogen atoms of the hydrocarbon group. From the viewpoint of heat resistance, the hydrogen atom of the hydrocarbon group is preferably at least 80 mol%, more preferably at least 90 mol% It is preferably 100 mol% substituted.

Examples of the halosulfonyl group include FSO ₂ group, ClSO ₂ group, BrSO ₂ group and ISO ₂ group, and FSO ₂ group is preferable.

Z is preferably a monovalent halogenated hydrocarbon group or a cyano group which may have a substituent other than the halo group and the halo group when M is a phosphorus atom, a boron atom, an arsenic atom or an antimony atom, more preferably a fluoro group, a cyano group , Fluorinated alkyl group, fluorinated aryl group or fluorinated alkylaryl group. The fluoroalkyl group is preferably a perfluoroalkyl group, and the perfluoroalkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. Specific examples thereof include CF ₃ group, CF ₃ CF ₂ group, (CF ₃ ) ₂ CF ₃ group, CF ₃ CF ₂ CF ₂ group, CF ₃ CF ₂ CF ₂ CF ₂ group, (CF ₃ ) ₂ CFCF ₂ group , CF ₃ CF ₂ (CF ₃ ) CF ₃ group, and (CF ₃ ) ₃ C group. The fluorinated aryl group is preferably a perfluoroaryl group, and the perfluoroaryl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. Specific examples thereof include, for example, a pentafluorophenyl group and the like. The fluoroalkylaryl group is preferably a perfluoroalkylaryl group, and the perfluoroalkylaryl group preferably has 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms. Specific examples include, for example, 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 halosulfonyl group or a halogenated alkylsulfonyl group, particularly preferably an 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, and (CF ₃ ) ₃ CSO ₂ group.

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

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

In the case where M is a nitrogen atom, a + b is 2. When M is a boron atom, a + b is 4, and M is a phosphorus atom, an arsenic atom Or an antimony atom, a + b is 6. When a plurality of Z and R ⁰ are present, they may be the same or different.

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

In the present invention, preferred examples of (Z _a R ⁰ _b M) ^- include anions represented by any one of the following formulas (1a) to (1c).

^{_{[(R 1a) l PHal 6}} -l] - (1a)

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

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

(1b), R ^1b independently represents a phenyl group substituted with a halogenated hydrocarbon group, a cyano group or a nitro group or a cyano group, B represents a boron atom, Hal represents a halo group, and q represents an integer of from 0 to When R ^1b and Hal are plural, they may be the same or different.]

[(EA) ₂ N] ^- (1c)

(In the formula (1c), EA independently represents a cyano group, an FSO ₂ group or an alkyl fluoro sulfonyl group, provided that at least one of the two EA groups represents a cyano group or an FSO ₂ group.

R ^1a represents a halogenated hydrocarbon group, and examples of the halogenated hydrocarbon group include a halogenated hydrocarbon group exemplified in the description of Z above. In the present invention, R &^lt; ^1a &^gt; is preferably an alkyl fluoride group, more specifically, an alkyl fluoride group exemplified in the description of Z above.

R ^1b independently represents a phenyl group substituted with a halogenated hydrocarbon group, a cyano group or a nitro group or a cyano group. Examples of the halogenated hydrocarbon group include the halogenated hydrocarbon groups exemplified in the description of Z above. In the present invention, R ^1b is preferably an alkyl fluoride group, an aryl fluoride group, a cyano group, or a trifluoromethyl group or a phenyl group substituted with a fluorine atom. More specifically, the groups exemplified in the explanation of Z are preferable.

Hal in accordance with the formulas (1a) and (1b) is preferably a fluoro group from the viewpoint of heat resistance.

EA according to formula (1c) represents a cyano group, an FSO ₂ group or an alkyl fluoro sulfonyl group. As the fluorinated alkylsulfonyl group, the fluorinated alkylsulfonyl group exemplified in the explanation of Z is preferable. In the formula (1c), it is preferable that EA is either a cyano group or a FSO ₂ group, or one is an FSO ₂ group and the other is an alkyl fluoro sulfonyl group.

Representative examples of the anion represented by the formula (1a) include those exemplified in the paragraph [0041]. In _{particular, 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 ^- is preferred.

Representative examples of the anion represented by the formula (1b) include the same examples as those exemplified in the paragraph [0040] above. Among them, ^{_{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 ^- is preferred.

Examples of suitable anions among the anions represented by the formula (1c) include those exemplified in the paragraph [0044]. Among them, [(CN) ₂ N] ^- is preferable.

The anion moiety according to the component (C ² ) is a structural unit represented by any one of the following formulas (2 ') to (5').

(In the formulas (2 ') to (5'),

R ¹ , R ¹¹ , R ²¹ and R ³¹ independently represent a methyl group, a trifluoromethyl group or a hydrogen atom,

R ¹² and R ¹³ independently represent a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group,

R _f is a hydrogen atom, a halo group, or a substituted or unsubstituted hydrocarbon group, at least one of R _f is an alkyl group having a fluorine atom or a fluorine atom,

Y represents a divalent group or a single bond,

D represents a divalent organic group,

W represents a monovalent group having a linking group containing a carbon atom, a hydrogen atom or an atom other than a halogen atom between C-C bonds of a halo group, a halogenated hydrocarbon group, or a halogenated hydrocarbon group,

A represents a divalent group or a single bond,

G represents a divalent organic group containing a fluorine atom or a single bond,

Ar represents a substituted arylene group having at least one halo group,

E represents a divalent group or a single bond,

n represents an integer of 0 to 3,

and p represents an integer of 1 to 8.)

R ¹ , R ¹¹ , R ²¹ and R ³¹ are preferably a methyl group, a trifluoromethyl group and a hydrogen atom, preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

As the halo group according 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 aliphatic hydrocarbon group .

The aliphatic hydrocarbon group may be linear or branched, and the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and the unsaturated aliphatic hydrocarbon group may have an unsaturated bond in the molecule or at an end thereof. Among them, the aliphatic hydrocarbon group is preferably an alkyl group, and the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms. Specific examples of the alkyl group include the same ones as described above.

The alicyclic hydrocarbon group may be a bridged alicyclic hydrocarbon group having 2 to 4 rings. The alicyclic hydrocarbon group is preferably an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms and 3 to 12 carbon atoms. Specific examples thereof include the same cycloalkyl groups and crosslinking alicyclic hydrocarbon groups described above.

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

The aromatic hydrocarbon group is preferably an aryl group, and the aryl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. Specific examples thereof include a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, and an anthracenyl group, among which a phenyl group is preferable.

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

The aromatic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an aralkyl group, and the aralkyl group preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms. Specific examples thereof include a benzyl group, a phenethyl group, an a-methylbenzyl group, and a 2-phenylpropan-2-yl group.

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, , An alicyclic saturated hydrocarbon-substituted alkyl group, a phenyl group, an alkyl-substituted phenyl group, and an aralkyl group are more preferable, and an alkyl group is particularly preferable.

As the halogen atom in the halogenated hydrocarbon group according to W, a fluorine atom is preferable from the viewpoint of the heat resistance of the colorant, and the fluorine atom may substitute some or all of the hydrogen atoms of the hydrocarbon group. By selecting a fluorine atom as a substituent, it is considered that a salt having a stronger ion binding force is formed and the heat resistance is increased.

W may also be a monovalent group having a linking group containing a carbon atom, a hydrogen atom or an atom other than a halogen atom between the CC bonds of the halogenated hydrocarbon group. Examples of the linking 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. When the linking group has carbon atoms, the carbon number of the hydrocarbon group forming the skeleton of the halogenated hydrocarbon group means the total number of carbon atoms excluding the carbon atoms constituting the linking group.

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

(In the formula (11)

R ⁴⁰ represents a hydrogen atom, a fluorine atom, an alkyl group, an alkyl fluoride group, an alicyclic hydrocarbon group, an alkoxy group, an alkoxy group, R ⁴¹ COOR ⁴² - or R ⁴³ COOR ⁴⁴ CFH-,

R ⁴¹ and R ⁴³ independently represent an alkyl group, an alicyclic hydrocarbon group or a substituted or unsubstituted aryl group,

R ⁴² and R ⁴⁴ independently represent an alkanediyl group,

r represents one or more integers,

"*" Indicates a binding hand.)

(In the formula (12)

R ⁴⁵ to R ⁴⁹ independently represent a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkyl fluoride group or an alkoxy group,

&Quot; * " indicates a combined hand.

Provided that at least one of R ⁴⁵ to R ⁴⁹ is a fluorine atom or an alkyl fluoride group]

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

Further, the number of carbon atoms of the fluorinated alkyl group according to R ⁴⁰ is preferably 1 to 20, more preferably 1 to 8, still more preferably 1 to 4. In the present specification, the fluorinated alkyl group may be a straight chain or branched chain, and specific examples thereof include those in which a part or all of the hydrogen atoms of the alkyl group described above are substituted with fluorine atoms, and a perfluoroalkyl group is particularly preferable.

The alicyclic hydrocarbon group according to R ⁴⁰ may be a bridged alicyclic hydrocarbon group having 2 to 4 rings. The carbon number of the alicyclic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12. Specific examples include the same ones as described above.

The carbon number of the alkoxy group according to R ⁴⁰ is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 4. Specific examples include the same ones as described above.

The carbon number of the fluorinated alkoxy group according to R ⁴⁰ is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4. Specific examples include those in which a part or all of hydrogen atoms of the aforementioned alkoxy groups are substituted with fluorine atoms.

In R ⁴¹ COOR ⁴² - and R ⁴³ COOR ⁴⁴ CFH- according to R ⁴⁰ , R ⁴¹ and R ⁴³ independently represent an alkyl group, an alicyclic hydrocarbon group or a substituted or unsubstituted aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 8. The carbon number of the alicyclic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12. The carbon number of the aryl group is preferably 6 to 14, more preferably 6 to 10. Specific examples thereof include the same ones as described above. The substituent of the aryl group includes, for example, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halo group, or a trifluoromethyl group. The position and the number of the substituent are arbitrary, and when two or more substituents are present, the substituents may be the same or different.

Of these, R ^{40 is preferably a} fluorine atom, an alkyl fluoride group, an alicyclic hydrocarbon group, an alkoxy fluoride group, R ⁴¹ COOR ⁴² - or R ⁴³ COOR ⁴⁴ CFH-, more preferably a fluorine atom, an alicyclic hydrocarbon group, An alkoxy group, R ⁴¹ COOCH ₂ CH ₂ - or R ⁴³ COOCH ₂ CH ₂ CFH-.

R ⁴² and R ⁴⁴ independently represent an alkanediyl group. The alkanediyl group may be linear or branched, and preferably has 1 to 10 carbon atoms. Specific examples thereof include a methylene group, an ethylene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, A butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,4-diyl group, a pentane-1,5-di Diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, octane-1,8-diyl group, decane-1,10-diyl group and the like. Among them, an alkanediyl group having 2 to 6 carbon atoms is preferable, an alkanediyl group having 2 to 4 carbon atoms is more preferable, and an ethylene group is preferable from the viewpoint of ease of production.

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

In the formula (12), examples of the alkyl group, fluorinated alkyl group and alkoxy group according to R ⁴⁵ to R ⁴⁹ include the same structures as those of the alkyl group, fluorinated alkyl group and alkoxy group according to R ⁴⁰ in the above formula (11) have. Provided that at least one of R ⁴⁵ to R ⁴⁹ is a fluorine atom or a fluorinated alkyl group, but is preferably in the R ⁴⁵ to R ^49, at least three fluorine atoms or fluorinated alkyl group.

Examples of the divalent organic group according to D and G include a divalent hydrocarbon group, a group formed by combining a divalent hydrocarbon group and a linking group containing an atom other than a carbon atom and a hydrogen atom, And a group substituted with 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 be any of a straight chain and 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 alkenediyl group. The carbon number of the alkanediyl group is preferably 1 to 20, more preferably 2 to 12, still more preferably 2 to 6. The carbon number of the alkenediyl group is preferably 2 to 20, more preferably 2 to 12, still more preferably 2 to 6. Specific examples of the alkenediyl group include, for example, an ethene-1,1-diyl group, an ethene-1,2-diyl group, a propene-1,2-diyl group, Butene-1, 3-diyl group, 1-butene-1, 4-diyl group, 2-pentene- Dienes, and 3-hexene-1, 6-diyl groups. Specific examples of the alkanediyl group include the same ones as described above.

The bivalent alicyclic hydrocarbon group includes, for example, a cycloalkylene group and a cycloalkenylene group, and the number of carbon atoms thereof is preferably 3 to 20, more preferably 3 to 12. Specific examples include monocyclic hydrocarbon ring groups such as cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclobutenylene group, cyclopentenylene group and cyclohexenylene group, 1,4-norbornylene group, 2, Norbornylene group such as 5-norbornylene group and the like, and a bridged cyclic hydrocarbon ring group such as 1,5-adamantylene group and 2,6-adamantylene group.

The bivalent aromatic hydrocarbon group includes, for example, an arylene group, and the number of carbon atoms thereof is preferably from 6 to 20, and more preferably from 6 to 10. [ Specific examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, and an anthryl group.

As the divalent organic group, an arylenealkanediyl group formed by combining an arylene group and an alkanediyl group may be used. The carbon number of the arylenealkanediyl group is preferably 7 to 15, more preferably 7 to 13. Specific examples include phenylene C _1-6 alkanediyl groups such as a phenylene methylene group, a phenylenedimethylene group, a phenylenetrimethylene group, a phenylene tetramethylene group, a phenylene penta methylene group, and a phenylene hexamethylene group . In the arylenealkanediyl group, although ortho, meta and para are present, para chain is preferable in view of low steric hindrance.

Examples of the group formed by combining a divalent hydrocarbon group and a linking group containing an atom other than a carbon atom and a hydrogen atom include at least one kind selected from an alkanediyl group having 1 to 10 carbon atoms and / or an arylene group having 6 to 20 carbon atoms And -O-, -S-, - (CO) O-, -O (CO) -, -CO-, -NR'-, -CONR '- (wherein R' is a hydrogen atom or a halogen atom An alkyl group having 1 to 8 carbon atoms), and -SO ₂ -, and the like.

G is a divalent organic group substituted by a fluoro group, but the substitution position of the fluoro group is arbitrary, and a part of the organic group may be substituted or all may be substituted.

Of these, D is preferably an alkanediyl group or an arylene group, and G is preferably an alkanediyl group having a fluorine atom, and the fluorine atom preferably substitutes all of the alkanediyl groups.

As the divalent group according to Y, A and E, a divalent group containing a hetero atom other than the above-mentioned divalent organic group can be mentioned. Examples of the divalent group containing a heteroatom include -O-, -S-, - (CO) O-, -O (CO) -, -CO-, -NR'-, -CONR '- '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 structure as that described above.

Of these, Y, A and E are preferably a divalent group containing a hetero atom, more preferably -O-, - (CO) O-, or -CONH-.

The aliphatic hydrocarbon group according to R ¹² and R ¹³ may be any of linear, branched and cyclic, and the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The unsaturated aliphatic hydrocarbon group may contain an unsaturated aliphatic hydrocarbon group, You can have it anywhere in the end. The substituent of the aliphatic hydrocarbon group includes, for example, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, and an amino group. Among them, an 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, still more preferably 1 to 6. Specific examples include the same ones as described above.

As the halo group according to R _f , a fluoro group is preferred.

As the hydrocarbon group according to R _f , the same structure as the hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group according to W can be adopted, but an alkyl group is preferable, and the carbon number thereof is preferably 1 to 20, 1 to 12, more preferably 1 to 6. Specific examples include the same ones as described above.

Of these, R _f is preferably a fluoro group or a perfluoroalkyl group. Specific examples of the perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, an undecafluoropentyl group, a tridecafluorohexyl group, a pentadecafluoro group, (1-trifluoromethyl) tetrafluoroethyl group, a (1-trifluoromethyl) hexafluoropropyl group, a hexadecylfluoroethyl group, a heptadecafluorooctyl group, a nonadecafluorononyl group, 1,1-bistrifluoromethyl-2,2,2-trifluoroethyl group, and the like.

The arylene group according to Ar has preferably 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. Specific examples of the arylene group include the same ones as described above. The halo group may substitute part or all of the arylene group, and the halo group is preferably a fluoro group.

n represents an integer of 0 to 3, but is preferably an integer of 0 to 2, more preferably 0 or 1.

p represents an integer of 1 to 8, but an integer of 1 to 6 is preferable, and an integer of 2 to 6 is more preferable.

(C ² ) may have a structural unit other than the structural unit represented by the general formulas (2 ') to (5') (hereinafter also referred to as "another structural unit"). Examples of such structural units include at least one kind of monomer unit selected from the unsaturated monomer (d1) and the unsaturated monomer (d2), which is exemplified in the item of the binder resin (D) described later. Among them, from the viewpoint of dispersibility, it is preferable to have the unsaturated monomer (d2) as a monomer unit, and it is more preferable to have the (meth) acrylic acid ester as a monomer unit.

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

That is, the ratio p of the structural units represented by the formulas (2 ') to (5') and the ratio r of the other structural units in the total structural units of the anion portion according to the component (C ² ) 95 to 50/50 is preferable, and 10/90 to 30/70 is more preferable.

(C ² ) component has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran) of usually 1,000 to 50,000, preferably 3,000 to 20,000 to be. By adopting this form, heat resistance, film properties, electrical characteristics, pattern shape, and resolution can be improved.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the component (C ² ) in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3.0 to be. Herein, Mn is the number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran).

The component (C ² ) can be produced by a known method. For example, the component (C ² ) can be produced by the same method as in the example of JP-A-2012-194466. The present colorant thus obtained is soluble in various organic solvents including propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether, and has excellent heat resistance.

Next, the cation moiety of the component (C ¹ ) and the component (C ² ) 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 extinction coefficient in the visible light region (380 nm to 780 nm) is 10,000 or less, preferably 5,000 or less, more preferably 3,000 or less. Specific examples thereof include ammonium cations, phosphonium cations, sulfonium cations, iodonium cations and diazonium cations. The ammonium cations are preferably organic ammonium cations, and examples thereof include tetramethylammonium, tetraethylammonium, monostearyltrimethylammonium, distearyldimethylammonium, tistearylmonomethylammonium, cetyltrimethylammonium, trioctylmethylammonium , Dioctyldimethylammonium, monolauryltrimethylammonium, dilauryldimethylammonium, trilaurylmethylammonium, triamylbenzylammonium, trihexylbenzylammonium, trioctylbenzylammonium, trilaurylbenzylammonium, benzyldimethylstearylammonium, Benzyldimethyloctylammonium, dialkyl (alkyl is C14 to C18) dimethylammonium, and the like. As the phosphonium cation, an organic phosphonium cation is preferable and, for example, methyltrioctylphosphonium, octyltributylphosphonium, dodecyltributylphosphonium, hexadecyltributylphosphonium, dicyclodioctylphosphonium, etc. Dialkyldialylphosphoniums such as tetraalkylphosphonium and benzyltributylphosphonium; dialkyldialylphosphoniums such as dibutyldiphenylphosphonium; and alkyltriphenylphosphoniums such as butyltriphenylphosphonium, benzyltriphenyl And tetraarylphosphonium such as phosphonium. Examples of the sulfonium cation include the cations described in paragraph [0063] of JP-A No. 2009-073871. Examples of the iodonium cation include the cations described in paragraph [0065] of JP-A No. 2009-073871. Examples of the diazonium cation include the cations described in paragraph [0374] of JP-A No. 2002-33227.

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

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

In the present invention, the specific compound (C) may be used alone or in admixture of two or more, but it is preferable that at least the component (C ² ) is contained in view of heat resistance and electrical characteristics. (C ² ) is preferably a polymer having a structural unit represented by the formula (2), (4) or (5), and the polymer having a structural unit represented by the formula (2) desirable.

In the present invention, (C) of the content of a particular compound is a polymer having a structural unit represented by (C ¹⁾ compound, or (C ²⁾ Formula (2) to (5) represented by the above formula (1) When either polymer is used, it is preferably 10 to 500 parts by mass, more preferably 20 to 300 parts by mass, further preferably 30 to 200 parts by mass, relative to 100 parts by mass of the (A) colorant. (C ¹ ) When any one of the polymer represented by the above formula (1) and the polymer having the structural unit represented by the above formula (2) to (5) is used in combination with (C ² ) A) is preferably 10 to 500 parts by mass, more preferably 15 to 300 parts by mass, further preferably 20 to 200 parts by mass based on 100 parts by mass of the colorant. By adopting this form, a colored hardened film having high heat resistance can be obtained.

In particular, in the case of a coloring composition comprising a dye as a coloring agent, the content of the specific compound (C) is preferably in the following form.

(C ¹ ) as the specific compound (C) is preferably 1.0 to 10 moles, more preferably 1.5 to 8 moles, further more preferably 2 to 7 moles, ^per 1 mole of the dye.

(C ² ) as the specific compound (C), the amount of the anion in the component (C ² ) is preferably 1.0 to 10 moles, more preferably 1.5 to 8 moles, and more preferably 2 to 7 moles per mole of the dye .

(C) When the component (C ¹ ) and the component (C ² ) are used in combination as the specific compound, the total amount of the anion moiety in the (C ¹ ) component and the (C ² ) component is preferably 1.0 to 10 moles per mole of the dye More preferably 1.2 to 8 moles, further more preferably 1.5 to 5 moles.

By adopting this form, a colored hardened film having high heat resistance can be obtained.

The number of moles of the anion moiety in the component (C ² ) can be determined as follows. For example, the component (C ² ) is a binary copolymer of the monomer X and the monomer Y, and the structural units represented by the formulas (2) to (5) are derived from the monomer X and the other structural unit is derived from the monomer Y Occation,

m = W _C / {W _X + (Y _r x W _Y / X _p )}

to be. here,

m: the number of moles of anions in the component (C ² )

W _C : mass of component (C ² )

W _X : molecular weight of monomer X

W _Y : molecular weight of monomer Y

X _p : ratio (mol number) of the structural unit derived from monomer X

Y _r : ratio (molar number) of the structural unit derived from monomer Y

to be.

- (D) Binder Resin -

The coloring composition of the present invention may contain (D) a binder resin. This makes it possible to improve alkali solubility and storage stability of the coloring composition. The binder resin (D) is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as a " carboxyl group-containing polymer ") is preferable. For example, an ethylenically unsaturated monomer having at least one carboxyl group (hereinafter also referred to as " unsaturated monomer (d1) (Hereinafter also referred to as " unsaturated monomer (d2) ").

Examples of the unsaturated monomer (d1) include unsaturated monomers such as (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], omega-carboxypolycaprolactone mono , p-vinylbenzoic acid, and the like.

These unsaturated monomers (d1) may be used alone or in combination of two or more.

As the unsaturated monomer (d2), for example,

N-substituted maleimide such as N-phenylmaleimide, N-cyclohexylmaleimide;

Aromatic vinyl compounds such as styrene,? -Methylstyrene, p-hydroxystyrene, p-hydroxy-? -Methylstyrene, p-vinylbenzyl glycidyl ether and acenaphthylene;

Acrylates such as methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) (Meth) acrylate, polyethylene glycol (having a degree of polymerization of 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (having a degree of polymerization of 2 to 10) (Meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, propylene glycol Acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) Meth) acrylic (Meth) acryloyloxymethyl] -3-ethyloxetane, 3 - [(meth) acryloyloxymethyl] oxetane, 3- The same (meth) acrylic acid ester;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) Vinyl ethers such as;

And a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane.

These unsaturated monomers (d2) may be used alone or in admixture of two or more.

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 mass%, more preferably 10 to 40 mass%. By copolymerizing the unsaturated monomer (d1) in such a range, a colored composition having excellent alkali developability and storage stability can be obtained.

As specific examples of the copolymer of the unsaturated monomer (d1) and the unsaturated monomer (d2), for example, JP-A-7-140654, JP-A-8-259876, Japanese Patent Laid-Open Nos. 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118 And Japanese Patent Application Laid-Open No. 2004-101728.

Further, in the present invention, for example, Japanese Patent Application Laid-Open No. 5-19467, Japanese Patent Application Laid-Open No. 6-230212, Japanese Patent Application Laid-Open No. 7-207211, (Meth) acryloyl groups such as (meth) acryloyl groups on the side chains as disclosed in JP-A-9-325494, JP-A-11-140144, May also be used as a binder resin.

The binder resin in the present invention has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran) of usually 1,000 to 100,000, preferably 3,000 To 50,000. By adopting this form, the residual film ratio, pattern shape, heat resistance, electrical characteristics and resolution of the coating film are further increased, and generation of dried foreign matter at the time of coating can be suppressed to a high level.

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, more preferably 1.0 to 3.0. The term "Mn" as used herein refers to the number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran).

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

In the present invention, the binder resins may be used alone or in combination of two or more.

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. By adopting such a form, the alkali developability, the storage stability of the colored composition, and the chromaticity characteristics can be further enhanced.

- Photopolymerization initiator -

The coloring composition of the present invention may contain a photopolymerization initiator. Thereby, the coloring composition can be imparted with radiation sensitivity. The photopolymerization initiator used in the present invention is a compound which generates active species capable of initiating polymerization of the polymerizable compound by exposure to radiation such as visible light, ultraviolet light, deep ultraviolet light, electron beam, and X-ray.

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, an O-acyloxime compound, an onium salt compound, a benzoin compound, a benzophenone compound, Polynuclear quinone compounds, diazo compounds, imidosulfonate compounds and the like.

In the present invention, the photopolymerization initiator may be used alone or in combination of two or more. As the photopolymerization initiator, at least one member selected from the group consisting of a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, and an O-acyloxime compound is preferable.

Of the preferred photopolymerization initiators in the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like.

Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- -Morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Specific examples of the imidazole 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 non-imidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor in combination in order to improve the sensitivity. The term "hydrogen donor" as used herein means a compound capable of providing a hydrogen atom to a radical generated from a nonimidazole compound by exposure. Examples of the hydrogen donor include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis Ethylamino) benzophenone, and the like. In the present invention, the hydrogen donors may be used singly or in combination of two or more, but it is preferable to use one or more kinds of mercaptan hydrogen donors and one or more amine hydrogen donors in combination to further improve the sensitivity .

Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4 (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) - And triazine compounds having a halomethyl group such as 4,6-bis (trichloromethyl) -s-triazine.

Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O-benzoyloxime), ethanone, 1- [ 1- (9-ethyl-6- (2-methyl-4-tetrahydro-naphthalen- Yl) -, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6-2- -1,3-dioxolanyl) methoxybenzoyl-9H-carbazol-3-yl] -, 1- (O-acetyloxime). NCI-831, NCI-930 (manufactured by ADEKA), DFI-020 and DFI-091 (manufactured by Daito Kikusu Kabushiki Kaisha), and the like can be used as commercially available products of O- It can also be used.

In the present invention, when a photopolymerization initiator other than a non-imidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination. Examples of such sensitizers include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone , Ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino- ) Coumarin, and 4- (diethylamino) chalcone.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, per 100 parts by mass of the polymerizable compound (B). By adopting this form, the curability and the film property can be further enhanced.

-menstruum-

The coloring composition of the present invention contains the above components (A) to (C), and optionally other components, but usually is formulated as a liquid composition by blending a solvent.

The solvent may be appropriately selected and used as long as the components (A) to (C) and other components constituting the coloring composition are dispersed or dissolved, and they are not reacted with these components and have appropriate volatility.

Among these solvents, for example,

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono- -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- Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;

(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol and cyclohexanol;

Ketoalcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, 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 acetate, dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate, 3-methoxybutyl acetate and 3-methyl-3-methoxybutyl acetate;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Alkoxycarboxylates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate and 3-methyl- Acid esters;

Amyl acetate, n-butyl acetate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, propyl acetate, isopropyl acetate, n- , N-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate;

Aromatic hydrocarbons such as toluene and xylene;

Amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone;

And the like.

Among these solvents, (poly) alkylene glycol monoalkyl ethers, lactic acid alkyl esters, (poly) alkylene glycol monoalkyl ether acetates, other ethers, ketones , Diacetates, alkoxycarboxylic acid esters and other esters are preferable, and 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, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, - hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, butyrate n -Butyl, ethyl pyruvate and the like are preferable.

In the present invention, the solvents may be used alone or in admixture of two or more.

Although the content of the solvent is not particularly limited, the total amount of each component excluding the solvent of the coloring composition is preferably 5 to 50 mass%, more preferably 10 to 40 mass%. By using this form, it is possible to obtain a colorant dispersion having good dispersibility and stability, and a coloring composition having good applicability and stability.

-additive-

The coloring composition of the present invention may contain various additives as required.

Examples of the additive include fillers such as glass and alumina; High molecular compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); Surfactants such as fluorine surfactants and silicone surfactants; Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like Adhesion promoters; Di-t-butylphenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4 (3-t-butyl-4-hydroxy-5-methylphenyl) propionyl] -1,1-dimethylethyl] -2,4,8,10-tetraoxa-spiro [5.5] undecane, thiodiethylene bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Antioxidants; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; An anti-aggregation agent such as sodium polyacrylate; Amino-1-pentanol, 3-amino-1,2-propane, 3-amino-1-pentanol, Diol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and the like; A developing agent such as mono [2- (meth) acryloyloxyethyl succinic acid], phthalic acid mono [2- (meth) acryloyloxyethyl], omega -carboxylic polycaprolactone mono (meth) .

Method for producing coloring composition

The coloring composition of the present invention may be prepared by any suitable method, for example, (A) a colorant, (B) a polymerizable compound, and (C ²⁾ component and the (C ¹⁾ at least one selected from the group consisting of components Can be produced by mixing species. In the case of using both a dye and a pigment as a coloring agent, examples of the method for producing the dye include those disclosed in JP-A-2008-58642 and JP-A-2010-132874. Specifically, as disclosed in Japanese Patent Application Laid-Open No. 2010-132874, a dye solution is passed through a first filter, and then a dye solution passed through a first filter is mixed with a separately prepared pigment dispersion or the like, And then passing the coloring composition through a second filter. Further, it is also possible to dissolve the dye, components (B) and (C), and other components to be used as needed in a solvent, pass the obtained solution through the first filter, And then mixing the resultant coloring composition with a pigment dispersion, and passing the obtained coloring composition through a second filter. Further, after the dye solution is passed through the first filter, the dye solution which has passed through the first filter is mixed with and dissolves the components (B) and (C) and, if necessary, the other components used, A method in which the solution is passed through a second filter and further passed through a second filter is mixed with a separately prepared pigment dispersion and the obtained color composition is passed through a third filter.

In the production method of the coloring composition of the present invention, it is preferable that (A) the organic dye is contained as the coloring agent because the desired effect of the present invention is easily obtained.

Colored cured film and manufacturing method thereof

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

Hereinafter, a colored cured film used for a color filter and a method of forming the colored cured film will be described.

As a method of manufacturing a color filter, first, the following method can be mentioned. First, a light-shielding layer (black matrix) is formed on the surface of the substrate so as to partition a portion for forming a pixel as necessary. Subsequently, a blue liquid composition of the radiation sensitive coloring composition of the present invention, for example, is coated on the substrate, and then the liquid is baked and the solvent is evaporated to form a coating film. Subsequently, this coating film is exposed through a photomask and then developed with an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, by post-baking, a pixel array in which a blue pixel pattern (colored cured film) is arranged in a predetermined arrangement is formed.

Subsequently, the respective radiation-sensitive coloring compositions were applied, prebaked, exposed, developed, and post-baked in the same manner as above using each of the green and red radiation sensitive coloring compositions to form a green pixel array and a red And pixel arrays are sequentially formed on the same substrate. Thereby, a color filter in which the three primary color pixel arrays of blue, green, and red are 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 above.

The black matrix can be formed by forming a metal thin film of chromium or the like formed by sputtering or vapor deposition into a desired pattern using a photolithography method. However, by using a radiation-sensitive coloring composition in which a black pigment is dispersed, It may be formed in the same manner as in the pixel formation.

Examples of the substrate used for forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.

If desired, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum deposition, or the like.

When the radiation sensitive coloring composition is applied to a substrate, a suitable coating method such as a spraying method, a roll coating method, a rotation coating method (spin coating method), a slit die coating method (slit coating method) However, it is particularly preferable to employ a spin coating method or a slit die coating method.

The prebaking is usually carried out in combination with reduced pressure drying and heat drying. The reduced pressure drying is usually carried out until 50 to 200 Pa is reached. The conditions for heating and drying are usually about 70 to 110 DEG C for about 1 to 10 minutes.

The coating thickness is a film thickness after drying, usually 0.6 to 8 占 퐉, preferably 1.2 to 5 占 퐉.

Examples of the light source of radiation used when forming at least one kind selected from the pixels and the black matrix are a halogen lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, A lamp light source, and a laser light source such as an argon ion laser, a YAG laser, an XeCl excimer laser, or a nitrogen laser. As an exposure light source, an ultraviolet LED may be used. Radiation with a wavelength in the range of 190 to 450 nm is preferred.

The exposure dose of the radiation is generally preferably from 10 to 10,000 J / m < 2 >.

Examples of the alkali developer include sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] 1,5-diazabicyclo- [4.3.0] -5-nonene and the like are preferable.

To the alkali developing solution, a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like may be added in an appropriate amount. After the alkali development, it is usually washed with water.

As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a puddle (liquid immersion) development method, or the like can be applied. The developing conditions are preferably 5 to 300 seconds at room temperature.

The post-baking condition is usually about 180 to 280 DEG C for about 10 to 60 minutes.

The film thickness of the thus formed pixel is usually 0.5 to 5 占 퐉, preferably 1.0 to 3 占 퐉.

As a second method for manufacturing a color filter, there is a method of obtaining pixels of respective colors by the inkjet method disclosed in Japanese Patent Laid-Open Nos. 7-318723 and 2000-310706 Can be adopted. In this method, a partition wall serving also as a light shielding function is first formed on the surface of the substrate. Subsequently, the liquid composition of the thermosetting coloring composition of the present invention, for example, a blue color is ejected in the formed partition by an ink jet apparatus, followed by prebaking to evaporate the solvent. Subsequently, this coating film is exposed, if necessary, and then post-baked to form a blue pixel pattern.

Subsequently, a green pixel pattern and a red pixel pattern are successively formed on the same substrate using the respective green or red thermosetting coloring compositions in the same manner as described above. Thereby, a color filter in which the three primary color pixel patterns of blue, green, and red are 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 above.

In addition, the partition wall has a thicker film thickness than that of the black matrix used in the above-mentioned first method, because it functions not only to shield the light-shielding function but also to prevent the thermosetting coloring composition of each color discharged in the partition from being mixed. Thus, the barrier ribs are usually formed using a black radia radiation composition.

The substrate or radiation source used for forming the color filter, and the methods and conditions for pre-baking and post-baking are the same as those for the first method described above. Thus, the film thickness of the pixel formed by the ink-jet method is about the same as the height of the partition wall.

A protective film is formed on the thus-obtained pixel pattern as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer may be formed to form a color filter. The spacer is usually formed using a radiation sensitive composition, but it may also be a spacer (black spacer) having light shielding properties. In this case, a coloring and radiation-sensitive composition in which a black coloring agent is dispersed is used, but the coloring composition of the present invention can be suitably used for forming such a black spacer.

The coloring composition of the present invention can be suitably used for forming any colored cured film such as each color pixel, a black matrix, and a black spacer used in the color filter.

The color filter including the colored cured film of the present invention thus formed is extremely useful for a color liquid crystal display element, a color (TV camera) image pickup tube element, a color sensor, an organic EL display element, Do. The display device described later may be one having at least one colored cured film formed using the coloring composition of the present invention.

Display element

The display element of the present invention comprises 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 an electronic paper.

The color liquid crystal display element having the colored cured film of the present invention may be of a transmissive type or a reflective type, and a suitable structure may be adopted. For example, the color filter may be formed on a substrate different from the substrate on which the thin film transistor (TFT) is disposed, and a structure in which the substrate on which the driving substrate and the color filter are formed faces each other via the liquid crystal layer A substrate on which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate on which ITO (indium oxide doped with indium oxide) electrode is formed are opposed to each other with a liquid crystal layer interposed therebetween May be employed. The latter structure has the advantage that the aperture ratio can be remarkably improved and a bright and high-precision liquid crystal display element can be obtained. When adopting the latter structure, the black matrix or the black spacer may be formed on either the substrate on which the color filter is formed or the substrate on which the ITO electrode is formed.

The color liquid crystal display device having the colored cured film of the present invention may have a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). Examples of white LEDs include white LEDs that combine red LEDs, green LEDs, and blue LEDs to obtain white light by mixing colors, white LEDs that combine blue LEDs, red LEDs, and green phosphors to obtain white light by mixing colors, A white LED that obtains white light by mixing a red light emitting phosphor and a green light emitting phosphor, a white LED that obtains white light by mixing a blue LED and a YAG phosphor, a blue LED, an orange light emitting phosphor, and a green light emitting phosphor, A white LED for obtaining white light, an ultraviolet LED, a white LED for obtaining a white light by mixing a red light emitting phosphor, a green light emitting phosphor and a blue light emitting phosphor in combination, and the like.

The color liquid crystal display device having the colored cured film of the present invention may be applied to a color liquid crystal display device such as TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In- Planes Switching) type, VA (Vertical Alignment) Compensated Birefringence) type liquid crystal mode can be applied.

Further, the organic EL display device having the colored cured film of the present invention can have a suitable structure, and includes, for example, a structure disclosed in Japanese Patent Laid-Open Publication No. 11-307242.

Further, the electronic paper having the colored hardened film of the present invention can have a suitable structure, for example, a structure disclosed in Japanese Patent Laid-Open No. 2007-41169.

<Examples>

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

&Lt; Synthesis of dyes >

Synthesis Example 1

With reference to Example 2 of WO 2010/123071, the following compounds were obtained. This is called dye A. Dye A is a triarylmethane-based basic dye.

Synthesis Example 2

With reference to Synthesis Example 1 of JP-A-2012-107192, the following compounds were obtained. This is called dye B. Dye B is a xanthene basic dye.

&Lt; Synthesis of Component (C ² ) >

Synthesis Example 3

(Synthesis of monomer (1)]

According to the following reaction formula, Monomer (1) was synthesized by the following procedure.

A stirrer, a thermometer, a dropping funnel and a reflux condenser were placed in a 300-mL four-necked flask equipped with a stirrer, and 14.5 g (0.080 mol) of sodium aditionate and 12.1 g (0.12 mol) of triethylamine were placed. Then, while stirring, a solution of 9.56 g (0.040 mole) of 5-bromo-4,4,5,5-tetrafluoropentan-l-ol dissolved in 80 g of acetonitrile was added dropwise from the dropping funnel over 15 minutes. Subsequently, the mixture was heated in an oil bath and allowed to react at 60 占 폚 for 5 hours under a nitrogen stream. After completion of the reaction, the reaction mixture was cooled to 25 캜 and allowed to stand for 15 minutes. The organic layer was separated, further 100 g of acetonitrile was added to the aqueous layer, and the organic layer was separated and concentrated under reduced pressure together with the previous organic layer. The obtained residue was dried under reduced pressure at 40 占 폚 to obtain 11.4 g (0.0350 mol, yield: 88%) of viscous oily substance. ^It was confirmed by the measurement of ¹ H and ¹⁹ F-NMR spectra (solvent: deuterated methanol) that the obtained compound was the compound represented by the above formula (1-b).

Subsequently, 80 ml of water, 60 mg of sodium tungstate dihydrate and 4.5 g of 30% by mass aqueous hydrogen peroxide solution were added to the compound (1-b) obtained above, and the mixture was heated at 60 占 폚 for 1 hour. After completion of the reaction, the reaction mixture was cooled to 25 DEG C and sodium hydrogen sulfite was added to decompose excess hydrogen peroxide, followed by concentration under reduced pressure. The residue was dissolved in methanol and the insolubles were filtered off and the resulting solution was concentrated under reduced pressure. The obtained residue was dried under reduced pressure at 50 캜 to obtain 9.90 g (0.0290 mol, yield: 83%) of viscous oily substance. ^It was confirmed by the measurement of ¹ H and ¹⁹ F-NMR spectra (solvent: deuterated methanol) that the obtained compound was the 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, and the compound (1-c) obtained above and 50 mL of dichloromethane were added. The mixture was cooled to 5 캜 under a nitrogen stream and stirred. Then, 4.33 g (0.043 mol) of triethylamine was added, stirred for a while, and 3.58 g (0.034 mol) of methacrylic acid chloride was added dropwise over 15 minutes. Thereafter, the inner temperature was heated to 25 캜 and stirred for 6 hours. Thereafter, the reaction mixture was poured into 100 g of water to separate the 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 resulting residue was purified by column chromatography to obtain 10.1 g (0.0247 mol, yield: 85%) of viscous oily substance. ^It was confirmed by the measurement of ¹ H and ¹⁹ F-NMR spectra (solvent: deuterated chloroform) that the obtained compound was a compound represented by the above formula. This is referred to as monomer (1).

[Synthesis of Polymer (1)]

4.50 g of the monomer (1), 5.50 g of methyl methacrylate, 0.713 g of? -Thioglycerol and 20 g of cyclohexanone were mixed and uniformly dissolved. The solution was heated to 100 占 폚 while stirring under a nitrogen stream. While stirring at the same temperature, a solution obtained by dissolving 0.541 g of?,? '- azobisisobutyronitrile in 10.4 g of cyclohexanone was added dropwise over 30 minutes. After completion of the dropwise addition, stirring was further continued at the same temperature for 3 hours Respectively. After cooling the reaction solution to room temperature, 60 g of acetone was added to obtain a homogeneous solution, which was added dropwise to 1.1 L of hexane. The resultant precipitate was filtered off and washed with hexane. The obtained solid was dried under reduced pressure at 50 캜 to obtain 8.90 g of a polymer represented by the above structural formula. The obtained polymer had Mw of 7,900 and Mn of 3,600, and it was confirmed by the ¹ H-NMR spectrum (solvent: deuterated acetone) measurement that the ratio of x and y was 1 / 4.91 as the molar ratio (x / y). This is referred to as 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)]

7.51 g of the polymer (2) represented by the structural formula was obtained in the same manner as in Synthesis Example 1, except that 4.57 g of the following monomer (2) was used instead of the monomer (1) in the synthesis of the polymer (1). The obtained polymer (2) had Mw of 8,600 and Mn of 3,700, and it was confirmed by a ¹ H-NMR spectrum (solvent: deuterated acetone) measurement that the ratio of x and y was 1 / 4.30 as a mole ratio (x / Respectively. The monomer (2) was synthesized according to Synthesis Example 1 of JP-A-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)]

In the synthesis of the polymer (1), 7.51 g of the polymer (3) represented by the structural formula was obtained in the same manner as in Synthesis Example 1, except that 2.39 g of the vinylsulfonic acid triethylamine salt was used instead of the monomer (1). The obtained polymer (3) had Mw of 8,200 and Mn of 3,800, and it was confirmed by a ¹ H-NMR spectrum (solvent: deuterated acetone) measurement that the ratio of x and y was 1 / 4.66 as a molar ratio (x / Respectively.

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).

&Lt; Preparation of colorant solution >

Production Example 1

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

Production Example 2

C.I. 10 parts by mass of 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).

Production Example 3

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

&Lt; Synthesis of binder resin >

Synthesis Example 6

To a flask equipped with a cooling tube and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was charged and replaced with nitrogen. 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, 15 parts by mass of 2-hydroxyethyl methacrylate 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 2,2'-azobis (2,4-dimethyl Valeronitrile) (6 parts by mass) was added dropwise over 1 hour, and the mixture was polymerized at this temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 占 폚 and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The resulting binder resin had Mw of 12,200 and Mn of 6,500. This binder resin is referred to as &quot; binder resin (D1) &quot;.

&Lt; Production of Pigment Dispersion >

Production Example 4

12 parts by mass of a mixture of CI Pigment Blue 15: 6 / CI Pigment Violet 23 = 80/20 (by mass ratio) as a colorant and 100 parts by mass of BIG 2001 (Dispersive: BYK, ), 0.8 parts by mass of Soluspus 12000 as a dispersing aid, and 78.9 parts by mass of propylene glycol monomethyl ether acetate as a solvent were treated with a bead mill to prepare a pigment dispersion (a-1).

&Lt; Preparation and evaluation of colored composition >

Example 1

13.5 parts by mass of the pigment dispersion (a-1) and 7.2 parts by mass of the dye solution (A-1) as the coloring agent, 30.0 parts by mass of the binder resin (D1) solution as the binder resin (B), 30 parts by mass of the dipentaerythritol 13.7 parts by mass of a mixture of lithol hexaacrylate and dipentaerythritol pentaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Kabushiki Kaisha) was used, and as a component (C ¹ ), trifluoromethane sulfonimide acid , 1.8 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, -930 (manufactured by Adeka Co., Ltd.), 0.05 part by mass of Megaface F-554 (manufactured by DIC Corporation) as a fluorine surfactant, and propylene glycol monomethyl ether acetate as a solvent were mixed to obtain a solid content concentration of 20 Mass% of coloring composition (S-1) was prepared All.

Evaluation of heat resistance

The coloring composition (S-1) was coated on a soda glass substrate having a SiO ₂ film formed on the surface thereof to prevent elution of sodium ions using a spin coater, prebaked on a hot plate at 90 캜 for 2 minutes, Thereby forming a coating film having a film thickness of 2.5 mu m.

Subsequently, after cooling the substrate to room temperature, radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed to an exposure amount of 400 J / m 2 through each photomask using a high-pressure mercury lamp Respectively. Subsequently, a developer containing 0.04 mass% potassium hydroxide aqueous solution at 23 占 폚 was ejected onto the substrate at a developing pressure of 1 kgfcm2 / (nozzle diameter of 1 mm) to perform showering for 90 seconds. Thereafter, this substrate was washed with ultrapure water, air-dried, and further baked in a clean oven at 200 캜 for 30 minutes to form a dot pattern on the substrate.

The chromaticity coordinate value (x, y) and the magnetic pole value (Y) in the CIE colorimetric system were measured for the obtained dot pattern using a color analyzer (MCPD2000 manufactured by Otsuka Denshi Co., Ltd.) Respectively.

Subsequently, after the substrate was further baked at 230 캜 for 90 minutes, the chromaticity coordinate value (x, y) and the stimulus value (Y) were measured, and the color change before and after further baking, that is,? E ^* _ab was evaluated . As a result, the case where the value of DELTA E ^* _ab was less than 2.0 was evaluated as &quot;?&Quot;, the case where the value of DELTA E ^* _ab was less than 2.0 was evaluated as & The evaluation results are shown in Table 1. Further, the smaller the? E ^* _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 kind of the dye solution and / or the content of the component (C ¹ ) in Example 1 were changed as shown in Table 1. Subsequently, the 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 component (C ² ) shown in Table 2 was used instead of the component (C ¹ ) in Example 1. Subsequently, the heat resistance was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Claims (7)

(A) a colorant, (B) polymerizing a coloring composition containing a compound (C ²⁾ to the formula (2), (3), (4) or (5) any of the polymer 1 having a structural unit represented by the &Lt; / RTI &gt;

(In the formulas (2) to (5)
R ¹ , R ¹¹ , R ²¹ and R ³¹ independently represent a methyl group, a trifluoromethyl group or a hydrogen atom,
R ¹² and R ¹³ independently represent a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group,
R _f is a hydrogen atom, a halo group, or a substituted or unsubstituted hydrocarbon group, at least one of R _f is an alkyl group having a fluorine atom or a fluorine atom,
Y represents a divalent group or a single bond,
D represents a divalent organic group,
W represents a monovalent group having a linking group containing a carbon atom, a hydrogen atom or an atom other than a halogen atom between the CC bond of a halo group, a halogenated hydrocarbon group or a halogenated hydrocarbon group,
A represents a divalent group or a single bond,
G represents a divalent organic group containing a fluorine atom, or a single bond,
Ar represents a substituted arylene group having at least one halo group,
E represents a divalent group or a 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) According to claim 1, (C ²⁾ Formula (2), (3), (4) or (5) the content of polymer having a structural unit represented by (A) 10 with respect to a coloring agent 100 parts by weight to 500 Coloring composition. (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 ^{&lt; + &} gt ^; 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 alkylaryl group,
M represents a nitrogen atom, a phosphorus atom, a boron atom, an arsenic atom or an antimony atom,
a represents an integer of 1 to 6,
b represents an integer of 0 to 5,
Provided that a + b is 2, 4 or 6, and when plural Z and R ⁰ are present, they may be the same or different) The coloring composition according to any one of claims 1 to 3, wherein (A) the colorant comprises a dye. (A) a colorant, (B) a polymerizable compound, and at least one member selected from the group consisting of a component (C ² ) and a component (C ¹ ). A colored cured film formed using the coloring composition according to any one of claims 1 to 4. A display device comprising the colored cured film according to claim 6.