KR101892777B1 - Colored composition, color filter, and display element - Google Patents

Abstract

The present invention provides a coloring composition capable of producing a color filter excellent in solvent resistance as well as heat resistance. The coloring composition of the present invention is a coloring composition comprising (A) a colorant, (B) a binder resin, (C) a compound having two or more ethylenically unsaturated groups, and (D) a photopolymerization initiator, wherein (A) , A halogenated hydrocarbon group and a halosulfonyl group, and (D) a photocatalytic initiator, which contains an intermolecular hydrogen-derived photo radical initiator. .

Description

COLORED COMPOSITION, COLOR FILTER, AND DISPLAY ELEMENT [0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coloring composition, a color filter, and a display device, and more particularly to a coloring composition, a color filter and a display device which are suitably used for a color filter such as a transmissive or reflective color liquid crystal display device, A color filter having a coloring layer formed using the coloring composition, and a display device having the color filter.

In the production of a color filter using a coloring and radiation-sensitive composition, a coloring and radiation-sensitive composition of a pigment dispersion type is coated on a substrate and dried, and then the dry film is irradiated with a desired pattern (hereinafter referred to as "exposure" (Refer to Patent Documents 1 and 2) are known. Further, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (Patent Document 3) is also known.

However, it is known that it is effective to use a dye as a coloring agent in order to realize high brightness and high color purity of a display element or high-definition of a solid-state image pickup element. However, when a dye is used as a coloring agent, there is a problem in that heat resistance and light resistance are deteriorated as compared with the case of using a pigment. In order to solve such a problem, for example, Patent Document 4 proposes the use of a triarylmethane compound having a bistrifluoromethane sulfonylimide anion or a tris trifluoromethanesulfonylmethane 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 International Publication No. 2010/123071

However, when a basic dye having an anion moiety having a group having a strong electron attractive force as proposed in Patent Document 4 is used, there is a problem that the solvent resistance of the colored layer constituting the color filter is remarkably lowered. From the above background, it is strongly desired to develop a coloring composition capable of producing a color filter having excellent solvent resistance as well as heat resistance.

Accordingly, an object of the present invention is to provide a coloring composition capable of producing a color filter having excellent heat resistance and excellent solvent resistance. Another object of the present invention is to provide a color filter comprising a coloring layer formed using the coloring composition, and a display device having the color filter.

As a result of intensive studies, the present inventors have found that the aforementioned problems can be solved by using a basic dye having a specific anion moiety in combination with a specific photopolymerization initiator.

That is, the present invention relates to a colored composition comprising (A) a colorant, (B) a binder resin, (C) a compound having two or more ethylenically unsaturated groups, and (D)

(Hereinafter referred to as " specific coloring agent ") having at least one electron-withdrawing group selected from the group consisting of cyano group, halogenated hydrocarbon group and halosulfonyl group as the coloring agent (A)

(D) a photo-radical initiator which is an intermolecular hydrogen-drawing type as a photopolymerization initiator.

In the present invention, it is preferable to contain a non-imidazole-based compound as the intermolecular hydrogen-derived photo radical initiator.

The present invention also provides a color filter comprising a colored layer formed using the coloring composition, and a display element comprising the color filter. Here, the " colored layer " means each color pixel, a black matrix, a black spacer, etc. used in the color filter.

When the coloring composition of the present invention is used, a coloring layer having excellent heat resistance and excellent solvent resistance can be formed.

Therefore, the coloring composition of the present invention is suitable for the production of various color filters including a color filter for a color liquid crystal display element, a color filter for color separation of a solid-state image pickup element, a color filter for an organic EL display element, Can be used.

Hereinafter, the present invention will be described in detail.

Coloring composition

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

- (A) Colorant -

The coloring composition of the present invention is characterized by containing a basic colorant having an anion having at least one electron-withdrawing group selected from the group consisting of a specific colorant, namely, a cyano group, a halogenated hydrocarbon group and a halosulfonyl group as a colorant. The basic colorant is an ionic coloring agent in which the cation part is a chromophore, and is preferably a basic dye.

In the coloring composition of the present invention, the specific coloring agents may be used alone or in combination of two or more.

First, an anion portion in a specific coloring agent will be described.

The anion moiety in a specific colorant is not particularly limited as long as it is an anion having at least one electron-withdrawing group selected from the group consisting of a cyano group, a halogenated hydrocarbon group and a halosulfonyl group, and examples thereof include the following formulas (1a) to ). ≪ / RTI >

(In the formula (1a), R ¹ represents a halogenated hydrocarbon group which may have a linking group, and a represents an integer of 1 or more.)

(In the formula (1b), R ² independently represents a cyano group, a halosulfonyl group or a halogenated alkylsulfonyl group which may have a linking group, and when R ² is a halogenated alkylsulfonyl group which may have a linking group, R ² They may be bonded to each other to form a ring.)

(In the formula (1c), R ³ represents a halogenated hydrocarbon group which may have a linking group, P represents a phosphorus atom, Hal represents a halo group, and when a plurality of R ³ and Hal are present, they may be the same or different. and b represents an integer of 1 to 6.)

(In the formula (1d), R ⁴ represents a halogenated hydrocarbon group or cyano group which may have a linking group, B represents a boron atom, Hal represents a halo group, and when a plurality of R ⁴ and Hal are present, C represents an integer of 1 to 4).

(In the formula (1e), R ⁵ independently represents a halosulfonyl group or a halogenated alkylsulfonyl group.)

Examples of the hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group of R ¹ , R ³ and R ⁴ in formula (1a) (when a = 1), formula (1c) and formula (1d) (Iv) an aromatic hydrocarbon group, (v) an alicyclic hydrocarbon group, (e) an alicyclic hydrocarbon group having an alicyclic hydrocarbon group as a substituent (hereinafter referred to as an alicyclic hydrocarbon substituted aliphatic hydrocarbon group) (Vi) an aliphatic hydrocarbon group having an aromatic hydrocarbon group as a substituent (hereinafter referred to as an " aromatic hydrocarbon-substituted aliphatic hydrocarbon group ") as an aliphatic hydrocarbon group-substituted aromatic hydrocarbon group (hereinafter referred to as " aliphatic hydrocarbon- And the like. The hydrocarbon group constituting the skeleton of R ¹ , R ³ and R ⁴ is preferably the following characteristic group from the viewpoint of solubility in an organic solvent.

(i) The aliphatic hydrocarbon group is preferably an alkyl group, and may be linear or branched. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 20, especially 1 to 8. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl and octyl. As the alicyclic hydrocarbon group (ii), an alicyclic saturated hydrocarbon group is preferable, and the number of carbon atoms thereof is preferably 3 to 20, especially 3 to 12. Specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The alicyclic hydrocarbon-substituted aliphatic hydrocarbon group (iii) is preferably an alicyclic saturated hydrocarbon-substituted alkyl group, and the alkyl group may be linear or branched. The number of carbon atoms of the alicyclic hydrocarbon-substituted aliphatic hydrocarbon group is preferably 4 to 20, especially 6 to 14. Specific examples thereof include a cyclohexylmethyl group and a cyclohexylethyl group. The aromatic hydrocarbon group (iv) preferably has 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. Specific examples thereof include a phenyl group and a naphthyl group. (v) The aliphatic hydrocarbon-substituted aromatic hydrocarbon group is preferably an alkyl-substituted phenyl group, and the alkyl moiety may be linear or branched. The number of carbon atoms of the aliphatic hydrocarbon-substituted aromatic hydrocarbon group is preferably 7 to 30, especially 7 to 20. Specific examples include a tolyl group, a xylyl group, an ethylphenyl group, an isopropylphenyl group, and a nonylphenyl group. As the aromatic hydrocarbon-substituted aliphatic hydrocarbon group (vi), an aralkyl group is preferable, and its carbon number is preferably 7 to 30, especially 7 to 20. Specific examples thereof include a benzyl group and a phenethyl group.

(Iv) an aromatic hydrocarbon group, (v) an aliphatic hydrocarbon-substituted aromatic hydrocarbon group, or (iii) an alicyclic hydrocarbon-substituted aromatic hydrocarbon group, (vi) an aromatic hydrocarbon-substituted aliphatic hydrocarbon group is preferable, and an alkyl 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 halogen in the halogenated hydrocarbon group, fluorine is preferable from the viewpoint of the heat resistance of the colorant. By selecting fluorine as a substituent, it is considered that the anion portion of the present colorant becomes a conjugate base of an organic acid having a stronger acidity than that of the present colorant, so that a salt having a stronger ion binding force is formed and the heat resistance is enhanced.

Examples of the linking group in the halogenated hydrocarbon group of R ¹ , R ³ and R ⁴ and the halogenated alkylsulfonyl group of R ² include -O-, -S-, -CO-, -COO-, -CONH-, -SO ₂ - and so on. The carbon number in the paragraph <0034> means the total carbon number of the portion excluding the carbon atoms constituting the linking group.

In the present invention, from the viewpoint of the heat resistance of the coloring agent, R ¹ , R ³ and R ⁴ are preferably groups represented by the following formula (1-1) or (1-2) The group represented by the following formula (1-1) which forms a base is particularly preferable.

(Wherein R ¹⁹ 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 ²⁰ COOR ²¹ - or R ²⁰ COOR ²¹ CFH- (R ²⁰ Represents an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group or a substituted or unsubstituted aryl group, and R ²¹ represents an alkanediyl group, n represents an integer of 1 or more, and " * " )

(In formula (1-2), R ²² to R ²⁶ are each independently represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluorinated alkyl or alkoxy, "*" represents a bonding hand. However, R ²² to R ^And at least one of them is a fluorine atom or an alkyl fluoride group.

In the formulas (1-1) and (1-2), the alkyl group, fluorinated alkyl group, alkoxy group and fluorinated alkoxy group preferably have 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 8 carbon atoms. In the formula (1-1), the number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 12, more preferably 3 to 7.

In the formula (1-1), R ^{19 is preferably a} fluorine atom, an alkyl fluoride group, an alicyclic hydrocarbon group, an alkoxy fluoride group, R ²⁰ COOR ²¹ - or R ²⁰ COOR ²¹ CFH-, a fluorine atom, an alicyclic hydrocarbon group, Particularly preferred are perfluoroalkoxy groups, R ²⁰ COOCH ₂ CH ₂ - or R ²⁰ COOCH ₂ CH ₂ CFH-.

R ²⁰ represents an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group, or a substituted or unsubstituted aryl group, but the alkyl group may be linear or branched, and the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms . The alicyclic hydrocarbon group may be a 2 to 4-membered bridged alicyclic hydrocarbon group, and the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. As the heteroaryl group, a group composed of a 5-10 membered aromatic heterocycle containing at least one hetero atom selected from a nitrogen atom, an oxygen atom and a sulfur atom is preferable. As the aryl group, an aryl group having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms is preferable, and a phenyl group is particularly preferable. Examples of the substituent include, 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, , The substituents may be the same or different.

R ²¹ represents an alkanediyl group, and its carbon number is preferably 1 to 12, more preferably 1 to 6. Specific examples include methylene, ethylene, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane- A butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,4-diyl group, a pentane-1,5-diyl group, A hexane-1,5-diyl group, and a hexane-1,6-diyne group. Among them, an ethylene group is preferable from the viewpoint of easiness of production.

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

In the formula (1-2), it is preferable that at least three of R ²² to R ²⁶ are a fluorine atom or an alkyl fluoride group.

Examples of the halosulfonyl group of R ² and R ^{5 in} the formulas (1b) and (1e) include FSO ₂ group, ClSO ₂ group, BrSO ₂ group and ISO ₂ group. Among them, FSO ₂ group is preferable Do.

In the formulas (1b) and (1e), the alkyl group constituting the skeleton of the halogenated alkylsulfonyl group of R ² and R ⁵ may be linear or branched and preferably has 1 to 8 carbon atoms. Specific examples of the alkyl group include the same alkyl groups as those of the halogenated hydrocarbon group. The halo group in the halogenated alkylsulfonyl group is preferably a fluoro group.

As the halogenated alkylsulfonyl group, a perfluoroalkylsulfonyl group is preferable, and for example, 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, may be _{CF 3 CF 2 CF 2 CF 2} SO 2 _{group, (CF 3) 2 CFCF 2} SO 2 group, a CF ₃ CF ₂ (CF _{3) 2} CFSO group, (CF _{3) 3} CSO ₂ groups. Among them, CF ₃ SO ₂ group is preferable.

The anion represented by the above formula (1a) is a group in which a SO ₃ - group is substituted for a halogenated hydrocarbon group of R ¹ , and a is preferably an integer of 1 to 4, and particularly preferably 1 or 2. In this case, the halogenated hydrocarbon group of R &^lt; 1 &gt; may be a 1 to 4-valent halogenated hydrocarbon group. Examples of the 2- to 4-valent halogenated hydrocarbon group include groups (i) to (vi) exemplified in the hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group, Of which one to three hydrogen atoms have been removed from the hydrocarbon group.

Specific examples of the anion represented by the formula (1a) include anions represented by the following formulas (1a-1) and (1a-2).

(In the formula (1a-1), R ^1a represents a monovalent halogenated hydrocarbon group which may have a linking group.

In formula (1a-2), R ^1b represents a halogenated alkanediyl group which may have a linking group.)

Representative examples of the anion represented by the above formula (1a-1) include, for example, the anions shown in the following group a and group b.

[Compound group a]

[Compound group b]

Representative examples of the anion represented by the above formula (1a-2) include, for example, the anions shown in the following group of compounds c.

[Compound group c]

Representative examples of the anion represented by the formula (1b) include, 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 }; ^-, and the like ^{_{-, [(FSO 2) N}} {CF 3 CF 2 (CF 3) CFSO 2}] -, [(FSO 2) N {(CF 3) 3 CSO 2}].

[Compound group d]

Representative examples of anions represented by the above formula (1c) include, for example, (CF ₃ ) ₃ PF ₃ ^- , (C ₂ F ₅ ) ₂ PF ₄ ^- , (C ₂ F ₅ ) ₃ PF ₃ ^- , _{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 ^- . Among _{these, (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 - .

Examples representative of the anion represented by the formula (1d), for example ^{_{(CF 3) 4 B -,}} (CF 3) 3 BF -, (CF 3) 2 BF 2 -, (CF 3) BF 3 -, ( ^{_{C 2 F 5) 4 B -}} , (C 2 F 5) 3 BF -, (C 2 F 5) BF 3 -, (C 2 F 5) 2 BF 2 -, (CF 3) (C 2 F 5) _{^{2 BF -, (C 6 F}} 5) 4 B -, [(CF 3) 2 C 6 H 3] 4 B -, (CF 3 C 6 H 4) 4 B -, (C 6 F 5) 2 BF 2 _{^{-, (C 6 F 5)}} BF 3 -, (C 6 H 3 F 2) 4 B -, B (CN) 4 -, B (CN) F 3 -, B (CN) 2 F 2 -, B ( ^{_{CN) 3 F -, (CF}} 3) 3 B (CN) -, (CF 3) 2 B (CN) 2 -, (C 2 F 5) 3 B (CN) -, (C 2 F 5) 2 B ^{_{(CN) 2 -, (nC}} 3 F 7) 3 B (CN) -, (nC 4 F 9) 3 B (CN) -, (nC 4 F 9) 2 B (CN) 2 -, (nC 6 F ^{_{13) 3 B (CN) -}} , (CHF 2) 3 B (CN) -, (CHF 2) 2 B (CN) 2 -, (CH 2 CF 3) 3 B (CN) -, (CH 2 CF 3 ^{_{) 2 B (CN) 2 -}} , (CH 2 C 2 F 5) 3 B (CN) -, (CH 2 C 2 F 5) 2 B (CN) 2 -, (CH 2 CH 2 C 3 F 7) ₂ B (CN) ₂ ^- , (nC ₃ F ₇ CH ₂ ) ₂ B (CN) ₂ ^- , and (C ₆ H ₅ ) ₃ B (CN) ^- . Among ^{_{these, B (CN) 4 -,}} B (CN) F 3 -, B (CN) 2 F 2 -, B (CN) 3 F -, (CF 3) 4 B -, (C 6 F 5) 4 B ^- , and [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ^- are preferable.

Examples representative of the anion represented by the general formula (1e), for example _{(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 -, (ClSO 2) 3 C -, (BrSO 2) 3 C -, ( ISO ₂ ) ₃ C ^- . Among them, (CF ₃ SO ₂ ) ₃ C ^- is preferable.

When the specific colorant is a basic colorant having the specific anion moiety as described above, the cation moiety is not particularly limited, and examples thereof include an azine colorant, an oxazine colorant, a thiazine colorant, an azo colorant, an anthraquinone colorant, Based coloring agents, diarylmethane-based coloring agents, triarylmethane-based coloring agents, phthalocyanine-based coloring agents, ketone-based coloring agents, thiazole-based coloring agents, acridine-based coloring agents, quinoline-based coloring agents, cyanine-based coloring agents and methine-based coloring agents.

Among these, a xanthene colorant and a triarylmethane colorant are preferable, and it is particularly preferable to use a triarylmethane colorant together with a photo-radical initiator of an intermolecular hydrogen-drawing type in that a desired effect can be obtained more remarkably.

The triarylmethane type colorant preferably has a cation represented by the following formula (2). Cations represented by the following formula (2) include various resonance structures. In the present specification, the cations represented by the following formula (2) are equivalent to the cations represented by the following formula. Hereinafter, in the case where a resonance structure exists also for a cation represented by each formula, it is assumed to be equivalent to a cation represented by the formula.

(Ar represents an arene ring,

R ⁶ and R ⁷ independently represent a hydrogen atom, a straight or cyclic alkyl group having 1 to 8 carbon atoms, a phenyl group, or a group having an ethylenically unsaturated bond,

R ⁸ and R ⁹ independently represent a hydrogen atom, a straight or cyclic alkyl group having 1 to 8 carbon atoms, a phenyl group, or a group having an ethylenically unsaturated bond,

R ¹⁰ represents a hydrogen atom, a chlorine atom, a straight or cyclic alkyl group of 1 to 8 carbon atoms or -COOR ¹⁷ (R ¹⁷ represents a hydrogen atom or a straight or cyclic alkyl group of 1 to 8 carbon atoms)

R ¹¹ and R ¹⁴ independently represent a hydrogen atom, a straight or cyclic alkyl group having 1 to 8 carbon atoms, or R ¹¹ and R ¹⁴ are integrated to form a sulfur atom,

R ¹² and R ¹³ independently represent a hydrogen atom, a chlorine atom, or a straight or cyclic alkyl group having 1 to 8 carbon atoms,

Y represents a hydrogen atom or a group represented by the following formula (3)

R ¹⁵ and R ¹⁶ independently represent a hydrogen atom, a straight or cyclic alkyl group having 1 to 8 carbon atoms, a phenyl group, or a group having an ethylenically unsaturated bond.

As the arene ring in Ar, an arene ring having 6 to 20, more preferably 6 to 10 carbon atoms is preferable, and specific examples thereof include a benzene ring, a naphthalene ring, a biphenyl ring, and an anthracene ring.

R ⁶ to R ¹⁴ (including the R ¹⁷ in -COOR ^17), R ^15, and as the carbon number of chain or cyclic alkyl group of 1 to 8 in the R ^16, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl A cyclohexyl group, a cyclohexyl group, a cycloheptyl group, a cycloheptyl group, a cycloheptyl group, a cyclohexyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, A tert-butyl group, an isooctyl group, a tert-octyl group, and a 2-ethylhexyl group.

Examples of the group having an ethylenically unsaturated bond in R ⁶ to R ⁹ , R ¹⁵ and R ¹⁶ include, but are not limited to, CH ₂ ═CH-COO-R ¹⁸ -, CH ₂ ═C (CH ₃ ) R ¹⁸ -, CH ₂ ═CH-Ph-R ¹⁸ -, CH ₂ ═C (CH ₃ ) -Ph-R ¹⁸ - and CH ₂ ═CH-CO- wherein R ¹⁸ is an alkyl having 1 to 4 carbon atoms And Ph represents a phenylene group), and the like.

Examples of the alkanediyl group having 1 to 4 carbon atoms for R ¹⁸ include a methylene group, an ethylene group, a trimethylene group, a propylene group, and a tetramethylene group.

Among the cations represented by the above formula (2), cations represented by the following formula (4) are particularly preferred from the viewpoint of improvement in luminance and color purity.

(In formula ^{(4), R 6, R} 7, R 8, R 9, R 15 and R ¹⁶ is ^{R 6, R 7, R 8} , R 9, R 15 in the above formulas (2) and (3) And R ^16. )

In the above formula (4), R ⁶ , R ⁷ , R ¹⁵ and R ¹⁶ are preferably a linear or cyclic alkyl group having 1 to 8 carbon atoms and more preferably 1 to 6 carbon atoms, and R ⁸ preferably has 1 to 8 carbon atoms, Preferably a straight or cyclic alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ⁹ is preferably a straight or cyclic alkyl group having 1 to 6 carbon atoms, more preferably 1 to 6 carbon atoms, or a hydrogen atom.

Representative examples of the cation represented by the above formula (2) include, for example, the cations shown in the following group of compounds e.

[Compound group e]

Examples of the coloring agent other than the triarylmethane coloring agent include a methine-based coloring agent having a cation described in Chemical Formula (I) of Japanese Patent Laid-Open Publication No. 2010-209191, a methine coloring agent having a cation represented by Chemical Formula (1) And a xanthene-based colorant having a cation described in JP-A-

The specific coloring agent can be produced by a known method. For example, it can be produced by referring to Japanese Patent Application Laid-Open No. 2007-503477 and International Publication No. 2010/123071.

When a specific colorant is, for example, a triarylmethane-based dye, it is blue to red when it is dissolved in an organic solvent. Therefore, by using the compound alone or in combination with other coloring agents, for example, , And a coloring composition for forming a black colored layer. In addition, when a xanthene colorant is used, it is purple to red when it is dissolved in an organic solvent. Therefore, when the above compound is used alone or mixed with another colorant appropriately, for example, a blue pixel, a red pixel, And the like.

As the other coloring agents, colors and materials can be appropriately selected depending on the application. Specifically, it is possible to use any of pigments, dyes and natural pigments. However, since the coloring layer constituting the color filter is required to have high color purity, brightness, contrast, light shielding, etc., at least one kind selected from pigments and dyes Is preferably used.

Examples of the organic pigment include organic pigments and inorganic pigments. Examples of the organic pigments include pigments classified by the color index (published by CI., The Society of Dyers and Colourists). Specifically, the color index (C.I.) name is attached as follows.

C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Blue 1, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 80, C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180, C.I. Pigment Yellow 211, C.I. Pigment Orange 38, C.I. Pigment Violet 23.

Examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, spinach (red iron oxide (III)), cadmium, Cobalt rust, amber, titanium black, synthetic iron black, and carbon black.

When the pigment is used as another colorant in the present invention, the pigment may be purified and used by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination thereof. The pigment may be used by modifying its particle surface with a resin as necessary. As the resin for modifying the particle surface of the pigment, for example, a vehicle resin disclosed 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. The organic pigment may also be used by finely pulverizing the primary particles by so-called salt milling. As a method of the salt milling, for example, a method disclosed in Japanese Unexamined Patent Application Publication No. 08-179111 can be adopted.

As the dye, there can be appropriately selected from among various kinds of oil-soluble dyes, direct dyes, acid dyes, metal complex dyes and the like and, for example, those having the following color index (C.I.) names.

C.I. Solvent Yellow 4, C.I. Solvent Yellow 14, C.I. Solvent Yellow 15, C.I. Solvent Yellow 24, C.I. Solvent Yellow 82, C.I. Solvent Yellow 88, C.I. Solvent Yellow 94, C.I. Solvent Yellow 98, C.I. Solvent Yellow 162, C.I. Solvent Yellow 179;

C.I. Solvent Red 45, C.I. Solvent Red 49;

C.I. Solvent Orange 2, C.I. Solvent Orange 7, C.I. Solvent Orange 11, C.I. Solvent Orange 15, C.I. Solvent Orange 26, C.I. Solvent Orange 56;

C.I. Solvent Blue 35, C.I. Solvent Blue 37, C.I. Solvent Blue 59, C.I. Solvent Blue 67;

C.I. Acid Yellow 17, C.I. Acid Yellow 29, C.I. Acid Yellow 40, C.I. Acid Yellow 76;

C.I. Acid Red 91, C.I. Acid Red 92, C.I. Acid Red 97, C.I. Acid Red 114, C.I. Acid Red 138, C.I. Acid Red 151;

C.I. Acid Orange 51, C.I. Acid Orange 63;

C.I. Acid Blue 80, C.I. Acid Blue 83, C.I. Acid Blue 90;

C.I. Acid Green 9, C.I. Acid Green 16, C.I. Acid Green 25, C.I. Acid Green 27.

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

The proportion of the total of the specific coloring agent and other coloring agents to be used as required is usually from 5 to 70% by mass, more preferably from 5 to 70% by mass, in the solid content of the coloring composition, from the viewpoint of forming a pixel having a high luminance and excellent color purity or a black matrix having excellent light- By mass to 5% by mass to 60% by mass. The solid content referred to herein is a component other than the solvent described later.

In the present invention, when a specific colorant is used in combination with another colorant, the content of the specific colorant is preferably 5 to 80% by mass, more preferably 15 to 70% by mass and further preferably 30 to 60% by mass in the total colorant. Among them, when the triarylmethane type coloring agent as the specific coloring agent and the other coloring agent are used in combination, the content of the triarylmethane type coloring agent is preferably 20 to 80 mass%, more preferably 20 to 60 mass%, further preferably 30 to 50 mass% % By mass.

When a pigment is used as a colorant in the present invention, it may be used together with a dispersant and a dispersion auxiliary agent as required. As the dispersing agent, for example, a suitable dispersing agent such as cationic, anionic, or nonionic type can be used, and a polymer dispersant is preferable. Specific examples thereof include a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene alkyl phenyl ether-based dispersant, a polyethylene glycol diester dispersant, a sorbitan fatty acid ester- And the like.

Dispersing agents such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 and BYK-LPN21324 (all manufactured by BYK), urethane dispersants Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170 and Disperbyk-182 (all manufactured by BYK), Solsperse 76500 (manufactured by Lubrizol Corporation) , Azisper PB822, Ajisper PB880, Ajisper PB881 (manufactured by Ajinomoto Fine Techno Co., Ltd., Japan) as a polyethylene-based dispersant, Solsperse 24000 (manufactured by Lubrizol Corporation) Manufactured by Kabushiki Kaisha).

Examples of the dispersion aid include pigment derivatives, and specific examples thereof include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone. The content of the dispersing agent and the dispersion auxiliary agent can be suitably determined within a range not hindering the object of the present invention.

- (B) Binder Resin -

The binder resin in the present invention 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 referred to as "carboxyl group-containing polymer") is preferable, and for example, an ethylenically unsaturated monomer having at least one carboxyl group (hereinafter referred to as "unsaturated monomer (b1)") (Hereinafter referred to as " unsaturated monomer (b2) ").

Examples of the unsaturated monomer (b1) include mono [2- (meth) acryloyloxyethyl], [omega] -carboxypolycaprolactone mono (meth) acrylate, maleic anhydride, , p-vinylbenzoic acid, and the like.

These unsaturated monomers (b1) may be used alone or in admixture of two or more.

As the unsaturated monomer (b2), 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, polyethyleneglycol (having a degree of polymerization of 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (having a degree of polymerization of 2 to 10) , Polypropylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan- (Meth) acrylate of glycidyl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (Meth) acrylate, 3,4- (Meth) acrylate esters such as cisiclohexylmethyl (meth) acrylate, 3 - [(meth) acryloyloxymethyl] oxetane and 3- [(meth) acryloyloxymethyl] ;

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 macromonomers 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 (b2) may be used alone or in admixture of two or more.

In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50 mass%, more preferably 10 to 40 mass%. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

As specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), for example, Japanese Patent Application Laid-Open Nos. 7-140654, 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 Unexamined Patent Application Publication No. 5-19467, Japanese Unexamined Patent Application Publication No. 6-230212, Japanese Unexamined Patent Application Publication No. 7-207211, (Meth) acryloyl group and the like as a side chain, as disclosed in JP-A-09-325494, JP-A-11-140144 and JP-A-2008-181095 Containing polymer may 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 GPC (dissolution solvent: tetrahydrofuran), usually 1,000 to 100,000, preferably 3,000 to 50,000. When the Mw is too small, there is a risk that the residual film ratio or the like of the resulting film may deteriorate, the pattern shape, the heat resistance and the like may be impaired, and further the electrical characteristics may deteriorate. On the other hand, Furthermore, there is a fear that dry foreign matter tends to be generated at the time of application by the slit nozzle method.

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

The binder resin in the present invention can be prepared 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. 07/029871 The structure thereof, Mw, and Mw / Mn can be controlled by the method described above.

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 from 10 to 1,000 parts by mass, preferably from 20 to 500 parts by mass, more preferably from 50 to 50 parts by mass, based on 100 parts by mass of the total amount of the specific coloring compound and other coloring agents to be used, To 400 parts by mass, more preferably 100 to 300 parts by mass. If the content of the binder resin is too small, for example, alkali developability may deteriorate or the storage stability of the resulting colored composition may deteriorate. On the other hand, when the content is too large, the concentration of the colorant relatively decreases, May be difficult to achieve.

- (C) a compound having two or more ethylenically unsaturated groups -

In the present invention, the compound (C) having two or more ethylenically unsaturated groups is not particularly limited, but a compound having two or more (meth) acryloyl 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 (Meth) acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, a (meth) acrylate having a hydroxyl group and an acid anhydride (Meth) acrylate having a carboxyl group which is obtained by reacting a polyfunctional (meth) acrylate.

Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, And an aliphatic polyhydroxy compound having the same trivalent or more. 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 2 An anhydride, and a tetrabasic acid dianhydride such as benzophenone tetracarboxylic acid dianhydride.

Examples of the caprolactone-modified polyfunctional (meth) acrylate include the 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 di (meth) acrylate modified with at least one selected from the group consisting of ethylene oxide of bisphenol A and propylene oxide of bisphenol A, Tri (meth) acrylate modified with at least one member selected from ethylene oxide and propylene oxide of isocyanuric acid, at least one member selected from ethylene oxide of trimethylol propane and propylene oxide of trimethylol propane Tri (meth) acrylate modified with at least one selected from the group consisting of tri (meth) acrylate, pentaerythritol ethylene oxide, and pentaerythritol propylene oxide, pentaerythritol ethylene oxide And propylene oxide of pentaerythritol, tetra (meth) acrylate modified with at least one member selected from dipenta (Meth) acrylate modified with at least one member selected from the group consisting of ethylene oxide of dipropylene glycol and dipropylene glycol, propylene oxide of dipentaerythritol and dipentaerythritol, Hexa (meth) acrylate modified by at least one kind selected therefrom.

Of these, polyfunctional (meth) acrylates, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethane (meth) acrylates and carboxyl groups obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) (Meth) acrylate having a number average molecular weight of 1,000 or less. 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 and the surface smoothness of the colored layer is excellent and background contamination and film residue do not easily occur on the substrate of the unexposed portion and on the light shielding layer.

In the present invention, the compounds (C) having two or more ethylenic unsaturated groups may be used alone or in admixture of two or more.

The content of the compound (C) having two or more ethylenically unsaturated groups in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 500 parts by mass, further preferably 50 to 300 parts by mass, relative to 100 parts by mass of the binder resin (B) Mass part, particularly preferably from 80 to 200 mass parts. In this case, if the content of the compound having two or more ethylenic unsaturated groups is too small, there is a fear that sufficient curability may not be obtained. On the other hand, when the content of the compound having two or more ethylenically unsaturated groups is too large, when the alkali developing property is imparted to the coloring composition of the present invention, the alkali developability is lowered, Film residue tends to be easily generated.

- (D) Photopolymerization initiator -

(D) The photopolymerization initiator is an active species capable of initiating the polymerization reaction of the compound (C) having two or more ethylenically unsaturated groups by exposure to radiation such as visible light, ultraviolet light, deep ultraviolet light, electron beam, &Lt; / RTI &gt; The coloring composition of the present invention is characterized by containing, as (D) a photopolymerization initiator, an intermolecular hydrogen-drawing type photo radical initiator. Thereby, a colored composition capable of forming a colored layer excellent in solvent resistance can be obtained.

Examples of the photo-radical initiator of intermolecular hydrogen-drawing type include nonimidazole-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and polynuclear quinone-based compounds. Of these, a nonimidazole-based compound is preferable.

In the present invention, the intermolecular hydrogen-derived photo radical initiators may be used alone or in combination of two or more.

The non-imidazole compound is a compound having at least one skeleton represented by the following formula (5), (6) or (7).

As a specific example thereof, for example,

Bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (Halogen-substituted phenyl) tetrakis (including alkoxy) such as bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) Carbonylphenyl) biimidazole;

Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl- Bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Bis (halogen-substituted phenyl) tetraphenylbiimidazole such as tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-

.

The imidazole-based compounds may be used alone or in combination of two or more.

Among these imidazole-based compounds, 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 and 2,2'-bis (2,4,6-trichlorophenyl) 4 ', 5,5'-tetraphenyl-1,2'-biimidazole is preferable, and 2,2'-bis (2-chlorophenyl) -4,4' 1,2'-biimidazole is preferred.

In the present invention, the content of the intermolecular hydrogen-derived photo radical initiator is usually from 0.01 to 50 parts by mass, preferably from 1 to 40 parts by mass, per 100 parts by mass of the (C) compound having two or more ethylenically unsaturated groups, Preferably 5 to 30 parts by mass, more preferably 10 to 30 parts by mass.

In the present invention, when a non-imidazole-based compound is used as a photopolymerization initiator, it is preferable to further use the following hydrogen donor in view of further improving the sensitivity. The term " hydrogen donor " as used herein means a compound capable of providing a hydrogen atom with respect to a radical generated from a nonimidazole-based compound by exposure. The hydrogen donor in the present invention is preferably a mercaptan-based compound or an amine-based compound as defined below.

The mercapanic compound means a compound having a benzene ring or a heterocyclic ring as a parent nucleus and having at least one, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the above-mentioned mother nucleus (hereinafter referred to as &Quot; ternary hydrogen donor "). The amine compound means a compound having a benzene ring or a heterocyclic ring as a parent nucleus and having at least one amino group directly bonded to the above-mentioned mother nucleus, preferably 1 to 3, more preferably 1 to 2 (hereinafter referred to as " Amine-based hydrogen donor "). Further, such a hydrogen donor may have both a mercapto group and an amino group.

Hereinafter, the hydrogen donor will be described in more detail.

The mercaptan-based hydrogen donor may have at least one benzene ring or at least one heterocyclic ring, and may have both a benzene ring and a heterocyclic ring. In the case of having two or more such rings, a condensed ring may be formed.

When the mercapto-based hydrogen donor has two or more mercapto groups, one or more of the remaining mercapto groups may be substituted with an alkyl group, an aralkyl group, or an aryl group, as long as at least one free mercapto group remains have. Furthermore, as long as at least one glass mercapto group remains, there may be a structural unit in which two sulfur atoms are bonded through a divalent organic group such as an alkylene group, or a structural unit in which two sulfur atoms are bonded in the form of a disulfide.

The mercaptan-based hydrogen donor may be substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group or the like at a position other than a mercapto group.

Specific examples of such mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole, And mercapto-substituted heterocyclic compounds such as 2-mercapto-2,5-dimethylaminopyridine.

Of these mercaptan-based hydrogen donors, mercapto-substituted benzoxazole such as mercapto-substituted benzothiazole and 2-mercaptobenzoxazole such as 2-mercaptobenzothiazole is preferable, and further mercapto-substituted benzothiazole Preferred is 2-mercaptobenzothiazole.

The amine-based hydrogen donor may have at least one benzene ring or at least one heterocyclic ring, and may have both a benzene ring and a heterocyclic ring. In the case of having two or more such rings, a condensed ring may be formed.

The amine-based hydrogen donor may be a primary amino group or a secondary amino group or a tertiary amino group in which at least one of the amino groups is substituted with an alkyl group or a substituted alkyl group, An alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group and the like.

Specific examples of such amine-based hydrogen donors include amino-substituted benzophenones such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone; Diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, and 4-dimethylaminobenzonitrile.

Of these amine-based hydrogen donors, amino-substituted benzophenones such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone are preferable, and 4,4'- (Diethylamino) benzophenone is preferred.

In addition, the amine-based hydrogen donor has an action as a sensitizer even in the case of a photopolymerization initiator other than the imidazole-based compound.

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

In the present invention, when the hydrogen donor is used in combination with the imidazole-based compound, the content of the hydrogen donor is preferably 0.01 to 40 parts by mass, more preferably 0.01 to 40 parts by mass, per 100 parts by mass of the (C) compound having two or more ethylenically unsaturated groups Preferably 1 to 30 parts by mass, particularly preferably 1 to 20 parts by mass. When the content of the hydrogen donor is too small, the effect of improving the sensitivity tends to be lowered. On the other hand, if it is too large, the formed colored layer tends to be easily detached from the substrate at the time of development.

The content of the hydrogen donor in 100 parts by mass of the nonimidazole-based compound is preferably 5 to 60 parts by mass, more preferably 10 to 40 parts by mass.

In the present invention, as a photopolymerization initiator, a photopolymerization initiator in an intramolecular bonding cleavage type can be used together with a photopolymerizable initiator of an intermolecular hydrogen-drawing type. Examples of the photopolymerization initiator of the intramolecular bond-cleavable type include a photopolymerization initiator such as an acetophenone-based compound, a triazine-based compound, an O-acyloxime-based compound, an onium salt-based compound, a benzoin-based compound, Based compounds and the like. Of these, at least one member selected from the group consisting of an acetophenone compound, a triazine compound, and an O-acyloxime compound is preferable.

The content ratio of the intermolecular hydrogen-derived photo radical initiator is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more in the total photopolymerization initiator . The upper limit is not particularly limited, but is preferably 90% by mass or 80% by mass.

- (E) Anionic surfactant -

When a basic dye or a basic lake pigment is used as a coloring agent, the heat resistance of the pigment can be enhanced by containing (E) anionic surfactant. The anionic surfactant is not particularly limited, and examples thereof include a carboxylic acid surfactant, a phosphoric acid surfactant, and a sulfonic acid surfactant.

Specific examples of the carboxylic acid-based surfactant include stearic acid monoethanolamine salt, sodium stearate, amine salt of polyetherester acid, and the like.

Specific examples of the phosphate surfactant include hydroxyethylen oxide phosphate ester, sodium salt of hydroxyethylene oxide phosphate ester, ethylene oxide alkyl phosphate ester, and polyoxyethylene styrenated phenyl ether phosphate ester. have.

Specific examples of the sulfonic acid surface active agent include sodium dodecylbenzenesulfonate, triethanolamine laurylsulfate, ammonium laurylsulfate, sodium laurylsulfate, sodium dialkylsulfosuccinate, sodium alkylnaphthalenesulfonate, alkyldiphenyl ether di Ammonium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate, ammonium polyoxyethylene nonyl propenyl phenyl ether sulfate, and the like can be used. .

Of these, a phosphoric acid surfactant and a sulfonic acid surfactant are preferred from the viewpoint of enhancing a desired effect. Among the phosphoric acid surfactants, hydroxyethylen oxide phosphate ester, ethylene oxide alkyl phosphate ester, and polyoxyethylene styrenated phenyl ether phosphate ester are particularly preferable. Among the sulfonic acid surfactants, alkyl ether ammonium sulphate such as polyoxyethylene alkyl ether sulphate ammonium is particularly preferable, and specific examples include ammonium polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate and the like. The (E) anionic surfactants may be used alone or in combination of two or more.

The content of the (E) anionic surfactant is preferably 5 to 50 parts by mass, particularly preferably 20 to 40 parts by mass with respect to 100 parts by mass of the colorant. By containing an anionic surfactant in such a range, it becomes possible to form a colored layer which does not deteriorate the chromaticity characteristics even after a high-temperature heating process.

- (F) a crosslinking agent other than a compound having two or more ethylenically unsaturated groups,

The coloring composition of the present invention can further improve heat resistance and solvent resistance by containing a crosslinking agent (hereinafter also simply referred to as "(F) crosslinking agent") other than the compound (C) having two or more ethylenically unsaturated groups. Examples of the crosslinking agent (F) include compounds having two or more epoxy groups, compounds having two or more groups selected from N-methylol group and N-alkoxymethyl group, and the like.

The compound having two or more epoxy groups is preferably a compound having at least two oxetanyl groups, and specific examples thereof include 3,7-bis (3-oxetanyl) -5-oxa- - (1,3-bis (3-ethyl-3-oxetanylmethoxy) methyl] propane diisocyanate) bis- (3-ethyloxetane) Benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [ 3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis Tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyl dimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl- (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis 3-oxetanylmethyl) ether, dipentaerythritol hexacis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentaquis Caprolactone-modified dipentaerythritol hexaquis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol Ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis Ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis ), And the ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether and the like.

Examples of the compound having a total of two or more groups selected from an N-methylol group and an N-alkoxymethyl group include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and benzoguanamine structure refer to a chemical structure having at least one triazine ring as a basic skeleton and a chemical structure having at least one phenyl-substituted triazine ring as a basic skeleton, and a melamine compound, a benzoguanamine compound, And a condensate thereof. Specific examples of such compounds include compounds represented by the following formulas (8) to (12).

In the formulas (8) to (12), R represents, independently of each other, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group.

In the present invention, the (F) crosslinking agent may be used singly or in a mixture of two or more.

The content of the (F) crosslinking agent in the present invention is preferably 10 to 500 parts by mass, particularly preferably 30 to 200 parts by mass, per 100 parts by mass of the binder resin (B). By including (F) a cross-linking agent in this range, heat resistance and solvent resistance can be further increased.

- (G) Solvent-

The coloring composition of the present invention contains the above components (A) to (D), and optionally other components to be added, and is usually prepared as a liquid composition by blending a solvent.

The solvent may be appropriately selected and used as long as it dissolves or dissolves the components (A) to (D) constituting the coloring composition and other components, does not react with these components, and has appropriate volatility.

As such a solvent, 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 (meth) acrylate such as propylene glycol monoethyl ether Termini and the like;

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

And the like.

Of these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate are preferable from the viewpoints of solubility, pigment dispersibility, Butylene glycol diacetate, 1,6-hexanediol, 1,6-hexanediol, 1,6-hexanediol, 1,6-hexanediol, 1,6-hexanediol, Diethyl acetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, Amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate and ethyl pyruvate are preferable.

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

The content of the solvent is not particularly limited, but from the viewpoint of coatability, stability, and the like of the obtained coloring composition, an amount such that the total concentration of each component from which the solvent is removed from the coloring composition is preferably 5 to 50 mass% By mass to 40% by mass.

-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-based surfactants and silicone-based 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; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; 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; Developing improvers such as mono [2- (meth) acryloyloxyethyl succinate], mono [2- (meth) acryloyloxyethyl] phthalate, and? -Carboxylic polycaprolactone mono (meth) acrylate; Siloxane oligomers having a reactive functional group disclosed in JP-A-2008-242078, and the like.

The coloring composition of the present invention can be prepared by a suitable method. When the specific coloring agent is a basic dye, for example, Japanese Patent Laid-Open Publication No. 2008-58642, Japanese Patent Application Laid-Open No. 2010-132874 &Lt; / RTI &gt; When a pigment is used together with a basic dye (a specific coloring agent), as disclosed in JP-A-2010-132874, a dye solution containing a specific coloring agent is passed through a first filter, Mixing the thus-obtained dye solution with a separately prepared pigment dispersion or the like, and passing the obtained coloring composition through a second filter. It is also possible to dissolve the basic dye (specific coloring agent), the components (B) to (D), and optionally the components (E) to (F) and the additive component in the solvent (G) A method may be adopted in which after passing through a filter, a solution having passed through the first filter is mixed with a separately prepared pigment dispersion, and the resulting colored composition is passed through a second filter. The dye solution containing the specific coloring agent is passed through the first filter and then passed through the first filter and the components (B) to (D) Component and the additive component are mixed and dissolved, the obtained solution is passed through a second filter, the solution passed through the second filter is mixed with a separately prepared pigment dispersion, and the resulting colored composition is passed through a third filter May also be employed.

Color filter and manufacturing method thereof

The color filter of the present invention comprises a colored layer formed using the coloring composition of the present invention.

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 divide a portion for forming a pixel, if necessary. Subsequently, a liquid composition of the blue radiation-sensitive composition of the present invention containing a specific coloring agent, for example, is applied onto the substrate, and then the substrate is prebaked to evaporate the solvent to form a coating film. Subsequently, the coating film is exposed through a photomask, and then developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, by post-baking, a pixel array in which blue pixel patterns are arranged in a predetermined arrangement is formed.

Subsequently, the respective coloring and radiation-sensitive compositions are applied, prebaked, exposed, developed, and post-baked in the same manner as above using each of the green or red colored radiation sensitive compositions to form a green pixel array and red pixels Arrays are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of three primary colors of red, green, and blue are arranged on a substrate is obtained. However, the order of forming the pixels of each color in the present invention is not limited to the above. Further, in the first method of manufacturing a color filter, at least one of the blue, green, and red pixel arrays may be a colored layer formed using the coloring composition of the present invention.

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. By using a coloring and radiation-sensitive composition in which a black coloring agent is dispersed, It may be formed in the same manner as in the pixel formation. The coloring composition of the present invention can be suitably used for forming such a black matrix.

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

If necessary, the substrate 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 coloring and radiation-sensitive 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 or a bar coating method can be employed. A coating method, and a slit die coating method.

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, a XeCl excimer laser, or a nitrogen laser. Radiation with a wavelength in the range of 190 to 450 nm is preferable.

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

Examples of the alkali developing solution include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7- Diazabicyclo- [4.3.0] -5-nonene and the like are preferable.

A water-soluble organic solvent such as methanol or ethanol, a surfactant or the like may be added to the alkali developing solution 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 120 to 280 ° C for about 10 to 60 minutes. From the viewpoint of the heat resistance of the specific colorant, the post baking temperature is preferably 240 ° C or less, particularly preferably 230 ° C or less.

The film thickness of the thus formed pixel is usually 0.5 to 5 占 퐉, preferably 1 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, first, a partition wall serving also as a light shielding function is formed on the surface of the substrate. Subsequently, the liquid composition of the blue colored thermosetting composition of the present invention containing a specific coloring agent, for example, is ejected by an ink jet apparatus in the partition wall formed, and then the liquid is subjected to prebaking to evaporate the solvent. Subsequently, after the coating film is exposed, post-baking is performed 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 colored thermosetting compositions of green or red, in the same manner as described above. Thereby, a color filter in which pixel patterns of three primary colors of red, green, and blue are arranged on a substrate is obtained. However, the order of forming the pixels of each color in the present invention is not limited to the above. Also in the second method for manufacturing a color filter, any one or more of the pixel arrays of blue, green, and red may be a colored layer formed using the coloring composition of the present invention.

In addition, the barrier ribs have a thicker film thickness than the black matrix used in the first method because they function not only to block light, but also to prevent coloring of the colored thermosetting composition of each color ejected into the compartment. 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, and the coloring composition of the present invention can be suitably used for forming such a black spacer.

The color filter of the present invention thus obtained is very useful for a color liquid crystal display element, a color image pickup tube element, a color sensor, an organic EL display element, and an electronic paper because of its extremely high luminance and color purity.

Display element

The display device of the present invention comprises the color filter 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 color filter of the present invention may be of a transmissive type or a reflective type, and may have a suitable structure. 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 the substrate on which the color filter is formed and the substrate for driving may be opposed to each other with the liquid crystal layer interposed therebetween , 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, a substrate on which ITO (indium tin oxide) electrode or IZO (mixture of indium oxide and zinc oxide) The liquid crystal layer may be opposed to the liquid crystal layer. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

The color liquid crystal display device having the color filter of the present invention may include 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 for obtaining a white light by mixing a red light emitting phosphor and a green light emitting phosphor and a white LED for obtaining a white light by mixing a blue LED and a YAG based phosphor, a blue LED, an orange light emitting phosphor and a green light emitting phosphor, A white LED for obtaining white light by mixing white light, an ultraviolet LED and a red LED, a white LED for obtaining a white light by mixing a green light emitting fluorescent substance and a blue light emitting fluorescent substance, and the like.

The color liquid crystal display device having the color filter of the present invention may be applied to a color liquid crystal display device such as a twisted nematic (TN) type, a super twisted nematic (STN) type, an in-plane switching (IPS) type, a vertical alignment (VA) type, an optically compensated birefringence ) Type liquid crystal mode can be applied.

Further, the organic EL display device having the color filter of the present invention can adopt a suitable structure, for example, a structure disclosed in Japanese Patent Application Laid-Open No. 11-307242.

Further, the electronic paper having the color filter of the present invention can adopt a suitable structure, for example, a structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

[Example]

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; Production of Pigment Dispersion >

Pigment Dispersion Production Example 1

As a colorant, C.I. , 15.5 parts by mass of Pigment Blue 15: 6, 12.5 parts by mass (solids concentration = 40% by mass) of BYK-LPN21116 (manufactured by BYK) as a dispersant and 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent , And treated with a beads mill to prepare a pigment dispersion (A-1).

&Lt; Preparation of dye solution >

Dye Solution Preparation Example 1

5 parts by mass of the compound A represented by the following formula and 95 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare a dye solution A. [

Dye Solution Preparation Example 2

5 parts by mass of the compound B represented by the following formula and 95 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare a dye solution B.

Dye solution Preparation Example 3

5 parts by mass of a compound C represented by the following formula and 95 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare a dye solution C. [

Dye solution Preparation Example 4

5 parts by mass of a compound D represented by the following formula and 95 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare a dye solution D. [

Dye Solution Preparation Example 5

5 parts by weight of a compound E represented by the following formula and 95 parts by weight of propylene glycol monomethyl ether as a solvent were mixed to prepare a dye solution E.

&Lt; Synthesis of binder resin >

Synthesis Example 1

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. The mixture was heated to 80 占 폚 and, at the same temperature, 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 캜 and further polymerized for 1 hour to obtain a binder resin solution (solid concentration = 33% by mass).

The resulting binder resin had Mw = 12,200 and Mn = 6,500. This binder resin is referred to as " binder resin (b) ".

&Lt; Preparation and evaluation of colored composition >

Example 1

13.6 parts by mass of the pigment dispersion (A-1), 27.2 parts by mass of the dye solution A, 21.6 parts by mass of the binder resin (b) solution as the binder resin, and M- 402 (dipenta 9.2 parts by mass of a mixture of 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl- 1.7 parts by mass of 2'-biimidazole, 0.3 parts by mass of 4,4'-bis (diethylamino) benzophenone as a hydrogen donor and 0.2 parts by mass of 2-mercaptobenzothiazole as a fluorine surfactant, 0.2 part by mass of manufactured Megaface F-554, and 3-methoxybutyl acetate as a solvent were mixed to prepare a colored composition having a solid content concentration of 20 mass%.

The obtained coloring composition was coated on a glass substrate using a spin coater and then pre-baked on a hot plate at 80 DEG C for 10 minutes to form a coating film having a thickness of about 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 2,000 J / m ² on each coating film without using a photomask using a high-pressure mercury lamp Respectively. Thus, two evaluation substrates on which a blue evaluation cured film was formed were produced on the substrate.

Evaluation of heat resistance

One of two evaluation substrates was post-baked for 1 hour in a clean oven at 230 캜. For the substrates before and after post-baking, the color difference (DELTA Eab *) was measured by a color analyzer (MCPD2000, manufactured by Otsuka Denshi Co., Ltd.). When? Eab * was less than 3.0, it was evaluated as "? &Quot;, and when it was 3.0 or more and less than 5.0, it was evaluated as " The lower the value of [Delta] Eab *, the better. The evaluation results are shown in Table 2.

Solvent-resistant  evaluation

The remaining one of the two evaluation boards obtained above was immersed in propylene glycol monomethyl acetate at 25 캜 for 30 minutes. The film thickness before and after this treatment was measured with a contact type film thickness measuring instrument (Alpha Step IQ, KLA Tencor), and the residual film ratio (film thickness after processing / film thickness before processing × 100) was calculated. The case where the residual film ratio was 90% or more was evaluated as " ", the case where the residual film ratio was 80% or more and less than 90% was evaluated as " Further, the higher the residual film ratio, the better. The evaluation results are shown in Table 2.

Examples 2 to 9 and Comparative Examples 1 to 5

A coloring composition was prepared in the same manner as in Example 1, except that the kind and amount of the constituent components were changed as shown in Table 1. Then, the obtained coloring composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

In Table 1, the respective components are as follows.

C-1: M-402 (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Toagosei Co.,

D-1: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-

D-2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-

D-3: 4,4'-bis (diethylamino) benzophenone (hydrogen donor)

D-4: 2-mercaptobenzothiazole (hydrogen donor)

D-5: A photopolymerization initiator represented by the following formula (13)

E-1: fluorochemical surfactant Megacafe F-554 manufactured by DIC Kabushiki Kaisha

E-2: A commercially available phosphoric acid surfactant (hydroxyethylene oxide phosphate ester)

E-3: A commercially available sulfonic acid surfactant (polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate)

Claims (8)

(A) a colorant, (B) a binder resin, (C) a compound having two or more ethylenically unsaturated groups, and (D) a photopolymerization initiator,
(A) a colorant having an anion having at least one electron-withdrawing group selected from the group consisting of a cyano group, a halogenated hydrocarbon group and a halosulfonyl group,
(D) an intermolecular hydrogen withdrawing photo radical initiator as a photopolymerization initiator,
Wherein the anion having an electron-withdrawing group is an anion represented by any one of the following formulas (1a) to (1e).

(In the formula (1a), R ¹ represents a fluorinated hydrocarbon group which may have a linking group, and a represents an integer of 1 or more)

(In the formula (1b), R ² independently represents a cyano group, a halosulfonyl group or a halogenated alkylsulfonyl group which may have a linking group, and when R ² is a halogenated alkylsulfonyl group which may have a linking group, R ² They may be bonded to each other to form a ring)

(In the formula (1c), R ³ represents a halogenated hydrocarbon group, P represents a phosphorus atom, Hal represents a halo group, and when plural R ³ and Hal are present, b may be the same or different, Lt; / RTI &gt;

(In the formula (1d), R ⁴ represents a halogenated hydrocarbon group or cyano group, B represents a boron atom, Hal represents a halo group, and when plural R ⁴ and Hal are present, Represents an integer of 1 to 4)

(In the formula (1e), R ⁵ represents, independently of each other, a halosulfonyl group or a halogenated alkylsulfonyl group) (A) a colorant, (B) a binder resin, (C) a compound having two or more ethylenically unsaturated groups, and (D) a photopolymerization initiator,
(A) a colorant having an anion having at least one electron-withdrawing group selected from the group consisting of a cyano group, a halogenated hydrocarbon group and a halosulfonyl group,
(D) a nonimidazole-based compound as a photopolymerization initiator
Wherein the anion having an electron-withdrawing group is an anion represented by any one of the following formulas (1a) to (1e).

(In the formula (1a), R ¹ represents a fluorinated hydrocarbon group which may have a linking group, and a represents an integer of 1 or more)

(In the formula (1b), R ² independently represents a cyano group, a halosulfonyl group or a halogenated alkylsulfonyl group which may have a linking group, and when R ² is a halogenated alkylsulfonyl group which may have a linking group, R ² They may be bonded to each other to form a ring)

(In the formula (1c), R ³ represents a halogenated hydrocarbon group, P represents a phosphorus atom, Hal represents a halo group, and when plural R ³ and Hal are present, b may be the same or different, Lt; / RTI &gt;

(In the formula (1d), R ⁴ represents a halogenated hydrocarbon group or cyano group, B represents a boron atom, Hal represents a halo group, and when plural R ⁴ and Hal are present, Represents an integer of 1 to 4)

(In the formula (1e), R ⁵ represents, independently of each other, a halosulfonyl group or a halogenated alkylsulfonyl group) The coloring composition according to claim 1 or 2, further comprising a fluorine-based surfactant or a silicon-based surfactant as a surfactant. The coloring composition according to claim 1 or 2, wherein the basic colorant is a triarylmethane type colorant. The coloring composition according to claim 1, wherein the proportion of the intermolecular hydrogen-drawing type photo radical initiator is 50 mass% or more in the total photopolymerization initiator. The coloring composition according to claim 2, wherein the content of the nonimidazole-based compound in the total photopolymerization initiator is 50% by mass or more. A color filter comprising a colored layer formed by using the coloring composition according to claim 1 or 2. A display device comprising the color filter according to claim 7.