KR20140001807A - Colored composition, color filter and display device - Google Patents

Abstract

An assignment of the present invention is to provide a colored composition with excellent heat resistance. Solutions for the assignment are (A) a compound represented by the following chemical formula 1, (B) a binder resin, and (C) a colored composition including a cross-linking agent. <Chemical formula 1> [ In the chemical formula 1, X+ indicates cationic chromophore, Z indicates an electron withdrawing group, R0 indicates an alkyl group, aryl group, a cycloalkyl group, or an alkylaryl group, M indicates nitrogen atom, phosphorous atom, borax atom, arsenic atom, and antimony atom. If multiple Z and R0 exist respectively, Z and R0 can be identical or different from each other, a indicates an integer of 1-6, b indicates an integer of 0-5, and a+b equals to 2, 4 or 6. If M indicates the nitrogen atom, Z can have at least one among a cyano group and a halosulfonyl group].

Description

Colored composition, color filter, and display element {COLORED COMPOSITION, COLOR FILTER AND DISPLAY DEVICE}

This invention relates to a coloring composition, a color filter, and a display element, More specifically, it is used suitably for color filters, such as a transmissive or reflective color liquid crystal display element, a solid-state image sensor, an organic electroluminescent display element, an electronic paper, etc. It relates to a coloring composition, a color filter having a colored layer formed using the coloring composition, and a display element provided with the color filter.

In manufacturing a color filter using a colored radiation sensitive composition, after apply | coating a pigment dispersion type colored radiation sensitive composition on a board | substrate and drying, a dry coating film is irradiated to a desired pattern shape (henceforth "exposure"). The method (patent documents 1-2) of obtaining the pixel of each color is known by developing. Further, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (Patent Document 3) is also known. Moreover, the method (patent document 4) which obtains the pixel of each color by the inkjet system using the pigment dispersion type coloring thermosetting composition is also known.

By the way, in order to implement | achieve high brightness of a display element, high color purity, or high definition of a solid-state image sensor, it is known that it is effective to use dye as a coloring agent. For example, Patent Document 5 proposes the use of a triarylmethane dye having a specific structure.

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 Laid-Open No. 2008-304766

However, in the triaryl methane dye proposed in Patent Literature 5, the heat resistance is insufficient, and the predominance of the chromaticity characteristics of the pigment is lost when the heating (post-baking) process after exposure and development such as exceeding 200 ° C is performed. . In the above background, development of the coloring composition which has the heat resistance required for manufacture of a color filter is strongly requested.

Therefore, the subject of this invention is providing the coloring composition excellent in heat resistance. Moreover, the subject of this invention is providing the color filter which comprises the coloring layer which maintains the outstanding chromaticity characteristic, and the display element provided with the said color filter.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, it was found that the said subject can be solved by containing the basic dye which has a specific anion part as a coloring agent.

That is, this invention provides the coloring composition containing (A) the compound represented by following General formula (hereinafter also called a "specific coloring compound"), (B) binder resin, and (C) crosslinking agent.

[Formula 1, X ⁺ represents a cationic chromophore, Z represents an electron withdrawing group, R ⁰ represents an alkyl group, an aryl group, a cycloalkyl group or an alkylaryl group, M is a nitrogen atom, phosphorus atom, boron atom, arsenic An atom or an antimony atom, each of which may be the same or different when a plurality of Z and R ⁰ are present, a represents an integer of 1 to 6, b represents an integer of 0 to 5, and a + b represents 2 , 4 or 6, provided that when M is a nitrogen atom, Z has at least one of a cyano group and a halosulfonyl group]

In addition, the present invention provides a color filter comprising a colored layer containing the compound represented by the formula (1), and a display element provided with the color filter. Here, "colored layer" means each color pixel used for a color filter, a black matrix, a black spacer, etc.

In addition, the present invention is to provide a colorant represented by the following formula (12).

[In Formula 12, X ⁺ represents a cationic chromophore.]

When using the coloring composition of this invention containing a specific coloring compound, since the heat resistance required for manufacture of a color filter can be fully satisfied, the coloring layer which maintains the outstanding chromaticity characteristic can be formed even if it carries out a high temperature heating process. have.

Therefore, the coloring composition of this invention is very preferable for preparation of various color filters, including the color filter for color liquid crystal display elements, the color filter for color separation of a solid-state image sensor, the color filter for organic electroluminescent display elements, and the color filter for electronic paper. Can be used.

Hereinafter, the present invention will be described in detail.

Coloring composition

Hereinafter, the structural component of the coloring composition of this invention is demonstrated.

-(A) specific coloring compound-

The coloring composition of this invention contains a specific coloring compound, ie, the compound represented by the said Formula (1). Certain colored compounds are compounds in which the maximum extinction coefficient in the visible region (380 nm to 780 nm) is usually at least 3,000, which is different from triarylsulfonium hexafluorophosphoric acid, which is known as a photoacid generator that absorbs ultraviolet rays to generate acids. .

In the coloring composition of this invention, a specific coloring compound can be used individually or in mixture of 2 or more types.

First, in the formula 1 (Z _a R _b M ^{0) -} will be described.

Z is not particularly limited as long as it is an electron withdrawing group, but for example, a monovalent organic group having a halo group, a halo group, a cyano group, a cyano group, a monovalent organic group having a nitro group, a halosulfonyl group, The alkyl sulfonyl group which may have a halo group, etc. are mentioned. When M is a phosphorus atom, a boron atom, an arsenic atom, or an antimony atom, Z is preferably a halo group, a monovalent organic group having a halo group, a cyano group, a monovalent organic group having a cyano group, or a monovalent organic group having a nitro group. . On the other hand, when M is a nitrogen atom, Z which M has other than a cyano group or a halosulfonyl group is preferably a monovalent organic group having a halo group or an alkylsulfonyl group which may have a halo group.

Although a fluoro group, a chloro group, a bromo group, and an iodo group are mentioned as said halo group, A fluoro group is preferable from a heat resistant viewpoint.

Although it does not specifically limit as monovalent organic group which has the said halo group, For example, a monovalent halogenated hydrocarbon group is mentioned, The said halogenated hydrocarbon group may have substituents other than a halo group.

As the hydrocarbon group forming the skeleton of the halogenated hydrocarbon group, an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group is preferable, and an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, and 7 to 7 carbon atoms. 20 alkylaryl groups are more preferable.

The alkyl group may be linear or branched, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, second butyl group, third butyl group, isobutyl group, amyl group, third Amyl group, hexyl group, heptyl group, octyl group, isooctyl group, 3rd octyl group, 2-ethylhexyl, etc. are mentioned.

Moreover, as a cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group is mentioned, for example.

As an aryl group, a phenyl group, a naphthyl group, an anthranyl group is mentioned, for example.

As an alkylaryl group, group which the above-mentioned C1-C8 alkyl group substituted by the C6-C14 aryl group is mentioned, for example.

As the halo group in the halogenated hydrocarbon group, a fluoro group is preferable. Although the said halo group can substitute a part or all of the hydrogen atoms of a hydrocarbon group, Especially the hydrogen atom of a hydrocarbon group becomes like halo group Preferably it is 80 mol% or more, More preferably, it is 90 mol% or more, Especially preferably, 100 mol% It is preferable that it is substituted. Thereby, heat resistance can be improved further.

Although it does not specifically limit as monovalent organic group which has a cyano group, For example, the monovalent hydrocarbon group substituted by the cyano group is mentioned, The monovalent hydrocarbon group may have substituents other than a cyano group. As monovalent hydrocarbon group, an aryl group is preferable and a phenyl group is especially preferable.

Although it does not specifically limit as monovalent organic group which has a nitro group, For example, the monovalent hydrocarbon group substituted by the nitro group is mentioned, A monovalent hydrocarbon group may have substituents other than a nitro group. As monovalent hydrocarbon group, an aryl group is preferable and a phenyl group is especially 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 forming the skeleton of the alkylsulfonyl group and the halogenated alkylsulfonyl group may be linear or branched, and the carbon number is preferably 1 to 8. As a specific example of the said alkyl group, the thing similar to the alkyl group in a halogenated hydrocarbon group is mentioned.

Moreover, as a halo group in a halogenated alkylsulfonyl group, a fluoro group is preferable. Although the said halo group can substitute a part or all of the hydrogen atoms of a hydrocarbon group, from a heat resistant viewpoint, the hydrogen atom of a hydrocarbon group becomes like this a halo group preferably 80 mol% or more, More preferably, 90 mol% or more, Especially preferably, It is preferable that 100 mol% is substituted.

Examples of halosulfonyl groups include FSO ₂ groups, ClSO ₂ groups, BrSO ₂ groups, and ISO ₂ groups, with FSO ₂ groups being preferred.

In the present invention, as M, when M is a phosphorus atom, a boron atom, an arsenic atom or an antimony atom, a monovalent halogenated hydrocarbon group and a cyano group which may have a substituent other than a halo group and a halo group are preferable, and in particular, fluoro Group, cyano group, fluorinated alkyl group, aryl fluoride group or fluorinated alkylaryl group is preferable. In the fluorinated alkyl group, a perfluoroalkyl group having 1 to 6 carbon atoms (more preferably 1 to 4), and a perfluoroaryl group having 6 to 14 (more preferably 6 to 10) carbon atoms in the aryl fluoride group In the aryl group, perfluoroalkylaryl groups having 7 to 20 (more preferably 7 to 16) carbon atoms are each preferable. Specifically, for example, CF ₃ group, CF ₃ CF ₂ group, (CF ₃ ) ₂ CF group, CF ₃ CF ₂ CF ₂ group, CF ₃ CF ₂ CF ₂ CF ₂ group, (CF ₃ ) ₂ CFCF ₂ And a phenyl group substituted with a group, a CF ₃ CF ₂ (CF ₃ ) CF group, a (CF ₃ ) ₃ C group, a pentafluorophenyl group, or a CF ₃ group.

On the other hand, when M is a nitrogen atom, as Z which M has other than a cyano group or a halosulfonyl group, a halogenated alkylsulfonyl group is preferable and especially an alkylsulfonyl fluoride group is preferable. Specifically, 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, CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ Group, a (CF ₃ ) ₂ CFCF ₂ SO ₂ group, a CF ₃ CF ₂ (CF ₃ ) CFSO ₂ group, a (CF ₃ ) ₃ CSO ₂ group, and the like.

Although R <^0> represents an alkyl group, an aryl group, a cycloalkyl group, or an alkylaryl group, the thing similar to the alkyl group, aryl group, cycloalkyl group, and alkylaryl group in the halogenated hydrocarbon group mentioned above is mentioned as a preferable group.

M represents a nitrogen atom, a phosphorus atom, a boron atom, an arsenic atom or an antimony atom, but from the viewpoint of safety, M is preferably a nitrogen atom, a phosphorus atom or a boron atom. In addition, although a + b represents 2, 4 or 6, when M is a nitrogen atom, a + b is 2, and when M is a boron atom, a + b is 4 and M is an atom and an arsenic atom. Or in the case of an antimony atom, a + b is 6;

a represents an integer of 1 to 6 and b represents an integer of 0 to 5, but in the case where a plurality of Z and R ⁰ are present, they may be the same or different. In the present invention, it is preferable that b = 0, that is, a is 2, 4 or 6.

In the present invention, the desired ^{_{(Z a R 0 b M)}} - Order anion, represented by the anion, the following general formula (1b) represented by the following general formula (1a) as the like anion represented by the formula (1c) .

[In Formula (1a), R <^1> represents a halogenated hydrocarbon group, P represents a phosphorus atom, Hal represents a halo group, and when two or more R <^1> , Hal exists, they may be same or different, c is 0 An integer of from 6 to 6]

[In Formula (1b), R <^2> represents a halogenated hydrocarbon group, a cyano group, or the phenyl group substituted by the nitro group or the cyano group independently of each other, B represents a boron atom, Hal represents a halo group, R <^2> , When a plurality of Hal are each present, they may be the same or different, and d represents an integer of 0 to 4].

[In Formula (1c), EA independently represents a cyano group, an FSO ₂ group, or an alkylsulfonyl fluoride group, provided that at least one of the two EAs represents a cyano group or an FSO ₂ group.]

The definitions of the symbols in the formulas (1a), (1b) and (1c) will be described.

Although R <^1> represents a halogenated hydrocarbon group, the halogenated hydrocarbon group mentioned by the description of said Z is mentioned as said halogenated hydrocarbon group. In the present invention, R ¹ is preferably a fluorinated alkyl group, and more specifically, a fluorinated alkyl group exemplified in the description of Z is preferable.

R ² independently represents a halogenated hydrocarbon group, a cyano group, or a phenyl group substituted with a nitro group or cyano group, but examples of the halogenated hydrocarbon group include halogenated hydrocarbon groups exemplified in the description of Z. In the present invention, R ² is preferably a fluorinated alkyl group, an aryl fluoride group, a cyano group, or a phenyl group substituted with a trifluoromethyl group or a fluorine atom, and more specifically, a group exemplified in the description of Z is preferable. .

In the formulas (1a) and (1b), as Hal, a fluoro group is preferable from the viewpoint of heat resistance of the colorant.

In Formula (1c), EA represents a cyano group, an FSO ₂ group, or an alkylsulfonyl fluoride group. As the alkyl fluoride sulfonyl group, an alkyl sulfonyl group exemplified in the description of Z is preferable. In formula (1c), it is preferable that EA is both a cyano group or an FSO ₂ group, or one is an FSO ₂ group, and the other is an alkylsulfonyl fluoride group.

Examples representative of the anion represented by the formula (1a), for example, ^{_{PF 6 -, (CF 3)}} 3 PF 3 -, (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 - , and the like. 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.

Examples representative of the anion represented by the formula (1b), for example, ^{_{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 F 13) 3 B} (CN) -, (CHF 2) 3 B (CN) -, (CHF 2) 2 B (CN) 2 -, (CH 2 CF 3) 3 B (CN) -, ( _{CH 2 CF 3) 2 B (} CN) 2 -, (CH 2 C 2 F 5) 3 B (CN) -, (CH 2 C 2 F 5) 2 B (CN) 2 -, (CH 2 CH 2 C _{3 F 7) 2 B (CN} ) 2 -, (nC 3 F 7 CH 2) 2 B (CN) 2 -, (C 6 H 5) 3 B (CN) -, tetrakis (pentafluorophenyl) borate Anion etc. are mentioned. Among ^{_{them, BF 4 -, B (CN}} ) 3 F -, (CF 3) 4 B -, (C 6 F 5) 4 B -, [(CF 3) 2 C 6 H 3] 4 B -, tetrakis Preferred are (pentafluorophenyl) borate anions.

Preferred anions among the anions represented by the above formula (1c) 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 }] ^- , [(FSO ₂ ) N {CF ₃ CF ₂ (CF ₃ ) CFSO ₂ }] ^- , [(FSO ₂ ) N {(CF ₃ ) ₃ CSO ₂ }] ^- and the like. Of _{these, [(CN) 2 N]} - it is particularly preferred.

Next, X <^+> in General formula (1 ⁾ is demonstrated.

X ⁺ is a cationic chromophore, that is X ⁺ (Z _a R ⁰ _b M) ^- is a cation which forms a basic coloring agent as is not particularly limited, for example, triarylmethane-based chromophores, methine-based chromophores, azo chromophore, Diaryl methane chromophore, quinone imine chromophore, anthraquinone chromophore, phthalocyanine chromophore, xanthene chromophore, etc. are mentioned.

As the triaryl methane chromophore, one represented by the following general formula (2) is preferable. In addition, although various resonance structures exist in the cation represented by following formula (2), in this specification, it is assumed that it is equivalent to the cation represented by following formula regarding the said resonance structure. The same applies to the cations represented by the formulas below.

[In Formula 2, Ar represents an aromatic hydrocarbon group, R ³ and R ⁴ independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁵ and R ⁶ independently represent a hydrogen atom, 1 to 8 carbon atoms Represents an alkyl group or a phenyl group, R ⁷ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, -COOR '(R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) or a chlorine atom, and R ⁸ and R ¹¹ Are independently of each other a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, or R ⁸ and R ¹¹ are taken together to represent a sulfur atom, and R ⁹ and R ¹⁰ are independently of each other a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or chlorine An atom, and Y represents a hydrogen atom or a group represented by the following Formula 3]

[In Formula 3, R ¹² and R ¹³ independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.]

As an aromatic hydrocarbon group in Ar, a C6-C20 (more preferably C6-C10) aromatic hydrocarbon group is preferable, Specifically, it is 2-2 from arene rings, such as a benzene ring, a naphthalene ring, a biphenyl ring, an anthracene ring, etc. The group which removed four hydrogen atoms is mentioned.

The alkyl group having 1 to 8 carbon atoms in R ³ to R ¹¹ (including R ′ in —COOR ′) and R ¹² and R ¹³ according to Formula 3 may be the same as the alkyl group in Z. The group can be mentioned.

In the present invention, the cation represented by the following formula (4) is particularly preferable among the cations represented by the above formula (2) from the viewpoint of improving luminance and color purity.

[In the formula ^{4, R 3, R 4,} R 5, R 6, R 12 and R ¹³ is ^{R 3, R 4, R 5} , R 6, R 12 and R ¹³ with the consent of the above formulas (2) and (3) being〕

In the above formula (4), R ³ , R ⁴ , R ¹² and R ¹³ are preferably an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 6 carbon atoms), and as R ⁵ , more preferably 1 to 8 carbon atoms (more preferably). Is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ⁶ is preferably an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 6 carbon atoms) or a hydrogen atom.

As a representative example of the cation represented by the said Formula (2), although the cation shown in the following compound group c and the compound group d is mentioned, for example, Compound c2, compound c3, and compound c4 are preferable.

[Compound group c]

[Compound group d]

As the methine-based chromophore, those represented by the following formulas (5-1) to (5-3) are preferable.

[In Formulas (5-1) to (5-3), R ³¹ represents a hydrogen atom or a halo group, and R ³² , R ³³ , R ³⁴ and R ³⁵ independently represent an alkyl group having 1 to 6 carbon atoms, R ³⁶ represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, G represents -CH = CH-, -CH = CH-NR ^37- (R ³⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH = N-NR ^37- (R ³⁷ is synonymous with the above) or -N = N-NR ^37- (R ³⁷ is synonymous with the above), and R ^a represents ^a substituted or unsubstituted aromatic hydrocarbon group or Substituted or unsubstituted heterocyclic group]

As R ^a, a group represented by the following formulas (5a) to (5g) is preferable.

[In Formulas (5a) to (5g), R ³⁸ and R ⁴⁵ each independently represent an alkyl group having 1 to 6 carbon atoms, R ³⁹ represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ⁴⁰ , R ⁴² , R ⁴³ and R ⁴⁴ independently of one another represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴¹ and R ⁴⁶ independently of each other represent a hydrogen atom, a halo group, an alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted group Ring alkyl group having 1 to 6 carbon atoms, nitro group, hydroxyl group or cyano group]

As a substituent of the said alkyl group, a halo group, a cyano group, a hydroxyl group, etc. are mentioned.

As a representative example of a cation represented by the said Formula (5-1)-(5-3), the cation shown to the following compound group e is mentioned, for example.

[Compound group e]

As said azo chromophore, it is preferable to represent with the following general formula (6-1)-(6-6).

[In Formulas (6-1) to (6-6), R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ^55, and R ⁵⁷ independently represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. , R ⁵⁶ and R ⁶⁰ each independently represent a hydrogen atom, a halo group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a hydroxyl group or a cyano group, and R ⁵⁸ is an alkyl group having 1 to 6 carbon atoms R ⁵⁹ represents a group forming a quaternary ammonium, and R ^b represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group.

As R ^59, -NR ⁶¹ C _ma H _2ma N ⁺ R ⁶² R ⁶³ R ⁶⁴ (ma is an integer of 1 to 5, R ⁶¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁶² , R ⁶³ and R ⁶⁴ independently of each other represents an alkyl group having 1 to 6 carbon atoms, -COC _ma H _2ma N ⁺ R ⁶² R ⁶³ R ⁶⁴ (ma, R ⁶² , R ⁶³ and R ⁶⁴ are _identical to the above), -C _ma H _2ma N ⁺ (NH ₂ ) R ⁷⁴ R ⁷⁵ (ma is synonymous with above, R ⁷⁴ and R ⁷⁵ independently of each other represent an alkyl group having 1 to 6 carbon atoms), or the following formula (6-i) or (6 Groups represented by -ii) are preferred.

[In formulas (6-i) and (6-ii), R ⁶¹ and ma are as defined above]

As said R <^b> , the group represented by the following general formula (6a)-(6e), and a substituted or unsubstituted phenyl group are preferable.

[In Formulas (6a) to (6d), R ⁶⁵ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and R ⁶⁶ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. , R ⁶⁷ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ⁶⁸ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁶⁹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁷⁰ To R ⁷³ each independently represent a hydrogen atom, a halo group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a hydroxyl group or a cyano group]

The substituent of the alkyl group may be a halo group, a hydroxyl group, a cyano group, -CONH ₂ group, and the like. As a substituent of the said phenyl group, a halo group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a hydroxyl group, a cyano group, a nitro group, etc. are mentioned.

As a representative example of a cation represented by the said Formula (6-1)-(6-6), the cation shown to the following compound group f or compound group g is mentioned, for example.

[Compound group f]

[Compound group g]

As said diarylmethane type chromophore, it is preferable to represent with following General formula (7-1) or (7-2).

[In Formulas (7-1) and (7-2), R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁶ , R ⁸⁷ , R ⁸⁸ and R ⁸⁹ are each independently an alkyl group having 1 to 6 carbon atoms. R ⁸⁵ , R ⁹⁰ and R ⁹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

As a representative example of a cation represented by said general formula (7-1)-(7-2), the cation shown to the following compound group h is mentioned, for example.

[Compound group h]

As said quinone imine chromophore, it is preferable to represent with following General formula (8-1)-(8-3).

[In Formulas (8-1) to (8-3), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁸ , R ¹⁰⁹ , R ¹¹⁰ , R ¹¹¹ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ and R ¹¹⁸ independently of one another represent a hydrogen atom, a substituted or unsubstituted alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, a phenyl group or a benzyl group, and R ¹⁰⁷ and R ¹¹³ represent each other Independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ¹¹² represents —NR ¹¹⁹ R ¹²⁰ (R ¹¹⁹ and R ¹²⁰ independently represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms). , Hydroxyl group, nitro group or cyano group, Q represents an oxygen atom or a sulfur atom]

As a substituent of the said alkyl group, a halo group, a hydroxyl group, a cyano group, etc. are mentioned.

As a representative example of a cation represented by the said Formula (8-1)-(8-3), the cation shown to the following compound group i is mentioned, for example.

[Compound Group i]

As said anthraquinone chromophore, it is preferable to represent with the following general formula (9-1) or (9-2).

[In Formulas (9-1) and (9-2), R ¹³¹ , R ^135, and R ¹³⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted phenyl group. R ¹³² , R ¹³³ , R ¹³⁴ , R ¹³⁸ , R ¹³⁹ and R ¹⁴⁰ independently represent an alkyl group having 1 to 6 carbon atoms, and R ¹³⁷ represents a methylene group or a substituted or unsubstituted alkylene group.]

As a substituent of the said alkyl group or a phenyl group, a C1-C6 alkyl group, a halo group, a hydroxyl group, a cyano group, etc. are mentioned. Moreover, as said alkylene group, C2-C4 alkylene groups, such as an ethylene group, trimethylene group, a propylene group, and a tetramethylene group, are mentioned, As a substituent of an alkylene group, a hydroxyl group, a cyano group, a nitro group, etc. are mentioned. .

As a representative example of a cation represented by the said General formula (9-1) or (9-2), the cation shown to the following compound group j is mentioned, for example.

[Compound Group j]

The phthalocyanine-based chromophore is preferably represented by the following formula (10).

[In Formula 10, CuPc represents a copper phthalocyanine residue and T represents a group represented by the following general formula (10a) or (10b).

[In Formulas (10a) and (10b), R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ , R ¹⁵⁶ , R ¹⁵⁷ and R ¹⁵⁸ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group. P represents an integer of 2 to 8 independently of each other, mb represents an integer of 1 to 5]

As a representative example of a cation represented by the said Formula (10), the cation shown to the following compound group k is mentioned, for example.

[Compound group k]

As the xanthene chromophore, one represented by the following formula (11) is preferable.

[In Formula 11, R ¹⁶¹ to R ¹⁶⁴ independently represent a hydrogen atom or a phenyl group, the phenyl group is a halo group, an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, -SO ₃ ^- ,- SO ₃ H, -SO ₃ R ^166, or -SO ₂ N (R ¹⁶⁷⁾ may be substituted with R ^168, R ¹⁶⁵ is _{^{-SO 3 -, -SO 3 H,}} -SO 3 R 166 , or -SO ₂ N (R ¹⁶⁷ ) represents R ¹⁶⁸ , and in the case where a plurality of R ¹⁶⁵ 's are present, they may be the same or different, R ¹⁶⁶ represents an alkyl group having 1 to 8 carbon atoms, and R ¹⁶⁷ and R ¹⁶⁸ are each independently a hydrogen atom or C 1 To an alkyl group of 8 to 8, the alkyl group may be substituted with a halo group or an alkoxy group having 1 to 6 carbon atoms, mc represents an integer of 0 to 5]

Among the cations represented by the above formula (11), a cation represented by the following formula (11a) is particularly preferable.

In the formula (11a), R ¹⁶⁹ are independently a hydrogen atom, -SO ₃ from each other ^- _{represent, -SO 3 H, -SO 3 R} 166 , or _{^{-SO 2 NHR 167, R 165,}} R 166 and R ¹⁶⁷ is I agree with the above]

As a representative example of a cation represented by the said General formula (11a), the cation shown to the following compound group m is mentioned, for example.

[Compound group m]

In addition, as a cationic chromophore represented by X <^+> , the cation shown to the following compound group n is mentioned, for example.

[Compound Group n]

Although a specific coloring compound can be manufactured by a well-known method, it can be manufactured by a salt exchange reaction, for example as disclosed in Unexamined-Japanese-Patent No. 2007-503477. In this case, (Z _a R _b M ^{0) -} there is a need for a salt of an anion represented by a commercially available product may be used as the salt, methods known, for example, Japanese Patent Publication No. 2004-533473, Japanese Unexamined What was synthesize | combined with reference to patent publication 2006-517546 etc. can also be used.

For example, when a specific coloring compound is, for example, X ⁺ is a triarylmethane-based chromophore, it is blue to red when dissolved in an organic solvent, so that the compound is used alone or in appropriate mixing with other coloring agents. For example, it can apply to the coloring composition for forming a blue pixel, a red pixel, and a black colored layer.

As another coloring agent, a color and a material can be selected suitably according to a use. Specifically, all pigments, dyes and natural dyes can be used. However, since a high color purity, brightness, contrast, light shielding property, etc. are required for the colored layer which comprises a color filter, using a pigment and / or dye is preferable. desirable.

Any of organic pigments and inorganic pigments may be used as the pigment, and examples of the organic pigments include compounds classified as pigments in the color index (C.I .; issued by The Society of Dyers and Colourists). Specifically, what is attached to the following color index (C.I.) names is mentioned.

C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 17, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 55, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168, C.I. Pigment Yellow 180, C.I. Pigment Yellow 211;

C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 43, C.I. Pigment Orange 46, C.I. Pigment Orange 49, C.I. Pigment Orange 61, C.I. Pigment Orange 64, C.I. Pigment Orange 68, C.I. Pigment Orange 70, C.I. Pigment Orange 71, C.I. Pigment Orange 72, C.I. Pigment Orange 73, C.I. Pigment Orange 74;

C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 5, C.I. Pigment Red 17, C.I. Pigment Red 31, C.I. Pigment Red 32, C.I. Pigment Red 41, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 170, C.I. Pigment Red 171, C.I. Pigment Red 175, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment Red 180, C.I. Pigment Red 185, C.I. Pigment Red 187, C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 207, C.I. Pigment Red 209, C.I. Pigment Red 214, C.I. Pigment Red 220, C.I. Pigment Red 221, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 262, C.I. Pigment Red 264, C.I. Pigment Red 272;

C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, C.I. Pigment Violet 36, C.I. Pigment Violet 38;

C.I. Pigment Blue 1, C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 60, C.I. Pigment Blue 80;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment green 58;

C.I. Pigment Brown 23, C.I. Pigment Brown 25;

C.I. Pigment Black 1, C.I. Pigment Black 7.

Examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, bengal (red iron oxide (III)), cadmium, ultramarine blue, royal blue, and chromium oxide. And cobalt rust, umber, titanium black, synthetic iron black and carbon black.

In the present invention, the pigment may be purified by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof. The pigment may also be used by modifying its particle surface with a resin, if desired. As the resin for modifying the particle surface of the pigment, for example, a 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 No. 9-71733, Japanese Patent Application Laid-Open No. 9-95625, Japanese Patent Application Laid-Open No. 9-124969 Can be adopted. In addition, the organic pigment is preferably used to refine 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.

Moreover, as said dye, it can select suitably from various oil-soluble dyes, direct dye, acid dye, a metal complex dye, etc., For example, the thing of which the following color index (C.I.) name is attached.

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 total content ratio of the specific coloring compound and other coloring agents used in some cases is usually 5 to 70% by mass in the solid content of the coloring composition, in that a pixel having high brightness and excellent color purity or a black matrix having excellent light shielding properties is formed. Preferably it is 5-60 mass%. Solid content here is components other than the solvent mentioned later.

In the case of using the pigment as another colorant in the present invention, the pigment may be used together with a dispersant and a dispersing aid if desired. As the dispersant, for example, suitable dispersants such as cationic, anionic, and nonionic systems can be used, but a polymer dispersant is preferable. Specifically, urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkylphenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants, polyester dispersants, acrylic dispersants Etc. can be mentioned.

Such dispersants are commercially available, for example, as an acrylic dispersant, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, manufactured by BYK Corporation), urethane dispersants As Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Corporation), Solsperth 76500 (manufactured by Lubrizol Co., Ltd.), As a polyethylene imine-based dispersant, Solsper Sper 24000 (manufactured by Lubrizol Co., Ltd.), polyester-based dispersant azisper PB821, azisper PB822, azisper PB880, azisper PB881 (above, Ajinomoto finetechno Kabushiki Kaisha Production).

Moreover, as said dispersion adjuvant, a pigment derivative is mentioned, for example, A copper phthalocyanine, a diketopyrrolopyrrole, the sulfonic acid derivative of quinophthalone, etc. are mentioned specifically ,. In addition, content of a dispersing agent and a dispersal auxiliary agent can be suitably determined within the range which does not impair the objective of this invention.

(B) binder resin

Although it does not specifically limit as binder resin in this invention, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Especially, the polymer which has a carboxyl group (henceforth a "carboxyl group-containing polymer") is preferable, for example, copolymerization different from the ethylenically unsaturated monomer which has one or more carboxyl groups (henceforth "unsaturated monomer (b1)"). The copolymer of possible ethylenically unsaturated monomer (henceforth "unsaturated monomer (b2)") is mentioned.

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth) acrylate. and p-vinyl benzoic acid.

These unsaturated monomers (b1) can be used individually or in mixture of 2 or more types.

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;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate , Polyethylene glycol (n = 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (n = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylic Latex, polypropylene glycol (n = 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8- Mono (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glyc Cydyl (meth) acrylate, 3,4-epoxycyclohexylme (Meth) acrylate, 3 - [(meth) acryloyl-oxy-methyl] oxetane, 3- (meth) acrylic acid ester such as ethyl-3-oxetane [(meth) acryloyl-yloxymethyl];

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 (b2) can be used individually or in mixture of 2 or more types.

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% by mass, more preferably 10 to 40% by mass. By copolymerizing an unsaturated monomer (b1) in such a range, the coloring composition excellent in alkali developability and storage stability can be obtained.

As a specific example of the copolymer of an unsaturated monomer (b1) and an unsaturated monomer (b2), For example, Unexamined-Japanese-Patent No. 7-140654, Unexamined-Japanese-Patent No. 8-259876, Unexamined-Japanese-Patent Japanese Patent Laid-Open No. 10-31308, Japanese Patent Laid-Open No. 10-300922 Japanese Patent Laid-Open No. 11-174224 Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. 2000-56118 The copolymer disclosed in Unexamined-Japanese-Patent No. 2004-101728, etc. are mentioned.

In addition, in this invention, Unexamined-Japanese-Patent No. 5-19467, Unexamined-Japanese-Patent No. 6-230212, Unexamined-Japanese-Patent No. 7-207211, Unexamined-Japanese-Patent As disclosed in Japanese Patent Application Laid-Open No. 09-325494, Japanese Patent Application Laid-Open No. Hei 11-140144, Japanese Patent Application Laid-Open No. 2008-181095, and the like, a polymerizable unsaturated bond such as a (meth) acryloyl group is added to a side chain thereof. You may use the carboxyl group-containing polymer which has as binder resin.

The binder resin in this invention has the weight average molecular weight (Mw) of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran) normally 1,000 to 100,000, Preferably it is 3,000 to 50,000. If Mw is too small, the remaining film ratio or the like of the resulting film may be lowered, the pattern shape, heat resistance, or the like may be impaired, or the electrical properties may be deteriorated. Moreover, there exists a possibility that a dry foreign material may arise easily at the time of application | coating by a slit nozzle system.

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

Although the binder resin in this invention can be manufactured by a well-known method, it is disclosed, for example by Unexamined-Japanese-Patent No. 2003-222717, 2006-259680, international publication 07/029871, etc. The structure, Mw, and Mw / Mn can also be controlled by the method.

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

In this invention, content of binder resin is 10-1,000 mass parts normally with respect to a total of 100 mass parts of a specific coloring compound and the other coloring agent used as needed, Preferably it is 20-500 mass parts. When the content of the binder resin is too small, for example, alkali developability may decrease or the storage stability of the resulting colored composition may decrease. On the other hand, when the content of the binder resin is too high, the concentration of the colorant decreases relatively. There is a fear that it is difficult to achieve the color density.

- (C) Crosslinking agent -

In the present invention, the (C) crosslinking agent 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, the (C) crosslinking agent is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups, particularly having two or more (meth) acryloyl groups. It is preferred to use a compound and a compound having two or more N-alkoxymethylamino groups in combination.

As a specific example of the said compound which has two or more (meth) acryloyl groups, the polyfunctional (meth) acrylate obtained by making an aliphatic polyhydroxy compound and (meth) acrylic acid react, and the polyfunctional (meth) acrylate modified with caprolactone , Polyfunctional urethane (meth) acrylate obtained by reacting alkylene oxide-modified polyfunctional (meth) acrylate, (meth) acrylate having hydroxyl group and polyfunctional isocyanate, (meth) acrylate having hydroxyl group and acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group obtained by making it react, etc. are mentioned.

Here, as the aliphatic polyhydroxy compound, for example, divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and The same trivalent or more aliphatic polyhydroxy compound is mentioned. As (meth) acrylate which has the said hydroxyl group, 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta, for example (Meth) acrylate, glycerol dimethacrylate, etc. are mentioned. As said polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, etc. are mentioned, for example. As acid anhydride, for example, anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydro phthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic dianhydride And tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

Moreover, as said caprolactone modified polyfunctional (meth) acrylate, the compound described in Paragraph [0015]-[0018] of Unexamined-Japanese-Patent No. 11-44955 is mentioned, for example. Examples of the alkylene oxide modified polyfunctional (meth) acrylates include ethylene oxide and / or propylene oxide modified di (meth) acrylates of bisphenol A, ethylene oxide and / or propylene oxide modified tri (meth) s of isocyanuric acid. Acrylate, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of trimethylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, ethylene oxide and / or pentaerythritol Propylene oxide modified tetra (meth) acrylate, ethylene oxide and / or propylene oxide modified penta (meth) acrylate of dipentaerythritol, ethylene oxide and / or propylene oxide modified hexa (meth) acrylate of dipentaerythritol, etc. Can be mentioned.

Moreover, as a compound which has the said 2 or more N-alkoxy methylamino group, the compound etc. which have a melamine structure, a benzoguanamine structure, a urea structure are mentioned, for example. In addition, a melamine structure and a benzoguanamine structure mean the chemical structure which has one or more triazine ring or a phenyl substituted triazine ring as a basic skeleton, and is a concept containing melamine, benzoguanamine, or condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ', N', N '', N '' - hexa (alkoxymethyl) Tetra (alkoxymethyl) benzoguanamine, N, N, N ', N'-tetra (alkoxymethyl) glycoluril and the like.

Of these polyfunctional monomers, polyfunctional (meth) acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, and polyfunctional urethane (meth) acrylates Polyfunctional (meth) acrylate having a carboxyl group, N, N, N ', N', N '', N ''-hexa (alkoxymethyl) melamine, N, N, N ', N'-tetra ( Alkoxymethyl) benzoguanamine is preferred. In the polyfunctional (meth) acrylate obtained by making a trivalent or more aliphatic polyhydroxy compound and (meth) acrylic acid react, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipenta In the polyfunctional (meth) acrylate which erythritol hexaacrylate has a carboxyl group, the compound obtained by making pentaerythritol triacrylate and succinic anhydride react, and the compound obtained by making dipentaerythritol pentaacrylate and succinic anhydride react It is especially preferable at the point that the intensity | strength of a colored layer is high, the surface smoothness of a colored layer is excellent, and it is hard to produce background contamination, a film residue, etc. on the board | substrate and the light shielding layer of an unexposed part.

In this invention, (C) crosslinking agent can be used individually or in mixture of 2 or more types.

As for content of (C) crosslinking agent in this invention, 10-1,000 mass parts is preferable with respect to 100 mass parts of (B) binder resin, and 20-500 mass parts is especially preferable. In this case, when there is too little content of a crosslinking agent, there exists a possibility that sufficient sclerosis | hardenability may not be obtained. On the other hand, when there is too much content of a crosslinking agent, when alkali developability is provided to the coloring composition of this invention, alkali developability will fall and a background contamination, a film residue, etc. will generate | occur | produce on the board | substrate or light-shielding layer of an unexposed part. It tends to be easy.

-(D) photoinitiator-

The coloring composition of this invention can be made to contain (D) photoinitiator. Thus, the coloring composition can be imparted with radiation sensitivity. The (D) photoinitiator used for this invention is a compound which generate | occur | produces the active species which can start superposition | polymerization of the said (C) crosslinking agent by exposure of radiation, such as visible light, an ultraviolet-ray, an ultraviolet-ray, an electron beam, X-rays.

Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, nonimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, -Diketone compounds, 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 thioxanone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, and an O-acyloxime compound is preferable.

Specific examples of the thioxanone compound in the photopolymerization initiator of the present invention include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone , 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone.

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

Specific examples of the imidazole-based 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 nonimidazole-based compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor in combination because it can improve the sensitivity. The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a nonimidazole-based compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis (dimethylamino) benzophenone, 4,4'- Ethylamino) benzophenone, and the like. In the present invention, the hydrogen donors may be used alone or in combination of two or more thereof. However, in combination of one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors, the sensitivity may be improved. More preferred.

Specific examples of the triazine-based 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-based compounds having a halomethyl group such as 4,6-bis (trichloromethyl) -s-triazine.

Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O-benzoyloxime), ethanone, 1- [ (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O- -9H-carbazol-3-yl] -, 1- (O-acetyloxime), ethanone, 1- [ -Dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -, 1- (O-acetyloxime).

In this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. 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 this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) crosslinking agents, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, when there is too little content of a photoinitiator, there exists a possibility that hardening by exposure may become inadequate, and when too large, there exists a tendency for the formed colored layer to fall off from a board | substrate at the time of image development.

-(E) solvent-

Although the coloring composition of this invention contains the said (A)-(C) component and the other component added arbitrarily, it is normally manufactured as a liquid composition by mix | blending a solvent.

As said solvent, as long as it does not react with these components, disperse | distributing or melt | dissolving or dissolving (A)-(C) component which comprises a coloring composition, and it has a suitable volatility, it can be used suitably.

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-n -Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene Glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl 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 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;

Alkoxy carboxyl, such as 3-methoxy methyl propionate, 3-methoxy ethylpropionate, 3-ethoxy ethyl propionate, 3-ethoxy ethyl propionate, ethyl ethoxy acetate, and 3-methyl-3- methoxy butyl propionate Acid esters;

Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate Other esters such as 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.

Among 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, from the viewpoint of solubility, pigment dispersibility, coating properties, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol Diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, N-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate and the like are preferred.

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

Although content of a solvent is not specifically limited, From the viewpoint of the applicability | paintability, stability, etc. of the coloring composition obtained, the quantity which the total concentration of each component except the solvent from the said coloring composition becomes 5-50 mass% is preferable, Especially 10 It is preferable that the amount will be from 40% by mass.

-additive-

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

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; Developability improvers such as succinic acid mono [2- (meth) acryloyloxyethyl], monophthalate [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth) acrylate; Siloxane oligomers having a reactive functional group disclosed in JP-A-2008-242078, and the like.

The coloring composition of this invention can be manufactured by a suitable method, As a manufacturing method, the method disclosed by Unexamined-Japanese-Patent No. 2008-58642, 2010-132874, etc. are mentioned, for example. have. When using a pigment as another coloring agent with a specific coloring compound, as disclosed in Unexamined-Japanese-Patent No. 2010-132874, after passing through the 1st filter the dye solution containing a specific coloring compound, The method of manufacturing by mixing the dye solution which passed the filter with the pigment dispersion liquid etc. which were prepared separately, and passing the obtained coloring composition through a 2nd filter is preferable. Moreover, the dye containing a specific coloring compound, the said (B)-(C) component, and the said (D) component and the additive component as needed are dissolved in (E) solvent, and the obtained solution is passed through a 1st filter. After making it pass, the method which manufactures by mixing the solution which passed the 1st filter with the pigment dispersion liquid prepared separately, and passing the obtained coloring composition through a 2nd filter is also preferable. Moreover, after passing the dye solution containing a specific coloring compound through a 1st filter, the dye solution which passed the 1st filter, said (B)-(C) component, and said (D)-(E) as needed By mixing and dissolving the component and the additive component, passing the obtained solution through the second filter, further mixing the solution passed through the second filter with the pigment dispersion prepared separately, and passing the obtained coloring composition through the third filter. The manufacturing method is also preferable.

Color filter and its manufacturing method

The color filter of this invention is equipped with the coloring layer containing a specific coloring compound.

As a method of manufacturing a color filter, the following method is mentioned first. First, on the surface of a board | substrate, a light shielding layer (black matrix) is formed so that the part which forms a pixel may be divided as needed. Next, after apply | coating the liquid composition of the blue radiation sensitive composition containing a specific coloring compound, on this board | substrate, prebaking is performed and the solvent is evaporated and a coating film is formed. Next, after exposing through a photomask to this coating film, it develops using alkaline developing solution and removes and removes the unexposed part of a coating film. Thereafter, by post-baking, a pixel array in which blue pixel patterns are arranged in a predetermined array is formed.

Subsequently, using each colored radiation-sensitive composition of green or red, coating, prebaking, exposure, development, and post-baking of each colored radiation-sensitive composition are performed in the same manner as described above, whereby a green pixel array and a red pixel are used. Arrays are formed sequentially on the same substrate. Thereby, a color filter is obtained in which pixel arrays of three primary colors of red, green, and blue are arranged on a substrate. However, in this invention, the order which forms the pixel of each color is not limited to said thing.

The black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method, but using the colored radiation-sensitive composition in which black colorant is dispersed, the pixel It may be formed in the same manner as in the case of forming. The coloring composition of the present invention can be suitably used for the formation of 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 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 colored radiation-sensitive composition is applied to the substrate, appropriate coating methods such as spraying, roll coating, spin coating (spin coating), slit die coating, and bar coating can be employed. It is preferable to employ | adopt the slit die coating method.

Prebaking is normally performed combining a 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.

Coating thickness is 0.6-8.0 micrometers normally as film thickness after drying, Preferably it is 1.2-5.0 micrometers.

As a light source of radiation used when forming a pixel and / or a black matrix, for example, xenon lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, argon lamp etc. Although laser light sources, such as an ion laser, a YAG laser, an XeCl excimer laser, a nitrogen laser, etc. are mentioned, the radiation in the range whose wavelength is 190-450 nm is preferable.

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

As the alkaline developer, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5- Aqueous solutions, such as diazabicyclo- [4.3.0] -5-nonene, are preferable.

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

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

Although the conditions of post-baking are about 10 to 60 minutes normally at 120-280 degreeC, in terms of the heat resistance of this coloring agent, the temperature of post-baking becomes like this. Preferably it is 240 degrees C or less, Especially preferably, it is 230 degrees C or less.

The film thickness of the pixel thus formed is usually 0.5 to 5.0 m, preferably 1.0 to 3.0 m.

Further, as a second method of manufacturing a color filter, a method of obtaining pixels of each color by an inkjet method disclosed in Japanese Patent Laid-Open No. 7-318723, Japanese Patent Laid-Open No. 2000-310706, or the like is disclosed. It 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, after discharging the liquid composition of the blue coloring composition containing a specific coloring compound in the formed partition by an inkjet apparatus, prebaking is performed and the solvent is evaporated. Subsequently, this coating film is exposed as needed, and then hardened by post-baking to form a blue pixel pattern.

Subsequently, using the green or red coloring composition, a green pixel pattern and a red pixel pattern are sequentially formed on the same board | substrate similarly to the above. Thereby, the color filter by which the pixel pattern of three primary colors of red, green, and blue is arrange | positioned on a board | substrate is obtained. However, in this invention, the order which forms the pixel of each color is not limited to said thing.

In addition, since the partition performs not only a light shielding function but also a function for preventing the coloring composition of each color discharged in the compartment from mixing, the film thickness is thicker than that of the black matrix used in the first method. Therefore, a partition is normally formed using a black radiation sensitive composition.

The substrate and the light source of the radiation used when the color filter is formed, as well as the prebaking and postbaking methods and conditions are the same as those of the first method described above. Thus, the film thickness of the pixel formed by the inkjet system is about the same as the height of a partition.

After forming a protective film on the pixel pattern obtained in this way as needed, a transparent conductive film is formed by sputtering. After forming a transparent conductive film, a spacer can be formed further and it can be set as a color filter. Although a spacer is normally formed using a radiation sensitive composition, it can also be set as the spacer (black spacer) which has light shielding property. In this case, although the colored radiation-sensitive composition in which the black coloring agent was disperse | distributed is used, the coloring composition of this invention can be used suitably also for formation of such a black spacer.

Since the color filter of this invention obtained in this way is extremely high in brightness | luminance and color purity, it is very useful for a color liquid crystal display element, a color image tube element, a color sensor, an organic EL display element, an electronic paper, etc.

Display element

The display element of this invention is equipped with the color filter of this invention. As a display element, a color liquid crystal display element, an organic electroluminescent display element, an electronic paper, etc. are mentioned.

The color liquid crystal display element provided with the color filter of this invention can take a suitable structure. For example, the color filter is formed on a substrate separate from the driving substrate on which the thin film transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed have a structure in which the color filter is opposed through the liquid crystal layer. And a substrate in 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 in which an ITO (indium oxide doped tin) electrode is formed via a liquid crystal layer. You can also take The latter structure can remarkably improve the aperture ratio, and has the advantage that a bright and high precision liquid crystal display element is obtained.

The color liquid crystal display device having the color filter of the present invention may include a backlight unit having 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 combination of a blue LED and 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 including the color filter of the present invention includes a twisted nematic (TN) type, a super twisted nematic (STN) type, an in-plane switching switching (IPS) type, a vertical alignment (VA) type, and an OCB (Optically Compensated Birefringence) type. Appropriate liquid crystal modes such as a mold can be applied.

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

Moreover, the electronic paper provided with the color filter of this invention can take a suitable structure, for example, the structure disclosed by Unexamined-Japanese-Patent No. 2007-41169.

<Examples>

Hereinafter, an Example is given and embodiment of this invention is described further more concretely. However, the present invention is not limited to the following examples.

Synthesis and Evaluation of Specific Coloring Compounds

1. Synthesis of Specific Coloring Compounds

Synthesis Example 1

1.4 g (2.72 mmol) of CI basic blue 7 (Cl ^- salt of compound c2 of the compound group c), 0.768 g (4.08 mmol) of potassium tetrafluoroborate (manufactured by Wako Pure Chemical Industries, Ltd.), 20 mL of chloroform and 10 mL of water were added, and the mixture was stirred at room temperature for 7 hours. After separating and removing the aqueous layer, the organic layer was washed with water twice and concentrated under reduced pressure, and the obtained solid was dried under reduced pressure to obtain 1.70 g of a dark solid (yield 80.2%). Let this be compound A. The ¹ H-NMR (solvent: deuterated chloroform) spectrum of Compound A was as follows, and it was confirmed that it is a target compound.

Synthesis Example 2

A specific colored compound was synthesized in the same manner as in Synthesis Example 1 except that lithium hexafluorophosphate (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of potassium tetrafluoroborate in Synthesis Example 1 to synthesize ¹ H-NMR (solvent: deuterated). Chloroform) measurement confirmed that it was the desired compound. Let this be compound B. The ¹ H-NMR spectrum of Compound B is as follows.

Synthesis Example 3

* Except that the Preparation Example 1 in place of tetrakis borate, potassium borate, potassium tetrafluoroborate in (benzene pentafluorophenyl) (Wako jyunya kkusa, Ltd.) in the same manner as in Synthesis Example 1 Synthesis of specific coloring compound, ¹ H- It confirmed that it was a target compound by NMR (solvent: deuterated chloroform) measurement. Let this be compound C. The ¹ H-NMR spectrum of the compound C is as follows.

Synthesis Example 4

A specific colored compound was synthesized in the same manner as in Synthesis Example 1 except that K [BF (CN) ₃ ] was used instead of potassium tetrafluoroborate in Synthesis Example 1 to measure ¹ H-NMR (solvent: deuterated chloroform). It confirmed that it was a target compound by Let this be compound D. The ¹ H-NMR spectrum of the compound C is as follows.

Synthesis Example 5

7 instead of CI Basic Blue in Synthetic Example 1, CI Basic Blue 11 ^- except that the (Cl of Compound c4 of the compound group c salts) In the same manner as in Synthesis Example 1 to synthesize the particular coloring compound, ¹ H-NMR (Solvent: Deuterated Chloroform) By the measurement, it was confirmed that it was the target compound.

Synthesis Example 6

7 instead of CI Basic Blue according to Synthesis Example 1 and CI Basic Violet ¹⁶ except that the (Cl of compound e2 of the group of compounds e salt) In the same manner as in Synthesis Example 1 to synthesize the particular coloring compound, ¹ H-NMR (Solvent: Deuterated Chloroform) By the measurement, it was confirmed that it was the target compound.

Synthesis Example 7

In Synthesis Example 1, a specific colored compound was synthesized in the same manner as in Synthesis Example 1 except that CI Basic Blue 41 (methane sulfate of Compound f13 of Compound F) was used instead of CI Basic Blue 7. Thus, ¹ H-NMR ( Solvent: Deuterated chloroform) measurement confirmed that it was the target compound.

Synthesis Example 8

7 instead of CI Basic Blue in Synthetic Example 1, CI Basic Blue ³ except that the (the compound group of i compounds i4 of Cl salt) in the same manner as in Preparation Example 1 to synthesize the particular coloring compound, ¹ H-NMR (Solvent: Deuterated Chloroform) By the measurement, it was confirmed that it was the target compound.

Synthesis Example 9

7 instead of CI Basic Blue in Synthetic Example 1, CI Basic Blue 22 ^- except that the (Cl of Compound j1 of the compound group j salt) In the same manner as in Synthesis Example 1 to synthesize the particular coloring compound, ¹ H-NMR (Solvent: Deuterated Chloroform) By the measurement, it was confirmed that it was the target compound.

Example 1

A specific coloring compound was synthesized in the same manner as in Synthesis Example 1 except that Dicyanamid Sodium (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of potassium tetrafluoroborate in Synthesis Example 1, and ¹ H-NMR (solvent: deuterated chloroform ) It was confirmed that it was the target compound by measurement. Let this be compound E. The ¹ H-NMR spectrum of the compound C is as follows.

Example 2

The CI Basic Blue 3, instead of CI Basic Blue 7 in Synthetic Example 1, synthesis of specific coloring compound except that the DC analog mid sodium borate in place of potassium tetrafluoroborate, respectively in the same manner as in Synthesis Example 1, ¹ H- It confirmed that it was a target compound by NMR (solvent: deuterated chloroform) measurement.

Example 3

The CI Basic Blue 22, CI Basic Blue 7, instead of in the synthesis example 1, in place of potassium borate was used in a DC analog mid sodium respectively in the same manner as in Synthesis Example 1 Synthesis of specific coloring compound, and tetrafluoroethylene, ¹ H- It confirmed that it was a target compound by NMR (solvent: deuterated chloroform) measurement.

2. Evaluation of Specific Coloring Compounds

Compound A obtained in Synthesis Example 1 was dissolved in at least 10 mass% in cyclohexanone, and the solution was blue. 10 mass% or more of the specific coloring compounds obtained by the synthesis examples 2-9 and Examples 1-3 were all dissolved in cyclohexanone.

In addition, the 5% mass reduction temperature of the specific colored compound obtained by the synthesis examples 1-9 and Examples 1-3 was all 250 degreeC or more based on the thermogravimetry-differential heat simultaneous measurement analysis. On the other hand, C.I. Basic Blue 7, C.I. Basic Blue 11, C.I. Basic Violet 16, C.I. Basic Blue 41, C.I. Basic Blue 3 and C.I. The 5% mass reduction temperature, based on the thermogravimetric-differential thermal simultaneous analysis of Basic Blue 22, was all less than 200 ° C.

&Lt; Production of Pigment Dispersion >

Production Example 1

As a colorant, C.I. Pigment Blue 15: 6 using 15 parts by mass, 12.5 parts by mass of BYK-LPN21116 (manufactured by BYK Corporation) as a dispersant (solid content concentration = 40 mass%), and 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent. Treatment with a bead mill produced a pigment dispersion (A-1).

Production Example 2

As a colorant, C.I. Pigment Blue 15: 6 instead of C.I. A pigment dispersion (A-2) was prepared in the same manner as in Production Example 1 except that Pigment Violet 23 was used.

<Production of Dye Solution>

Production Example 3

Dye solution A was prepared by mixing 5 parts by mass of compound A as a colorant and 95 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

Production Example 4

Dye solution B was prepared by mixing 5 parts by mass of compound B as a colorant and 95 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

Production Example 5

Dye solution C was prepared by mixing 5 parts by mass of compound C as a colorant and 95 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

Production Example 6

Dye solution D was prepared by mixing 5 parts by mass of compound D as a colorant and 95 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

Production Example 7

Dye solution E was prepared by mixing 5 parts by mass of compound E as a colorant and 95 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

Production Example 8

As a colorant, C.I. Dye solution F was prepared by mixing 5 parts by mass of Basic Blue 7 and 95 parts by mass of propylene glycol monomethyl ether as a solvent.

<Synthesis of Binder Resin>

100 mass parts of propylene glycol monomethyl ether acetates were thrown into the flask provided with the cooling tube and the stirrer, and nitrogen-substituted. It heats at 80 degreeC, and at the same temperature, 100 mass parts of propylene glycol monomethyl ether acetates, 20 mass parts of methacrylic acid, 10 mass parts of styrene, 5 mass parts of benzyl methacrylate, and 15 mass of 2-hydroxyethyl methacrylate Part, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of mono (2-acryloyloxyethyl) succinic acid and 2,2'-azobis (2,4-dimethyl Valeronitrile) 6 parts by mass of a mixed solution was added dropwise over 1 hour, and polymerized for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration = 33% by mass). Obtained binder resin was Mw = 12,200 and Mn = 6,500. This binder resin is referred to as "binder resin (B1)".

&Lt; Preparation and evaluation of colored composition >

Example 4

13.6 mass parts of pigment dispersion liquid (A-1), 27.2 mass parts of dye solution A, 18.1 mass parts of binder resin (B1) solution as binder resin, Toagosei Co., Ltd. M-402 (Dipentaerythritol hexaacryl) as a crosslinking agent 5.5 parts by mass and a mixture of dipentaerythritol pentaacrylate) and MW-30 (N, N, N ', N', N '', N ''-hexa (methoxymethyl) manufactured by Sanwa Chemical Co., Ltd. Melamine is the main component, weight average polymerization degree 1.3) 2.4 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (manufactured by Ciba Specialty Chemicals, Inc., trade name IRGACURE369) as a photopolymerization initiator. ) 2.2 parts by mass, 0.2 parts by mass of Megapack F-554 manufactured by DIC Corporation as a fluorine-based surfactant, and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a coloring composition (CR1) having a solid content of 20% by mass. .

After apply | coating a coloring composition (CR1) on a glass substrate using a spin coater, it prebaked for 10 minutes on the 80 degreeC hotplate, and formed the coating film. By changing the rotation speed of the spin coater, three coating films having different film thicknesses were formed by the same operation.

Subsequently, after cooling these substrates to room temperature, using a high pressure mercury lamp, the radiation including each wavelength of 365 nm, 405 nm and 436 nm in each coating film, without going through a photomask, was exposed to an exposure amount of 2,000 J / m ² . It exposed. Thereafter, discharging the developing solution to the developing pressure 1 kgf / cm ² (nozzle diameter 1 mm) containing 0.04% by weight aqueous potassium hydroxide solution of 23 ℃ with respect to these substrates were subjected to a shower development for 90 seconds. Then, after wash | cleaning this board | substrate with ultrapure water and air drying, the cured film for evaluation was formed by performing post-baking for 30 minutes in a 230 degreeC clean oven further.

About three obtained cured films, the chromaticity coordinate value (x, y) and the stimulus value (Y) in a CIE colorimeter were measured with the C light source and 2 degree visual field using the color analyzer (MCPD2000 by Otsuka Denshi Co., Ltd.). Further, the film thickness of the obtained cured film was measured using Alpha Step IQ manufactured by KLA-Tencor. From the measurement result, the chromaticity coordinate value x, the stimulus value Y, and the film thickness in chromaticity coordinate value y = 0.080 were calculated | required. The evaluation results are shown in Table 1. The larger the magnetic pole value Y, the higher the light transmittance (luminance), and the thinner the film thickness, the higher the coloring power.

The substrate on which the cured film was formed was sandwiched between two deflection plates, the deflection plate on the front side was rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the rear side, and the luminance meter LS-100 (Minolta Co., Ltd.) The maximum and minimum values of the light intensity transmitted through And the value which divided the maximum value by the minimum value about each cured film was made into contrast ratio. From the measurement results, the contrast ratio at the chromaticity coordinate value y = 0.080 was determined. The evaluation results are shown in Table 1.

Example 5

15.5 parts by mass of the pigment dispersion (A-1), 22.3 parts by mass of the dye solution B, 16.1 parts by mass of the binder resin (B1) solution as a binder resin, and M-402 (Dipentaerythritol hexaacryl) manufactured by Toagosei Co., Ltd. 5.5 parts by mass and a mixture of dipentaerythritol pentaacrylate) and MW-30 (N, N, N ', N', N '', N ''-hexa (methoxymethyl) manufactured by Sanwa Chemical Co., Ltd. Melamine is the main component, weight average polymerization degree 1.3) 2.4 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (manufactured by Ciba Specialty Chemicals, Inc., trade name IRGACURE369) as a photopolymerization initiator. ) 2.2 parts by mass of DIC Corporation Megapack F-554 as a fluorine-based surfactant and 0.2 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a colored composition (CR2) having a solid content of 20% by mass. .

It evaluated like Example 4 except having used coloring composition (CR2) instead of coloring composition (CR1). The evaluation results are shown in Table 1.

Example 6

16.2 parts by mass of the pigment dispersion (A-1), 21.3 parts by mass of the dye solution C, 16.1 parts by mass of the binder resin (B1) solution as a binder resin, and M-402 (Dipentaerythritol hexaacryl) manufactured by Toagosei Co., Ltd. 5.5 parts by mass and a mixture of dipentaerythritol pentaacrylate) and MW-30 (N, N, N ', N', N '', N ''-hexa (methoxymethyl) manufactured by Sanwa Chemical Co., Ltd. Melamine is the main component, weight average polymerization degree 1.3) 2.4 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (manufactured by Ciba Specialty Chemicals, Inc., trade name IRGACURE369) as a photopolymerization initiator. ) 2.2 parts by mass of DIC Corporation Megapack F-554 as a fluorine-based surfactant and 0.2 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a colored composition (CR3) having a solid content of 20% by mass. .

It evaluated like Example 4 except having used coloring composition (CR3) instead of coloring composition (CR1). The evaluation results are shown in Table 1.

Example 7

15.5 parts by mass of the pigment dispersion (A-1) and 23.2 parts by mass of the dye solution D, 16.1 parts by mass of the binder resin (B1) solution as a binder resin, and M-402 (Dipentaerythritol hexaacryl) manufactured by Toagosei Co., Ltd. 5.5 parts by mass and a mixture of dipentaerythritol pentaacrylate) and MW-30 (N, N, N ', N', N '', N ''-hexa (methoxymethyl) manufactured by Sanwa Chemical Co., Ltd. Melamine is the main component, weight average polymerization degree 1.3) 2.4 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (manufactured by Ciba Specialty Chemicals, Inc., trade name IRGACURE369) as a photopolymerization initiator. ) 2.2 parts by mass of DIC Corporation Megapack F-554 as a fluorine-based surfactant and 0.2 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a coloring composition (CR4) having a solid content of 20% by mass. .

It evaluated like Example 4 except having used coloring composition (CR4) instead of coloring composition (CR1). The evaluation results are shown in Table 1.

Example 8

13.6 mass parts of pigment dispersion liquid (A-1), 25.2 mass parts of dye solution E, 18.1 mass parts of binder resin (B1) solution as binder resin, Toagosei Co., Ltd. M-402 (Dipentaerythritol hexaacryl) as a crosslinking agent 5.5 parts by mass and a mixture of dipentaerythritol pentaacrylate) and MW-30 (N, N, N ', N', N '', N ''-hexa (methoxymethyl) manufactured by Sanwa Chemical Co., Ltd. Melamine is the main component, weight average polymerization degree 1.3) 2.4 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (manufactured by Ciba Specialty Chemicals, Inc., trade name IRGACURE369) as a photopolymerization initiator. ) 2.2 parts by mass of DIC Corporation Megapack F-554 as a fluorine-based surfactant and 0.2 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a coloring composition (CR5) having a solid content of 20% by mass. .

It evaluated like Example 4 except having used coloring composition (CR5) instead of coloring composition (CR1). The evaluation results are shown in Table 1.

Comparative Example 1

18.1 parts by mass of the pigment dispersion (A-1), 4.5 parts by mass of the pigment dispersion (A-2), 16.1 parts by mass of the binder resin (B1) solution as the binder resin, and 5.5 parts by mass of M-402 manufactured by Toagosei Co., Ltd. 2.4 parts by mass of Sanwa Chemical Co., Ltd. MW-30 and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (manufactured by Ciba Specialty Chemicals, Inc.) as a photopolymerization initiator IRGACURE369) 2.2 parts by mass of DIC Corporation Megapack F-554 as a fluorine-based surfactant, 0.2 parts by mass, and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a coloring composition (CR6) having a solid content of 20% by mass. It was.

It evaluated like Example 4 except having used coloring composition (CR6) instead of coloring composition (CR1). The evaluation results are shown in Table 1.

Comparative Example 2

18.1 parts by mass of the pigment dispersion (A-1), 24.2 parts by mass of the dye solution F, 16.1 parts by mass of the binder resin (B1) solution as a binder resin, 5.5 parts by mass of M-402 manufactured by Toagosei Co., Ltd. 2.4 parts by mass of MEI-30 manufactured by Kaisha Chemical Co., Ltd., 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one as a photopolymerization initiator (manufactured by Ciba Specialty Chemicals, trade name IRGACURE369) 2.2 0.2 mass part of DIC Corporation Megapack F-554 as a mass part and fluorine-type surfactant, and propylene glycol monomethyl ether acetate as a solvent were mixed, and the coloring composition (CR7) of 20 mass% of solid content concentration was prepared.

It evaluated like Example 4 except having used coloring composition (CR7) instead of coloring composition (CR1). The evaluation results are shown in Table 1.

In Table 1, "B15: 6" means C.I. Pigment Blue 15: 6 refers to C.I. Pigment violet 23, "BB-7" is C.I. Each stands for Basic Blue 7.

Claims (9)

(A) The coloring composition containing the compound represented by following formula (1), (B) binder resin, and (C) crosslinking agent.
&Lt; Formula 1 >

[In Formula 1, X ⁺ represents a cationic chromophore, 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 phosphorus atom or a boron atom, Z, When there are a plurality of R ⁰ 's each, they may be the same or different, a represents an integer of 1 to 6, b represents an integer of 0 to 5, and a + b is 4 or 6,
However, when M is a phosphorus atom, wherein _{^{(Z a R 0 b M)}} - a is to anions represented by the following general formula (1a), when M is a boron atom, the _{^{(Z a R 0 b M)}} - to a It is an anion represented by general formula (1b).

In general formula (1a), R <^1> represents a halogenated hydrocarbon group, P represents a phosphorus atom, Hal represents a halo group, and when two or more R <^1> , Hal exists, they may be same or different, and c is 0- Represents an integer of 6

In general formula (1b), R <^2> represents a cyano group, B represents a boron atom, Hal represents a halo group, and when ^two or more R <^2> , Hal exists, they may be same or different, d is 1- Represents an integer of 4] The coloring composition of Claim ¹ whose R <^1> is a fluorinated alkyl group and said Hal is a fluoro group in the said General formula (1a). According to claim 1, wherein the anion represented by the formula ^{_{(1a) PF 6 -, (}} CF 3) 3 PF 3 -, (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 ^- or _{(C 2 F 5) (CF} 3) 2 PF 3 - a coloring composition is selected from the. The coloring composition of Claim 1 whose said Hal is a fluoro group in the said General formula (1b). According to claim 1, wherein the anion represented by the formula _{(1b) B (CN) 4} -, B (CN) F 3 -, B (CN) 2 F 2 - or B (CN) ₃ F ^- is selected from Coloring composition. The coloring composition of Claim 1 whose said (C) crosslinking agent is a compound which has two or more polymerizable groups. The method according to any one of claims 1 to 6, wherein X ⁺ is a triarylmethane chromophore, a methine chromophore, an azo chromophore, a diarylmethane chromophore, a quinoneimine chromophore, an anthraquinone chromophore, or a xanthene-based chromophore A coloring composition that is a chromophore. A color filter comprising a colored layer containing a compound represented by the following formula (1).
&Lt; Formula 1 >

[In Formula 1, X ⁺ represents a cationic chromophore, 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 phosphorus atom or a boron atom, Z, When there are a plurality of R ⁰ 's each, they may be the same or different, a represents an integer of 1 to 6, b represents an integer of 0 to 5, and a + b is 4 or 6,
However, when M is a phosphorus atom, wherein _{^{(Z a R 0 b M)}} - a is to anions represented by the following general formula (1a), when M is a boron atom, the _{^{(Z a R 0 b M)}} - to a It is an anion represented by general formula (1b).

In general formula (1a), R <^1> represents a halogenated hydrocarbon group, P represents a phosphorus atom, Hal represents a halo group, and when two or more R <^1> , Hal exists, they may be same or different, and c is 0- Represents an integer of 6

In general formula (1b), R <^2> represents a cyano group, B represents a boron atom, Hal represents a halo group, and when ^two or more R <^2> , Hal exists, they may be same or different, d is 1- Represents an integer of 4] The display element provided with the color filter of Claim 8.