TWI467329B - Colorant, coloring composition, color filter and display element - Google Patents

Description

Colorant, coloring composition, color filter, and display element

The present invention relates to a coloring composition, a color filter, and a display element, and more particularly to color filter applied to a transmissive or reflective type color liquid crystal display element, solid-state imaging element, organic EL display element, electronic paper, or the like. A coloring agent for a sheet, a colored composition containing the coloring agent, a color filter including a coloring layer containing the coloring agent, and a display element including the color filter.

When a color filter is produced using a coloring sensitizing radiation composition, it is known that a pigment dispersion type color sensitizing radiation composition is applied onto a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape (hereinafter A method of performing development to obtain pixels of respective colors (Patent Documents 1 to 2). Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is also known (Patent Document 3). Further, a method of obtaining a pixel of each color by an inkjet method using a pigment-dispersed coloring resin composition is known (Patent Document 4).

Further, it is known that in order to achieve high luminance of a display element, high color purity, or high definition of a solid-state imaging element, it is effective to use a dye as a colorant. For example, in Patent Document 5, it is proposed to use a specific structure. Is a dye.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-144502

[Patent Document 2] Japanese Patent Laid-Open No. 3-53201

[Patent Document 3] Japanese Patent Laid-Open No. Hei 6-35188

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-310706

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2008-242311

However, it is proposed in Patent Document 5. There is a problem in that the dye has a poor voltage holding ratio of the color filter. From the background as described above, it is strongly desired to develop a coloring composition suitable for producing a color filter having a good voltage holding ratio.

Therefore, an object of the present invention is to provide a colored composition suitable for forming a coloring layer having excellent voltage holding ratio. Further, an object of the present invention is to provide a color filter including a coloring layer formed of the coloring composition and a display element including the color filter.

In view of the above-described actual circumstances, the inventors of the present invention have intensively studied and found that the above problems can be solved by using a coloring agent having a specific structure, and the present invention has been completed.

That is, the present invention provides the following components (A), (B) and (C) The coloring composition.

(A) having a polymerizable unsaturated group in the color developing portion A coloring agent (hereinafter also referred to as "the present coloring agent"); (B) a binder resin; and (C) a crosslinking agent.

Further, the present invention provides a color filter including a coloring layer formed using the colored composition, and a display element including the color filter. Here, the "colored layer" means each color pixel, black matrix, black spacer, or the like used for the color filter.

Furthermore, the present invention provides a coloring agent having a structure represented by the following formula (1).

[In the formula (1), R ^a represents a group having a polymerizable unsaturated group; and R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms; Or a phenyl group (the alkyl group, a cycloalkyl group, or a phenyl group may have a substituent); and R ⁵ and R ⁶ independently of each other represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a chlorine atom; and r represents 1 to 5; integer, r is an integer of 2 or more, plural r ^a may be the same or different. ]

When the colored composition of the present invention is used, a coloring layer excellent in voltage holding ratio can be formed. Therefore, the coloring composition of the present invention can be extremely suitably used for producing a color filter for display elements, a color filter for color separation of solid-state imaging elements, a color filter for organic EL display elements, and color filter for electronic paper. A variety of color filters represented by the film.

[Formation of the Invention]

Hereinafter, the present invention will be described in detail.

Coloring composition

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

- (A) colorant -

The colored composition of the present invention contains the present colorant as (A) a colorant.

The coloring agent has a polymerizable unsaturated group in the color developing portion. The coloring agent is not particularly limited. The polymerizable unsaturated group may, for example, be a (meth)acryl fluorenyl group, a vinyl aryl group, a vinyloxy group or an allyl group. Among them, a (meth) acrylonitrile group is preferred.

In the present invention, the inventors presume that the present colorant is unsaturated by polymerization when exposed or post-baking by having a polymerizable unsaturated group. The crosslinking reaction occurs at the base to suppress dissolution of the dye into the liquid crystal, and thus exhibits a good voltage holding ratio.

The preferred coloring agent in the present invention has a structure represented by the following formula (1). A coloring agent.

[In the formula (1), R ^a represents a group having a polymerizable unsaturated group; and R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms; Or a phenyl group (the alkyl group, a cycloalkyl group, or a phenyl group may have a substituent); and R ⁵ and R ⁶ independently of each other represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a chlorine atom; and r represents 1 to 5; integer, r is an integer of 2 or more, plural r ^a may be the same or different. ]

Examples of the alkyl group having 1 to 8 carbon atoms in R ¹ to R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a third butyl group, and an isobutyl group. Base, pentyl, third amyl, hexyl, heptyl, octyl, isooctyl, trioctyl, 2-ethylhexyl and the like. Among them, an alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred.

Examples of the cycloalkyl group having 3 to 8 carbon atoms in R ¹ to R ⁴ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Among them, a cycloalkyl group having 5 to 7 carbon atoms is preferred, and a cyclohexyl group is more preferred.

The alkyl group having 1 to 8 carbon atoms, the cycloalkyl group having 3 to 8 carbon atoms, or the phenyl group in R ¹ to R ⁴ may have a substituent. As the substituent, for example, a halogen atom, -R ⁷ , -OH, -OR ⁷ , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁷ , -SO can be preferably used. ₃ R ⁷ , -SO ₂ NHR ⁸ , -SO ₂ NR ⁸ R ⁹ , -SO ₃ -, and the like.

Here, R ⁷ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. Here, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom, a carbonyl group or -NR ⁷ -.

R ⁸ and R ⁹ independently of each other represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms (preferably 3 to 8) or -G, or R. A heterocyclic group having 2 to 10 carbon atoms formed by bonding ⁸ and R ^{9 to} each other. Wherein, the hydrogen atom contained in the alkyl group and the cycloalkyl group may be substituted with a hydroxyl group, a halogen atom, -G, -CH=CH ₂ or -CH=CHR ⁷ , and the methylene group contained in the alkyl group and the cycloalkyl group The group may be substituted with an oxygen atom, a carbonyl group or -NR ⁷ -, and the hydrogen atom contained in the heterocyclic group may be substituted with -R ⁷ , -OH or -G.

M represents a sodium atom or a potassium atom.

G represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms. Here, the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group may be substituted with -OH, -R ⁷ , -OR ⁷ , -NO ₂ , -CH=CH ₂ , -CH=CHR ⁷ or a halogen atom.

The saturated hydrocarbon group in R ⁷ may be any of a linear chain, a branched chain, and a cyclic chain as long as the carbon number is 1 to 10, and may have a bridge structure. Specifically, in addition to the alkyl group similar to the above R ¹ to R ^{4 ,} a mercapto group, a fluorenyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclodecyl group may be mentioned. Further, examples of the group in which the methylene group contained in the saturated hydrocarbon group is substituted with an oxygen atom may, for example, be methoxypropyl group, ethoxypropyl group, 2-ethylhexyloxypropyl group or methoxy group. Heji and so on.

Further, specific examples of the alkyl group, the cycloalkyl group and the substituent of the phenyl group -CO ₂ R ⁷ in R ¹ to R ⁴ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and an isopropoxycarbonyl group. , butoxycarbonyl, cyclohexyloxycarbonyl, methoxypropoxycarbonyl and the like. Further, specific examples of -SO ₃ R ⁷ include a methylsulfonyl group, an ethylsulfonyl group, a hexylsulfonyl group, a sulfonyl group, and the like.

Specific examples of the heterocyclic group formed by bonding R ⁸ and R ^{9 to} each other include pyrrole, pyridine, hydrazine, isoindole, quinoline, isoquinoline, oxazole, phenanthridine, acridine, and brown. Thio Wait.

Specific examples of the aromatic hydrocarbon group in G include a phenyl group, a naphthyl group, an anthracenyl group and the like. Further, specific examples of the aromatic heterocyclic group include a furyl group, a thienyl group, a pyridyl group, and a pyrrolyl group. Azolyl, different Azolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, pyrimidinyl and the like.

Examples of the alkyl group having 1 to 8 carbon atoms in R ⁵ and R ⁶ include the same alkyl groups as described above.

r represents an integer of 1 to 5, and when r is an integer of 2 or more, a plurality of R ^a may be the same or different, and r is preferably 1 or 2, more preferably 1.

As the present colorant in the present invention, a coloring agent having a structure represented by the following formula (2) can be further preferably used. Further, it is preferred that the -COOR ^b group in the formula (2) is substituted with an ortho position on the benzene ring.

[In the formula (2), R ^b represents a group having a polymerizable unsaturated group; and R ¹ to R ^{6 have the} same meanings as R ¹ to R ⁶ in the above formula (1). ]

Examples of the group having a polymerizable unsaturated group in R ^b include the same groups as described above. From the viewpoint of easiness of the crosslinking reaction, as the polymerizable unsaturated group in the present invention, a (meth) acrylonitrile group can be preferably used. A preferred example of R ^b is a group represented by the following formula (2a) or (2b).

[In the formulae (2a) and (2b), R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a methyl group.

Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a substituted or unsubstituted alkanediyl group having 1 to 12 carbon atoms.

Z represents a -CO- group or a -COO-(*) group (wherein * represents a linkage to Y ² ).

Q represents a divalent alicyclic hydrocarbon group.

P ¹ represents an integer from 0 to 12.

p ² and p ³ independently represent an integer of 0-6. ]

R ¹⁰ and R ¹¹ are preferably a methyl group among a hydrogen atom and a methyl group.

Examples of the alkanediyl group having 1 to 12 carbon atoms in Y ¹ to Y ⁴ include a methylene group, an ethylidene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, and a propane- 1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1, 4-diyl, pentane-1,2-diyl, pentane-1,3-diyl, pentane-1,4-diyl, pentane-1,5-diyl, hexane-1, 5-diyl, hexane-1,6-diyl, octane-1,8-diyl, decane-1,10-diyl, etc., of which an alkanediyl group having 2 to 8 carbon atoms is preferred. More preferably, it is an alkanediyl group having 2 to 6 carbon atoms.

Examples of the substituent of the alkanediyl group include a hydroxyl group, a halogen atom, a (meth)acryloxy group, and a phenoxy group. Among them, a hydroxyl group is preferred.

The divalent alicyclic hydrocarbon group in Q is preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms, more preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms. Further, the alicyclic hydrocarbon group may be a 2 to 4 ring crosslinked cyclic hydrocarbon group.

As R ^b , a (meth) propylene decyloxyalkyl group is preferred. Further, the total number of carbon atoms of the (meth) propylene methoxyalkyl group is preferably 4 to 16, and particularly preferably 4 to 10.

p ^{1 is} preferably an integer of 0 to 3, and p ² and p ³ are preferably each independently an integer of 0 to 3.

The coloring agent having the structure represented by the above formula (2) can be obtained, for example, by an esterification reaction of a compound represented by the following formula (3) with a compound having a hydroxyl group and a (meth)acryloyl group. As the esterification reaction, a known method can be used. Further, it is preferred that the -COOH group in the formula (3) is substituted at the ortho position on the benzene ring.

[In the formula (3), R ¹ to R ^{6 have the} same meanings as R ¹ to R ⁶ in the above formula (1).

X ^- represents an anion. ]

The compound having a hydroxyl group and a (meth)acrylinyl group may have one or more hydroxyl groups and a (meth)acrylonium group in the compound, and the number of bonds of the hydroxyl group and the (meth)acryloyl group. The key position is arbitrary. Further, as the hydroxyl group, any of an alcoholic hydroxyl group and a phenolic hydroxyl group can be used. Further, when other substituents are contained in addition to the hydroxyl group and the (meth)acrylonium group, the kind, the bonding position, and the number of bonds are not limited.

Preferred as a hydroxyl group and a (meth) acrylonitrile group For example, a compound represented by the following formula (3a) or (3b) can be mentioned.

[In the formulae (3a) and (3b), R ¹⁰ , R ¹¹ , Y ¹ , Y ² , Y ³ , Y ⁴ , Z, Q, p ¹ , p ² and p ^{3 are} synonymous with the above. ]

Preferable specific examples of the compound having a hydroxyl group and a (meth)acrylinyl group include compounds represented by the following formulas (2-1) to (2-4).

[In the formula (2-1), R ¹² represents a hydrogen atom or a methyl group.

a and b independently represent an integer of 0 to 2, and c represents an integer of 1 to 6.

However, when at least one selected from the group consisting of a and b is an integer of 1 or more, the -CH(OH)- group, the -CH(CH ₃ )- group and the -CH ₂ - group may be bonded in an arbitrary order. ]

[In the formula (2-2), R ¹³ represents a hydrogen atom or a methyl group.

d and e independently represent integers from 1 to 12. ]

[In the formula (2-3), R ¹⁴ represents a hydrogen atom or a methyl group.

f and g independently represent integers from 1 to 12. ]

[In the formula (2-4), R ¹⁵ represents a hydrogen atom or a methyl group.

W represents a divalent group selected from the group consisting of the groups represented by the following formulas (I) to (IV).

h and i independently represent integers from 0 to 6. ]

Examples of the compound represented by the formula (2-1) include 2-hydroxyethyl (meth)acrylate, 1-methyl-2-hydroxyethyl (meth)acrylate, and (meth)acrylic acid 2. -Methyl-2-hydroxyethyl ester, 3-hydroxypropyl (meth)acrylate, 1-glyceryl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxyl (meth)acrylate Amyl ester, 6-hydroxyhexyl (meth)acrylate, 7-hydroxyheptyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 9-hydroxydecyl (meth)acrylate, (methyl) ) 10-hydroxydecyl acrylate, 11-hydroxyundecyl (meth)acrylate, 12-hydroxydodecyl (meth)acrylate, and the like.

In addition, examples of the compound represented by the formula (2-2) include 2-(6-hydroxyhexyloxy)ethyl (meth)acrylate and 3-(6-hydroxyl)(meth)acrylate.醯oxy)propyl ester, 4-(6-hydroxyhexyloxy)butyl (meth)acrylate, 5-(6-hydroxyhexyloxy)pentyl (meth)acrylate, (meth)acrylic acid 6-(6-hydroxyhexyloxy)hexyl ester or the like (6-hydroxyhexyloxy)alkyl (meth)acrylate; etc.; as (meth)acrylic acid (6-hydroxyhexyloxy) alkane Commercially available products of the base esters include PLACEL FM1D and PLACCEL FM2D (above, DAICEL Chemical Industry Co., Ltd.).

In addition, examples of the compound represented by the formula (2-3) include 2-(3-hydroxy-2,2-dimethylpropoxycarbonyloxy)ethyl (meth)acrylate, (a) 3-(3-hydroxy-2,2-dimethylpropoxycarbonyloxy)propyl acrylate, 4-(3-hydroxy-2,2-dimethylpropoxycarbonyl)(meth)acrylate Oxy)butyl acrylate, 5-(3-hydroxy-2,2-dimethylpropoxycarbonyloxy)pentyl (meth)acrylate, 6-(3-hydroxy-2,2 (meth)acrylate -(Methyl)acrylic acid (3-hydroxy-2,2-dimethyl group) such as dimethylpropoxycarbonyloxy)hexyl ester A propoxycarbonyloxyalkylalkyl ester or the like; a commercially available product of (3-hydroxy-2,2-dimethylpropoxycarbonyloxy)alkyl (meth)acrylate, which may be mentioned The trade name is HEMAC1 (DAICEL Chemical Industry Co., Ltd.).

In addition, examples of the compound represented by the formula (2-4) include 4-hydroxycyclohexyl (meth)acrylate and (4-hydroxymethylcyclohexyl)methyl (meth)acrylate. 2-(4-(2-hydroxyethyl)cyclohexyl]ethyl acrylate, 3-hydroxybicyclo[2.2.1]hept-5-en-2-yl (meth)acrylate, (methyl) Acrylic acid (3-hydroxymethylbicyclo[2.2.1]hept-5-en-2-yl)methyl ester, 2-[3-(2-hydroxyethyl)bicyclo(2.2.1]g -5-Ace-2-yl]ethyl ester, 8-hydroxybicyclo[2.2.1]hept-5-en-2-yl (meth)acrylate, 2-hydroxyoctahydro-4(meth)acrylate, 7-Methylene fluoren-5-yl ester, (meth)acrylic acid (2-hydroxymethyl octahydro-4,7-methylene fluoren-5-yl) methyl ester, (meth)acrylic acid 2-[ 2-(2-hydroxyethyl) octahydro-4,7-methylene fluoren-5-yl]ethyl ester, 3-hydroxyadamantan-1-yl (meth)acrylate, (meth)acrylic acid ( 3-Hydroxymethyladamantan-1-yl)methyl ester, 2-[3-(2-hydroxyethyl)adamantan-1-yl]ethyl (meth)acrylate, and the like.

Among these compounds having a hydroxyl group and a (meth)acrylinyl group, from the viewpoint of reactivity, the following compounds and the like are preferable: 1) a and b in the formula (2-1) are 0, and c a compound of 2 to 6, 2) where a in the formula (2-1) is 1, b is 0, and c is a compound of 1 to 5, and 3) d in the formula (2-2) is 2 or 3, And a compound in which e is 1, 4) a compound in the formula (2-3) wherein f is 2 or 3, and g is 1, 5) h in the formula (2-4) is 1 or 2, or i is 1 Or 2, and W is a compound of the group represented by the formula (I) or the formula (IV).

Among them, 2-hydroxyethyl (meth)acrylate and (meth)acryl are preferred. Acid 1-glyceride, 6-hydroxyhexyl (meth)acrylate, 2-(6-hydroxyhexyloxy)ethyl (meth)acrylate, 2-(3-hydroxy-2, (meth)acrylate 2-Dimethylpropoxycarbonyloxy)ethyl ester, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, (meth)acrylic acid (3-hydroxymethyladamantan-1-yl) Methyl ester, etc.

Examples of the compound having a hydroxyl group and a (meth)acrylonium group other than the compound represented by the formulae (2-1) to (2-4) include 4-hydroxyphenyl (meth)acrylate and neopentyl. Tetrahydrin tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dimethacrylate, and a compound represented by the following compound group a.

In the present invention, the compound having a hydroxyl group and a (meth)acrylinyl group may be used singly or in combination of two or more.

Next, X ^- in the above formula (3) will be described.

X ^{- is} not particularly limited, and examples thereof include a halogen ion, a boron anion, a phosphate anion, a carboxylic acid anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, a methide anion, and the like.

Examples of the halogen ion include fluoride ion and chlorine ion. Sub, bromide, iodide, etc.

Further, examples of the boron anion include inorganic boron anions such as BF ₄ ^- ; (CF ₃ ) ₄ B ^- , (CF ₃ ) ₃ BF ^- , (CF ₃ ) ₂ BF ₂ ^- , and (CF ₃ ) BF _{3 .} ^- , (C ₂ F ₅ ) ₄ B ^- , (C ₂ F ₅ ) ₃ BF-, (C ₂ F ₅ )BF ₃ ^- , (C ₂ F ₅ ) ₂ BF ₂ ^- , (CF ₃ ) (C ₂ F ₅ ) ₂ BF ^- , (C ₆ F ₅ ) ₄ B ^- , [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ^- , (CF ₃ C ₆ H ₄ ) ₄ B ^- , (C ₆ F ₅ ) ₂ BF ₂ ^- , (C ₆ F ₅ )BF ₃ ^- , (C ₆ H ₃ F ₂ ) ₄ B ^- , B(CN) ₄ ^- , B(CN)F ₃ ^- , B(CN) ₂ F ₂ ^- , B(CN) ₃ F ^- , (CF ₃ ) ₃ B(CN) ^- , (CF ₃ ) ₂ B(CN) ₂ ^- , (C ₂ F ₅ ) ₃ B(CN) ^- , (C ₂ F _{5 2} B(CN) ₂ ^- , (nC ₃ F ₇ ) ₃ B(CN) ^- , (nC ₄ F ₉ ) ₃ B(CN) ^- , (nC ₄ F ₉ ) ₂ B(CN) ₂ ^- , ( nC ₆ F ₁₃ ) ₃ B(CN) ^- , (CHF ₂ ) ₃ B(CN) ^- , (CHF ₂ ) ₂ B(CN) ₂ ^- , (CH ₂ CF ₃ ) ₃ B(CN) ^- , (CH ₂ CF ₃ ) ₂ B(CN) ₂ ^- , (CH ₂ C ₂ F ₅ ) ₃ B(CN) ^- , (CH ₂ C ₂ F ₅ ) ₂ B(CN) ₂ ^- , (CH ₂ CH ₂ C ₃ F ₇ ) ₂ B(CN) ₂ ^- , (nC ₃ F ₇ CH ₂ ) ₂ B(CN) ₂ ^- , (C ₆ H ₅ ) ₃ B(CN) ^- , tetraphenylborate, tetra(monofluoro Phenyl)borate, tetrakis(difluorophenyl)borate, four (three Phenyl)borate, tetrakis(tetrafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(tetrafluoromethylphenyl)borate, tetrakis(tolyl)borate, tetrakis(xylene) Borate, (triphenyl, pentafluorophenyl) borate, [paras(pentafluorophenyl), phenyl] borate, tridecahydro-7,8-dicarbonyl undecanoate (tridecahydride- In addition to the organic boron anion, the Japanese Laid-Open Patent Publication No. Hei 10-195119, JP-A-2010-094807, JP-A-2006-243594, and JP-A-2006-243594 The boron anion described in Japanese Laid-Open Patent Publication No. Hei 08-015521, and the like.

Further, examples of the phosphoric acid anion include inorganic phosphate anions such as HPO ₄ ^2- , PO ₄ ^3- and PF ₆ ^- ; (C ₂ F ₅ ) ₂ PF ₄ ^- and (C ₂ F ₅ ) ₃ PF ₃ ^- , [(CF ₃ ) ₂ CF] ₂ PF ₄ ^- , [(CF ₃ ) ₂ CF] ₃ PF ₃ , (nC ₃ F ₇ ) ₂ PF ₄ ^- , (nC ₃ F ₇ ) ₃ PF ₃ ^- , (nC ₄ F ₉ ) ₃ PF ₃ ^- , (C ₂ F ₅ )(CF ₃ ) ₂ PF ₃ ^- , [(CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ^- , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ^- (nC ₄ F ₉ ) ₂ PF ₄ ^- , (nC ₄ F ₉ ) ₃ PF ₃ ^- , (C ₂ F ₄ H)(CF ₃ ) ₂ PF ₃ ^- , (C ₂ F ₃ H ₂ ) ₃ PF ₃ ^- , (C ₂ F ₅ )(CF ₃ ) ₂ PF ₃ ^- , octyl phosphate anion, dodecyl phosphate anion, octadecyl phosphate anion, phenyl phosphate anion, nonylphenyl phosphate anion, etc. Phosphate anion.

In addition, as the carboxylic acid anion, for example, CH ₃ COO ^- , C ₂ H ₅ COO ^- , C ₆ H ₅ COO ^- and the like may be mentioned, and in addition, Japanese Laid-Open Patent Publication No. 2009-265641, A carboxylic acid anion described in JP-A-2008-096680.

Further, examples of the sulfate anion include a sulfate anion and a sulfite anion.

Examples of the organic sulfonic acid anion include alkylsulfonic acid anions such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, and nonafluorobutanesulfonic acid; benzenesulfonic acid, benzenedisulfonate ion, and p-toluenesulfonate; An arylsulfonic acid anion such as an acid, p-trifluoromethanesulfonic acid, pentafluorobenzenesulfonic acid, naphthalenesulfonic acid or naphthalene disulfonate ion, in addition to 2-(methyl)acrylonitrile Base-1,1,2,2-tetrafluoroethanesulfonic acid, 2-(4-vinylphenoxy)-1,1,2,2-tetrafluoroethanesulfonic acid, in International Publication No. 2011/037195 An organic sulfonic acid anion described in Japanese Laid-Open Patent Publication No. 3,372,221, and Japanese Patent Application Laid-Open No. 2011-070172.

Further, examples of the nitrogen anion include [(CN) ₂ N] ^- , [(FSO ₂ ) ₂ N] ^- , [(FSO ₂ ) N(CF ₃ SO ₂ )] ^- , [(CF ₃ SO) ₂ ) ₂ N] ^- , [(FSO ₂ )N(CF ₃ CF ₂ SO ₂ )] ^- , [(FSO ₂ )N{(CF ₃ ) ₂ CFSO ₂ }] ^- , [(FSO ₂ )N(CF ₃ CF ₂ CF ₂ SO ₂ )] ^- , [(FSO ₂ )N(CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ )] ^- , [(FSO ₂ )N{(CF ₃ ) ₂ CFCF ₂ SO ₂ }] ^- , [(FSO ₂ )N{CF ₃ CF ₂ (CF ₃ )CFSO ₂ }] ^- , [(FSO ₂ )N{(CF ₃ ) ₃ CSO ₂ }] ^-, etc., in addition to The nitrogen anions described in Japanese Laid-Open Patent Publication No. 2011-133341, and the Japanese Laid-Open Patent Publication No. JP-A-2010-090341.

Further, examples of the methide anion include (CF ₃ SO ₂ ) ₃ C ^- , (CF ₃ CF ₂ SO ₂ ) ₃ C ^- , [(CF ₃ ) ₂ CFSO ₂ ] ₃ C ^- , (CF ₃ CF ₂ CF ₂ SO ₂ ) ₃ C ^- , (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ ) ₃ C ^- , [(CF ₃ ) ₂ CFCF ₂ SO ₂ ] ₃ C ^- , [CF ₃ CF ₂ (CF ₃ ) CFSO ₂ ] ₃ C ^- , [(CF ₃ ) ₃ CSO ₂ ] ₃ C ^- , (FSO ₂ ) ₃ C ^- and the like, and in addition to the above, JP-A-2011-145540, The methide anion described in the specification of the Japanese Patent Publication No. 5,554,664, the Japanese Patent Publication No. 2005-309408, the Japanese Patent Publication No. 2004-085657, and the Japanese Patent Publication No. 2010-505787.

The coloring agent may also have a polymerizable unsaturated group in the color developing portion. A system of lake pigment. The lake pigment refers to a pigment which makes a soluble dye into an insoluble pigment by using a precipitating agent; examples of the precipitating agent include barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, and tannic acid. , CATANOL, TAMOL, composite heteropoly acid called phosphonic acid (phosphoric acid, phosphomolybdic acid, phosphotungstic acid, lanthanum tungsten molybdate, lanthanum tungstic acid, lanthanum molybdate, phosphotungstic acid, phosphotungstic acid , phosphomolybdic acid) and so on. The present colorant which is a lake pigment can be produced, for example, by esterification of a compound represented by the above formula (3) with a compound having a hydroxyl group and a (meth)acryl fluorenyl group by using a precipitating agent. The compound obtained by the reaction is laked.

The colored composition of the present invention may further contain other coloring agents as a coloring agent together with the present coloring agent. Other coloring agents are not particularly limited, and colors and materials can be appropriately selected depending on the application.

As the other coloring agent, any pigment other than the coloring agent, a dye other than the coloring agent, and a natural coloring matter may be used, and in the sense of obtaining a pixel having high luminance and color purity, organic pigment or organic is preferable. dye.

As the organic pigment, for example, a compound classified as a pigment in a color index (C.I.; issued by The Society of Dyers and Colourists), that is, a compound having a color index (C.I.) name as described below, may be mentioned.

CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 5, CI Pigment Red 17, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 41, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, CI Pigment Red 48:4, CI Pigment Red 48:5, CI Pigment Red 49, CI Pigment Red 49:1, CI Pigment Red 49:2, CI Pigment Red 49:3, CI Pigment Red 52 : 1, CI Pigment Red 52: 2, CI Pigment Red 53: 1, CI Pigment Red 54, CI Pigment Red 57: 1, CI Pigment Red 58, CI Pigment Red 58: 1, CI Pigment Red 58: 2, CI Pigment Red 58:3, CI Pigment Red 58:4, CI Pigment Red 60:1, CI Pigment Red 63, CI Pigment Red 63:1, CI Pigment Red 63:2, CI Pigment Red 63:3, CI Pigment Red 64:1, CI Pigment Red 68, CI Pigment Red 81, CI Pigment Red 81:1, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 200, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 237, CI Pigment Red 239, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 247, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 262, CI Pigment Red 264, CI Pigment Red 272 and other red pigments; CI Pigment Violet 1, CI Pigment Violet 2, CI Pigment Violet 3, CI Pigment Violet 3:1, CI Pigment Violet 3:3, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 27, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38, CI .Pigment pigment purple 39 and other purple pigments; CI pigment blue 1, CI pigment blue 2, CI pigment blue 3, CI pigment blue 9, CI pigment blue 10, CI pigment blue 14, CI pigment blue 15, CI pigment blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 17:1, CI Pigment Blue 24, CI Pigment Blue 24:1, CI Pigment Blue 56, CI Pigment Blue 60, CI Pigment Blue 61, CI Pigment Blue 62, CI Pigment Blue 80 and other blue pigments.

In the present invention, when a pigment is used as another coloring agent, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. . Further, the surface of the pigment particles may be modified with a resin as needed. The resin which is modified by the surface of the pigment particle, for example, a vehicle resin described in JP-A-2001-108817 or a commercially available resin for dispersing various pigments. Further, it is preferred that the organic pigment be used by so-called salt milling to refine the primary particles. As a method of salt milling, for example, a method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111 can be employed.

In the present invention, when a pigment is used as the other coloring agent, a well-known dispersing agent and a dispersing aid may be further contained. Examples of the known dispersant include a polyurethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, and a polyoxyethylene alkyl phenyl ether dispersant. A polyethylene glycol diester-based dispersing agent, a sorbitan fatty acid ester-based dispersing agent, a polyester-based dispersing agent, an acrylic dispersing agent, and the like, and examples of the dispersing aid include a pigment derivative and the like.

Such a dispersing agent is commercially available. For example, as an acrylic dispersing agent, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above BYK-Chemie (BYK)) As a polyurethane dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above BYK-Chemie (BYK)) As a polyethyleneimine-based dispersing agent, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), etc., and as a polyester-based dispersing agent, Adisper PB821 is exemplified. , Adisper PB822, Adisper PB880, Adisper PB881 (above is Ajinomoto Fine-Techno Co., Ltd.) and the like.

In addition, specific examples of the pigment derivative include a copper phthalocyanine, a diketopyrrolopyrrole, and a sulfonic acid derivative of quinacridone.

As the organic dye, in the dye to which the color index (C.I.) is given, the following organic dye can be preferably used.

For example, red dyes such as CI Solvent Red 45, CI Solvent Red 49; blue solvents such as CI Solvent Blue 35, CI Solvent Blue 37, CI Solvent Blue 59, CI Solvent Blue 67; CI Acid Red 91, CI Acid Red 92, CI Acid red dyes such as acid red 97, CI acid red 114, CI acid red 138, CI acid red 151; acid blue dyes such as CI Acid Blue 80, CI Acid Blue 83, and CI Acid Blue 90.

The colored composition of the present invention is preferably used to form a red pixel or a blue pixel. When the red pixel is formed, the (A) coloring agent is preferably at least one selected from the group consisting of a red coloring agent and a purple coloring agent containing the coloring agent and other coloring agents. On the other hand, when forming a blue pixel, as the (A) coloring agent, at least one selected from the group consisting of a blue coloring agent and a purple coloring agent containing the present coloring agent and other coloring agents is preferable. As the red coloring agent, the red pigment, the red dye, and the acid red dye described above can be exemplified, and among them, C.I. Pigment Red 177, C.I. Pigment Red 242, C.I. Pigment Red 254, and the like are preferable. As a purple colorant, The above purple pigment can be exemplified, and among them, C.I. Pigment Violet 23 and the like are preferable. The blue coloring agent, the blue dye, and the acid blue dye may be exemplified as the blue coloring agent. Among them, C.I. Pigment Blue 1, C.I. Pigment Blue 15:6, and the like are preferable.

The other coloring agents in the present invention may be used singly or in combination of two or more.

The content ratio of the (A) colorant is usually 5 to 70% by mass, preferably 5, in terms of the solid content of the coloring composition, from the viewpoint of forming a pixel having high luminance and excellent color purity or a black matrix having excellent light shielding properties. ~60% by mass. The solid content referred to herein means a component other than the solvent to be described later.

- (B) Adhesive Resin -

The (B) binder resin in the present invention is not particularly limited, and is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. In particular, a polymer having a carboxyl group (hereinafter also referred to as a "carboxyl group-containing polymer") is preferable, and examples thereof include an ethylenically unsaturated monomer having a carboxyl group (hereinafter, also referred to as "unsaturated". A copolymer of a monomer (b1)") and another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as "unsaturated monomer (b2)").

Examples of the unsaturated monomer (b1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2-(methyl)acryloxyethyl)ester, and ω-. Carboxypolycaprolactone mono(meth)acrylate, p-vinylbenzoic acid, and the like.

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

Further, as the unsaturated monomer (b2), for example, an N-position substituted cis-butyl group such as N-phenylbutyleneimine or N-cyclohexylmethyleneimine may be mentioned. An enediamine imine; an aromatic vinyl such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, terpene a compound; such as methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate Ester, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene Glycol (degree of polymerization 2~10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isophthalic acid (meth) acrylate Ester, tricyclo[5.1.02 ^2,6 ]non-8-yl ester, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, (meth)acrylic acid 4 -hydroxyphenyl ester, pair Ethylene oxide modified (meth) acrylate of phenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, 3-[(meth) propylene oxime (Meth) oxime, (meth) acrylate such as 3-[(methyl) propylene oxymethyl]-3-ethyl oxime; such as cyclohexyl vinyl ether, isodecyl vinyl ether, Tricyclo[5.2.1.0 ^2,6 ]癸-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, vinyl 3-(vinyloxymethyl)-3-ethyloxonium An ether; such as polystyrene, poly(methyl) methacrylate, poly(methyl) methacrylate, polyoxyalkylene, etc. having a mono(methyl) acrylonitrile group at the end of the polymer molecular chain; Macromonomers, etc.

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 from 5 to 50% by mass, further preferably 10 ~40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a coloring composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include JP-A-7-140654, JP-A-8-259876, and JP-A JP-A, Japan. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The copolymer disclosed in the above.

In the present invention, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth)acrylonyl group in a side chain as disclosed in JP-A-H08-140095, and the like, is disclosed as a binder resin.

In the binder resin of the present invention, the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter, abbreviated as GPC) (dissolving solvent: tetrahydrofuran) is usually 1,000 to 100,000. Preferably, it is 3,000 to 50,000. If Mw is too small, you may get The residual film rate of the film to be obtained is lowered, or the pattern shape, heat resistance, and the like are impaired, or the electrical characteristics are poor. On the other hand, if the film size is too large, the resolution may be lowered, or the pattern shape may be impaired, or the slit nozzle may be used. It is easy to produce dry foreign matter during coating.

Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. Here, Mn refers to a number average molecular weight in terms of polystyrene measured by GPC (solution solvent: tetrahydrofuran).

The binder resin in the present invention can be produced by a known method, and can be disclosed, for example, in JP-A-2003-222717, JP-A-2006-259680, and International Publication No. 07/029871. The method controls its structure, Mw, Mw/Mn.

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

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. If the content of the binder resin is too small, for example, the alkali developability may be lowered, or the storage stability of the obtained colored composition may be lowered. On the other hand, if it is too large, it may be difficult to realize the film as the concentration of the colorant is relatively lowered. The desired color density.

-(C) Crosslinker -

In the present invention, the (C) crosslinking agent means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an epoxy group, an oxypropylene group, an N-alkoxymethylamino group, and the like. . In the present invention, a compound having two or more (meth)acryl fluorenyl groups or a compound having two or more N-alkoxymethylamino groups is preferred as the (C) crosslinking agent.

Specific examples of the compound having two or more (meth) acryloyl fluorenyl groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid. An ester-modified polyfunctional (meth) acrylate, an alkylene oxide-modified polyfunctional (meth) acrylate, a polyfunctional amine obtained by reacting a hydroxyl group-containing (meth) acrylate with a polyfunctional isocyanate A carbamic acid ester (meth) acrylate, a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group and an acid anhydride, or the like.

Here, examples of the aliphatic polyhydroxy compound include a divalent aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, or polypropylene glycol; for example, glycerin or trimethylolpropane. A ternary or higher aliphatic polyhydroxy compound such as pentaerythritol or dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane bis(meth)acrylate, and pentaerythritol tri(methyl). Acrylate, dipentaerythritol penta (meth) acrylate, glyceryl dimethacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include acid anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, such as pyrophyllite. A tetrabasic acid dianhydride such as an acid anhydride, a biphenyltetracarboxylic dianhydride, or a benzophenone tetracarboxylic dianhydride.

In addition, as the above-mentioned caprolactone-modified polyfunctional (meth) acrylate, a compound described in paragraphs [0015] to [0018] of JP-A-11-44955 is exemplified. The above-mentioned alkylene oxide-modified polyfunctional (meth) acrylate may, for example, be bisphenol A bis(meth)acrylate modified with at least one selected from the group consisting of ethylene oxide and propylene oxide. And modifying at least one modified isocyanuric acid tris(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide, and at least one selected from the group consisting of ethylene oxide and propylene oxide a trimethylolpropane tri(meth)acrylate, at least one modified pentaerythritol tri(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide, selected from the group consisting of At least one modified neopentyltetrakis(meth)acrylate of oxyethane and propylene oxide, at least one modified dipentaerythritol selected from the group consisting of ethylene oxide and propylene oxide An alcohol penta (meth) acrylate, at least one modified pentaerythritol hexa(meth) acrylate selected from the group consisting of ethylene oxide and propylene oxide.

In addition, examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. Further, the melamine structure and the benzoguanamine structure mean that there are one or more three Ring or phenyl substituted three The chemical structure of the ring as a basic skeleton also includes the concept of melamine, benzoguanamine or their condensates. Specific examples of the compound having two or more N-alkoxymethylamino groups include N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, and N. , N, N', N'-tetrakis(alkoxymethyl)benzoguanamine, N, N, N', N'-tetrakis(alkoxymethyl) glycoluril, and the like.

Among these crosslinking agents, it is preferred to make a trivalent or higher fat Polyfunctional (meth) acrylate obtained by reacting a polyhydroxy compound with (meth)acrylic acid, polycaprol (meth) acrylate modified by caprolactone, polyfunctional urethane (methyl) Acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N", N"-hexa(alkoxymethyl) melamine, N, N, N', N' - Tetrakis(alkoxymethyl)benzoguanamine. The strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and the unexposed portion is less likely to cause scumming or film residue on the substrate and the light shielding layer, and the trihydric or higher aliphatic polyhydroxy compound is Among the polyfunctional (meth) acrylates obtained by the reaction of (meth)acrylic acid, trimethylolpropane triacrylate, neopentyl alcohol triacrylate, dipentaerythritol pentaacrylate, and new are particularly preferred. Pentaerythritol hexaacrylate, in a polyfunctional (meth) acrylate having a carboxyl group, particularly preferably a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, and dipentaerythritol pentaacrylate A compound obtained by reacting with succinic anhydride.

In the present invention, the (C) crosslinking agent may be used singly or in combination of two or more.

The content of the (C) crosslinking agent in the present invention is preferably 10 to 1,000 parts by mass, particularly preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) coloring agent. At this time, if the content of the crosslinking agent is too small, sufficient hardenability may not be obtained. On the other hand, when the content of the crosslinking agent is too large, when the alkali developability is imparted to the colored composition of the present invention, the alkali developability is lowered, and the unexposed portion is liable to cause scalping or film on the substrate or the light shielding layer. Residual trends such as.

-Photopolymerization initiator -

The coloring composition of the present invention can contain a photopolymerization initiator. by Thus, the coloring composition can be imparted with susceptibility to radiation. The photopolymerization initiator used in the present invention is a compound which emits an active species which can initiate polymerization of a (C) crosslinking agent by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray.

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, and the like. Compound, O-mercapto oxime compound, sulfonium salt compound, benzoin compound, benzophenone compound, α-diketone compound, polycyclic guanidine compound, diazo compound, quinone A sulfonate-based compound or a phosphonium salt-based compound.

In the present invention, the photopolymerization initiator may be used singly or in combination of two or more. The photopolymerization initiator is preferably selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and three At least one of a compound and an O-mercapto lanthanide compound.

In a preferred photopolymerization initiator of the present invention, specific examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropyl group. Thiophenone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4- Diisopropyl thioxanthone and the like.

Further, specific examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Polinylphenyl)butan-1-one and the like.

Further, as a specific example of the biimidazole-based compound, 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.

Further, when a biimidazole-based compound is used as the photopolymerization initiator, it is preferred to use a hydrogen donor in combination from the viewpoint of improving the sensitivity. The term "hydrogen donor" as used herein refers to a compound capable of supplying a hydrogen atom to a radical generated by a biimidazole-based compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. A thiol-based hydrogen donor such as azole; an amine-based hydrogen donor such as 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone . In the present invention, the hydrogen donor may be used alone or in combination of two or more. From the viewpoint of further improving the sensitivity, it is preferred to combine one or more kinds of thiol-based hydrogen donors and one or more amines. The hydrogen donor is used.

In addition, as the above three Specific examples of the compound include 2,4,6-tris(trichloromethyl)-s-three. 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-three ,2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three Three with a halomethyl group a compound.

Further, as a specific example of the O-indenyl lanthanide compound, Take 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzamide), ethyl ketone, 1-[9-ethyl-6 -(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-acetamidine), ethyl ketone, 1-[9-ethyl-6-(2-A 4--4-hydrofuranylmethoxybenzylidene)-9H-indazol-3-yl]-, 1-(O-acetamidine), ethyl ketone, 1-[9-ethyl-6-{ 2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene}-9H-indazol-3-yl]-, 1-(O - 醯肟) and so on. As a commercial item of the O- mercapto oxime compound, NCI-831, NCI-930 (above, ADEKA Co., Ltd.), etc. can also be used.

In the present invention, when a photopolymerization initiator other than a biimidazole-based compound such as an acetophenone-based compound is used, a sensitizer may be used in combination. As such a sensitizer, for example, 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-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(2-B Amino group) Chalcone and the like.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, per 100 parts by mass of the (C) crosslinking agent. At this time, if the content of the photopolymerization initiator is too small, the hardening by exposure may be insufficient. On the other hand, if the amount is too large, the formed coloring layer tends to fall off from the substrate during development.

- solvent -

The colored composition of the present invention contains the above components (A) to (C) and optionally added other components, and usually, a solvent is prepared to prepare a liquid composition. As the above solvent, the components (A) to (C) constituting the colored composition are used. Other components are dispersed or dissolved, do not react with these components, have appropriate volatility, and can be appropriately selected for use.

Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Alcohol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl Ether, 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, tripropylene glycol monoethyl ether, etc. Alcohol monoalkyl ethers; alkyl lactate such as methyl lactate or ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2-B (cyclo)alkyl alcohols such as cyclohexanol and cyclohexanol; ketone alcohols such as diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether Acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, acetic acid 3 (poly) olefinic diol monoalkyl ether acetates such as methoxybutyl ester, 3-methyl-3-methoxybutyl acetate, etc.; diethylene glycol dimethyl ether, diethylene glycol methyl ether , other ethers such as diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; propylene glycol diacetate, 1,3-butanediol diacetate a diacetate such as 1,6-hexanediol diacetate; Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, propionic acid 3 - alkoxycarboxylates such as methyl-3-methoxybutyl ester; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, acetic acid Isoamyl ester, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, B Other esters such as methyl acetate, ethyl acetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N,N-dimethylformamide, N,N-II A decylamine such as methyl acetamide or N-methylpyrrolidone or an indoleamine.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol are preferable from the viewpoints of solubility, pigment dispersibility, coating properties and the like. Monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butane Alcohol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ester, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, butyric acid Isopropyl ester, n-butyl butyrate, ethyl pyruvate, and the like.

In the present invention, the solvent may be used singly or in combination of two or more.

The content of the solvent is not particularly limited, and the total concentration of each component other than the solvent of the colored composition is preferably 5 to 50% by mass. The amount is more preferably 10 to 40% by mass. By adopting such a method, it is possible to obtain a colorant dispersion having good dispersibility and stability and a coloring composition having good coatability.

-additive-

The colored composition of the present invention may contain various additives as needed.

Examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); a surfactant such as a fluorine-based surfactant or a quinone-based surfactant; Vinyltrimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldi Methoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxy Baseline, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxy a adhesion promoter such as decane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane; 2,2-thiobis ( Antioxidant such as 4-methyl-6-tertiary butyl phenol) or 2,6-di-tributyl phenol; 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)- Ultraviolet absorbers such as 5-chlorobenzotriazole and alkoxybenzophenone; anticoagulation such as sodium polyacrylate Collecting agent; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1- Residue improver such as pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid mono[2-(A Acryloxyethyl]ester, mono[2-(methyl)propenyloxyethyl phthalate A developer improving agent such as an ester or an ω-carboxypolycaprolactone mono(meth)acrylate; a siloxane oligomer having a reactive functional group disclosed in JP-A-2008-242078 or the like.

The colored composition of the present invention can be produced by a suitable method. When the coloring agent is a dye, for example, it can be prepared by a method disclosed in JP-A-2008-58642, JP-A-2010-132874, and the like. . When both the coloring agent and the pigment as the dye are used as the coloring agent, a method disclosed in Japanese Laid-Open Patent Publication No. 2010-132874, that is, after the dye solution containing the coloring agent is passed through the first filter, The dye solution that has passed through the first filter is mixed with a separately prepared pigment dispersion or the like, and the resulting colored composition is passed through a second filter to prepare. Further, it is also possible to employ a method in which the dye containing the present colorant and the above components (B) to (C) and other components used as needed are dissolved in a solvent so that the obtained solution passes through the first filter. The solution that passed through the first filter was mixed with the separately prepared pigment dispersion, and the resulting colored composition was passed through a second filter, thereby preparing. Further, a method in which the dye solution containing the coloring agent is passed through the first filter, and the dye solution that has passed through the first filter and the components (B) to (C) and, if necessary, may be used. The other ingredients are mixed and dissolved, so that the obtained solution passes through the second filter, and the solution that has passed through the second filter is further mixed with the separately prepared pigment dispersion, so that the obtained colored composition passes through the third filter, thereby preparing .

Color filter and manufacturing method thereof

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

As a method of manufacturing a color filter, the first method is as follows. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide the portion where the pixel is formed, as needed. Next, a liquid composition of the blue radiation-sensitive composition of the present invention containing the coloring agent, for example, is applied onto the substrate, and then pre-baked to evaporate the solvent to form a coating film. Next, the coating film was exposed through a photomask, and then developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, by post-baking, a pixel array in which blue pixel patterns are arranged in a predetermined array is formed.

Next, using each of the green or red radiation-sensitive coloring compositions, the coating, prebaking, exposure, development, and post-baking of the respective radiation-sensitive coloring compositions are performed in the same manner as described above, and green color is sequentially formed on the same substrate. Pixel array and red pixel array. Thereby, a color filter in which a pixel array of three primary colors of red, green, and blue is disposed on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order. Further, in the first method of producing a color filter, it is preferable that at least one of the above-described red and blue pixel arrays is a coloring layer formed using the coloring composition of the present invention.

Further, the black matrix may be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern by photolithography, or a radiation-sensitive coloring composition in which a black colorant is dispersed may be used. It is formed in the same manner as the case of forming the above-described pixels. The colored composition of the present invention is also suitable for forming a black matrix.

Examples of the substrate used in forming the color filter include glass, ruthenium, polycarbonate, polyester, and aromatic polyamine. , polyamidimide, polyimine, and the like.

Further, as appropriate, these substrates may be subjected to an appropriate pretreatment such as chemical treatment such as a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum vapor deposition.

When a radiation sensitive coloring composition is applied onto a substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method, a slit die coating method, or a bar coating method can be employed. In order to adopt a spin coating method or a slit die coating method.

The prebaking is usually carried out by combining drying under reduced pressure and drying by heating. Drying under reduced pressure usually proceeds until it reaches 50 to 200 Pa. In addition, the conditions of heat drying are usually about 1 to 10 minutes at 70 to 110 °C.

The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, in terms of the film thickness after drying.

Examples of the light source used for forming the pixel and/or the black matrix include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure mercury. Light sources such as lamps or argon ion lasers, YAG lasers, XeCl excited molecular lasers, nitrogen lasers and other laser sources. As the exposure light source, an ultraviolet LED can also be used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.

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

Further, as the above alkaline developing solution, for example, sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diguanidine bicyclo-[5.4. An aqueous solution of 0]-7-undecene, 1,5-difluorenebicyclo-[4.3.0]-5-decene.

It is also possible to add an appropriate amount such as A in the above alkaline developing solution. A water-soluble organic solvent such as an alcohol or ethanol, a surfactant, or the like. Further, after alkaline development, water washing is usually carried out.

As the development treatment method, a shower development method, a spray development method, a dip development method, a paddle method, or the like can be used. The development conditions are preferably 5 to 300 seconds at normal temperature.

The post-baking conditions are usually about 10 to 60 minutes at 120 to 280 ° C. From the viewpoint of heat resistance of the coloring agent, the post-baking temperature is preferably 240 ° C or lower, and particularly preferably 230 ° C or lower.

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

In addition, as a second method of producing a color filter, a method of obtaining pixels of respective colors by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. In this method, first, a partition wall having a light blocking function is formed on the surface of the substrate. Next, the liquid composition of the thermosetting coloring composition of the present invention containing the blue color of the present coloring agent is ejected into the formed partition walls by an inkjet device, and then prebaked to evaporate the solvent. Next, the coating film is exposed as needed, and then cured by post-baking to form a blue pixel pattern.

Next, using a green or red thermosetting coloring composition, a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of three primary colors of red, green, and blue are arranged on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order. In addition, even in the second side of the manufacture of color filters In the method, it is also preferred that at least one of the above-described red and blue pixel arrays is a coloring layer formed using the coloring composition of the present invention.

Further, the partition wall has a function of not only a light-shielding function but also a coloring composition of each color discharged into the partition without color mixing, and therefore the film thickness is thicker than the black matrix used in the first method. Therefore, the partition walls are usually formed using a black sensitizing radioactive composition.

The substrate used for forming the color filter, the light source of the radiation, and the methods and conditions for prebaking and postbaking are the same as those of the first method described above. The film thickness of the pixel formed by the inkjet method is equivalent to the height of the partition wall.

After the protective film is formed on the pixel pattern thus obtained as needed, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, and may be a spacer having a light-shielding property (black spacer). At this time, a radiation-sensitive coloring composition in which a black colorant is dispersed is used, but the coloring composition of the present invention is also suitable for forming the above black spacer.

Since the color filter of the present invention thus obtained has extremely high brightness and color purity, it is very useful for a color liquid crystal display element, a color image pickup element, a color sensor, an organic EL display element, electronic paper, or the like.

Display component

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

A color liquid crystal display element having the color filter of the present invention can For the transmissive or reflective type, an appropriate structure can be employed. For example, a color filter may be formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate for driving and a substrate on which the color filter is formed may be opposed to each other with a liquid crystal layer interposed therebetween; A substrate on which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate on which an ITO (tin-doped indium oxide) electrode is formed may be opposed to each other with a liquid crystal layer interposed therebetween. structure. The structure of the latter can significantly increase the aperture ratio, and has the advantage of being able to obtain a bright and high-definition liquid crystal display element.

A color liquid crystal display device including the color filter of the present invention includes a backlight unit having a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED in which a combination of a red LED, a green LED, and a blue LED is obtained by color mixing can be used, and a combination of a blue LED, a red LED, and a green phosphor is obtained by color mixing to obtain white light. White LED, combined with blue LED, red illuminating phosphor and green illuminating phosphor, white LED obtained by color mixing, white LED with white LED and YAG phosphor A white LED that combines a blue LED, an orange illuminating phosphor, and a green illuminating phosphor to obtain white light by color mixing, and combines an ultraviolet LED, a red luminescent phosphor, a green luminescent phosphor, and a blue luminescent phosphor. A white LED or the like which obtains white light by color mixing.

In the color liquid crystal display device including the color filter of the present invention, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, and IPS can be used. Suitable liquid crystal modes such as (In-Planes Switching), VA (Vertical Alignment), and OCB (Optically Compensated Birefringence).

In addition, the organic EL display element having the color filter of the present invention may have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242.

In addition, the electronic paper provided with the color filter of the present invention may have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. 2007-41169 can be cited.

[Examples]

Hereinafter, embodiments of the present invention will be described more specifically by way of examples. However, the invention is not limited to the following examples.

<Synthesis and Evaluation of the Colorant>

1. Synthesis of the colorant

Synthesis Example 1

Anhydrous chloroform (170 parts by mass), camphorsulfonic acid (1.0 parts by mass), 4-(N,N-dimethylamino)pyridine (1.4 parts by mass), A was added to Basic Violet 10 (18 parts by mass). 2-Hydroxyethyl acrylate (18 parts by mass) was stirred for about 30 minutes. Thereafter, anhydrous ethyl chloroform (47 parts by mass) was added to 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (10.5 parts by mass) and dissolved in advance. After the resulting solution was stirred at room temperature for about 2 hours. After the liquid separation operation was performed twice with a 1 N aqueous hydrochloric acid solution (150 parts by mass), the organic layer was washed twice with 10% brine (150 parts by mass). Then, after adding 43 parts by mass of anhydrous magnesium sulfate and stirring for about 30 minutes, the desiccant was filtered, and the solvent was distilled off. Thus, 20.6 parts by mass of a compound represented by the following formula (A1) (recovery rate: 90%) was obtained. The obtained compound was used as a coloring agent (A-1).

Synthesis Example 2

The compound (A1) (20 parts by mass) and lithium bis(trifluoromethanesulfonyl) phthalimide (14.5 parts by mass) were placed in a 500 mL Erlenmeyer flask to which a stir bar was placed, and chloroform (130 parts by mass) was added thereto. It was stirred with ion-exchanged water (100 parts by mass) at room temperature for about 2 hours. Thereafter, the aqueous layer was separated and removed, and the organic layer was washed twice with ion-exchanged water (200 parts by mass). After concentrating the organic layer under reduced pressure, the residue was dried under reduced pressure at 50 ° C for 12 hours to obtain 26.6 parts by mass of a compound represented by the following formula (A2) (yield: 94%). The target compound was confirmed by ¹ H-NMR (solvent: deuterated chloroform). The obtained compound was used as a coloring agent (A-2).

Synthesis Example 3

In the same manner as in Synthesis Example 2, a coloring agent was synthesized in the same manner as in Synthesis Example 2 except that potassium tetracyanoborate was used instead of lithium bis(trifluoromethanesulfonyl) ruthenium in Synthesis Example 2, and ¹ H-NMR (solvent: The test was confirmed to be the target compound by deuterated chloroform. The obtained compound was used as a coloring agent (A-3).

Synthesis Example 4

In the same manner as in Synthesis Example 2, a coloring agent was synthesized in the same manner as in Synthesis Example 2 except that potassium trifluoromethanesulfonate was used instead of lithium bis(trifluoromethanesulfonyl) ruthenium in Synthesis Example 2, and ¹ H-NMR (solvent) : Deuterated chloroform) was confirmed to be the target compound. The obtained compound was used as a coloring agent (A-4).

Synthesis Example 5

In the synthesis example 2, potassium 2-propenyloxy-1,1,2,2-tetrafluoroethanesulfonate was used instead of lithium bis(trifluoromethanesulfonyl) ruthenium, in addition to the synthesis example. 2 A coloring agent was synthesized in the same manner, and it was confirmed by ¹ H-NMR (solvent: chloroform) to confirm the target compound. The obtained compound was used as a coloring agent (A-5).

Synthesis Example 6

In Synthesis Example 2, potassium 2-(4-vinylphenoxy)-1,1,2,2-tetrafluoroethanesulfonate was used in place of lithium bis(trifluoromethanesulfonyl) ruthenium, in addition to this. Further, a coloring agent was synthesized in the same manner as in Synthesis Example 2, and it was confirmed to be a target compound by ¹ H-NMR (solvent: deuterated chloroform). The obtained compound was used as a coloring agent (A-6).

Synthesis Example 7

In the same manner as in Synthesis Example 2, a coloring agent was synthesized in the same manner as in Synthesis Example 2 except that tris(trifluoromethylsulfonyl)methyl hydrazine was used instead of lithium bis(trifluoromethanesulfonyl) phthalimide. It was confirmed by ¹ H-NMR (solvent: deuterated chloroform) to be the target compound. The obtained compound was used as a coloring agent (A-7).

Synthesis Example 8

In the same manner as in Synthesis Example 1, except that 2-hydroxyethyl acrylate was used instead of 2-hydroxyethyl methacrylate, a coloring agent was synthesized by ¹ H-NMR (solvent: deuterated chloroform). ) The measurement was confirmed to be the target compound. The obtained compound was used as a coloring agent (A-8).

2. Evaluation of the colorant

The coloring agents (A-1) to (A-8) obtained in Synthesis Examples 1 to 8 were all dissolved in cyclohexanone at 10% by mass or more, and their solutions were blue.

Further, the temperature of the coloring agents (A-1) to (A-8) based on the thermogravimetric-differential heat simultaneous measurement analysis of 5% by weight is 250 °C or higher. On the other hand, the temperature of C.I. Basic Violet 10 based on the thermogravimetric-differential heat simultaneous measurement analysis of 5% by weight was less than 200 °C. Further, it can be said that the higher the temperature of the weight loss of 5% based on the thermogravimetric-differential heat simultaneous measurement analysis, the higher the heat resistance of the colorant.

<Preparation of dye solution>

Preparation Example 1

A dye solution (A-1) was prepared by mixing 20 parts by weight of the color former (A-1) and 80 parts by weight of propylene glycol monomethyl ether as a solvent.

Preparation Examples 2~8

In the preparation example 1, a dye solution (A-2) was prepared in the same manner as in Preparation Example 1 except that the colorants (A-2) to (A-8) were used instead of the colorant (A-1). A-8).

Preparation Example 9

In the preparation example 1, a dye solution (A-9) was prepared in the same manner as in Production Example 1, except that the basic violet 10 was used instead of the colorant (A-1).

<Synthesis of binder resin>

Synthesis Example 9

In a flask equipped with a condenser and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was charged and replaced with nitrogen. After heating to 80 ° C, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, and 5 parts by mass of benzyl methacrylate were added dropwise at the same temperature for 1 hour. 15 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenyl maleimide, 15 parts by mass of succinic acid A mixed solution of (2-propenyloxyethyl)ester and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was maintained at this temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The obtained binder resin had a Mw of 12,200 and an Mn of 6,500. This binder resin is referred to as "adhesive resin (B1)".

<Preparation of Pigment Dispersion>

Preparation Example 10

15 parts by mass of CI Pigment Red 254 was used as a colorant, and 12.5 parts by mass of BYK-LPN21116 (manufactured by BYK-Chemie (BYK) Co., Ltd.) (solid content concentration: 40% by mass) was used as a dispersing agent, and 72.5 parts by mass of propylene glycol monomethyl ether was used. The acetate was treated as a solvent by a bead mill to prepare a pigment dispersion (a-1).

<Preparation and evaluation of coloring composition>

Example 1

13.5 parts by mass of the pigment dispersion liquid (a-1), 7.2 parts by mass of the dye solution (A-1), 21.6 parts by mass of a binder resin (B1) solution as a binder resin, and 9.2 parts by mass as cross-linking M-402 (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate), 2.2 parts by mass of 2-benzyl-2- as a photopolymerization initiator Dimethylamino-1-(4- Phenylphenyl)butan-1-one (manufactured by Ciba Specialty Chemicals, trade name: IRGACURE 369), 0.1 part by mass of NCI-930 (made by ADEKA Co., Ltd.), and 0.2 part by mass of MEGAFAC as a fluorine-based surfactant F-554 (manufactured by DIC Corporation) and propylene glycol monomethyl ether as a solvent were prepared as a coloring composition (CR1) having a solid content concentration of 20% by mass.

The colored composition (CR1) was applied onto the glass substrate by a spin coater, and then prebaked for 10 minutes using a hot plate at 80 ° C to form a coating film. The same operation was carried out by changing the number of revolutions of the spin coater to form three coating films having different film thicknesses.

Next, after cooling these substrates to room temperature, radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm was exposed to each coating film at a exposure amount of 2,000 J/m ² without using a high-pressure mercury lamp. Thereafter, a developing solution composed of a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C was sprayed onto the substrates at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) to carry out shower development for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further baked in a clean oven at 230 ° C for 30 minutes to form a cured film for evaluation.

Evaluation of voltage retention rate (%)

An SiO ₂ film for preventing elution of sodium ions is formed on the surface, and the obtained coloring composition is spin-coated on a soda lime glass substrate on which an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape, and then heat is used at 100 ° C. The plate was prebaked for 1 minute to form a film having a film thickness of 2.0 μm. Next, the film was exposed without exposure to a mask at an exposure amount of 700 J/m ² . Thereafter, the substrate was immersed in a developing solution composed of a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C for 1 minute, and after development, it was washed with ultrapure water, air-dried, and further baked at 230 ° C for 30 minutes. Bake, harden the film to form a permanent hardened film. Next, the substrate on which the pixel was formed and the substrate on which the ITO electrode was deposited in a predetermined shape were bonded together with a sealant in which 1.8 mm of glass beads were mixed, and then a liquid crystal (MLC6608) manufactured by Merck was injected to prepare a liquid crystal cell. Next, the liquid crystal cell was placed in a thermostat at 60 ° C, and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage retention ratio measurement system (VHR-1A type, TOYO TECHNICA Co., Ltd.). The applied voltage at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio is a value obtained by (a liquid crystal cell potential difference after 16.7 milliseconds / a voltage applied at 0 milliseconds). When the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot maintain the predetermined voltage of 16.7 msec and the applied voltage at a predetermined level, and the liquid crystal cannot be sufficiently aligned, which may cause a "burn in" phenomenon such as afterimage.

Examples 2 to 8 and Comparative Example 1

In the same manner as in Example 1, except that the type and amount of the pigment dispersion liquid and the dye solution were changed as shown in Table 1, a colored composition was prepared. Then, the obtained coloring composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Claims (11)

A colored composition comprising the following components (A), (B), and (C): (A) having a polymerizable unsaturated group in a color developing portion a coloring agent; (B) a binder resin; and (C) a crosslinking agent. For example, the colored composition of claim 1 of the patent scope, wherein The coloring agent has a structure represented by the following formula (1). [In the formula (1), R ^a represents a group having a polymerizable unsaturated group; and R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms; Or a phenyl group, wherein the alkyl group, the cycloalkyl group, and the phenyl group may have a substituent; and R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a chlorine atom; and r represents 1 to 5; An integer, when r is an integer of 2 or more, a plurality of R ^a may be the same or different]. For example, the colored composition of claim 1 of the patent scope, wherein The coloring agent has a structure represented by the following formula (2). [In the formula (2), R ^b represents a group having a polymerizable unsaturated group; and R ¹ to R ^{6 are} synonymous with R ¹ to R ⁶ in the formula (1)]. Such as the colored composition of claim 2, wherein The coloring agent has a cation having a structure represented by the formula (1) and is selected from the group consisting of a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, and amethide anion. Relative anion (Counter anion). The colored composition of claim 1, which comprises at least one selected from the group consisting of a red colorant, a blue colorant, and a purple colorant. A colored composition according to claim 1, which comprises at least one selected from the group consisting of C.I. Pigment Red 177, C.I. Pigment Red 242, and C.I. Pigment Red 254. The colored composition according to any one of claims 1 to 3, wherein the polymerizable unsaturated group is a (meth) acrylonitrile group. The coloring composition of claim 3, wherein the R ^b group is a group represented by the following formula (2a) or (2b), [In the formulae (2a) and (2b), R ¹⁰ and R ¹¹ independently of each other represent a hydrogen atom or a methyl group; and Y ¹ , Y ² , Y ³ and Y ⁴ independently of each other represent a substituted or unsubstituted carbon number 1 Alkanediyl group of ~12; Z represents a -CO- group or a -COO-(*) group, wherein * represents a bond to Y ² ; Q represents a divalent alicyclic hydrocarbon group; and p ¹ represents 0 to 12 An integer; p ² and p ³ independently represent an integer from 0 to 6]. The colored composition of any one of claims 1 to 3, wherein the The coloring agent is obtained by esterification reaction of a compound represented by the following formula (3) with a compound having a hydroxyl group and a (meth)acrylinyl group. [; ^- X represents an anion of formula (3), R ¹ ~ R ⁶ and (1) the formula R ¹ ~ R ⁶ is synonymous]. A color filter comprising a coloring layer formed using the coloring composition according to any one of claims 1 to 9. A display element comprising a color filter as in claim 10 of the patent application.