JP2013010814A - Triarylmethane dye having polymerizable double bond, polymeric compound having triarylmethane dye on side chain, coloring composition for color filter, color filter, liquid crystal display device, and organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition excellent in heat resistance and light resistance, exhibiting no decrease in the display contrast due to diffusion of light, and capable of manufacturing a color filter having a strong coloring power and a high luminance; and to provide a high-luminance color filter obtained from the coloring composition, and a liquid crystal display device, and an EL display device having the color filter.SOLUTION: A polymeric compound having a triarylmethane dye on its side chain is obtained by reacting an isocyanate group or a blocked isocyanate group which a polymer has as its side chain with a primary or secondary amine group of the triarylmethane dye.

Description

  The present invention relates to a polymer compound polymerized from a dye having a polymerizable double bond, a colored composition containing a polymer compound having a dye in the side chain, a color filter using the colored composition, and a method for producing the same The present invention relates to a liquid crystal display device including the same and an organic EL display.

  In recent years, liquid crystal display devices have been evaluated for space saving, light weight, power saving, and the like because they are thin. In particular, the spread to display applications such as television receivers is rapidly advancing, and it is desired to improve display performance such as brightness, contrast, and visibility in all directions, and further increase the brightness of the color filters used therefor. High contrast is desired.

  As a method for producing a color filter, a printing method, an electrodeposition method, a pigment dispersion method, and the like are known. Among these, the pigment dispersion method is a photolithography method in which a colored composition in which a pigment is dispersed in various photosensitive compositions is used. This is a method for producing a color filter. Since the pigment dispersion method uses a pigment, it is excellent in heat resistance and light resistance, is suitable as a color filter for liquid crystal display devices, and has been widely used.

  However, it is known that a color filter produced using a pigment dispersion method diffuses light in a liquid crystal display device due to the influence of pigment fine particles, leading to a decrease in display contrast. As discussed, this diffusion does not go away completely as long as pigments are used.

  In order to solve this problem, it is conceivable to use a dye that develops color when dissolved in a colored composition. Conventionally, a color filter using a dye has been studied and proposed (Patent Document 3), but the coloring composition containing the dye has a new problem. That is, (a) a general dye has low solubility in an organic solvent used in a general color filter coloring composition. (B) Since the dye acts as a so-called “radical eater” that deactivates the generated radical polymerization terminal in radical polymerization generally used in the photolithography method, the exposure sensitivity is lowered and the coating film cannot be sufficiently cured. (C) Dyes are generally inferior in heat resistance and light resistance compared to pigments. (D) Elution occurs when the dye in the coating film is immersed in an organic solvent.

  To solve these problems, studies have been made to improve exposure sensitivity and heat resistance by using a binder resin having a unit structure containing an unsaturated double bond in the dye-containing coloring composition. Only the crosslinking density of the coating film is increased, and the elution property of the dye is not sufficiently ensured (Patent Document 4).

  In patent document 5, although the proposal which makes it easy to dye | saturate acidic dye by using resin which has an amine for binder resin is made, it is not necessarily chemically fixed but sufficient for improvement of tolerance. Does not contribute. In Patent Document 6, an anthraquinone dye having a reactive functional group epoxy or an ethylenic double bond is studied. Studies have been made to improve the resistance by immobilizing the dye in the resin skeleton by imparting such a functional group to the dye. However, anthraquinone has a small color value (low coloring power), and it has been difficult to obtain a sufficiently colored coating with a dye alone.

  Further, Patent Documents 7 to 9 use a triarylmethane dye basic dye (cationic dye) having strong coloring power and have a double bond in the counter anion of the dye. Since the triarylmethane structure serving as the chromophore is not fixed to the resin, the heat resistance and light resistance are not improved enough to withstand the color filter manufacturing process and usage environment.

JP-A-8-179111 JP-A-10-130547 JP-A-6-75275 Japanese Patent No. 4090292 JP 2001-183830 A JP 2000-44822 A JP 2003-246935 A JP 2004-292507 A JP 2004-292508 A

  The present invention has been made in view of the above circumstances, and is a coloring composition that is excellent in heat resistance and light resistance, has no reduction in display contrast due to light diffusion, and can produce a color filter with strong coloring power and high brightness, and the coloring composition An object of the present invention is to provide a high brightness color filter obtained from a product, a liquid crystal display device including the color filter, and an EL display.

As means for solving the above-mentioned problems, the invention according to claim 1 is characterized in that the polymer has an isocyanate group or a blocked isocyanate group as a side chain,
A primary or secondary amine group of a triarylmethane dye;
Is a polymer compound having a triarylmethane dye in the side chain, which is characterized in that

  The invention according to claim 2 is characterized in that the triarylmethane dye has a structure represented by the following general formula (1), and the triarylmethane dye according to claim 1 has a side chain. It is a polymer compound possessed by

（式中、Ｒ_１〜６それぞれ独立に、水素原子、置換基を有してもよい炭素数１〜６のアルキル基、置換基を有してもよいフェニル基、又は置換基を有してもよいベンジル基を表し、ただし、Ｒ_１〜６のうち、少なくとも１つは水素原子である。置換基を有してもよい炭素数１〜６のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、イソブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシプロピル基、２−スルホエチル基、カルボキシエチル基、シアノエチル基、メトキシエチル基、エトキシエチル基、ブトキシエチル基、トリフルオロメチル基、ペンタフルオロエチル基を表し、置換基を有していてもよいフェニル基、ベンジル基における置換基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔ―ブチル基、ペンチル基の（Ｃ１〜Ｃ５）アルキル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子のハロゲン原子、スルホン酸基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ｔ―ブトキシ基、ヘキシルオキシ基の（Ｃ１〜Ｃ６）アルコキシ基、ヒドロキシエチル基、ヒドロキシプロピル基のヒドロキシ（Ｃ１〜
Ｃ５）アルキル基、メトキシエチル基、エトキシエチル基、エトキシプロピル基、ブトキシエチル基の（Ｃ１〜Ｃ５）アルコキシ（Ｃ１〜Ｃ５）アルキル基、２―ヒドロキシエトキシ基のヒドロキシ（Ｃ１〜Ｃ５）アルコキシ基、２―メトキシエトキシ基、２―エトキシエトキシ基（Ｃ１〜Ｃ５）等のアルコキシ（Ｃ１〜Ｃ５）アルコキシ基、２―スルホエチル基、カルボキシエチル基、シアノエチル基を表し、Ｒ_７〜２０それぞれ独立に、水素原子、置換基を有してもよい炭素数１〜６のアルキル基又はハロゲン原子である。置換基を有してもよい炭素数１〜６のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、イソブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシプロピル基、２−スルホエチル基、カルボキシエチル基、シアノエチル基、メトキシエチル基、エトキシエチル基、ブトキシエチル基、トリフルオロメチル基、ペンタフルオロエチル基を表し、ハロゲン原子としてはフッ素、塩素、臭素、ヨウ素を表し、Ｘ⁻はカウンターアニオンであり、塩化物イオン、スルホニウム塩（ベンゼンスルホン酸、１−ナフタレンスルホン酸、２−ナフタレンスルホン酸、メタンスルホン酸のアニオン）、又は強酸、超強酸（六フッ化アンチモンや六フッ化リン酸、トリフルオロメタンスルホン酸）のアニオン、トリストリフルオロメタンスルホニルメチドアニオンを表す。）
また、請求項３に記載の発明は、トリアリールメタン染料が下記一般式（２）により表される構造を有することを特徴とする請求項１に記載のトリアリールメタン染料を側鎖に持つ高分子化合物である。

(In the formula, each of R _{1 to 6} independently has a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted phenyl group, or a substituent. A benzyl group, wherein at least one of R _{1 to 6} is a hydrogen atom, and the alkyl group having 1 to 6 carbon atoms which may have a substituent includes a methyl group, an ethyl group, Propyl group, butyl group, isobutyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, hydroxyethyl group, hydroxypropyl group, hydroxypropyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxy Represents an ethyl group, a butoxyethyl group, a trifluoromethyl group, or a pentafluoroethyl group, and includes an optionally substituted phenyl group or benzyl group; Examples of the substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, (C1-C5) alkyl group of pentyl group, halogen atom of fluorine atom, chlorine atom, bromine atom and iodine atom. Atom, sulfonic acid group, methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, hexyloxy group (C1-C6) alkoxy group, hydroxyethyl group, hydroxypropyl group hydroxy (C1-
C5) alkyl group, methoxyethyl group, ethoxyethyl group, ethoxypropyl group, butoxyethyl group (C1-C5) alkoxy (C1-C5) alkyl group, 2-hydroxyethoxy group hydroxy (C1-C5) alkoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group (C1-C5) alkoxy (C1-C5) alkoxy group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, R _7-20 each independently, hydrogen It is a C1-C6 alkyl group which may have an atom and a substituent, or a halogen atom. Examples of the alkyl group having 1 to 6 carbon atoms which may have a substituent include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a hydroxyethyl group, Represents a hydroxypropyl group, a hydroxypropyl group, a 2-sulfoethyl group, a carboxyethyl group, a cyanoethyl group, a methoxyethyl group, an ethoxyethyl group, a butoxyethyl group, a trifluoromethyl group, a pentafluoroethyl group, and a halogen atom is fluorine, Represents chlorine, bromine and iodine, X ⁻ is a counter anion, chloride ion, sulfonium salt (anion of benzenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, methanesulfonic acid), strong acid, super Strong acids (antimony hexafluoride and phosphoric acid hexafluoride , Trifluoromethanesulfonic acid) anion, tristrifluoromethanesulfonylmethide anion. )
The invention according to claim 3 is characterized in that the triarylmethane dye has a structure represented by the following general formula (2). It is a molecular compound.

（Ｘ⁻はカウンターアニオンであり、塩化物イオン、ベンゼンスルホン酸、１−ナフタレンスルホン酸、２−ナフタレンスルホン酸、メタンスルホン酸、六フッ化アンチモンや六フッ化リン酸、トリフルオロメタンスルホン酸、４フッ化ホウ素酸、トリストリフルオロメタンスルホニルメチドアニオンを表す。）
また、請求項４に記載の発明は、１級あるいは２級のアミン基を持つトリアリールメタン染料の該アミン基に、重合性二重結合及びイソシアネート基あるいはブロック化されたイソシアネート基を持つ化合物の該イソシアネート基あるいはブロック化されたイソシアネート基を反応させたことを特徴とする重合性二重結合を持つトリアリールメタン染料である。

(X ^- is a counter anion, a chloride ion, benzenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, methanesulfonic acid, antimony hexafluoride and phosphorus hexafluoride acid, trifluoromethanesulfonic acid, 4 (Represents fluoroboric acid, tristrifluoromethanesulfonylmethide anion.)
In the invention according to claim 4, a compound having a polymerizable double bond and an isocyanate group or a blocked isocyanate group is added to the amine group of a triarylmethane dye having a primary or secondary amine group. A triarylmethane dye having a polymerizable double bond, wherein the isocyanate group or a blocked isocyanate group is reacted.

  In the invention according to claim 5, the triarylmethane dye has a structure represented by the following general formula (1), and an amine group of the triarylmethane dye has a polymerizable double bond and an isocyanate group. Alternatively, the triarylmethane dye having a polymerizable double bond according to claim 4, wherein the isocyanate group or the blocked isocyanate group of a compound having a blocked isocyanate group is reacted.

（式中、Ｒ_１〜６はそれぞれ独立に、水素原子、置換基を有してもよい炭素数１〜６のアルキル基、置換基を有してもよいフェニル基、又は置換基を有してもよいベンジル基を表し、ただし、Ｒ_１〜６のうち、少なくとも１つは水素原子である。置換基を有してもよい炭素数１〜６のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、イソブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシプロピル基、２−スルホエチル基、カルボキシエチル基、シアノエチル基、メトキシエチル基、エトキシエチル基、ブトキシエチル基、トリフルオロメチル基、ペンタフルオロエチル基を表し、置換基を有していてもよいフェニル基、ベンジル基における置換基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔ―ブチル基、ペンチル基の（Ｃ１〜Ｃ５）アルキル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、スルホン酸基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ｔ―ブトキシ基、ヘキシルオキシ基の（Ｃ１〜Ｃ６）アルコキシ基、ヒドロキシエチル基、ヒドロキシプロピル基のヒドロキシ（Ｃ１〜Ｃ５）アルキル基、メトキシエチル基、エトキシエチル基、エトキシプロピル基、ブトキシエチル基の（Ｃ１〜Ｃ５）アルコキシ（Ｃ１〜Ｃ５）アルキル基、２―ヒドロキシエトキシ基等のヒドロキシ（Ｃ１〜Ｃ５）アルコキシ基、２―メトキシエトキシ基、２―エトキシエトキシ基（Ｃ１〜Ｃ５）等のアルコキシ（Ｃ１〜Ｃ５）アルコキシ基、２―スルホエチル基、カルボキシエチル基、シアノエチル基を表し、Ｒ_７〜２０はそれぞれ独立に、水素原子、置換基を有してもよい炭素数１〜６のアルキル基又はハロゲン原子である。置換基を有してもよい炭素数１〜６のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、イソブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシプロピル基、２−スルホエチル基、カルボキシエチル基、シアノエチル基、メトキシエチル基、エトキシエチル基、ブトキシエチル基、トリフルオロメチル基、ペンタフルオロエチル基を表し、ハロゲン原子としてはフッ素、塩素、臭素、ヨウ素を表し、Ｘ⁻はカウンターアニオンを表し、塩化物イオン、スルホニウム塩（ベンゼンスルホン酸、１−ナフタレンスルホン酸、２−ナフタレンスルホン酸、メタンスルホン酸のアニオン）、又は強酸、超強酸（六フッ化アンチモンや六フッ化リン酸、トリフルオロメタンスルホン酸など）のアニオン表し、トリストリフルオロメタンスルホニルメチドアニオンを表す。）
また、請求項６に記載の発明は、トリアリールメタン染料が、下記一般式（２）により表される構造を有し、前記トリアリールメタン染料のアミン基に、重合性二重結合及びイソシアネート基あるいはブロック化されたイソシアネート基を持つ化合物の該イソシアネート基あるいはブロック化されたイソシアネート基を反応させたことを特徴とする請求項４に記載の重合性二重結合を持つトリアリールメタン染料である。

(Wherein R _{1 to 6} each independently have a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted phenyl group, or a substituent. A benzyl group which may be substituted, provided that at least one of R _{1 to 6} is a hydrogen atom, and the alkyl group having 1 to 6 carbon atoms which may have a substituent includes a methyl group and an ethyl group; Propyl group, butyl group, isobutyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, hydroxyethyl group, hydroxypropyl group, hydroxypropyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, Represents an ethoxyethyl group, a butoxyethyl group, a trifluoromethyl group, a pentafluoroethyl group, an optionally substituted phenyl group, a benzyl group Examples of the substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, (C1-C5) alkyl group of pentyl group, fluorine atom, chlorine atom, bromine atom, iodine atom, etc. Halogen atom, sulfonic acid group, methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, hexyloxy group (C1-C6) alkoxy group, hydroxyethyl group, hydroxypropyl group hydroxy (C1-C5) Alkyl group, methoxyethyl group, ethoxyethyl group, ethoxypropyl group, butoxyethyl group (C1-C5) alkoxy (C1-C5) alkyl group, hydroxy (C1-C5) alkoxy group such as 2-hydroxyethoxy group, -Alkoxy such as methoxyethoxy group, 2-ethoxyethoxy group (C1 to C5) (C1 C5) represents an alkoxy group, a 2-sulfoethyl group, a carboxyethyl group, a cyanoethyl group, and R _{7 to 20} each independently represent a hydrogen atom, a C 1-6 alkyl group or a halogen atom that may have a substituent. Examples of the alkyl group having 1 to 6 carbon atoms which may have a substituent include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, and a hydroxy group. Represents an ethyl group, a hydroxypropyl group, a hydroxypropyl group, a 2-sulfoethyl group, a carboxyethyl group, a cyanoethyl group, a methoxyethyl group, an ethoxyethyl group, a butoxyethyl group, a trifluoromethyl group, a pentafluoroethyl group, and a halogen atom. is fluorine, chlorine, bromine, represents iodine, X ^- a counter anion Chloride ion, sulfonium salt (anion of benzenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, methanesulfonic acid), strong acid, super strong acid (antimony hexafluoride, hexafluorophosphoric acid, trifluoro) Represents an anion of lomethanesulfonic acid, etc., and represents a tristotrifluoromethanesulfonylmethide anion. )
In the invention according to claim 6, the triarylmethane dye has a structure represented by the following general formula (2), and an amine group of the triarylmethane dye has a polymerizable double bond and an isocyanate group. Alternatively, the triarylmethane dye having a polymerizable double bond according to claim 4, wherein the isocyanate group or the blocked isocyanate group of a compound having a blocked isocyanate group is reacted.

（式中、Ｘ⁻はカウンターアニオンであり、塩化物イオン、ベンゼンスルホン酸、１−ナフタレンスルホン酸、２−ナフタレンスルホン酸、メタンスルホン酸、六フッ化アンチモンや六フッ化リン酸、トリフルオロメタンスルホン酸、４フッ化ホウ素酸、トリストリフルオロメタンスルホニルメチドアニオン、のいずれかを表す。）
また、請求項７に記載の発明は、前記重合性二重結合を持つトリアリールメタン染料と重合性二重結合を持つモノマーを共重合したことを特徴とする請求項４〜６のいずれか一項に記載のトリアリールメタン染料を側鎖に持つ高分子化合物である。

(Wherein, X ^- is a counter anion, a chloride ion, benzenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, methanesulfonic acid, antimony hexafluoride and hexafluorophosphate, trifluoromethanesulfonate It represents any of acid, tetrafluoroboric acid, tristrifluoromethanesulfonylmethide anion.)
The invention described in claim 7 is characterized in that the triarylmethane dye having a polymerizable double bond and a monomer having a polymerizable double bond are copolymerized. A polymer compound having the triarylmethane dye described in the item in the side chain.

  The invention according to claim 8 is characterized in that the dye in the polymer compound having the dye in the side chain is in the range of 1% by mass to 50% by mass. A polymer compound having the triarylmethane dye according to any one of the above in its side chain.

  The invention according to claim 9 is a polymer compound having the triarylmethane dye according to any one of claims 1 to 3, 7 and 8 as a side chain, and at least one kind. A color filter coloring composition comprising: a polymerizable monomer; and at least one photopolymerization initiator.

  The invention described in claim 10 is a color filter including a colored pixel formed by using the colored composition according to claim 9.

  An eleventh aspect of the present invention is a liquid crystal display device comprising the color filter according to the tenth aspect.

  The invention according to claim 12 is an organic EL display device comprising the color filter according to claim 10.

According to the present invention, it is possible to obtain a coloring composition that is capable of producing a color filter having excellent coating film chromaticity, high brightness, no deterioration of display contrast due to light diffusion, and excellent heat resistance and light resistance.
It is possible to provide a liquid crystal display device and an EL display including a high brightness color filter excellent in heat resistance and light resistance, and a high brightness color filter excellent in heat resistance and light resistance.

It is sectional drawing which shows the color filter which concerns on the 2nd Embodiment of this invention. It is sectional drawing which shows an example of a liquid crystal display device provided with the color filter shown in FIG. It is sectional drawing which shows an example of EL display provided with the color filter shown in FIG.

  Hereinafter, various embodiments of the present invention will be described. As a result of investigations to solve the above problems, the present inventors have used a triarylmethane dye having a primary or secondary amine group as a coloring material in a coloring composition for a color filter. Copolymerizes a polymer compound having a triarylmethane dye in the side chain obtained by reacting with an isocyanate compound having a heavy bond, a triarylmethane dye containing a double bond, and a monomer having a polymerizable double bond. It was found that a dye compound having high heat resistance can be obtained by using a high molecular weight compound obtained by the above method.

  The polymer compound having a triarylmethane dye in the side chain has a structure represented by the following general formula (3).

本発明に用いるトリアリールメタン染料は、１級あるいは２級アミンを有するものであれば特に制限なく用いることができる。例えば、Ｃ．Ｉ．Ｂａｓｉｃ Ｖｉｏｌｅｔ １、２、１４、Ｃ．Ｉ．Ｂａｓｉｃ Ｂｌｕｅ７、１１、２６、Ｃ．Ｉ．Ｂａｓｉｃ Ｒｅｄ９、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ８３、９０、９１、９３、１０８などが挙げられる。特にＣ．Ｉ．Ｂａｓｉｃ Ｂｌｕｅ ７が着色性、色再現性の観点から好ましい。これらの染料は、それぞれの発色団に置換基を有していてもよく、また元の構造が持つ２級あるいは３級アミン基が持つアルキル基がその他の構造に置き換わっていてもよい。例として、Ｃ．Ｉ．Ｂａｓｉｃ Ｂｌｕｅ ７で説明する。ただし、これに限定されるものではない。

The triarylmethane dye used in the present invention can be used without particular limitation as long as it has a primary or secondary amine. For example, C.I. I. Basic Violet 1, 2, 14, C.I. I. Basic Blue 7, 11, 26, C.I. I. Basic Red 9, C.I. I. Acid Blue 83, 90, 91, 93, 108 and the like. In particular, C.I. I. Basic Blue 7 is preferable from the viewpoint of colorability and color reproducibility. These dyes may have a substituent in each chromophore, and the alkyl group of the secondary or tertiary amine group of the original structure may be replaced with another structure. As an example, C.I. I. This will be described in Basic Blue 7. However, it is not limited to this.

C. I. The structure of Basic Blue 7 is the structure shown in the general formula (4), but R _1-6 and R _7-20 shown in the general formula (5) are replaced with other substituents even if this structure itself is not. May be.

（Ｒ_１〜６はそれぞれ独立に、水素原子、置換基を有してもよい炭素数１〜６のアルキル基、置換基を有してもよいフェニル基、又は置換基を有してもよいベンジル基を表す。ただし、Ｒ_１〜６のうち、少なくとも１つは水素原子である。置換基を有してもよい炭素数１〜６のアルキル基としては、例えばメチル基、エチル基、プロピル基、ブチル基、イソブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシプロピル基、２−スルホエチル基、カルボキシエチル基、シアノエチル基、メトキシエチル基、エトキシエチル基、ブトキシエチル基、トリフルオロメチル基、ペンタフルオロエチル基を表す。置換基を有していてもよ
いフェニル基、ベンジル基における置換基としては、例えばメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔ―ブチル基、ペンチル基等の（Ｃ１〜Ｃ５）アルキル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、スルホン酸基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ｔ―ブトキシ基、ヘキシルオキシ基の（Ｃ１〜Ｃ６）アルコキシ基、ヒドロキシエチル基、ヒドロキシプロピル基等のヒドロキシ（Ｃ１〜Ｃ５）アルキル基、メトキシエチル基、エトキシエチル基、エトキシプロピル基、ブトキシエチル基等の（Ｃ１〜Ｃ５）アルコキシ（Ｃ１〜Ｃ５）アルキル基、２―ヒドロキシエトキシ基等のヒドロキシ（Ｃ１〜Ｃ５）アルコキシ基、２―メトキシエトキシ基、２―エトキシエトキシ基（Ｃ１〜Ｃ５）等のアルコキシ（Ｃ１〜Ｃ５）アルコキシ基、２―スルホエチル基、カルボキシエチル基、シアノエチル基を表す。好ましくは、水素原子、無置換の炭素数１〜６のアルキル基、無置換のフェニル基、又は無置換のベンジル基表し、Ｒ_７〜２０はそれぞれ独立に、水素原子、置換基を有してもよい炭素数１〜６のアルキル基又はハロゲン原子である。置換基を有してもよい炭素数１〜６のアルキル基としては、例えばメチル基、エチル基、プロピル基、ブチル基、イソブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシプロピル基、２−スルホエチル基、カルボキシエチル基、シアノエチル基、メトキシエチル基、エトキシエチル基、ブトキシエチル基、トリフルオロメチル基、ペンタフルオロエチル基等が挙げられ、ハロゲン原子としてはフッ素、塩素、臭素、ヨウ素等が挙げられる。好ましくは、水素原子、無置換アルキル基又は塩素原子を表し、トリアリールメタン染料のアニオン部（カウンターアニオンと称する）は塩化物イオンが一般的であるが、耐性向上のためにはスルホニウム塩（例えばベンゼンスルホン酸、１−ナフタレンスルホン酸、２−ナフタレンスルホン酸、メタンスルホン酸などのアニオン）や、いわゆる強酸、超強酸（例えば六フッ化アンチモンや六フッ化リン酸、トリフルオロメタンスルホン酸）、トリストリフルオロメタンスルホニルメチドアニオンを表す。）
本発明に係るトリアリールメタン染料を側鎖に持つ高分子化合物は、上述のトリアリールメタン染料にイソシアネート基を反応することで重合性二重結合を導入し、該二重結合を他のモノマーと共重合することで染料含有高分子化合物を得る。あるいは、イソシアネート基を含むモノマーを他のモノマーと共重合することでイソシアネート基を含むポリマーを合成し、このイソシアネート基とトリアリールメタン染料を反応させて本発明に係る染料含有高分子化合物を得ても構わない。

(R _1-6 may each independently have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a substituent. Represents a benzyl group, wherein at least one of R _{1 to 6} is a hydrogen atom, and examples of the alkyl group having 1 to 6 carbon atoms which may have a substituent include a methyl group, an ethyl group, and propyl; Group, butyl group, isobutyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, hydroxyethyl group, hydroxypropyl group, hydroxypropyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl Group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, phenyl group optionally having substituent (s), benzyl group Examples of substituents include (C1-C5) alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, and pentyl groups, fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. A halogen atom such as sulfonic acid group, methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, hexyloxy group (C1-C6) alkoxy group, hydroxyethyl group, hydroxypropyl group and other hydroxy (C1 -C5) Alkyl group, methoxyethyl group, ethoxyethyl group, ethoxypropyl group, butoxyethyl group and the like (C1-C5) alkoxy (C1-C5) alkyl group, hydroxy such as 2-hydroxyethoxy group (C1-C5) Alcohol such as alkoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group (C1-C5), etc. Xi (C1-C5) alkoxy group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, preferably a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, an unsubstituted phenyl group, or unsubstituted R _{7 to 20} each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or a halogen atom, and 1 carbon atom which may have a substituent. As the alkyl group of ˜6, for example, methyl group, ethyl group, propyl group, butyl group, isobutyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, hydroxyethyl group, hydroxypropyl group, hydroxypropyl group, 2- Sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoro Examples thereof include a methyl group and a pentafluoroethyl group, and examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like. Preferably, it represents a hydrogen atom, an unsubstituted alkyl group or a chlorine atom, and the anion portion (referred to as counter anion) of the triarylmethane dye is generally a chloride ion, but for improving resistance, a sulfonium salt (for example, Benzenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, anions such as methanesulfonic acid), so-called strong acids, super strong acids (for example, antimony hexafluoride, hexafluorophosphoric acid, trifluoromethanesulfonic acid), tris Represents trifluoromethanesulfonylmethide anion. )
The polymer compound having a triarylmethane dye in the side chain according to the present invention introduces a polymerizable double bond by reacting an isocyanate group with the above-described triarylmethane dye, and the double bond is combined with another monomer. A dye-containing polymer compound is obtained by copolymerization. Alternatively, a polymer containing an isocyanate group is synthesized by copolymerizing a monomer containing an isocyanate group with another monomer, and the isocyanate group and the triarylmethane dye are reacted to obtain a dye-containing polymer compound according to the present invention. It doesn't matter.

  In any method, a polymerizable monomer having an isocyanate group is required. Such an isocyanate compound having a polymerizable double bond can be used without particular limitation, and can be selected from known ones. Since isocyanate is highly reactive, a blocked isocyanate having a blocked CNO group in which an isocyanate group is blocked is preferable in consideration of pod life and side reactions during polymerization.

  Examples of the blocked isocyanate include compounds in which an isocyanate group is blocked using a blocking agent having a phenol group, an imidazole group, a pyrazole group, an oxime group, a lactam group, an alcohol group, or the like with respect to the isocyanate group. The blocking agent may be any as long as the water-soluble vinyl resin is stable in an aqueous solution and the isocyanate group is unblocked at about 100 ° C. to 200 ° C. Methyl salicylate and imidazole containing a phenol group Examples include imidazole containing a group, 3,5-dimethylpyrazole containing a pyrazole group, methyl ethyl ketone oxime containing an oxime group, ε-caprolactam containing a lactam group, and ethylhexanol containing an alcohol group. is not. Examples include BURNOCK DB-980K (manufactured by DIC Corporation), Duranate TPA-B80E (manufactured by Asahi Kasei Chemicals Corporation), KA-1000 (manufactured by Sanyo Chemical Industries), and the like.

  Examples of the compound include 2-isocyanatoethyl (meth) acrylate (Karenz MOI Showa Denko) and Karenz MOI-EG (Showa Denko) containing an isocyanate group, and 2- (methacrylic acid) containing a blocked isocyanate group. Examples include, but are not limited to, 0- [1′-methylpropylideneamino] carboxyamino) ethyl (Karenz MOI-BM, manufactured by Showa Denko KK).

  Although the method in the case of coupling | bonding a triarylmethane dye and an isocyanate group previously and copolymerizing with another monomer after that is illustrated, it is not limited to this method. Triarylmethane dye is added to cyclohexanone and dissolved sufficiently, and the mixture is stirred while maintaining the temperature from room temperature to about 40 ° C. The isocyanate compound having a polymerizable double bond is used as it is in the case of a compound which is liquid at room temperature, and dissolved in cyclohexanone in the case of a solid. If necessary, 0.03 parts by mass of dibutylhydroxytoluene may be added to 100 parts by mass of the isocyanate compound so that the polymerization reaction does not proceed. The isocyanate compound is dropped into the dye solution over about 2 hours to allow the reaction to proceed. The amount of the isocyanate compound to be dropped is the same as that of the dye, or about 100 parts by mass to 110 parts by mass with respect to 100 parts by mass of the dye. By continuing the stirring for about 2 hours after completion of the dropping, a reaction product of the triarylmethane dye and the isocyanate compound is obtained.

  The resultant reaction product of the triarylmethane dye and the isocyanate compound is copolymerized with another monomer having a polymerizable vinyl bond to obtain a polymer compound containing the triarylmethane dye. The monomer having a vinyl bond can be used without particular limitation as long as it is a known monomer, but a vinyl compound, an acrylic compound or a methacrylic compound is preferable. Acrylic compounds or methacrylic compounds are particularly preferred.

  Examples include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, diethylene glycol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meta) ) Acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycid Various acrylics such as ruether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate Acid ester and methacrylate ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide And acrylonitrile. These can be used alone or in admixture of two or more.

  These monomers and the above triarylmethane dye compound are copolymerized to obtain a polymer compound having a triarylmethane dye in the side chain. As the method, a known polymerization method such as a general acrylic monomer can be used. For example, a cyclohexanone solution of 4,4′-azobisisobutyronitrile (AIBN) as a polymerization initiator is dropped into a cyclohexanone solution of the aforementioned triarylmethane dye compound and other acrylic monomers at 80 ° C. for about 1 hour. Heat. Further, in order to sufficiently react the unreacted monomer, AIBN is additionally added, and the mixture is further heated at 80 ° C. for about 3 hours.

  Next, a method of reacting an isocyanate group with a triarylmethane dye after polymerizing an isocyanate compound having a polymerizable double bond with another monomer will be described. However, it is not limited to this method.

  First, an isocyanate compound having a polymerizable double bond is polymerized with another monomer. As the isocyanate compound having a polymerizable double bond, it is preferable to use a blocked isocyanate.

  An example is shown. As an acrylic monomer containing a blocked isocyanate group, 2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate (Karenz MOI-BM, manufactured by Showa Denko KK) and other acrylic monomers are used as cyclohexanone. Dissolve in However, a monomer having a carboxylic acid that reacts with isocyanate (for example, methacrylic acid or acrylic acid) or a monomer having a hydroxyl group (for example, 2-hydroxyethyl methacrylate) cannot be used.

  To this cyclohexanone solution, a cyclohexanone solution of 4,4′-azobisisobutyronitrile (AIBN) as a polymerization initiator is added dropwise and heated at 80 ° C. for about 1 hour. Further, in order to sufficiently react the unreacted monomer, AIBN is additionally added and further heated at 80 ° C. for about 3 hours to obtain a resin which is a polymer compound having a blocked isocyanate group.

  A cyclohexanone solution of resin, which is a polymer compound having a blocked isocyanate group, is placed in a reaction vessel, heated to 155 ° C. to reflux, and stirred. A polymer compound having the dye in the side chain can be obtained by dripping the cyclohexanone solution of the dye into the reaction solution over 1 hour and further stirring for 5 hours.

  The content of the dye molecule in the polymer compound having the dye according to the present invention in the side chain is preferably 1% by mass to 50% by mass in the solid content of the polymer compound having the dye in the side chain. More preferably, it is 5 to 30% by mass. If it is less than 1% by mass, since the ratio of the dye to the solid content is small, the amount of the polymer compound of the dye necessary to obtain a sufficient color as a color filter increases, so that the coating film is not formed thick. It becomes difficult to manufacture. On the other hand, when the amount is 50% by mass or more, it is difficult to synthesize the resin because gelation occurs during the polymerization.

  The mass ratio of the dye in the polymer compound having a dye in the side chain here is the mass ratio of the dye structure in the total mass of the solid content of the polymer compound having the dye in the side chain, and the mass of the dye structure. Is the mass of the site derived from the chemical structure before reacting with the isocyanate group.

  In this invention, it is a coloring composition for color filters containing the high molecular compound which has this dye in a side chain, at least 1 type of polymerizable monomer, and at least 1 type of photoinitiator. In the coloring composition for a color filter according to the present invention, in addition to the polymer compound having the dye in the side chain, a known dye can be used for color adjustment.

  Examples of the known dye include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Tokuho 2592207, US Patent No. 4,808,501, U.S. Pat.No. 5,667,920, U.S. Pat.No. 5,059,500, JP-A-5-333207, JP-A-6-35183, Examples thereof include dyes described in JP-A-6-51115 and JP-A-6-194828.

Examples of these dyes include acid dyes, oil-soluble dyes, disperse dyes, reactive dyes, and direct dyes. For example, azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, stilbene dyes, diarylmethane dyes, triarylmethane dyes, fluorans Dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, fulgide dyes, nickel complex dyes, and azulene dyes.

  The mass concentration of the dye in the coloring composition is preferably 0.1% to 20%, more preferably 0.5% to 18%, still more preferably 0.5% to 15%. If the dye concentration is less than 0.1%, the dye concentration is low, and in order to form a colored pixel having a sufficient color as a color filter, the thickness of the colored pixel must be very large. Since it is difficult to form and productivity is deteriorated, there is a practical difficulty. On the other hand, if the concentration exceeds 20%, the concentration is too high, so that the dye may not be sufficiently dissolved and crystals may be deposited. Further, a colored composition is applied on the substrate to form a colored pixel, and an organic solvent is used. There is also a risk that the dye may be precipitated when drying.

  The coloring composition for a color filter according to the present invention can contain a pigment in addition to the dye. The mass concentration of the pigment in the coloring composition is preferably 0.1% to 50%, more preferably 0.5% to 40%, and still more preferably 0.5% to 30%. If it is less than 0.1%, the pigment concentration is low, and in order to form colored pixels of sufficient color as a color filter, it is difficult to form the pixels because the thickness of the colored pixels must be very large. Yes, there is a practical difficulty because productivity deteriorates, and if it exceeds 50%, the amount of resin for dispersing the pigment decreases, becomes unstable, and causes viscosity increase and contrast decrease due to pigment aggregation. It becomes.

  The pigment is not particularly limited, but a known pigment can be used without particular limitation. For example, as a red pigment, C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, 272, 279 and the like. In particular, C.I. I. Pigment Red 177, 242, and 254 are preferably used.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 144, 146, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 17 3, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214 and the like. I. Pigment Yellow 138, 139, 150 is preferably used.

  Examples of the orange pigment include CI Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73, and the like. I. Pigment Orange 36 is preferably used.

Examples of the green pigment include CI Pigment Green 7, 10, 36, 3
Green pigments such as 7, 58 can be used. I. Pigment Green 7, 36, and 58 are preferably used.

  Examples of blue pigments include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 80 and the like. I. Pigment Blue 15: 3, CI Pigment Blue 15: 6 can be used.

  Further, as a purple pigment, C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, etc. are used. I. Pigment Violet 23 is preferably used.

  Inorganic pigments include yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green and other metal oxide powders, metal sulfide powders, metal powders Etc. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.

  The pigment contained in the coloring composition is preferably subjected to a finer treatment and preferably has a small primary particle diameter in order to achieve high brightness and high contrast of the color filter. The primary particle diameter of the pigment was calculated by taking the pigment with a transmission electron microscope and analyzing the image of the photograph. Here, the primary particle diameter represents a particle diameter (equivalent circle diameter) corresponding to 50% of the total amount in the cumulative curve of the number particle size distribution.

  The primary particle diameter of the pigment is preferably 40 nm or less, more preferably 30 nm or less, and still more preferably 20 nm or less. Moreover, it is preferable that a primary particle diameter is 5 nm or more.

  When the primary particle diameter of the pigment is larger than the upper limit value, the visibility of the liquid crystal display device during black display is poor. Moreover, when smaller than a lower limit, pigment dispersion | distribution becomes difficult, it becomes difficult to maintain stability as a coloring composition and to ensure fluidity | liquidity. As a result, the luminance and color characteristics of the color filter are deteriorated.

  As a means for controlling the primary particle diameter of the pigment, a method of controlling the primary particle diameter by mechanically pulverizing the pigment (referred to as a grinding method), a solution dissolved in a good solvent is introduced into a poor solvent, and the desired primary particle diameter is controlled. There are a method for precipitating a pigment having a particle size (referred to as a precipitation method) and a method for producing a pigment having a desired primary particle size at the time of synthesis (referred to as a synthetic precipitation method). Depending on the synthesis method and chemical properties of the pigment to be used, an appropriate method can be selected for each pigment.

  Each method will be described below, but any of the above methods may be used as a method for controlling the primary particle size of the pigment contained in the colored composition used in the present invention. In the grinding method, the pigment is mechanically kneaded using a ball mill, sand mill or kneader together with a grinding agent such as a water-soluble inorganic salt such as salt and a water-soluble organic solvent that does not dissolve it (hereinafter, this treatment is salted). This is a method of obtaining a pigment having a desired primary particle size by washing and removing the inorganic salt and the organic solvent, followed by drying. However, since the pigment may crystallize by the salt milling treatment, a method of preventing crystal growth by adding a solid resin or a pigment dispersant that is at least partially dissolved in the organic solvent during the treatment is effective.

As for the ratio of the pigment to the inorganic salt, if the ratio of the inorganic salt is increased, the efficiency of refining the pigment is improved, but the productivity is lowered because the amount of pigment processed is reduced. In general, the pigment is used in an amount of 1 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 1 part by weight of the inorganic salt. Further, the water-soluble organic solvent is added so that the pigment and the inorganic salt are uniformly solidified, and usually depends on the blending ratio of the pigment and the inorganic salt, but it is usually 0. Used in an amount of 5 to 30 parts by mass.

  More specifically, with respect to the above grinding method, a small amount of a water-soluble organic solvent is added as a wetting agent to a mixture of a pigment and a water-soluble inorganic salt, and after kneading with a kneader or the like, the mixture is poured into water. Stir with a speed mixer to make a slurry. Next, this slurry is filtered, washed with water, and dried to obtain a pigment having a desired primary particle size.

  The precipitation method is a method in which a pigment is dissolved in an appropriate good solvent and then mixed with a poor solvent to precipitate a pigment having a desired primary particle size. The primary method depends on the type and amount of the solvent, the precipitation temperature, the precipitation rate, etc. The particle size can be controlled. In general, pigments are difficult to dissolve in solvents, so the solvents that can be used are limited. Examples include strongly acidic solvents such as concentrated sulfuric acid, polyphosphoric acid, and chlorosulfonic acid, or basic solvents such as liquid ammonia, dimethylformamide solution of sodium methylate, etc. It has been known.

  A typical example of this method is an acid pasting method in which a solution in which a pigment is dissolved in an acidic solvent is poured into another solvent and reprecipitated to obtain fine particles. Industrially, a method of injecting a sulfuric acid solution into water is generally used from the viewpoint of cost. The sulfuric acid concentration is not particularly limited, but is preferably 95 to 100% by mass. The amount of sulfuric acid used with respect to the pigment is not particularly limited. However, if the amount is too small, the solution viscosity is high and handling becomes bad. Conversely, if the amount is too large, the treatment efficiency of the pigment is lowered. It is preferable.

  The pigment need not be completely dissolved. The temperature at the time of dissolution is preferably from 0 to 50 ° C. Below this temperature, sulfuric acid may freeze and the solubility will be low. If the temperature is too high, side reactions tend to occur. The temperature of the water to be injected is preferably 1 to 60 ° C., and if the injection is started at a temperature higher than this temperature, it boils with the heat of dissolution of sulfuric acid, and the operation is dangerous. It will freeze at temperatures below this. The injection time is preferably 0.1 to 30 minutes with respect to 1 part of the pigment. As the time increases, the primary particle size tends to increase.

  The primary particle size of the pigment can be controlled while taking into account the fine particle size of the pigment by selecting a method that combines a precipitation method such as the acid pasting method and a grinding method such as the salt milling method. At this time, the fluidity as a dispersion can be secured, which is more preferable.

  At the time of salt milling or acid pasting, in order to prevent aggregation of the pigment accompanying the control of the primary particle size, the following dispersion aids such as a dye derivative, a resin-type pigment dispersant, and a surfactant can be used in combination. Further, by controlling the primary particle size in the form of coexistence of two or more kinds of pigments, even a pigment that is difficult to disperse alone can be finished as a stable dispersion.

  There is a leuco method as a special precipitation method. When a vat dye, such as a flavantron, perinone, perylene, or indanthrone, is reduced with alkaline hydrosulfite, the quinone group becomes a hydroquinone sodium salt (leuco compound) and becomes water-soluble. A pigment having a small primary particle size insoluble in water can be precipitated by adding an appropriate oxidizing agent to the aqueous solution for oxidation.

The synthetic precipitation method is a method of synthesizing a pigment and simultaneously depositing a pigment having a desired primary particle size. However, when the produced fine pigment is taken out of the solvent, if the pigment particles are not aggregated into large secondary particles, filtration, which is a general separation method, becomes difficult. It is applied to azo pigments synthesized in water.

  Furthermore, as a means of controlling the primary particle diameter of the pigment, the primary particle diameter of the pigment is reduced and dispersed simultaneously by dispersing the pigment for a long time with a high-speed sand mill or the like (so-called dry milling method in which the pigment is dry-pulverized). It is also possible.

  The binder resin as a pigment carrier contained in the coloring composition for a color filter of the present invention disperses the pigment, and is composed of a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and its precursor includes a monomer or an oligomer that is cured by irradiation with radiation to form a transparent resin. Or 2 or more types can be mixed and used.

  The binder resin as the pigment carrier can be used in an amount of 30 to 700 parts by mass, preferably 60 to 450 parts by mass with respect to 100 parts by mass of the pigment in the coloring composition. When a mixture of a transparent resin and its precursor is used as a pigment carrier, the transparent resin is 20 to 400 parts by weight, preferably 50 to 250 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition. Can be used. The precursor of the transparent resin can be used in an amount of 10 to 300 parts by mass, preferably 10 to 200 parts by mass with respect to 100 parts by mass of the pigment in the coloring composition.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins. Among these, acrylic resins are preferably used from the viewpoint of transparency.

  Active energy ray-curable resins include (meth) acrylic having a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group. A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting a compound or cinnamic acid is used. In addition, linear polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer can be converted to (meth) acrylic compounds having hydroxyl groups such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  As the binder resin used in the color filter coloring composition having the dye according to the present invention in the side chain, the same resin as the binder resin as the pigment carrier described above can be used. In particular, an acrylic resin is preferably used from the viewpoint of transparency. Monomers and oligomers that produce the binder resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and β-carboxy. Ethyl (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate Relate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) Acrylic esters and methacrylic esters such as acrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl ( Examples include meth) acrylamide, N-vinylformamide, acrylonitrile and the like. These can be used alone or in admixture of two or more.

  In the coloring composition according to the present invention, a thermosetting compound can be used in order to impart heat crosslinkability and improve heat resistance. Examples of the thermosetting compound include epoxy, rosin-modified maleic resin, rosin-modified fumaric acid resin, melamine compound, melamine resin, urea resin, phenol resin, and isocyanate compound. Among these, epoxy compounds, melamine, melamine compounds condensed with melamine, isocyanate compounds, and blocked isocyanate compounds having a block NCO group are preferable. In any case, a polyfunctional compound having two or more thermally reactive functional groups per molecule is preferable, and a tetrafunctional or more compound is more preferable.

  The epoxy compound can be used without particular limitation, and can be selected from known ones. The number of epoxy groups is not particularly limited, but those having two or more functional groups are preferred, and more preferably tetrafunctional or more. Examples thereof include Celoxide 2021P, Celoxide 3000, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.), AK601, EPPN series (manufactured by Nippon Kayaku Co., Ltd.), and the like.

  Melamine can be used without particular limitation, and can be selected from known melamines. For example, melamine compounds are exemplified below.

（式中、Ｒ_１、Ｒ_２、Ｒ_３はそれぞれ水素原子、メチロール基、アルコキシメチル基、アルコキシｎ−ブチル基、Ｒ_４、Ｒ_５、Ｒ_６はそれぞれメチロール基、アルコキシメチル基、アルコキシｎ−ブチル基であるが、Ｒ_１からＲ_６はアルコキシメチル基、アルコキシｎ−ブチル基を表す。）
二種類以上の繰り返し単位を組み合わせたコポリマーを用いてもよい。二種類以上のホモポリマー又はコポリマーを併用してもよい。また、上記以外に１，３，５−トリアジン環を有する化合物で例えば特開２００１−１６６１４４公報に記載のものを使用することができる。また下記一般式（７）に示す化合物も好適である。

(In the formula, R ₁ , R ₂ and R ₃ are each a hydrogen atom, a methylol group, an alkoxymethyl group, an alkoxy n-butyl group, R ₄ , R ₅ and R ₆ are a methylol group, an alkoxymethyl group and an alkoxy n- Although it is a butyl group, R ₁ to R ₆ represent an alkoxymethyl group or an alkoxy n-butyl group.)
A copolymer combining two or more kinds of repeating units may be used. Two or more homopolymers or copolymers may be used in combination. In addition to the above, compounds having a 1,3,5-triazine ring, for example, those described in JP-A No. 2001-166144 can be used. A compound represented by the following general formula (7) is also suitable.

（Ｒ_７からＲ_１４はそれぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基又は複素環基を表す。）
更には、メラミン樹脂とイソシアネート基を含有する化合物及び酸無水物とを反応させてなるメラミン化合物から選ばれた一つ以上であり、該メラミン化合物の質量平均分子量が２５００以上かつ固形分酸価が６０ｍｇＫＯＨ／ｇ以下であるとより好適である。従来のメラミン樹脂を多量に配合すると、感光性樹脂組成物の感度が低下して、十分な硬化に必要な露光時間が長くなり、生産性が悪くなるという問題があった。更に、感光性樹脂組成物のアルカリ現像性が悪化し、現像速度が適度に調整できず現像時間が長くなることや、逆に現像速度が速すぎて塗膜が基板から剥がれやすくなるといった不具合を生じることから、メラミン樹脂の添加量には限度があり、十分な熱硬化性樹脂の効果を発揮させることが難しくなる。

(R ₇ to R ₁₄ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.)
Furthermore, it is one or more selected from a melamine compound obtained by reacting a melamine resin with a compound containing an isocyanate group and an acid anhydride, and the mass average molecular weight of the melamine compound is 2500 or more and the solid content acid value is It is more preferable that it is 60 mgKOH / g or less. When a large amount of conventional melamine resin is blended, there is a problem that the sensitivity of the photosensitive resin composition decreases, the exposure time necessary for sufficient curing becomes long, and the productivity is deteriorated. Furthermore, the alkali developability of the photosensitive resin composition deteriorates, the development speed cannot be adjusted appropriately, the development time becomes long, and on the contrary, the development speed is too high and the coating film is easily peeled off from the substrate. As a result, there is a limit to the amount of melamine resin added, making it difficult to exhibit the effect of a sufficient thermosetting resin.

  Isocyanate compounds can be used without particular limitation, and can be selected from known ones. The number of isocyanate groups is not particularly limited, and examples thereof include aliphatic, aromatic or alicyclic mono- or diisocyanate and triisocyanate compounds.

  Since isocyanate has high reactivity, in view of pod life, a blocked isocyanate in which an isocyanate group is protected with a blocking agent is suitable. Examples of the blocked isocyanate include compounds in which an isocyanate group is blocked using a blocking agent having a phenol group, an imidazole group, a pyrazole group, an oxime group, a lactam group, an alcohol group, or the like with respect to the isocyanate group.

  In the coloring composition for a color filter according to the present invention, one or two or more kinds of organic solvents can be used for coating so that the dry film thickness is 0.2 to 5 μm. The organic solvent is selected in consideration of viscosity, surface tension, boiling point, solubility parameter, and the like from the viewpoints of applicability, drying property, film thickness uniformity, wettability and the like when applying the colored composition. For example, cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, 1-ethoxy-2-propyl acetate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether , Propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, ethyl lactate, methyl lactate, ethylbenzene, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone, ethyl acetate, isoamyl acetate, methanol, ethanol, isopropyl alcohol But, but not limited to, butanol, isobutyl ketone, petroleum solvent and the like. The organic solvent can be used in an amount of 100 to 2000 parts by mass, preferably 400 to 1000 parts by mass with respect to a total of 100 parts by mass of the solid content in the coloring composition.

  The color filter coloring composition according to the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition, and a silane coupling agent in order to improve the adhesion to the transparent substrate. An adhesion improver such as can also be contained. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned.

  Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4- Epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and other epoxysilanes, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- β (aminoethyl) γ-aminopropyltri Ethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- Examples include aminosilanes such as phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  Each colored composition according to the present invention contains at least one photopolymerization initiator. As photopolymerization initiators, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone compounds such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl Benzoin compounds such as dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenylsulfite Benzophenone compounds such as 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2 Thioxanthone compounds such as 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl)- 4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl)- s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bi (Trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6- Triazines such as triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) Oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, bis (2,4,6-trimethylbenzoyl) ) Phosphine compounds such as phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 9,10-phenanthrenequinone, camphorquinone Quinone compounds such as ethyl anthraquinone, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds, and the like. These photopolymerization initiators can be used alone or in combination. A photoinitiator can be used in the amount of 5-200 mass parts with respect to a total of 100 mass parts of the coloring material in a coloring composition, Preferably it is the quantity of 10-150 mass parts.

  The photopolymerization initiators may be used alone or in combination of two or more, or as sensitizers, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, Isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4 ′ Amine compounds such as -bis (diethylamino) benzophenone and 4,4'-bis (ethylmethylamino) benzophenone can also be used in combination.

  These sensitizers can be used alone or in combination. A sensitizer can be used in the quantity of 0.1-60 mass parts with respect to 100 mass parts of photoinitiators in a coloring composition.

  Furthermore, a polyfunctional thiol that functions as a chain transfer agent can be contained. The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, tris (2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-to Azine, 2- (N, N- dibutylamino) -4,6-dimercapto--s- triazine.

  These polyfunctional thiols can be used alone or in combination. The content of the polyfunctional thiol is preferably 0.05 to 100 parts by mass, preferably 0.1 to 60 parts by mass with respect to 100 parts by mass in total of the color materials in the coloring composition. .

  The photopolymerizable compound is a compound that can be polymerized by an active radical or an acid generated from a photopolymerization initiator by light irradiation. Examples of the photopolymerizable compound include compounds having a polymerizable carbon-carbon unsaturated bond.

  As the photopolymerizable compound, a known photopolymerizable compound can be used without particular limitation. As the photopolymerizable compound, a compound having at least one addition-polymerizable ethylenic double bond and having a boiling point of 100 ° C. or higher under normal pressure is preferable. It is more preferable that it is a (meth) acryl compound. From the viewpoint of sensitivity and high curing, the photopolymerizable compound is more preferably a polyfunctional (meth) acrylic compound.

  Examples of photopolymerizable compounds include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, Methylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Hexanediol di (meth) acrylate, trimethylolpropane tris (acryloyloxypropyl) ether, tris (acryloilo) Shiechiru) isocyanurate, such as those (meth) acrylated after adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylol ethane.

  In the photosensitive coloring composition for a color filter according to the present embodiment, it is preferable that the binder resin has an acid value when the unexposed portion is removed by alkali development in the pixel forming step. In order to ensure sufficient developability, it is preferably 20 to 250 (mg KOH / g), more preferably 50 to 200. If the acid value is less than 20, it is difficult to obtain sufficient developability, and if it exceeds 250, the acid of the binder resin may affect the dye, and heat resistance and light resistance may be deteriorated. The acid value here is a value evaluated by the method shown in JIS K0070.

  A third embodiment of the present invention is a color filter characterized by having colored pixels formed by curing the above-described colored composition. The color pixel obtained by hardening the coloring composition which concerns on the 2nd Embodiment of this invention mentioned above is included.

  The color filter according to the present embodiment includes a red pixel, a green pixel, and a blue pixel as necessary, and further, other color pixels such as a yellow pixel, a cyan pixel, a magenta pixel, and a transparent pixel as necessary. May be included. Other than the colored pixels according to the present invention, a known coloring composition containing a color pigment, a color dye, or both a color pigment and a color dye may be used.

  In the color filter according to the present embodiment, the colored pixels preferably have a film thickness of 0.1 μm to 5.0 μm, more preferably 0.5 μm to 4.0 μm, and still more preferably 1.0 μm to 3.0 μm. That is, when the blue pixel according to the present invention is formed by photolithography, it is difficult to form the pixel if the film thickness is less than 0.1 μm, and if the film thickness is more than 5 μm, the composition is applied to the coating film. This is because it becomes difficult to form and apply.

  The color filter which concerns on this embodiment comprises the blue pixel which consists of a blue coloring coating film formed on the transparent substrate using the blue coloring composition for color filters mentioned above. The color filter usually further includes a green pixel and a red pixel formed using a known coloring composition.

  That is, as shown in FIG. 1, the color filter 11 includes a black matrix 2 that is a light shielding film and a colored pixel 3 on a transparent substrate 1 such as glass. The colored pixel 3 includes a blue pixel 3B, a red pixel 3R, and a green pixel 3G formed using the above-described blue coloring composition.

  As the transparent substrate, a glass substrate 1 such as soda lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or the like is used. When the color filter 11 according to the present invention is incorporated in the liquid crystal display device 4, a transparent electrode layer made of indium oxide, tin oxide or the like is provided on the surface of the glass plate or resin plate for driving the liquid crystal after the liquid crystal panel is formed. 12 may be formed.

  5th embodiment of this invention is a manufacturing method of the color filter 11 characterized by hardening the above-mentioned coloring composition on a transparent substrate, and forming a colored pixel. Each colored pixel 3 can be formed by, for example, a printing method, an inkjet method, a photolithography method, or the like.

  The formation of each color coloring pixel 3 by the printing method can be performed by simply repeating the printing and drying of the colored composition prepared as the above-mentioned various printing inks. Is excellent. Furthermore, a fine pattern having high dimensional accuracy and smoothness can be printed by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  As a method of manufacturing the color filter 11 using the inkjet method, there is a method in which the black matrix 2 is formed on the glass substrate 1 and ink is applied to the openings of the black matrix 2 using an inkjet printing apparatus to form a colored portion. Proposed.

  Further, in this method, the material constituting the black matrix is made of a repellent material such as a fluorine compound or a silicon compound so that the ink is accurately filled into the predetermined opening and the mixed color in which the ink is mixed between the adjacent colored portions does not occur. Water material may be included.

  As an apparatus used for inkjet, there are a piezo conversion method and a heat conversion method depending on a difference in ink discharge method. In addition, the ink particleization frequency in the ink jet apparatus is about 5 to 100 KHz. The nozzle diameter in the ink jet apparatus is desirably about 5 to 80 μm. In addition, the ink jet apparatus may be one in which a plurality of heads are arranged and about 60 to 500 nozzles are incorporated in one head.

  After the colored portion pattern is formed by the ink jet method, a colored layer pattern is formed by heat treatment using a convection oven, an IR oven, a hot plate, or the like. According to the ink jet method, since a plurality of colors of ink can be applied simultaneously, the color filter 11 can be manufactured at a low cost by a simple process.

  When forming each color coloring pixel 3 by the photolithography method, the coloring composition prepared as the solvent developing type or alkali developing type coloring resist is applied to a transparent substrate by spray coating, spin coating, slit coating, roll coating, etc. By a coating method, coating is performed so that the dry film thickness is 0.2 to 10 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used. If necessary, the dried film is exposed to ultraviolet light through a pattern exposure photomask having a predetermined pattern provided in contact with or non-contact with the film.

  Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. In addition, in order to accelerate | stimulate superposition | polymerization of a coloring resist, it can also heat after image development as needed. According to the photolithography method, the color filter 11 with higher accuracy than the printing method can be manufactured.

  In developing the colored composition, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

  In order to increase the sensitivity of the film during UV exposure, the colored resist is applied and dried, and then water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition by oxygen. After the film to be formed is formed, ultraviolet exposure can be performed.

  The color filter 11 according to the present embodiment can be manufactured by an electrodeposition method, a transfer method, or the like in addition to the above method. The electrodeposition method uses a transparent conductive film formed on a transparent substrate, and a method for manufacturing the color filter 11 by electrodepositing each color-colored pixel on the transparent conductive film by electrophoresis of colloidal particles. It is.

  The transfer method is a method in which colored pixels 3 are formed in advance on the surface of a peelable transfer base sheet or transfer cylinder, and the colored pixels 3 are transferred to a desired transparent substrate. If the black matrix 2 is formed in advance before forming the colored pixels 3 on the transparent substrate or the reflective substrate, the contrast of the display panel can be further increased. As the black matrix, an inorganic film such as chromium, a chromium / chromium oxide multilayer film, titanium nitride, or a resin film in which a light shielding agent is dispersed may be used.

  In addition, when the color filter 11 according to the present invention is incorporated in the liquid crystal display device 4, a thin film transistor (TFT) is formed in advance on the transparent substrate or the reflective substrate, and then the colored pixel 3 can be formed. . By forming colored pixels on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

On the color filter according to the present embodiment, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, or the like may be formed as necessary. The color filter which concerns on this embodiment can be used suitably for the liquid crystal display device 4, an organic EL element, and an organic EL display. A liquid crystal display device according to the fourth embodiment of the present invention includes the color filter described above.

  FIG. 2 is a cross-sectional view schematically showing the liquid crystal display device 4 according to this embodiment. In FIG. 1, the liquid crystal display device 4 includes a pair of transparent substrates 5 and 6 that are disposed to face each other, and a liquid crystal (LC) 17 is sealed between them.

  A TFT (thin film transistor) array 7 is formed on the inner surface of the first transparent substrate 5, and a transparent electrode layer 8 made of, for example, ITO is formed thereon. An alignment layer 9 is provided on the transparent electrode layer 8. Further, on the outer surface of the transparent substrate 5, a polarizing plate 10 including a retardation film is formed.

  On the other hand, a color filter 11 is formed on the inner surface of the second transparent substrate 6. A transparent protective film (not shown) is formed as needed to cover the color filter 11, and further, a transparent electrode layer 12 made of, for example, ITO is formed thereon, and the alignment layer 13 covers the transparent electrode layer 12. Is provided. A polarizing plate 14 is formed on the outer surface of the transparent substrate 6. A backlight unit 16 including a three-wavelength lamp 15 is provided below the polarizing plate 10.

  The organic EL display device according to the fifth embodiment of the present invention includes the color filter 11 described above. As the structure of the organic EL display device, there are three types as shown in FIG. As shown in FIG. 3A, the first mold has a metal electrode 23 electrically connected to the TFT array 22 formed on the transparent substrate 21 and a transparent electrode 25 formed on the opposing sealing substrate 24. And a light emitting layer (organic EL layer) 26, and when a voltage is applied between both electrodes, the light emitted from the light emitting layer is extracted from the sealing substrate side.

  As shown in FIGS. 3B and 3C, the second type is a bottom emission type in which the positions of the metal electrode 23 and the transparent electrode 25 are switched and light is extracted from the TFT array 22 side. Further, the following three methods have been proposed as methods for extracting light. In other words, the first method is a method in which the light emitted from the light emitting layer 26 is converted into white light and white light is extracted as it is. The second method emits blue light in the light emitting layer 26, and this blue light is used as it is. At the same time, a part of the blue emitted light is made incident on a G (green) conversion layer and an R (red) conversion layer (not shown) provided on the light emitting layer 26, and G light and R color The third method forms a light emitting layer that emits R (red), a light emitting layer that emits G (green), and a light emitting layer that emits B (blue). In this method, three colors of emitted light are extracted.

  In the first method for extracting white light when colorizing the display screen of an organic EL display device, a desired wavelength region is obtained by passing the extracted light through a color filter 11 having R, G, and B colored light transmission layers. Light (color light) can be obtained.

  In the second method using the conversion layer and the third method in which three color light emitting layers are formed, the display screen can be colored by controlling the light emission of each color. However, the spectral characteristic of light obtained by such a method is different from the spectral characteristic of color light desired for color display. Therefore, it is necessary to pass the color light extracted by such a method through the color filter 11 to obtain the color light having a desired spectral characteristic.

  EXAMPLES Examples and comparative examples of the present invention will be shown below, and the present invention will be described more specifically. However, the present invention is not limited to the following examples. In the examples, “parts” and “%” represent “parts by mass” and “mass%”, respectively. The pigment symbol indicates a color index number. For example, “PB15: 6” indicates “CI Pigment Blue 15: 6”.

  The blue dye DB-1 was synthesized by dissolving 20 parts of a blue dye (CI Basic Blue 7, Tokyo Kasei Kogyo Co., Ltd.) in 1500 parts of water and stirring with 300 parts of acetonitrile in 300 parts of acetonitrile. A solution in which 21 parts of methium cesium salt was dissolved was added. After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water, and dried to obtain 15 parts of blue crystals of a blue dye (DB-1) represented by the following general formula (8).

（Ｘ１⁻はトリストリフルオロメタンスルホニウムメチドアニオンを表す。）
青色染料であるＤＢ−２の合成は、青色染料東京化成工業社製Ｃ．Ｉ．Ｂａｓｉｃ Ｂｌｕｅ ７東京化成工業社製）５．１４重量部を水５００重量部に溶解し、攪拌しながら１−ナフタレンスルホン酸ナトリウム４．６０重量部を加え、室温で１時間攪拌した。氷冷し、沈殿を濾取し、水で洗浄した。ケーキを風乾したのち、減圧乾燥を行い、下記一般式（９）で表される染料（ＤＢ−２）を６．１１重量部を得た。

(X1 ^- represents tris trifluoromethane sulfonium methide anion.)
The synthesis of DB-2, which is a blue dye, was performed by C.I. I. Basic Blue 7 (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.14 parts by weight was dissolved in 500 parts by weight of water, and 4.60 parts by weight of sodium 1-naphthalenesulfonate was added with stirring, followed by stirring at room temperature for 1 hour. The mixture was cooled on ice, and the precipitate was collected by filtration and washed with water. The cake was air-dried and then dried under reduced pressure to obtain 6.11 parts by weight of a dye (DB-2) represented by the following general formula (9).

（Ｘ２⁻は１−ナフタレンスルホニウムアニオンを表す。）
染料を側鎖に持つ高分子化合物であるＰＤ−１の合成は、２段階の反応から成り、アクリルモノマーとブロック化されたイソシアネート基であるブロックＮＣＯ基を持つアクリルモノマーであるカレンズＭＯＩ−ＢＭ（昭和電工社製）を重合して、ブロックＮＣＯ基を持つ高分子化合物であるアクリル樹脂を合成し、次に脱ブロック化し、高分子化合物であるアクリル樹脂のイソシアネート基と染料を反応させるものである。

(X2 ^- represents a 1-naphthalene sulfonium anion.)
The synthesis of PD-1, which is a polymer compound having a dye in the side chain, consists of a two-step reaction. The acrylic monomer and the Karenz MOI-BM (acrylic monomer having a blocked NCO group that is a blocked isocyanate group) Showa Denko Co., Ltd.) is polymerized to synthesize an acrylic resin, which is a polymer compound having a blocked NCO group, and then deblocked to react the isocyanate group of the acrylic resin, which is a polymer compound, with a dye. .

  The blocked NCO group, which is a blocked isocyanate group of Karenz MOI-BM, does not react at 80 ° C. where the polymerization reaction is carried out, but it can be deblocked at temperatures exceeding 140 to 150 ° C. at which the triarylmethane dye is added. Occurring reacts with the primary or secondary amine group of the triarylmethane dye, binds to the polymer, and the dye becomes the side chain.

  400 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 10 parts of methyl methacrylate (MMA), 30 parts of butyl methacrylate (BMA), 55 parts of benzyl methacrylate (BzMA), methacrylic acid 1 part of a mixture of 5 parts of 2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl acid (Karenz MOI-BM, Showa Denko) and 5 parts of 2,2'-azobisisobutyronitrile The polymerization reaction was carried out by adding dropwise over time. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then a solution in which 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. Solution was obtained. The mass average molecular weight of the acrylic resin was about 10,000.

  The obtained resin solution is put into a reaction vessel, heated to 155 ° C., stirred and refluxed. A dye solution in which 28 parts of a blue dye (DB-1) was dissolved in 250 parts of cyclohexanone was added dropwise over 1 hour. Thereafter, the mixture was stirred for 3 hours while maintaining at 155 ° C.

  The obtained polymer compound solution having the dye in the side chain was heated to evaporate the solvent, and 30 parts of the solution having a solid content concentration of 50% was added dropwise to 1000 parts of stirring methanol to obtain the dye. A polymer compound having a side chain was precipitated, and unreacted substances were dissolved in methanol and washed. Methanol was discharged, and the polymer compound having the deposited dye in the side chain was further washed with methanol and dried to obtain 20 parts of a polymer compound containing the dye. To this polymer compound, 80 parts of cyclohexanone was added to obtain a polymer compound solution (PD-1) having a dye having a solid concentration of 20% by mass in the side chain.

  The synthesis of PD-2, 3, 4, 5, 6 which is a polymer compound having a dye in the side chain was the same as PD-1 except that the dyes and monomers described in Table 1 were used. Polymeric compounds PD-2 to PD-4 having a side chain were obtained. As for PD-5 and PD6, an attempt was made to synthesize a polymer compound, but the target compound could not be obtained due to gelation. Azobisisobutyronitrile is not included in the table because it decomposes in the course of the polymerization reaction of the acrylic resin, partly desorbs as nitrogen gas, and the rest is taken into the resin.

  The synthesis of a triarylmethane dye having a polymerizable double bond is shown below. In a reaction vessel, 200 parts of cyclohexanone and 5 parts of 2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate (Karenz MOI-BM, Showa Denko KK) were heated to 155 ° C., stirred and refluxed. It was. A dye solution in which 28 parts of a blue dye (DB-1) was dissolved in 250 parts of cyclohexanone was added dropwise over 1 hour. Thereafter, the mixture was stirred for 3 hours while maintaining at 155 ° C. to obtain PD-7 which is a dye triarylmethane dye having a polymerizable double bond in which a blocked isocyanate group was added to the dye. Its chemical formula (10) is shown below.

（Ｘ１⁻はトリストリフルオロメタンスルホニウムメチドアニオンを表す。）
また染料を代え、青色染料にＤＢ−２を使用してＰＤ−７を合成した。染料をＤＢ−２としたことを除いて、ＰＤ−７と同様の方法で染料にブロックイソシアネート基を付加した重合性二重結合を持った染料トリアリールメタン染料であるＰＤ−８を得た。その化学式（１１）を下記に示す。

(X1 ^- represents tris trifluoromethane sulfonium methide anion.)
Also, PD-7 was synthesized using DB-2 as a blue dye instead of the dye. PD-8 which is a triarylmethane dye having a polymerizable double bond in which a blocked isocyanate group was added to the dye was obtained in the same manner as PD-7 except that the dye was DB-2. Its chemical formula (11) is shown below.

（Ｘ２⁻は１−ナフタレンスルホニウムアニオンを表す。）
合成した染料を側鎖に持つ高分子であるＰＤ−１〜ＰＤ−６及び重合性二重結合を持つ染料であるＰＤ−７、ＰＤ−８を表１に示す。

(X2 ^- represents a 1-naphthalene sulfonium anion.)
Table 1 shows PD-1 to PD-6 which are polymers having a synthesized dye in the side chain, and PD-7 and PD-8 which are dyes having a polymerizable double bond.

以下に、比較例１〜３にて用いたアクリル樹脂溶液の調製について説明する。樹脂の分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィ）により測定したポリスチレン換算の質量平均分子量である。反応容器にシクロヘキサノン３７０部を入れ、容器に窒素ガスを注入しながら８０℃に加熱して、同温度でメタクリル酸（ＭＡＡ）２０．０部、メチルメタクリレート（ＭＭＡ）１０．０部、ベンジルメタクリレート（ＢｚＭＡ）５５．０部、２-ヒドロキシエチルメタクリレート（ＨＥＭＡ）１５．０部、及び２，２’-アゾビスイソブチロニトリル４．０部の混合物を１時間かけて滴下し、重合反応を行った。

Below, preparation of the acrylic resin solution used in Comparative Examples 1-3 is demonstrated. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography). Put 370 parts of cyclohexanone in a reaction vessel and heat to 80 ° C. while injecting nitrogen gas into the vessel. At the same temperature, 20.0 parts of methacrylic acid (MAA), 10.0 parts of methyl methacrylate (MMA), benzyl methacrylate ( (BzMA) 55.0 parts, 2-hydroxyethyl methacrylate (HEMA) 15.0 parts, and a mixture of 2,2'-azobisisobutyronitrile 4.0 parts were added dropwise over 1 hour to carry out the polymerization reaction. It was.

  After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then a solution in which 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. Solution was obtained. The mass average molecular weight of the acrylic resin was about 40000.

  After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Then, an acrylic resin solution (P-1) was prepared.

Hereinafter, the production of the fine pigment used in the pigment dispersion will be described. 200 parts of blue pigment (CI Pigment Blue 15: 6, “LIONOLBLUEES” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1600 parts of sodium chloride, and 100 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.), 1 gallon kneader (manufactured by Inoue Seisakusho) And kneaded at 70 ° C. for 12 hours. Next, this mixture is poured into about 5 liters of warm water, stirred in a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered, washed with water to remove sodium chloride and diethylene glycol. , Dried at 80 ° C. for 24 hours to obtain 198 parts of a salt milled pigment (blue pigment B-1). As a pigment dispersion, 13.6 parts of a blue pigment (B-1) and a pigment derivative (D-1 ) After stirring and mixing 1.4 parts, 4.5 parts of acrylic dispersant (BYK-2001 manufactured by BYK-Chemie), 30.0 parts of acrylic resin solution (P-1), and 50.5 parts of cyclohexanone. Then, using a zirconia bead having a diameter of 0.1 mm, the mixture was dispersed for 2 hours with an Eiger mill, and then filtered with a 5 μm filter to prepare a pigment dispersion. The chemical formula (12) of the pigment derivative (D-1) is shown below.
Shown below.

A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 5 μm filter to obtain a colored composition.
Polymer compound having dye in side chain (PD-1) ... 41.1 parts by mass Monomer: Dipentaerythritol hexaacrylate ... 6.6 Mass part ("Aronix M402" manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator ... 3.2 parts by mass ("Irgacure-907" manufactured by Ciba Geigy)
Photosensitizer: 0.4 parts by mass ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
Organic solvent (cyclohexanone) ········································· 48.7 parts by mass Examples 2 to 6 and Comparative Examples 1 and 2 are polymers having a dye in the side chain. A colored composition was obtained in the same manner as in Example 1 except that the compounds, the acrylic resin solution, the dye, and the pigment dispersion were those shown in Table 2. In Table 2, the coloring composition according to Example 1 is also shown.

  The following describes the polymerization of triarylmethane dyes having a polymerizable double bond. PD-7, which is a triarylmethane dye having a polymerizable double bond, is heated to 80 ° C. while injecting nitrogen gas into the reaction vessel, and 10 parts of methyl methacrylate (MMA) and 55 parts of benzyl methacrylate (BzMA) A mixture of 30 parts of butyl methacrylate (BMA), 480 parts of a cyclohexanone solution of PD-7, which is a triarylmethane dye having a polymerizable double bond, and 5 parts of 2,2′-azobisisobutyronitrile. The solution was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then a solution in which 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. Solution was obtained. The mass average molecular weight of the acrylic resin was about 10,000.

  The obtained polymer having a triarylmethane dye in the side chain was heated to evaporate the solvent, and 30 parts of a solution having a solid content concentration of 50% was added dropwise to 1000 parts of stirring methanol to add tria. A polymer having a reel methane dye in the side chain was precipitated, and unreacted substances were dissolved in methanol and washed. Methanol was discharged, and the precipitated polymer having the triarylmethane dye in the side chain was further washed with methanol and dried to obtain 20 parts of a polymer having the triarylmethane dye in the side chain. To this polymer compound, 80 parts of cyclohexanone was added to obtain a polymer compound solution shown in Example 5 having a dye having a solid concentration of 20% by mass in the side chain.

  A polymer having a side chain of the dye shown in Example 6 having a solid content of 20% by mass, using PD-8 as a double bond-containing dye obtained by adding a blocked isocyanate group to the dye in the same manner as in Example 5. A compound solution was obtained.

  Table 2 shows the solution compositions of Examples 1 to 8, Comparative Examples 1 and 2, and Reference Example.

実施例１〜実施例８は本発明に係る染料を側鎖に持つ高分子化合物を用いた着色組成物の例であり、実施例７及び実施例８は本発明に係る染料を側鎖に持つ高分子化合物と顔料を併用した着色組成物の例である。比較例１〜比較例２は本発明の範囲外の染料を用いた着色組成物の例であり、参考例１はカラーフィルタ用として一般的に用いられる顔料を使用した本発明の範囲外の着色組成物の例である。

Examples 1 to 8 are examples of coloring compositions using a polymer compound having the dye according to the present invention in the side chain, and Examples 7 and 8 have the dye according to the present invention in the side chain. It is an example of the coloring composition which used the high molecular compound and the pigment together. Comparative Examples 1 and 2 are examples of coloring compositions using dyes outside the scope of the present invention, and Reference Example 1 is coloring outside the scope of the present invention using pigments commonly used for color filters. It is an example of a composition.

  The characteristics of Examples, Comparative Examples, and Reference Examples were evaluated. Regarding chromaticity and transmittance, the compositions of Examples 1 to 8 and Comparative Examples 1 and 2 and Reference Example were applied to a glass substrate by spin coating so that the film thickness after curing was 2 μm. After drying, the film was exposed to ultraviolet rays using an ultrahigh pressure mercury lamp. Thereafter, this substrate was heat-treated at 200 ° C. for 20 minutes to obtain a colored film.

  With respect to this colored film, the spectral transmittance was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.), and the chromaticity (Y, x, y) with a C light source was calculated. In addition, the calculation method of chromaticity was performed based on JISZ8701.

  For heat resistance evaluation, the coating compositions of Examples 1 to 6 and Comparative Examples 1 and 2 and Reference Example were prepared using the same method as the colored composition, and then the chromaticity before the heat resistance test was determined. Measurement was performed by the method described above. Next, the coated substrate was heated in a clean oven at 200 ° C. for 1 hour or 3 hours, taken out from the clean oven, and the chromaticity after the heat resistance test was also measured. The color difference ΔEab (C) before and after the test was calculated. If the color difference was less than 5.0, it was evaluated as ◯, if it was 5.0 or more and less than 8.0, Δ, and if it was 8.0 or more, ×.

  For light resistance evaluation, coating films were prepared in the same manner for the compositions of Examples 1 to 6 and Comparative Examples 1 and 2 and Reference Example. Next, a 6% aqueous solution of polyvinyl alcohol (Kuraray Poval PVA235 manufactured by Kuraray Co., Ltd.) was applied to the substrate as an oxygen barrier layer with a film thickness of 1 μm. Then, the light resistance test was implemented. The light resistance test was performed with a xenon weather meter (Toyo Seiki Seisakusho Co., Ltd., Ci-35 weatherometer, illuminance 0.5 mW, 340 nm) for 100 hours. After removal, the chromaticity after the light resistance test was measured by the method described above. The color difference ΔEab (C) before and after the test was calculated. If the color difference was less than 5.0, it was evaluated as ◯, if it was 5.0 or more and less than 8.0, Δ, and if it was 8.0 or more, ×.

  Table 3 shows the results of coating chromaticity, heat resistance evaluation, and light resistance evaluation.

本発明に係る染料を側鎖に持つ高分子化合物を使用した実施例１〜実施例６の着色組成物は、カラーフィルタ用として一般的に用いられるＣ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ１５：６を使用した参考例の着色組成物と比較して高い明度（Ｙ値）が得られている。

The colored compositions of Examples 1 to 6 using the polymer compound having the dye according to the present invention in the side chain are C.I. I. High brightness (Y value) is obtained as compared with the coloring composition of the reference example using Pigment Blue 15: 6.

  The colored compositions of Examples 1 to 6 using the polymer compound having the dye according to the present invention in the side chain have a color difference of less than 5.0 in the heat resistance test and the light resistance test, and good results. there were. On the other hand, Comparative Examples 1 and 2 using a dye outside the scope of the present invention were difficult to use because both the heat resistance and light resistance had a color difference of 5.0 or more.

DESCRIPTION OF SYMBOLS 1 ... Glass substrate 2 ... Black matrix 3 ... Colored pixel 4 ... Liquid crystal display device 5 ... 1st transparent substrate 6 ... 2nd transparent substrate 7 ... TFT array 8 ... Transparent electrode layer 9 ... Orientation layer 10 ... Polarizing plate 11 ... Color filter 12 ... Transparent electrode layer 13 ... Orientation layer 14 ... Polarizing plate 15 ... Three-wavelength lamp 16 ... Backlight unit 17 ... Liquid crystal (LC)
21 ... Transparent substrate 22 ... TFT array 23 ... Metal electrode 24 ... Sealing substrate 25 ... Transparent electrode 26 ... Light emitting layer

Claims (12)

An isocyanate group that the polymer has as a side chain or a blocked isocyanate group;
A primary or secondary amine group of a triarylmethane dye;
A polymer compound having a side chain with a triarylmethane dye, characterized by reacting The polymer compound having a triarylmethane dye as a side chain according to claim 1, wherein the triarylmethane dye has a structure represented by the following general formula (1).

(Wherein R _{1 to 6} each independently have a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted phenyl group, or a substituent. A benzyl group which may be substituted, provided that at least one of R _{1 to 6} is a hydrogen atom, and the alkyl group having 1 to 6 carbon atoms which may have a substituent includes a methyl group and an ethyl group; Propyl group, butyl group, isobutyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, hydroxyethyl group, hydroxypropyl group, hydroxypropyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, Represents an ethoxyethyl group, a butoxyethyl group, a trifluoromethyl group, a pentafluoroethyl group, an optionally substituted phenyl group, a benzyl group Examples of the substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, (C1-C5) alkyl group of pentyl group, fluorine atom, chlorine atom, bromine atom, and halogen atom of iodine atom. Atom, sulfonic acid group, methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, (C1-C6) alkoxy group of hexyloxy group, hydroxyethyl group, hydroxy (C1-C5) alkyl of hydroxypropyl group Group, methoxyethyl group, ethoxyethyl group, ethoxypropyl group, butoxyethyl group (C1-C5) alkoxy (C1-C5) alkyl group, 2-hydroxyethoxy group hydroxy (C1-C5) alkoxy group, 2-methoxy Alkoxy (C1-C5) such as ethoxy group, 2-ethoxyethoxy group (C1-C5) ) Represents an alkoxy group, a 2-sulfoethyl group, a carboxyethyl group, or a cyanoethyl group, and R _{7 to 20} are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms or a halogen atom. Examples of the alkyl group having 1 to 6 carbon atoms which may have a substituent include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, and a hydroxyethyl group. Represents a group, hydroxypropyl group, hydroxypropyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, represents fluorine, chlorine, bromine, iodine, X ^- is the counter anion Chloride ion, sulfonium salt (benzenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, anion of methanesulfonic acid), strong acid, super strong acid (antimony hexafluoride, hexafluorophosphoric acid, trifluoromethanesulfone) Acid) anion, and tristrifluoromethanesulfonylmethide anion. ) The polymer compound having a triarylmethane dye as a side chain according to claim 1, wherein the triarylmethane dye has a structure represented by the following general formula (2).

(X ^- is a counter anion, a chloride ion, benzenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, methanesulfonic acid, antimony hexafluoride and phosphorus hexafluoride acid, trifluoromethanesulfonic acid, 4 (Represents fluoroboric acid, tristrifluoromethanesulfonylmethide anion.) The isocyanate group or blocked isocyanate group of a compound having a polymerizable double bond and an isocyanate group or blocked isocyanate group is added to the amine group of a triarylmethane dye having a primary or secondary amine group. A triarylmethane dye having a polymerizable double bond characterized by reacting. The triarylmethane dye has a structure represented by the following general formula (1) and the amine group of the triarylmethane dye has a polymerizable double bond and an isocyanate group or a blocked isocyanate group. The triarylmethane dye having a polymerizable double bond according to claim 4, wherein an isocyanate group or a blocked isocyanate group is reacted.

(Wherein R _{1 to 6} each independently have a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted phenyl group, or a substituent. A benzyl group which may be substituted, provided that at least one of R _{1 to 6} is a hydrogen atom, and the alkyl group having 1 to 6 carbon atoms which may have a substituent includes a methyl group and an ethyl group; Propyl group, butyl group, isobutyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, hydroxyethyl group, hydroxypropyl group, hydroxypropyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, Represents an ethoxyethyl group, a butoxyethyl group, a trifluoromethyl group, a pentafluoroethyl group, an optionally substituted phenyl group, a benzyl group Examples of the substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, (C1-C5) alkyl group of pentyl group, fluorine atom, chlorine atom, bromine atom, iodine atom, etc. Halogen atom, sulfonic acid group, methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, hexyloxy group (C1-C6) alkoxy group, hydroxyethyl group, hydroxypropyl group hydroxy (C1-C5) Alkyl group, methoxyethyl group, ethoxyethyl group, ethoxypropyl group, butoxyethyl group (C1-C5) alkoxy (C1-C5) alkyl group, hydroxy (C1-C5) alkoxy group such as 2-hydroxyethoxy group, -Alkoxy such as methoxyethoxy group, 2-ethoxyethoxy group (C1 to C5) (C1 C5) represents an alkoxy group, a 2-sulfoethyl group, a carboxyethyl group, a cyanoethyl group, and R _{7 to 20} each independently represent a hydrogen atom, a C 1-6 alkyl group or a halogen atom that may have a substituent. Examples of the alkyl group having 1 to 6 carbon atoms which may have a substituent include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, and a hydroxy group. Represents an ethyl group, a hydroxypropyl group, a hydroxypropyl group, a 2-sulfoethyl group, a carboxyethyl group, a cyanoethyl group, a methoxyethyl group, an ethoxyethyl group, a butoxyethyl group, a trifluoromethyl group, a pentafluoroethyl group, and a halogen atom. is fluorine, chlorine, bromine, represents iodine, X ^- a counter anion Chloride ion, sulfonium salt (anion of benzenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, methanesulfonic acid), strong acid, super strong acid (antimony hexafluoride, hexafluorophosphoric acid, trifluoro) An anion of trimethane sulfonic acid, and the like, and tristrifluoromethanesulfonylmethide anion. ) The triarylmethane dye has a structure represented by the following general formula (2), and the compound of the triarylmethane dye has a polymerizable double bond and an isocyanate group or a blocked isocyanate group in the amine group. The triarylmethane dye having a polymerizable double bond according to claim 4, wherein an isocyanate group or a blocked isocyanate group is reacted.

(Wherein, X ^- is a counter anion, a chloride ion, benzenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, methanesulfonic acid, antimony hexafluoride and hexafluorophosphate, trifluoromethanesulfonate It represents any of acid, tetrafluoroboric acid, tristrifluoromethanesulfonylmethide anion.)   The triarylmethane dye according to any one of claims 4 to 6, wherein the triarylmethane dye having a polymerizable double bond and a monomer having a polymerizable double bond are copolymerized. High polymer compound.   The triarylmethane according to any one of claims 1, 2, 3, and 7, wherein a dye in the polymer compound having the dye in a side chain is in the range of 1% by mass to 50% by mass. A polymer compound with dye in the side chain.   A polymer compound having a side chain of the triarylmethane dye according to any one of claims 1 to 3, 7, and 8, at least one polymerizable monomer, and at least one photopolymerization. A coloring composition for a color filter, comprising an initiator.   The color filter containing the colored pixel formed using the coloring composition of Claim 9.   A liquid crystal display device comprising the color filter according to claim 10.   An organic EL display device comprising the color filter according to claim 10.

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