JP2013011869A - Coloring matter for color filter, colored resin composition using coloring matter, and color filter composed of resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high-quality color filter.SOLUTION: Provided are a coloring matter for color filter represented by the following formula (1), a colored resin composition for color filter containing the coloring matter, and a color filter pixel composed of a cured film of the colored resin composition.

Description

  The present invention relates to a dye used in forming a blue pixel of a color filter, a colored resin composition containing the dye, a color filter formed using the colored resin composition, and a color filter formed using the color filter. The present invention relates to an electronic display device such as a liquid crystal display device, an image sensor (CCD, CMOS), and an organic EL display.

  Liquid crystal display devices such as notebook computers, liquid crystal televisions, mobile phones, and other liquid crystal displays (LCD), organic EL displays, and image sensors (CCD, CMOS) used as input devices for digital cameras, color copiers, etc. A color filter is required for colorization. As a method for producing a color filter used for these liquid crystal display devices and solid-state imaging devices, there are a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method and the like. In recent years, a pigment dispersion method using a patterning method has become mainstream. As a patterning method, a photolithography method is typical, and a color filter is formed using a mixture of a photosensitive resin composition and a pigment dispersion. Recently, a method of forming a color filter by applying colored ink directly on a substrate without using a mask by an ink jet printer is also performed.

  It is particularly important to improve color purity, saturation, brightness, and contrast, which are characteristics required for a color filter. Since the light intensity of the backlight can be suppressed by improving the lightness and the power consumption is reduced as a result, this is a technology that is also necessary from an environmental point of view. In order to improve the color purity of the color filter, it is necessary to increase the content of the color pigment or to select a pigment having a better spectral waveform. On the other hand, in order to improve the brightness, it is necessary to increase the transmittance by reducing the pigment concentration or reducing the film thickness. In order to achieve both of these contradictory characteristics, a method of making pigment fine particles has also been performed. However, there is a limit to satisfy the dispersion stability of the photosensitive resin composition containing the pigment, and the light filter, the resistance to light, heat or solvent and the improvement of contrast in the pigment dispersion method, and the brightness is improved. Even now, it is not possible to achieve both tolerance and resistance.

  As another approach for solving the above problems, a color filter using a dye is being studied. If a dye is used, there is a merit that both color purity and lightness that cannot be achieved with a pigment can be achieved, and that light scattering can be suppressed because it is not a particle, so that contrast can be improved and a certain level of resistance can be achieved. However, display applications that require long-term reliability, such as televisions, require superior light characteristics and heat resistance, as well as excellent color characteristics. The demand for color filters using blue dyes is achieved. It has not been. Dyes generally have poorer resistance than pigments, and in particular, blue dyes are much less resistant than pigments. For example, Patent Documents 1 and 2 have reported on color filters using triphenylmethane compounds, but those having excellent color characteristics as blue have extremely poor light resistance and heat resistance and are not at a practical level. . Also, those with good tolerance have a high x value in the chromaticity coordinates, in other words, many reddish, and the color characteristics as blue are insufficient. Patent Document 3 describes a xanthene compound having excellent brightness. However, the color characteristics are reddish, and the color characteristics as blue are insufficient, and there is no description about resistance. Patent Document 4 describes a phthalocyanine dye having excellent resistance, but its color characteristic is not blue, but is generally cyan with a reddish hue. Therefore, a clear blue pixel cannot be formed. That is, in the field of liquid crystal display devices and solid-state image sensors, a highly durable color filter having a clear blue pixel and excellent in reliability is demanded, but it is almost never put into practical use.

JP-A-8-94826 Japanese Patent Laid-Open No. 2002-14222 JP 2010-32999 A Japanese Patent Application Laid-Open No. 60-249102 JP 63-172772 A

  The present invention relates to a color filter dye having clear blue characteristics and excellent color characteristics such as brightness, a colored resin composition containing the dye, and heat resistance and solvent resistance obtained using the colored resin composition An object of the present invention is to provide a high-quality and highly reliable color filter pixel which is excellent in properties and contrast.

  As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by using a colored resin composition containing a specific color material compound in the color filter pixel, and the present invention has been completed. I came to let you.

（式中、Ｘ_１及びＸ_２は、それぞれ独立にＣ１〜Ｃ３０のアルキル基を表す。Ｒ_１〜Ｒ_２１は、それぞれ独立に水素原子、Ｃ１〜Ｃ３０のアルキル基、Ｃ１〜Ｃ３０のアルコキシ基、Ｃ6〜Ｃ３０の芳香族炭化水素基、Ｃ3〜Ｃ３０の芳香族複素環基、ハロゲン原子、ニトロ基、フェノキシ基、カルボキシ基、カルボン酸エステル基、カルボン酸塩基、アルコキシカルボニル基、水酸基、スルホン酸基、スルホン酸エステル基、スルホン酸塩基、−ＳＯ_２ＮＨＲ_２２基または−ＳＯ_２ＮＲ_２３Ｒ_２４基を表し、Ｒ_１〜Ｒ_２１の少なくとも１つはスルホン酸基、スルホン酸エステル基、スルホン酸塩基、−ＳＯ_２ＮＨＲ_２２基または−ＳＯ_２ＮＲ_２３Ｒ_２４基のいずれかを表す。Ｒ_２２〜Ｒ_２４は、それぞれ独立にＣ１〜Ｃ３０のアルキル基を表す。スルホン酸塩基とカルボン酸塩基は1価のカチオンとの塩であり、1価のカチオンはＮａ^＋、Ｋ^＋または4級アンモニウムカチオンのいずれかである。）
で表されるカラーフィルター用色素。
２．式（１）のＸ_１及びＸ_２がメチル基である上記１項に記載のカラーフィルター用色素。
３．Ｒ_１〜Ｒ_２１がそれぞれ独立に水素原子、Ｃ１〜Ｃ４アルキル基、スルホン酸基、スルホン酸塩基、（Ｃ２〜Ｃ８）アルキルスルファモイル基又はジ（Ｃ１〜Ｃ４）アルキルスルファモイル基であり、かつ、Ｒ_１〜Ｒ_２１の少なくとも一つがスルホン酸基又はスルホン酸塩基である上記２項に記載のカラーフィルター用色素。
４．Ｒ_１〜Ｒ_２１のうち、一つがスルホン酸基又はスルホン酸塩基であり、（ａ）残りの基すべてが水素原子であるか、又は、（ｂ）残りの基のうち、４個がＣ１〜Ｃ４アルキル基であり、更に一つがスルホン酸基、スルホン酸塩基、Ｃ２〜Ｃ８アルキルスルファモイル基又はジ（Ｃ１〜Ｃ４アルキル）スルファモイル基であり、残りが水素原子である上記２項に記載のカラーフィルター用色素。
５．式（１）のＲ_１〜Ｒ_２１がそれぞれ独立に水素原子、Ｃ１〜Ｃ４アルキル基、スルホン酸基、スルホン酸ナトリウム基、２−エチルヘキサンスルファモイル基またはジエチルスルファモイル基であり、少なくとも一つはスルホン酸基又はスルホン酸ナトリウム基である上記２項に記載のカラーフィルター用色素。
６．Ｒ_１７〜Ｒ_２１のうち、一つがスルホン酸基又はスルホン酸ナトリウム基で、残りが水素原子であり、（ｉ）Ｒ_１〜Ｒ_１６の全てが水素原子であるか、又は、（ｉｉ）Ｒ_１〜Ｒ_５のうち２者がＣ１〜Ｃ４アルキル基であり、残りの基が水素原子、Ｒ_１２〜Ｒ_１６のうち２者がＣ１〜Ｃ４アルキル基であり、一つがスルホン酸基、スルホン酸ナトリウム基、２−エチルヘキサンスルファモイル基またはジエチルスルファモイル基であり、残りが水素原子である上記４項に記載のカラーフィルター用色素。
７． 上記２〜６項の何れか一項に記載のカラーフィルター用色素で着色された樹脂硬化膜を有するカラーフィルター。
８． 上記２〜６項の何れか一項に記載の式（１）のカラーフィルター用色素を、カラーフィルター用樹脂組成物中の固形分の総量に対して、０．５〜１０質量％の範囲で含有するカラーフィルター用樹脂組成物。
９．上記１〜６項のいずれか一項に記載のカラーフィルター用色素、バインダー樹脂、溶剤、硬化剤、及び、光重合開始剤または硬化促進剤の少なくとも何れか一方、を含有するカラーフィルター用着色樹脂組成物。
１０．下記式（２）

（式中、Ｒ_1a〜Ｒ_6aはそれぞれ独立に水素原子、Ｃ１〜Ｃ３０のアルキル基、フェニル基またはベンジル基を表す。Ｒ_7a〜Ｒ_20aは、それぞれ独立に水素原子、ハロゲン原子またはＣ１〜Ｃ６のアルキル基を表す。Ｚ⁻はＣ１〜Ｃ１０の高次ハロゲン化アルキル基を有するアルキルスルホニルメチドアニオン、アルキルスルホニルイミドアニオン、又はアルキルスルホネートを表す。）
で表される色素を含有する上記９項に記載のカラーフィルター用着色樹脂組成物。
１１．下記式（３）

（式中において、Ｒ_1c〜Ｒ_19c はそれぞれ独立に水素原子、Ｃ１〜Ｃ12のアルキル基、Ｃ１〜Ｃ１２のアルコキシ基またはハロゲン原子を表す。）
で表されるエポキシ樹脂を硬化剤として含有する上記９項または１０項に記載のカラーフィルター用着色樹脂組成物。
１２．金属フタロシアニン顔料を含む上記９項乃至１１項のいずれか一項に記載のカラーフィルター用着色樹脂組成物。
１３．上記９項乃至１２項のいずれか一項に記載の着色樹脂組成物を用い、パターニングされてなるカラーフィルター用着色硬化膜。
１４．上記１３項に記載のカラーフィルター用着色硬化膜からなるカラーフィルター。
１５．上記１４項に記載のカラーフィルターを装着してなる液晶表示装置および有機ＥＬディスプレイ。
１６．上記１４項に記載のカラーフィルターを装着してなる固体撮像素子。
１７．上記１項に記載の式（１）において、Ｘ_１及びＸ_２は、メチル基を表し、Ｒ_１〜Ｒ_２１は、それぞれ独立に水素原子、Ｃ１〜Ｃ３０のアルキル基、Ｃ１〜Ｃ３０のアルコキシ基、Ｃ６〜Ｃ３０の芳香族炭化水素基、Ｃ３〜Ｃ３０の芳香族複素環基、ハロゲン原子、ニトロ基、フェノキシ基、カルボキシ基、カルボン酸エステル基、カルボン酸塩基、アルコキシカルボニル基、水酸基、スルホン酸基、スルホン酸エステル基、スルホン酸塩基、−ＳＯ_２ＮＨＲ_２２基または−ＳＯ_２ＮＲ_２３Ｒ_２４基を表し、Ｒ_１〜Ｒ_２１の少なくとも１つはスルホン酸基、スルホン酸エステル基、スルホン酸塩基、−ＳＯ_２ＮＨＲ_２２基または−ＳＯ_２ＮＲ_２３Ｒ_２４基のいずれかを表し、Ｒ_２２〜Ｒ_２４は、それぞれ独立にＣ１〜Ｃ３０のアルキル基を表し、スルホン酸塩基とカルボン酸塩基は１価のカチオンとの塩であり、１価のカチオンはＮａ^＋、Ｋ^＋または４級アンモニウムカチオンのいずれかである色素。
１８．Ｒ_１〜Ｒ_２１のうち、一つがスルホン酸基又はスルホン酸塩基であり、（ａ）残りの基すべてが水素原子であるか、又は、（ｂ）残りの基のうち、４個がＣ１〜Ｃ４アルキル基であり、更に一つがスルホン酸基、スルホン酸塩基、（Ｃ２〜Ｃ８）アルキルスルファモイル基又はジ（Ｃ１〜Ｃ４）アルキルスルファモイル基であり、残りが水素原子である上記１７項に記載の色素。
１９． 上記１７項又は１８項に記載の色素のカラーフィルター製造のための使用。
That is, the present invention relates to the following inventions.
1. Following formula (1)

(Wherein, X ₁ and X ₂ each independently represent a C1 to C30 alkyl group. R _{1 to} R ₂₁ each independently represent a hydrogen atom, a C1 to C30 alkyl group, a C1 to C30 alkoxy group, C6-C30 aromatic hydrocarbon group, C3-C30 aromatic heterocyclic group, halogen atom, nitro group, phenoxy group, carboxy group, carboxylic acid ester group, carboxylic acid group, alkoxycarbonyl group, hydroxyl group, sulfonic acid group , Sulfonic acid ester group, sulfonic acid group, —SO ₂ NHR ₂₂ group or —SO ₂ NR ₂₃ R ₂₄ group, at least one of R _{1 to} R ₂₁ is a sulfonic acid group, sulfonic acid ester group, sulfonic acid group , _.R 22 _{to R 24} represent either a _-SO 2 _{NHR 22} group or _-SO 2 _NR 23 _{R 24} group is independently C1~C3 The. Sulfonate and carboxylate groups representing the alkyl group is a salt of a monovalent cation, a monovalent cation is Na ^+, is either K ⁺ or a quaternary ammonium cation.)
A color filter dye represented by
2. _2. The color filter dye according to 1 above, wherein X ₁ and X _{2 in} the formula (1) are methyl groups.
3. R _{1 to} R ₂₁ are each independently a hydrogen atom, a C1-C4 alkyl group, a sulfonic acid group, a sulfonic acid group, a (C2-C8) alkylsulfamoyl group or a di (C1-C4) alkylsulfamoyl group. The color filter dye according to 2 above, wherein at least one of R _{1 to} R ₂₁ is a sulfonic acid group or a sulfonic acid group.
4). Of R _{1 to} R ₂₁ , one is a sulfonic acid group or a sulfonic acid group, and (a) all the remaining groups are hydrogen atoms, or (b) four of the remaining groups are C 1 to C 1. 3. The C4 alkyl group, further one is a sulfonic acid group, a sulfonate group, a C2 to C8 alkylsulfamoyl group or a di (C1 to C4 alkyl) sulfamoyl group, and the rest is a hydrogen atom. Color filter dye.
5. R _{1 to} R _{21 in} formula (1) are each independently a hydrogen atom, a C1 to C4 alkyl group, a sulfonic acid group, a sodium sulfonate group, a 2-ethylhexanesulfamoyl group or a diethylsulfamoyl group, 3. The color filter dye as described in 2 above, wherein one is a sulfonic acid group or a sodium sulfonate group.
6). Of R _{17 to} R ₂₁ , one is a sulfonic acid group or a sodium sulfonate group, the remainder is a hydrogen atom, and (i) all of R _{1 to} R ₁₆ are hydrogen atoms, or (ii) R 2 of _{1 to} R ₅ are C1-C4 alkyl groups, the remaining groups are hydrogen atoms, 2 of R _{12 to} R ₁₆ are C1 to C4 alkyl groups, one is a sulfonic acid group, and sulfonic acid 5. The color filter dye as described in 4 above, which is a sodium group, a 2-ethylhexanesulfamoyl group or a diethylsulfamoyl group, and the remainder is a hydrogen atom.
7. A color filter having a cured resin film colored with the color filter dye according to any one of 2 to 6 above.
8). In the range of 0.5-10 mass% with respect to the total amount of the solid content in the resin composition for color filters, the pigment | dye for color filters of Formula (1) as described in any one of said 2-6. A resin composition for a color filter.
9. The coloring resin for color filters containing the pigment | dye for color filters as described in any one of said 1-6, a binder resin, a solvent, a hardening | curing agent, and at least any one of a photoinitiator or a hardening accelerator. Composition.
10. Following formula (2)

(Wherein R _{1a to} R _6a each independently represents a hydrogen atom, a C1 to C30 alkyl group, a phenyl group or a benzyl group. R _{7a to} R _20a each independently represents a hydrogen atom, a halogen atom or C1 to C6) .Z representing the alkyl group ^- represents an alkylsulfonyl methide anion, alkylsulfonyl imide anion, or alkyl sulfonates having higher halogenated alkyl group C1 -C10).
The colored resin composition for a color filter according to the above item 9, which contains a dye represented by the formula:
11. Following formula (3)

(In the formula, R _{1c to} R _19c each independently represents a hydrogen atom, a C1 to C12 alkyl group, a C1 to C12 alkoxy group, or a halogen atom.)
The colored resin composition for a color filter according to 9 or 10 above, which contains an epoxy resin represented by the formula: as a curing agent.
12 The colored resin composition for a color filter according to any one of the above items 9 to 11, comprising a metal phthalocyanine pigment.
13. A colored cured film for a color filter, which is patterned using the colored resin composition according to any one of Items 9 to 12.
14 14. A color filter comprising the colored cured film for color filter as described in 13 above.
15. 15. A liquid crystal display device and an organic EL display comprising the color filter according to 14 above.
16. 15. A solid-state imaging device comprising the color filter as described in 14 above.
17. In the formula (1) described in the above item 1, X ₁ and X ₂ represent a methyl group, and R _{1 to} R ₂₁ each independently represent a hydrogen atom, a C1 to C30 alkyl group, or a C1 to C30 alkoxy group. , C6-C30 aromatic hydrocarbon group, C3-C30 aromatic heterocyclic group, halogen atom, nitro group, phenoxy group, carboxy group, carboxylic acid ester group, carboxylic acid group, alkoxycarbonyl group, hydroxyl group, sulfonic acid Group, sulfonic acid ester group, sulfonic acid group, —SO ₂ NHR ₂₂ group or —SO ₂ NR ₂₃ R ₂₄ group, and at least one of R _{1 to} R ₂₁ is a sulfonic acid group, sulfonic acid ester group, sulfonic acid _base, represents any -SO 2 _{NHR 22} group or _-SO 2 _NR 23 _{R 24 group,} R 22 _{to R 24} are each independently C1~C30 Represents an alkyl group, sulfonate and carboxylate groups are salts with monovalent cations, monovalent cations Na ^+, dye is either K ⁺ or a quaternary ammonium cation.
18. Of R _{1 to} R ₂₁ , one is a sulfonic acid group or a sulfonic acid group, and (a) all the remaining groups are hydrogen atoms, or (b) four of the remaining groups are C 1 to C 1. 17 above, which is a C4 alkyl group, and one more is a sulfonic acid group, a sulfonic acid group, a (C2-C8) alkylsulfamoyl group or a di (C1-C4) alkylsulfamoyl group, and the remainder is a hydrogen atom. The dye according to item.
19. 19. Use of the dye according to item 17 or 18 for producing a color filter.

  The color filter dye represented by the formula (1) of the present invention and the colored resin composition containing the dye have color characteristics as clear blue and high brightness. Further, by using the colored resin composition, it is possible to provide a blue pixel of a high-quality and highly reliable color filter that is excellent in heat resistance, solvent resistance, contrast, and the like.

The color filter dye of the present invention is represented by the formula (1).
In Formula (1), X ₁ and X ₂ each independently represent a C1-C30 alkyl group, and the alkyl group is linear, branched or cyclic if it is an alkyl group having 1 to 30 carbon atoms. It is not limited to any of these. The alkyl group may have a substituent. Specific examples of the substituent include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a 2-sulfoethyl group, a carboxyethyl group, a cyanoethyl group, a methoxy group. Examples thereof include an ethyl group, an ethoxyethyl group, a butoxyethyl group, a trifluoromethyl group, a pentafluoroethyl group, a carbamoyl group, and a carboxy group.
Specific examples of the C1-C30 alkyl group in X ₁ and X ₂ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and an iso- Butyl group, pentyl group, 1-ethylpropyl group, 1-methylbutyl group, cyclopentyl group, hexyl group, 1-methylpentyl group, 1-ethylbutyl group, cyclohexyl group, hydroxypropyl group, 2-sulfoethyl group, carboxyethyl Group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, 2-heptyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group Octadecyl group, nonadecyl group, aralkyl group, eicosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, isoheptyl group, isooctyl group, isononyl group , Isodecyl group, isondecyl group, isododecyl group, isotridecyl group, isotetradecyl group, isopentadecyl group, isohexadecyl group, isoheptadecyl group, isooctadecyl group, isononadecyl group, isoaralkyl group, isoeicosyl group, isohenicosyl group, isodocosyl group, Isotricosyl group, isotetracosyl group, isopentacosyl group, isohexacosyl group, isoheptacosyl group, isooctacosyl group, isononacosyl group, isotriacontyl group, 1-methylhexyl group, 1-ethylheptyl group, 1-methylheptyl group, cyclohexyl group, 1-cyclohexylethyl group, 1-heptyloctyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexane Hexyl group, 2,6-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,3-dimethylcyclohexane Examples include a hexyl group, 3,3,5-trimethylcyclohexyl group, 4-t-butylcyclohexyl group, 2-ethylhexyl group, 1-adamantyl group, and 2-adamantyl group.
As preferred groups of X ₁ and X ₂ , a C1-C4 alkyl group can be exemplified independently, and a C1-C3 alkyl group is more preferred. The alkyl group is more preferably unsubstituted, and more preferably when it is linear. Both X ₁ and X ₂ may be the same or different, but usually the same alkyl group is preferred. In the case of the same C1-C4 alkyl group (more preferably C1-C3 alkyl group), it is unsubstituted and a straight chain is preferable. It is particularly preferred when both are methyl or ethyl groups. Most preferably, both are methyl groups.

In formula (1), R _{1 to} R ₂₁ are each independently a hydrogen atom, a C1 to C30 alkyl group, a C1 to C30 alkoxy group, a C6 to C30 aromatic hydrocarbon group, or a C3 to C30 aromatic complex. ring group, a halogen atom, a nitro group, a phenoxy group, a carboxy group, a carboxylic acid ester group, a carboxylic acid salt, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, a sulfonic acid ester group, sulfonate, group -SO ₂ NHR ₂₂ or It represents a -SO ₂ NR ₂₃ R _{24 group,} at least one sulfonic acid group R 1 _{to R 21,} sulfonic acid ester group, _sulfonate, of -SO 2 NHR ₂₂ group or _-SO 2 NR ₂₃ R ₂₄ group Represents either. R ₂₂ to R ₂₄ each independently represents an alkyl group of C1-C30. The sulfonate group and the carboxylate group are salts with monovalent cations, which are either N ⁺ , K ⁺ or quaternary ammonium cations.

The C1-C30 alkyl group in R _{1 to} R ₂₁ is not limited to any one of linear, branched and cyclic as long as it has 1 to 30 carbon atoms, and has a substituent. Also good. Specific examples of the substituent that the alkyl group may have and specific examples of the alkyl group include the same as those described in the description of the C1-C30 alkyl group in X ₁ and X ₂ , and C1- A C4 alkyl group is preferred.
The C1-C30 alkoxy group in R _{1 to} R ₂₁ may have a substituent. Specific examples of the substituent include the same substituents that the C1-C30 alkyl group in X ₁ and X ₂ may have. Specific examples of the alkyl group of C1-C30 within the alkoxy group of the C1-C30, include the same as described in the description of the alkyl group of C1-C30 in _{X 1} and _{X 2.} Specific examples of the alkoxy group include alkoxy groups having an alkyl group described in the specific examples of the C1 to C30 alkyl group.

The C6-C30 aromatic hydrocarbon group in R _{1 to} R ₂₁ is a substituent obtained by removing one hydrogen atom from an aromatic hydrocarbon having 6 to 30 carbon atoms. Specific examples of the aromatic hydrocarbon group Examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, and a benzopyrenyl group. The C6-C30 aromatic hydrocarbon group may have a substituent, and specific examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a sulfo group, a carboxy group, an alkoxycarbonyl group, and a carbamoyl group. Group, cyano group and the like.
The C3-C30 aromatic heterocyclic group in R _{1 to} R ₂₁ is a substituent obtained by removing one hydrogen atom from an aromatic heterocyclic ring having 3 to 30 carbon atoms, and is a specific example of an aromatic heterocyclic ring. Includes a pyridyl group, a pyrazyl group, a pyrimidyl group, a quinolyl group, an isoquinolyl group, a pyrrolyl group, an indolenyl group, an imidazolyl group, a carbazolyl group, a thienyl group, and a furyl group. The C3-C30 aromatic heterocyclic group may have a substituent, and specific examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a sulfo group, a carboxy group, an alkoxycarbonyl group, Examples thereof include a carbamoyl group and a cyano group.

Specific examples of the halogen atom in R _{1 to} R ₂₁ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Specific examples of the carboxylic ester group in R _{1 to} R ₂₁ include methyl carboxylate, ethyl carboxylate, isopropyl carboxylate, and benzyl carboxylate.
Specific examples of the quaternary ammonium cation constituting the carboxylate group and the sulfonate group in R _{1 to} R ₂₁ include tetraalkylammonium cations such as tetramethylammonium cation, ethyltrimethylammonium cation, and tetrapropylammonium cation. .
Examples of the alkoxycarbonyl group in R _{1 to} R ₂₁ include C1 to C30 alkoxycarbonyl groups. Specific examples of the alkyl group of C1~C30 in the alkoxycarbonyl group include the same as described in the description of the alkyl group of C1~C30 in _{X 1} and _{X 2.} Specific examples of the alkoxycarbonyl group include alkoxycarbonyl groups having an alkyl group described in the specific examples of the C1-C30 alkyl group in X ₁ and X ₂ .
Specific examples of the sulfonate ester in R _{1 to} R ₂₁ include C1-C4 alkylsulfonyl such as methanesulfonyl, ethanesulfonyl, hexanesulfonyl and the like.

In formula (1), R _{22 to} R ₂₄ each independently represent a C1 to C30 alkyl group, and the alkyl group is linear, branched or cyclic if it is an alkyl group having 1 to 30 carbon atoms. It is not limited to any of these. The alkyl group may have a substituent. Specific examples of the alkyl group and specific examples of the substituent include the same as those described in the description of the C1-C30 alkyl group in X ₁ and X ₂ and the description of the substituent.

Specific examples of the —SO ₂ NHR ₂₂ group in R _{1 to} R ₂₁ include a sulfamoyl group, a methanesulfamoyl group, an ethanesulfamoyl group, a propanesulfamoyl group, an isopropanesulfamoyl group, and a butanesulfamoyl group. , Isobutane sulfamoyl group, pentanes sulfamoyl group, isopentane sulfamoyl group, cyclopentane sulfamoyl group, hexane sulfamoyl group, cyclohexane sulfamoyl group, heptane sulfamoyl group, 2-ethyl hexane sulfa Examples include a moyl group, 1,5-dimethylhexanesulfamoyl group, tricyclodecanesulfamoyl group, methoxypropanesulfamoyl group, ethoxypropanesulfamoyl group, isopropoxypropanesulfamoyl group and the like. Preferred examples of the —SO ₂ NHR ₂₂ group may include a (C2 to C12) alkylsulfamoyl group, more preferably a (C2 to C8) alkylsulfamoyl group, and even more preferably (C4 to C8). An alkylsulfamoyl group, most preferably a 2-ethylhexanesulfamoyl group.
Specific examples of the —SO ₂ NR ₂₃ R ₂₄ group in R _{1 to} R ₂₁ include a dimethylsulfamoyl group, a methylethylsulfamoyl group, a diethylsulfamoyl group, a dipropylsulfamoyl group, and a diisopropylsulfamoyl group. , Methylpropylsulfamoyl group, methylisopropylsulfamoyl group, ethylpropylsulfamoyl group, ethylisopropylsulfamoyl group, dibutylsulfamoyl group, methylbutylsulfamoyl group, diisobutylsulfamoyl group, ethylbutyl Examples thereof include a sulfamoyl group and a dipentylsulfamoyl group. Preferred examples of the —SO ₂ NR ₂₃ R ₂₄ group may include a di (C1-C4) sulfamoyl group, and more preferably a diethylsulfamoyl group.

As the —SO ₂ NHR ₂₂ group and —SO ₂ NR ₂₃ R ₂₄ group in R _{1 to} R ₂₁ , ethanesulfamoyl group, butanesulfamoyl group, isopentanesulfamoyl group, 2-ethylhexanesulfamoyl group , A dimethylsulfamoyl group, a diethylsulfamoyl group, and a dibutylsulfamoyl group are preferable, and a 2-ethylhexanesulfamoyl group or a diethylsulfamoyl group is preferable.
R _{1 to} R ₂₁ in formula (1) are each independently a hydrogen atom, a C1 to C4 alkyl group, a sulfonic acid group, a sodium sulfonate group, a 2-ethylhexanesulfamoyl group or a diethylsulfamoyl group. A group selected from the group consisting of a hydrogen atom, a C1-C4 alkyl group, a sulfonic acid group, a sodium sulfonate group, and a 2-ethylhexanesulfamoyl group is preferable.

Preferable examples of the color filter dye represented by the formula (1) include the following.
(I) In formula (1), X ₁ and X ₂ are methyl groups, and R _{1 to} R ₂₁ are each independently a hydrogen atom, a C1-C4 alkyl group, a sulfonic acid group, a sulfonic acid group, (C2-C8 ) A dye for a color filter, which is an alkylsulfamoyl group or a di (C1-C4) alkylsulfamoyl group, and at least one of R _{1 to} R ₂₁ is a sulfonic acid group or a sulfonic acid group.
(Ii) _{one of} R _{1 to} R ₂₁ is a sulfonic acid group or a sulfonate group, (a) all the remaining groups are hydrogen atoms, or (b) four of the remaining groups. Is a C1-C4 alkyl group, and the remaining one is a sulfonic acid group, a sulfonic acid group, a (C2-C8) alkylsulfamoyl group or a di (C1-C4) alkylsulfamoyl group, and the rest is hydrogen The color filter dye according to (i), which is an atom.
(Iii) The four C1-C4 alkyl groups in (b) are C1-C3 alkyl groups, and the remaining one is a sulfonic acid group, a sulfonate group, or a (C4-C8) alkylsulfamoyl group. The color filter dye according to (i) or (ii) above.
(Iv) Among R _{17 to} R ₂₁ , one is a sulfonic acid group or a sodium sulfonate group, the remainder is a hydrogen atom, and (a) all of R _{1 to} R ₁₆ are hydrogen atoms, or ( b) Two of R _{1 to} R ₅ are C1 to C4 alkyl groups, the remaining groups are hydrogen atoms, two of R _{12 to} R ₁₆ are C1 to C4 alkyl groups, and one is a sulfonic acid group The dye for color filters according to (i) or (ii) above, which is a sodium sulfonate group, a 2-ethylhexanesulfamoyl group or a diethylsulfamoyl group, and the remainder is a hydrogen atom.
(V) Among R _{17 to} R ₂₁ , one is a sulfonic acid group or a sodium sulfonate group, the remainder is a hydrogen atom, and (a) all of R _{1 to} R ₁₆ are hydrogen atoms, or ( b) Among R _{1 to} R ₁₆ , R ₁ , R ₅ , R ₁₂ and R ₁₆ are C1 to C3 alkyl groups, R ₁₄ is a hydrogen atom, a sulfonic acid group, a sulfonate group, or a (C4 to C8) alkylsulfur. The dye for a color filter according to any one of (i) to (iii) above, which is a famoyl group and the remainder is a hydrogen atom,
(Vi) X ₁ and X ₂ in the formula (1) are methyl groups, and among R _{1 to} R ₂₁ , R ₁ , R ₅ , R ₁₂ and R ₁₆ are methyl groups, and R ₁₄ is sulfonic acid. Group or a sodium salt of a sulfonic acid group, R ₁₇ is a sulfonic acid group or a sodium salt of a sulfonic acid group, and the other is a hydrogen atom.
(Vii) X ₁ and X ₂ in the formula (1) are methyl groups, and among R _{1 to} R ₂₁ , R ₁ , R ₅ , R ₁₂ and R ₁₆ are methyl groups, and R ₁₄ is 2-ethylhexane. A dye having a sulfamoyl group, R ₁₇ is a sulfonic acid group, and the others are hydrogen atoms. And _{X 1} and _{X 2} in (viii) Formula (1) is a methyl _group, among R 1 _{to R 21,} dye otherwise in R ₁₇ is a sulfonic acid group is a hydrogen atom.
The dyes (v) and (viii) are particularly preferred.

The compound of the formula (1) in the present invention is obtained by methylating the compound described in 0078 of Patent Document 3, or by condensing the sulfolane compound represented by the following formula (100) or the sulfolane ring of the sulfolane compound. Substitution represented by R _{1 to} R ₅ or R _{12 to} R ₁₆ corresponding to the formula (1) on a sulfolane compound having a substituent such as an alkyl group corresponding to the compound of the formula (1) on the benzene ring It can be obtained by reacting N-methylaniline which may have a group.

The pigment | dye of Formula (1) in this invention is suitable for coloring of resin for color filters. Therefore, the color filter having a cured resin film colored with the pigment of the formula (1) in the present invention has a clear blue color, high brightness, and high contrast as will be described later. The color filter having the cured resin film is a resin composition for a color filter containing the dye of the formula (1) in the present invention, and is obtained by preparing a cured resin film patterned on a substrate by a conventional method. Can do. The content of the pigment of the formula (1) contained in the cured resin film is not particularly limited as long as the cured resin film can be colored. Usually, it is about 0.5 to 15% (mass basis, the same shall apply hereinafter), preferably about 1 to 10%, more preferably about 1 to 6% with respect to the total amount of the cured film.
The resin composition for the color filter used here may be any resin composition that contains the dye of the formula (1) of the present invention and can be used for forming a cured film of the color filter. . The content of the pigment of the formula (1) contained in the resin composition for the color filter is about 0.5 to 15% (mass basis, the same applies hereinafter) with respect to the total solid content of the resin composition. , Preferably about 1 to 10%, more preferably about 1 to 6%.
In the present invention, “solid content” means a component excluding a solvent.
One preferred resin composition for a color filter will be specifically described below.

A preferred colored resin composition for color filters of the present invention (hereinafter also simply referred to as “colored resin composition”) is a color filter dye represented by the above formula (1), a binder resin, a solvent, a curing agent, and Contains at least one of a photopolymerization initiator and a curing accelerator. In the present specification, “at least one of” is used in the meaning of either one or both.
The color filter dye represented by the formula (1) may be used alone or in combination of two or more. The content is 100 parts by mass of the total solid content of the colored resin composition of the present invention (the total amount of components excluding the solvent composed of the colorant compound, the binder resin, the curing agent, etc. is used synonymously hereinafter). In general, the content is 0.01 to 70 parts by mass, preferably 0.5 to 30 parts by mass, and more preferably 1 to 30 parts by mass. Moreover, depending on the case, the content rate of 1-15 mass parts and also 1-10 mass parts is also preferable. When the content is too large, problems such as precipitation and agglomeration occur, and adhesion with the substrate is reduced due to insufficient curing. On the other hand, when the content is too small, there is a tendency that sufficient color purity cannot be obtained as color characteristics.

  The binder resin contained in the colored resin composition for a color filter of the present invention functions as a dispersant or / and a dispersion aid for the dispersion stability when the dye or pigment is dispersed. When the colored resin composition is used in a photolithography method, it is desirable that the binder resin is also soluble in an alkaline developer used in a development processing step when producing a color filter. In order to form a good fine pattern, it is desirable that the binder resin has sufficient curing characteristics with a photopolymerization initiator and a photopolymerizable monomer. Also, the binder resin must be compatible with constituent materials such as color filter dyes, photopolymerization initiators, photopolymerizable monomers, pigment dispersions, and the like, and the colored resin composition should not be stable so as not to cause precipitation or aggregation. Don't be. When the colored resin composition is used in the ink jet method, alkali solubility is not particularly required, and therefore a binder resin having good compatibility with other constituent materials may be selected.

A known resin can be used as the binder resin, but a polymer of an ethylenically unsaturated monomer is preferred. Preferred raw material monomers for the binder resin include an ethylenically unsaturated monomer having one or more carboxy groups or hydroxyl groups, or an ethylenically unsaturated monomer having an aromatic hydrocarbon group or an aliphatic hydrocarbon group. Can do. Although homopolymers of these raw material monomers can be used for the binder resin, a copolymer of these raw material monomers is usually used. The term ethylenically unsaturated monomer is used to mean a monomer having a polymerizable ethylene group. The binder resin has an average weight molecular weight of usually about 2000 to 400000, preferably about 3000 to 100000, more preferably about 5000 to 50000, and still more preferably about 6000 to 40000. In the case of a colored resin composition used for development, a copolymer of an ethylenically unsaturated monomer having at least one carboxy group or hydroxy group and an ethylenically unsaturated monomer having no such functional group is used. The binder resin is preferably a copolymer of at least two types of ethylenically unsaturated monomers, usually containing at least a (meth) acrylic monomer. In the present specification, terms such as “(meth) acryl” or “(meth) acrylate” are used in the meaning of “methacryl or / and acrylic” or “methacrylate or / and acrylate”. Moreover, a (meth) acryl monomer is used in the meaning of a monomer having a (meth) acryl group, and specifically includes either or both of (meth) acrylic acid and (meth) acrylate. In the copolymer, the structural unit derived from the (meth) acrylic monomer is usually in a proportion of 30 to 100 mol%, preferably 40 to 100 mol%, based on the total amount of the structural units contained in the copolymer. More preferably, a copolymer contained in the range of 50 to 100 mol% is preferable. In the present invention, a copolymer having such a component derived from a (meth) acrylic monomer as a main component is referred to as a (meth) acrylic copolymer. The main component is used in the meaning of the most constituent component among the constituent units in the copolymer. In the present invention, the binder resin is preferably a (meth) acrylic copolymer.
In addition, an epoxy compound having an epoxy group in the side chain or terminal of an aromatic hydrocarbon group or aliphatic hydrocarbon group can also be used. Furthermore, an epoxy (meth) acrylate resin obtained by adding (meth) acrylate to the epoxy compound is an ethylenically unsaturated monomer having a hydroxy group, and can be used as one of acrylate monomers. These monomers may be used alone or in combination of two or more. Usually, a polymer or copolymer of these monomers can be used as the binder resin. When used for development in an alkaline aqueous solution, a copolymer of the above carboxy group or hydroxyl group-containing (meth) acrylate and another copolymerizable monomer is desirable.

  Examples of the carboxy group-containing unsaturated monomer that can be used as a raw material for the binder resin include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; Unsaturated dicarboxylic acids (anhydrides) such as acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid; trivalent or higher unsaturated polycarboxylic acids (anhydrides) ); Monomonocarboxylic acids such as 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate and 2-acryloyloxyethyl 2-hydroxyethylphthalic acid Mention may be made of 2- (meth) acryloyloxyethyl ester. These ethylenically unsaturated monomers having a carboxy group can be used alone or in admixture of two or more.

  Examples of the hydroxyl group-containing unsaturated monomer that can be used as a raw material for the binder resin include a hydroxyl group-containing mono (meth) acrylate. For example, a (meth) acrylate compound of a polyhydric alcohol, preferably a (meth) acrylate compound of a di- or trialcohol can be mentioned. Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 5 -Hydroxypentyl (meth) acrylate, 4-hydroxypentyl (meth) acrylate, 3-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 5-hydroxyhexyl (meth) acrylate, 4-hydroxyhexyl (meta ) C2-C10 dialco such as acrylate, 5-hydroxy-3-methyl-pentyl (meth) acrylate, cyclohexane-1,4-dimethanol-mono (meth) acrylate, and glycerin monomethacrylate Mono (meth) acrylate compounds; 2- (2-hydroxyethyloxy) ethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and poly (ethylene glycol-propylene glycol) monomethacrylate And hydroxyl group-terminated polyalkylene glycol mono (meth) acrylates. These ethylenically unsaturated monomers having a hydroxyl group can be used alone or in admixture of two or more.

Examples of unsaturated monomers other than those described above that can be used as a raw material for the binder resin include unsaturated monomers having no hydroxyl group or carboxy group, and preferably vinyl compounds having no hydroxyl group or carboxy group. For example, aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-methoxystyrene; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, o- Phenylphee Unsaturated carboxylic acid esters such as glycidyl ether (meth) acrylate, o-phenylphenol (meth) acrylate hydroxyethylated product and phenoxyethyl (meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (Meth) acrylate, norbornyl (meth) acrylate, norbornylmethyl (meth) acrylate, phenylnorbornyl (meth) acrylate, cyanonorbornyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, Menthyl (meth) acrylate, Fentyl (meth) acrylate, Adamantyl (meth) acrylate, Dimethyladamantyl (meth) acrylate, Tricyclo [ 5.2.1.0 ^2,6 ] dec-8-yl = (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] dec-4-methyl = (meth) acrylate, cyclodecyl (meth) (Meth) acrylate compounds having an alicyclic skeleton such as acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid and t-butylcyclohexyl (meth) acrylate; methoxypolyethylene glycol monomethacrylate, lauroxypolyethylene glycol mono (meta ) Acrylate, octoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, nonyl phenoxy polyethylene glycol mono acrylate, nonyl phenoxy polypropylene glycol mono acrylate and allyloxy polyethylene glycol-polypropylene Alkyl-terminated polyalkylene glycol mono (meth) acrylates such as glycol mono (meth) acrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 3-aminopropyl acrylate and Unsaturated carboxylic acid aminoalkyl esters such as 3-aminopropyl methacrylate; glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate and 4-hydroxy Unsaturated carboxylic acid glycidyl esters such as butyl (meth) acrylate glycidyl ether; vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Acid vinyl esters; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and methallyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Acrylamide, methacrylamide, α-chloroacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, N- (meth) acryloylphthalimide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide and maleimide Unsaturated amides or unsaturated imides such as; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; and polystyrene, polymethyl acrylate, poly Chill methacrylate, poly n- butyl acrylate and macromonomers such as having a polymer terminus Monoakuriroiru group or mono-methacryloyl group of the molecular chain, such as poly n- butyl methacrylate and polysilicone. These unsaturated monomers can be used alone or in admixture of two or more.

As the binder resin, a homopolymer may be used in some cases, but a copolymer using at least two kinds of the above monomers is usually used. When the copolymer is produced, a polymerization initiator is used. Specific examples of the polymerization initiator used when synthesizing the copolymer are, for example, α, α′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile). ), T-butyl peroctoate, di-t-butyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, and the like. The usage-amount of a polymerization initiator is 0.01-25 mass parts with respect to 100 mass parts of all the monomers used for the synthesis | combination of a copolymer. In the case of synthesizing a copolymer, it is preferable to use an organic solvent, but one having sufficient dissolving power for the monofunctional monomer and polymerization initiator to be used is used. As an organic solvent which can be used for manufacture of binder resin, the thing similar to the organic solvent which the colored resin composition of this invention mentioned later contains is mentioned.
The reaction temperature when synthesizing the copolymer is preferably 50 to 120 ° C., particularly preferably 80 to 100 ° C. Moreover, it is preferable that reaction time is 1 to 60 hours, More preferably, it is 3 to 20 hours.
The preferred acid value of the copolymer is 10 to 300 (mgKOH / g), and the preferred hydroxyl value is 10 to 200 (mgKOH / g). Oxidation is a value measured according to JIS K-2501, and weight average molecular weight is a value calculated in terms of polystyrene based on the measurement results of GPC (Gel Permeation Chromatography). When the acid value or hydroxyl value is 10 or less, developability is lowered. As for the weight average molecular weight (Mw) of a copolymer, 2000-400000 are preferable and 3000-100000 are more preferable. When the weight average molecular weight is 2000 or less, or 400000 or more, sensitivity, developability and the like are lowered.
Incidentally, when development is not used in the production of the color filter, the acid value or hydroxyl value of the binder resin is not particularly problematic. Therefore, there is no problem even if the acid value or the hydroxyl value is zero.

  A polymer in which an unsaturated double bond is further introduced into the side chain of the copolymer is also useful as a binder resin. For example, (i) a maleic anhydride portion of a copolymer of maleic anhydride and copolymerizable styrene, vinylphenol, acrylic acid, acrylic ester, acrylamide, etc., with an alcoholic hydroxy group such as hydroxyethyl acrylate A compound obtained by reacting a half-ester by reacting an epoxy group-containing (meth) acrylate such as (meth) acrylate or glycidyl methacrylate, and (ii) an alcoholic hydroxy such as acrylic acid or an acrylic ester and hydroxyethyl acrylate Examples thereof include compounds obtained by reacting acrylic acid with the hydroxyl group of a copolymer with a (meth) acrylate having a group. Also, urethane resin, polyamide, polyimide resin, polyester resin, commercially available ACA-200M (manufactured by Daicel Corporation), ORGA-3060 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), AX3-BNX02 (manufactured by Nippon Shokubai Co., Ltd.), UXE- 3024, UXE-3000, ZGA-287H, TCR-1338H, ZXR-1722H, ZFR-1401H, ZCR-1642H (all manufactured by Nippon Kayaku Co., Ltd.) can also be used as the binder resin.

  Binder resin can be used individually or in mixture of 2 or more types in the colored resin composition of this invention. The content ratio of the binder resin in the colored resin composition of the present invention is usually 0.5 to 99 parts by mass, preferably 5 to 50 parts by mass, more preferably 100 parts by mass of the total solid content of the colored resin composition. 10 to 50 parts by mass. In some cases, a content ratio of 10 to 65 parts by mass is also preferable. When the content of the binder resin is less than 0.5 parts by mass, the alkali developability is deteriorated, and problems such as background contamination and film residue in areas other than the area where pixels are formed may occur.

  The organic solvent contained in the colored resin composition for a color filter of the present invention has sufficient dissolving power with respect to a binder resin, a photopolymerization initiator, and the like, which are components of the colored resin composition, and is used for synthesis of the binder resin Those having sufficient dissolving power for the monofunctional monomer and polymerization initiator used can be used. In addition, when preparing a pigment dispersion, those that can maintain dispersion stability can be used.

Specific examples of the organic solvent contained in the colored resin composition include aromatic solvents such as benzene such as benzene, toluene and xylene; cellosolve solvents such as cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve and methyl cellosolve acetate, Cellosolve acetates such as ethyl cellosolve acetate and butyl cellosolve acetate; Organic acid ester solvents such as (i) Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate (Ii) methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethoxy Propionates such as ethyl lopionate; (iii) lactates such as methyl lactate, ethyl lactate and butyl lactate; (iv) acetates such as methyl acetate, ethyl acetate and butyl acetate; diethylene glycol monoalkyl ethers such as , Diethylene glycol monomethyl ether and diethylene glycol monoethyl ether and the like, or ether solvents such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane; ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone and cyclohexanone; and methanol, ethanol, butanol, isopropyl alcohol and Examples include alcohol solvents such as benzyl alcohol, but are not limited thereto.
Usually, it is a cellosolve solvent, an organic acid ester solvent (preferably a C2-C4 organic acid ester solvent), an ether solvent, a ketone solvent, and the like, and preferably an organic acid ester solvent and a ketone solvent.

  The organic solvent can be used alone or in combination of two or more in the colored resin composition of the present invention. The amount of the organic solvent used is usually 40 to 10000 parts by mass, preferably 70 to 2000 parts by mass, more preferably 100 to 1000 parts by mass, and still more preferably 100 parts by mass of the total solid content of the colored resin composition. 200-900.

Examples of the curing agent contained in the colored resin composition for a color filter of the present invention include a photopolymerization monomer in the case of radical polymerization, an epoxy resin in the case of ion curing, and a melamine curing agent. Specific examples of these curing agents include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Triethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol hexa (meth) acrylate (manufactured by Nippon Kayaku Co., Ltd., Kayrad DPHA, etc.), glycerol (meth) acrylate, bisphenol-A type epoxy Sidi (meth) acrylate, bisphenol-F type epoxy di (meth) acrylate, bisphenol-fluorene type epoxy di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated Glycerin tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) ) Phenyl] fluorene and the like. As commercial products, Kayrad RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Kayarad DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.), UA-33H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-53H (Shin-Nakamura) (Meth) acrylate monomers such as Chemical Industry Co., Ltd.) and M-8060 (manufactured by Toagosei Co., Ltd.); Thiol polymerization monomers such as TEMPIC, TMMP, PMP and DPMP (all manufactured by Sakai Chemical Industry Co., Ltd.); Japan NC-6000, NC-6300, NC-6300H, NC-3000, EOCN-1020, XD-1000, EPPN-501H, BREN-S, NC-7300L, Daicel Chemical Industries, Ltd. 2021P, EHPE3150, Cyclomer M100, Epolide PB3600, Japan Epoxy resin products Epicoat 828, Epicoat YX8000, Epicoat YX4000, Printec products VG-3101L, Silaace S510 (Chisso Corporation), TEPIC (Nissan Chemical Industry Co., Ltd.) and other epoxy resins; and methylolated melamine and Mw-30 Melamine curing agents such as (Sanwa Chemical Co., Ltd.) can be mentioned, but are not limited thereto. In these, as a hardening | curing agent used with the colored resin composition of this invention, a photopolymerization monomer and / or an epoxy resin are preferable, and they may be used independently or may use both together. In some cases, the combined use of both is also preferred.
In the present invention, it is preferable to contain a (meth) acrylate monomer as a curing agent. A (meth) acrylate monomer alone may be used as a curing agent, or another curing agent may be used in combination with the (meth) acrylate monomer. As the curing agent used in combination, an epoxy resin is preferable. When a (meth) acrylate monomer and an epoxy resin are used in combination as a curing agent, the epoxy resin is usually 10 to 150 parts by mass, preferably 20 to 100 parts by mass with respect to 100 parts by mass of the (meth) acrylate monomer. It is preferred to use.

  As a hardening | curing agent which the colored resin composition for color filters of this invention contains, the epoxy resin represented by following formula (3) is also preferable.

Formula (3)

(In Formula (3), R _<1c > -R <_19c> represents a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, or a halogen atom each independently.
In particular, R _{1c to} R _19c are each independently preferably a hydrogen atom, a methyl group, an ethyl group, or a methoxy group. More preferably, at least R _17c , R _18c and R _19c are all methyl groups. More preferably, R _17c , R _18c and R _19c are methyl groups, and R _{1c to} R _16c are hydrogen atoms.
Examples of such an epoxy resin include 1- [4- (1-hydroxy-1-methyl-ethyl) -phenyl] ethanone and phenols (unsubstituted or C1-C12 alkyl group, C1-C12 alkoxy). Epoxy obtained as a main component by reaction of a phenol resin obtained by reaction with a group or a phenol having a halogen atom as a substituent) and epihalohydrin (at least one selected from epichlorohydrin and epibromohydrin) Examples of commercially available epoxy resins include VG-3101L manufactured by Printec Co., Ltd., NC-6000 and NC-6300 manufactured by Nippon Kayaku Co., Ltd.

  A hardening | curing agent can be used for the colored resin composition of this invention individually or in mixture of 2 or more types. Content of a hardening | curing agent is 1-80 mass parts normally with respect to 100 mass parts of total solids of a colored resin composition, Preferably it is 5-50 mass parts. When the amount is less than this range, the effects such as solvent resistance are reduced, and when the amount is too large, developability is lowered and development may not be possible. Moreover, the combination with the hardening accelerator for hardening an epoxy resin is preferable.

The colored resin composition for a color filter of the present invention contains one or more selected from the group consisting of a photopolymerization initiator and a curing accelerator.
When the colored resin composition contains a photopolymerizable monomer as a curing agent, it preferably contains a photopolymerization initiator, and when it contains an epoxy resin, it preferably contains a curing accelerator, both of the photopolymerizable monomer and the epoxy resin. When it contains, it is preferable to contain both a photoinitiator and a hardening accelerator.
As the photopolymerization initiator contained in the colored resin composition, those having sufficient sensitivity to ultraviolet rays emitted from an ultrahigh pressure mercury lamp generally used as an exposure light source are preferable. Any of a radical polymerizable photo radical initiator, an ion curable photo acid generator, a photo base generator, and the like can be used. Further, in order to cure with less exposure energy, a polymerization accelerator called a sensitizer can be used in combination.
Specific examples of the photopolymerization initiator include benzyl, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, benzoylbenzoic acid, esterified benzoylbenzoic acid, 4-benzoyl -4′-methyldiphenyl sulfide, benzyldimethyl ketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, isopropylthioxanthone, dimethylthioxanthone, diethylthioxanthone, diisopropylthioxanthone, dimethylaminomethylbenzoate, 1 -(4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl Phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, methylbenzoylformate, 2-methyl- 1- (4-Methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4-bis (trichloromethyl)- 6- (4-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-s-triazine, 2,4-bis (tribromomethyl) ) -6- (4′-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (tribromomethyl) -1,3,5-s-triazine, 2 4-bis (trichloromethyl) -6- (1,3-benzodioxolan-5-yl) -1,3,5-s-triazine, benzophenone, benzoylbenzoic acid, 1- (4-phenylsulfanylphenyl) butane- 1,2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4-methylsulfanylphenyl) butane -1-one oxime-O-acetate, 4,4′-bis (diethylamino) benzophenone, P-dimethylaminobenzoic acid isoamyl ester, P-dimethylaminobenzoic acid ethyl ester, 2,2′-bis (O-chlorophenyl)- 4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, diazonaphthoquinone initiator, And commercial KAYACURE ^RTM DMBI, KAYACURE ^RTM BDMK, KAYACURE ^RTM BP-100, KAYACURE ^RTM BMBI, Kayacure ^RTM DETX-S, Kayacure ^RTM EPA (all manufactured by Nippon Kayaku Co., Ltd.); Darocur ^RTM 1173 or Darocure ^RTM 1116 (both Irgacure ^RTM 907, Irgacure ^RTM 369, Irgacure ^RTM 379EG, Irgacure ^RTM OXE-01, Irgacure ^RTM OXE-02, Irgacure ^RTM PAG103 (all manufactured by BASF Japan KK); TME-Triazine (stock) Saniwa Chemical Co., Ltd.); biimidazole (manufactured by Kurokin Kasei Co., Ltd.); STR-110, STR-1 (both Respe Chemical Co., Ltd.) But not limited to these.

  A photoinitiator can be used individually or in combination of 2 or more types in the colored resin composition of the present invention. Content of a photoinitiator is 0.5-50 mass parts normally with respect to 100 mass parts of total solids of a colored resinous composition, Preferably it is 1-25 mass parts.

The curing accelerator contained in the colored resin composition for a color filter of the present invention is a reaction catalyst that promotes ion curing, for example, N-containing heterocyclic compounds such as primary to tertiary amines and imidazoles, acid anhydrides, and the like. Thing etc. are mentioned. Specific examples of amines include triethylamine, triethanolamine, Kayahard A-A, Kayabond C-100, Kayabond C-200S, Kayabond C-300S, and the like manufactured by Nippon Kayaku Co., Ltd. Specific examples of imidazole include Curesol ^RTM of Shikoku Kasei Kogyo Co., Ltd. or Respe Chemical Co., Ltd. (hereinafter the same) 2MZ-H, Curesol C11Z, Curesol C17Z, Cureazole 1,2DMZ, Curesol 2E4MZ, Cureazole 2PZ, Curesol 2P4MZ, Cureazole 1B2MZ , Curezol 1B2PZ, Curezol 2MZ-CN, Curezol C11Z-CN, Curezol 2E4MZ-CN, Curezol 2PZ-CN, Curezol C11Z-CNS, Curezol 2PZCNS-PW, Curezol-2MZ-A, Curezol C11Z-A4 2MA-OK, Curezol 2PZ-OK, Curezol 2PHZ-PW, Curezol 2P4MHZ- PW, Curezol TBZ, Curezol 2PZL-T, Curezol VT, Curezol SFZ and the like can be mentioned. Specific examples of the acid anhydride include maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic dianhydride, Kayahard MCD manufactured by Nippon Kayaku Co., Ltd. It is done. Among these, imidazoles are preferable as the curing accelerator, and Curezol 1B2PZ, Curezol 2PZ, Curezol 1B2MZ and Curezol 2E4MZ are more preferable from the viewpoint of reactivity.
Content of a hardening accelerator is 0.01-50 mass parts normally with respect to 100 mass parts of total solids of a colored resin composition, Preferably it is 0.05-20 mass parts. When the content of the curing accelerator is less than 0.01 parts by mass, the curability may be lowered, and when it is more than 50 parts by mass, the storage stability may be deteriorated.

In the colored resin composition for a color filter of the present invention, a pigment other than the above formula (1) may be used in combination as an optional component. The colorant that can be used in combination may be appropriately selected from dyes, organic pigments, and inorganic pigments, and there is no problem if used alone or in combination of two or more as required. Since the colored resin composition of the present invention relates to a blue pixel, it is usually preferable to use a known blue dye or violet dye, or a blue pigment or violet pigment.
When the dye other than the formula (1) is used in combination, the dye represented by the formula (1) and the dye other than the formula (1) are contained in 100 parts by mass of the total solid content of the colored resin composition of the present invention. If the total content is in the range of 0.01 to 70 parts by mass, preferably 0.5 to 50 parts by mass, they can be used in any proportion. Usually, the other dye is 0.5 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight, with respect to 1 part by weight of the dye represented by formula (1). More preferably, it is used in a ratio of 1 to 10 parts by mass. As other dyes, dyes represented by the following formula (2) and / or blue pigments described later are preferable.
One of the preferable embodiments in the colored resin composition of the present invention is an embodiment in which a dye represented by the following formula (2) is used in combination. The use ratio of the dye of the formula (1) and the dye of the formula (2) is not particularly limited, but the dye of the formula (2) is usually 0.2 to 10 with respect to 1 part by mass of the dye of the formula (1). It is a ratio of mass parts, preferably 0.5-3 mass parts.
Moreover, one of the preferable aspects in the colored resin composition of this invention is an aspect which uses a well-known blue pigment mentioned later together. In particular, C.I. I. Pigment Blue 15: 6 is a preferred pigment. The usage ratio of the blue pigment can be freely used within the range of the content ratio of the other dye. Usually, it is 1-20 mass parts with respect to 1 mass part of pigment | dye of Formula (1), Preferably it is a ratio of 2-15 mass parts.
In addition, in the colored resin composition of the present invention, an embodiment in which the dye of formula (2) is used in combination with the known blue pigment is one of the more preferred embodiments. The use ratio of the blue pigment and the dye of formula (2) can be freely changed within the above-mentioned range.

  There is no restriction | limiting in particular in the dye which can be used together with the colored resin composition of this invention, Acid dye, basic dye, direct dye, sulfur dye, vat dye, naphthol dye, reactive dye, disperse dye, etc. are mentioned. These dyes are not limited to those that are soluble in an organic solvent, and dyes that are insoluble in an organic solvent can be used as a dispersion.

  There are no particular restrictions on the organic pigments that can be used in combination with the colored composition of the present invention. Pigments such as linone, pyranthrone, indanthrone, anthrapyrimidine, dibromoanthanthrone, flavanthrone, perylene, perinone, quinophthalone, thioindigo, dioxazine, quinacridone, xanthene; acidic dyes, Examples include lake pigments and dyed lake pigments obtained by insolubilizing basic dyes, direct dyes and the like with respective precipitants. Specific examples of these dyes are color indexes such as pigment blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79; Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 4, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Pigment Blue 15: 6 and Pigment Violet 23 are preferable because of their good hue and resistance.

  The inorganic pigment that can be used in combination with the colored composition of the present invention is not particularly limited, and specific examples thereof include composite metal oxide pigments, carbon black, black low-order titanium oxide, titanium oxide, barium sulfate, zinc white, lead sulfate, Yellow lead, bengara, ultramarine, bitumen, chromium oxide, antimony white, iron black, lead tan, zinc sulfide, cadmium yellow, cadmium red, zinc, manganese violet, cobalt violet, barium sulfate, magnesium carbonate and other metal oxides, metals Examples thereof include sulfides, sulfates, metal hydroxides, and metal carbonates.

As a pigment | dye used together with the coloring composition of this invention, the pigment | dye represented by said Formula (2) is preferable.
In formula (2), R < _1a > -R < _6a > represents a hydrogen atom, a C1-C30 alkyl group, a phenyl group, or a benzyl group each independently.
Specific examples of the C1-C30 alkyl group represented by R _{1a to} R _6a include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 1-methylpropyl group (s-butyl group), an isobutyl group, and pentyl. Group, 1-ethylpropyl group, 1-methylbutyl group, cyclopentyl group, hexyl group, 1-methylpentyl group, 1-ethylbutyl group, cyclohexyl group, hydroxypropyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group , Methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, 2-heptyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group Group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group Group, nonadecyl group, aralkyl group, eicosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, isoheptyl group, isooctyl group, isononyl group, Isodecyl group, isondecyl group, isododecyl group, isotridecyl group, isotetradecyl group, isopentadecyl group, isohexadecyl group, isoheptadecyl group, isooctadecyl group, isononadecyl group, isoaralkyl group, isoeicosyl group, isohenicosyl group, isodocosyl group, isotricosyl Group, isotetracosyl group, isopentacosyl group, isohexacosyl group, isoheptacosyl group, isooctacosyl group, isononacosyl group, isotriacontyl group, 1-methyl Sil group, 1-ethylheptyl group, 1-methylheptyl group, 1-cyclohexylethyl group, 1-heptyloctyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2, 6-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3, 3,5-trimethylcyclohexyl group, 4-t-butylcyclohexyl group, 2-ethylhexyl group, 1-adamantyl group, 2-adamantyl group and the like can be mentioned.

The phenyl group or benzyl group represented by R _{1a to} R _6a may have a substituent. Examples of the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, t -(C1-C5) alkyl groups such as butyl group and pentyl group, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, sulfonic acid group, methoxy group, ethoxy group, propoxy group, butoxy group, t- (C1-C6) alkoxy groups such as butoxy group and hexyloxy group, hydroxy (C1-C5) alkyl groups such as hydroxyethyl group and hydroxypropyl group, methoxyethyl group, ethoxyethyl group, ethoxypropyl group and butoxyethyl group (C1-C5) alkoxy (C1-C5) alkyl group, hydroxy such as 2-hydroxyethoxy group (C1-C5) ) Alkoxy (C1-C5) alkoxy group such as alkoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group and the like.
R _{1a to} R _6a are each independently preferably a hydrogen atom or a C1-C30 alkyl group, and each independently a cyclohexyl having a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 alkyl group as a substituent. Groups are more preferred. One of R _{5a and} R _6a is a hydrogen atom, and the other is a C1-C4 alkyl group or a cyclohexyl group having a C1-C4 alkyl group as a substituent, and R _{1a to} R _4a are It is further preferred that each is independently a C1-C4 alkyl group.

In formula (2), R _<7a > -R < _20a > represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group each independently.
Examples of the halogen atom represented by R _{7a to} R _20a include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The C1~C6 alkyl group represented by R _7a to R _20a, for example a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, hydroxypropyl Group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group and the like.

As R _<7a > -R < _20a > in Formula (2), a hydrogen atom, a chlorine atom, or an unsubstituted C1-C6 alkyl group is preferable, and a hydrogen atom is more preferable.
In the formula (2), the anion part Z ⁻ represents an alkylsulfonylmethide anion, alkylsulfonylimide anion or alkylsulfonate having a C1 to C10 higher-order halogenated alkyl group. Specific examples thereof include tristrifluoromethanesulfonyl. Examples thereof include a methide anion, a bistrifluoromethanesulfonylimide anion, a trifluoromethylsulfonate, and a nonafluorobutylsulfonate, and a tristrifluoromethanesulfonylmethide anion is particularly preferable.

Although the specific example of the pigment | dye represented by Formula (2) is shown in the following Table 1 and Table 2, the pigment | dye represented by Formula (2) is not limited to these. In Table 1, Me represents a methyl group, Et represents an ethyl group, n-Bu represents a normal butyl group, i-Bu represents an isobutyl group, i-Pr represents an isopropyl group, and i-Pen represents an isopentyl group. , I-Hep is an isoheptyl group, Ph is a phenyl group, CH is a cyclohexyl group, MeCH is a methylcyclohexyl group, α is a tristrifluoromethanesulfonylmethide anion, β is a bistrifluoromethanesulfonylimide anion, γ Represents trifluoromethylsulfonate. Further, the carbon atoms represented by "*" in the column of the substituents R _{5 a} represents a bonding position of the substituent R _{5 a.}

As a preferable specific example of the combination dye represented by the formula (2),
(I) a dye in which R _{1a to} R _5a among R _{1a to} R _20a in formula (2) are an ethyl group, the other is a hydrogen atom, and Z is tristrifluoromethanesulfonylmethide; and (ii) formula (2) ) In R _{1a to} R _20a , R _{1a to} R _4a are ethyl groups, R _5a is a 2-methylcyclohexyl group, the other is a hydrogen atom, and Z is tristrifluoromethanesulfonylmethide.

  When using together the pigment | dye represented by Formula (2) in the colored resin composition for color filters of this invention, content of the pigment | dye represented by Formula (1) and the pigment | dye represented by Formula (2) is the above-mentioned. The content of the dye represented by the formula (2) is not less than the content of the dye represented by the formula (1), for example, because the contrast characteristics are excellent. When content of the pigment | dye represented by Formula (1) is 1-30 mass parts, preferable content of the pigment | dye represented by Formula (2) is 2-30 mass parts. However, the characteristics other than contrast such as brightness and resistance are not limited to this, and the characteristics may be excellent when the content ratio of the dye represented by the formula (1) is large.

The dye represented by the formula (2) can be obtained by a known synthesis method described in Yutaka Hosoda, “Theoretical Manufacturing Dye Chemistry” (pages 373 to 375) published by Gihodo Co., Ltd. anion Z of the) ^- are purchased commercially chlorine anion, can also be synthesized by addition of the corresponding salt or acid to salt exchange. For example, a dye in which the anion portion of the general formula (2) is a chlorine anion is reacted with a reaction solvent (eg, water, methanol, ethanol, isopropanol, acetone, N, N-dimethylformamide (hereinafter abbreviated as DMF), N-methyl 2-pyrrolidone (hereinafter abbreviated as NMP) and the like, and these solvents may be used alone or in combination. The desired product can be easily obtained by adding the amount, stirring at a predetermined temperature (for example, 0 to 100 ° C.), and collecting the precipitated crystals by filtration.

  In the case where the dye represented by the formula (1) and the dye optionally used in combination in the colored resin composition have low solubility, they may be dispersed in combination with a dispersing agent or a dispersion aid. As the agent or the like, a pigment-based dispersant, a resin-based dispersant, a surfactant, or the like that has good adsorptivity to the pigment is used. As a dye-based dispersant, a method of mixing a sulfonated dye or a metal salt thereof as described in Patent Document 4 with a dye, a method of mixing a substituted aminomethyl derivative, and the like are known as known techniques. Some resin-based dispersants are nonpolar nonionic, but polymer resins having an acid value, an amine value, and the like that give good pigment adsorbability are common, such as acrylic resins, polyurethane resins, and polycarboxylic acids. Examples include acids, polyamide resins, and polyester resins. Examples of commercially available resin dispersants include ED211 (manufactured by Enomoto Kasei), Ajisper PB821 (manufactured by Ajinomoto Fine Techno), Solsperse 5000 and Solsperse 71000 (manufactured by Avicia), Disperbyk-2001 (manufactured by Big Chemie Japan), and the like. .

  When the pigment insoluble in the organic solvent is, for example, an acid dye or a basic dye, it is modified with an amine salt dye by reacting an organic amine compound (for example, n-propylamine, ethylhexylpropionic acid amine, etc.) It is known that the organic amine compound is reacted with a sulfonic acid group to be modified into a dye having a sulfonamide group to make it soluble in an organic solvent. These amine-modified dyes can also be used in the colored resin composition of the present invention. Examples of amine-modifiable dyes include color indexes such as Solvent Blue 2, 3, 4, 5, 6, 23, 35, 36, 37, 38, 43, 48, 58, 59, 67, 70, 78, 98, 102, 104; Basic Blue 7; Acid Blue 80, 83, 90; Examples of violet dyes include Solvent Violet 8, 9; Violet 4, 5, 14; Basic Violet 10 and the like.

  The colored resin composition of the present invention is produced by mixing and stirring the dye represented by the formula (1), the binder resin, the solvent, the photopolymerization initiator, the curing agent, the curing accelerator, and the like with a dissolver or a homomixer. The In addition, other pigments and dyes can be added as necessary, but if the pigment or dye has low solubility, a dispersion is obtained by a disperser such as a paint shaker using an appropriate dispersant, In addition to the colored resin composition, it is mixed.

  If necessary, the colored resin composition of the present invention may further contain various additives such as fillers, surfactants, thermal polymerization inhibitors, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc. Can be added. In addition, the colored resin composition of the present invention can be microfiltered with a filter or the like in order to remove foreign matters after the preparation.

  Examples of a method for producing a colored cured film for a color filter (hereinafter also simply referred to as “colored cured film”) using the colored resin composition of the present invention include a photolithography method and an inkjet method. A photosensitive colored resin composition excellent in developability containing a polymerization initiator is used, and the latter does not necessarily require a photopolymerization initiator, and a thermosetting colored resin composition containing a curing accelerator is used.

For example, when using the colored resin composition of this invention by the inkjet method etc., you may use a thermal polymerization initiator together with a photoinitiator. Examples of the thermal polymerization initiator include azo compounds and organic peroxides, such as 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), Examples include 2,2′-azobis (2-methylbutyronitrile), di-t-butyl peroxide, dibenzoyl peroxide, cumylperoxyneodecanoate, and the like.
In addition, when using a thermal polymerization initiator together, what is necessary is just to use the quantity from which the sum total of a photoinitiator and a thermal polymerization initiator becomes in the range of content of said photoinitiator.

Examples of preferred colored resin compositions in the present invention are described below. All parts and percentages are parts by mass unless otherwise specified.
(I) In 100 parts of the total solid content of the colored resin composition, 0.5 to 30 parts of the dye represented by the formula (1), 5 to 50 parts of the binder resin, 5 to 50 parts of the curing agent, and , Containing at least one of a photopolymerization initiator or a curing accelerator, in the case of a photopolymerization initiator, the content thereof is 1 to 25 parts, and in the case of a curing accelerator, 0.05 to 20 parts, Furthermore, the coloring resin composition which contains 50-10000 parts with respect to 100 parts of total solids of a solvent.
(II) The colored resin composition according to (I) above, which contains a photopolymerizable monomer as a curing agent and contains a photopolymerization initiator.
(III) The colored resin composition according to the above (I) or (II), which contains an epoxy resin as a curing agent and contains a curing accelerator.
(IV) The colored resin composition according to any one of (I) to (III), wherein X ₁ and X ₂ are methyl groups in the dye represented by formula (1).
(V) In the dye represented by the formula (1), R _{1 to} R ₂₁ are each independently a hydrogen atom, a C1 to C4 alkyl group, a sulfonic acid group, a sulfonic acid group, or a (C2 to C8) alkylsulfamoyl group. Or a di (C1-C4) alkylsulfamoyl group, and at least one of R _{1 to} R ₂₁ is a sulfonic acid group or a sulfonic acid group, described in any one of (I) to (IV) above Colored resin composition.
(VI) In the dye represented by the formula (1), R _{1 to} R ₂₁ are each independently a hydrogen atom, a C1 to C4 alkyl group, a sulfonic acid group, a sodium sulfonate group, a 2-ethylhexanesulfamoyl group, or The colored resin composition according to any one of (I) to (V) above, which is a diethylsulfamoyl group and at least one is a sulfonic acid group or a sodium sulfonate group.
(VII) The dye represented by the formula (1) is one of R _{17 to} R ₂₁ , one of which is a sulfonic acid group or sodium sulfonate group, and the remainder is a hydrogen atom, and (a) R _{1 to} R ₁₆ All are hydrogen atoms, or (b) two of R _{1 to} R ₅ are C1 to C4 alkyl groups, the remaining groups are hydrogen atoms, and two of R _{12 to} R ₁₆ are C1 to C1. Any one of the above (I) to (VI), which is a C4 alkyl group, one is a sulfonic acid group, sodium sulfonate group, 2-ethylhexanesulfamoyl group or diethylsulfamoyl group, and the remainder is a hydrogen atom The colored resin composition according to claim 1.

(VIII) The dye represented by formula (1) is one of R _{17 to} R ₂₁ , one of which is a sulfonic acid group or sodium sulfonate group, and the remainder is a hydrogen atom, and (a) R _{1 to} R ₁₆ All are hydrogen atoms, or (b) in R _{1 to} R ₁₆ , R ₁ , R ₅ , R ₁₂ and R ₁₆ are C1 to C3 alkyl groups, R ₁₄ is a hydrogen atom, sulfonic acid group, sulfone The colored resin composition according to any one of (I) to (VII) above, which is an acid base or a 2-ethylhexanesulfamoyl group, and the remainder is a hydrogen atom.
(IX) Furthermore, the pigment | dye represented by the said Formula (2) is contained, Formula 1 is contained with 1-30 parts of pigment | dyes represented by Formula (1) in 100 parts of total solids of a colored resin composition. The colored resin composition according to any one of (I) to (VIII) above, which contains 2 to 30 parts of a dye represented by
(X) R < _1a > -R < _6a > of Formula (2) is a cyclohexyl group which has a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 alkyl group as a substituent each independently, The colored resin composition according to the above (IX), wherein R _{7a to} R _20a are all hydrogen atoms.
(XI) In formula (2), R _{1a to} R _4a are C1 to C4 alkyl groups, and R _5a and R _6a are each independently a hydrogen atom, a C1 to C4 alkyl group, or a C1 to C4 alkyl group. The colored resin composition according to (X) above, wherein at least one of R _5a and R _6a is a group other than hydrogen.
(XII) The use ratio of the dye of the formula (1) and the dye of the formula (2) is such that the dye of the formula (2) is 0.5 to 3 parts relative to 1 part of the dye of the formula (1). A colored resin composition as described in (XI) above.
(XIII) The colored resin composition according to any one of (I) to (XII), further including a blue pigment at a ratio of 1 to 20 parts with respect to 1 part of the dye of formula (1).
(XIV) The blue pigment is C.I. I. The colored resin composition according to (XIII), which is CI Pigment Blue 15: 6.
(XV) The colored resin composition according to the above (I) to (XIV), wherein the binder resin is a (meth) acrylic copolymer having a weight average molecular weight of 3000 to 100,000.
(XVI) The colored resin composition according to any one of (II) to (XV), wherein the photopolymerizable monomer is a (meth) acrylic monomer.

(XVII) The colored resin composition according to the above (I) to (XVI), which contains an epoxy resin as a curing agent.
(XVIII) As a curing agent, both (meth) acrylic monomer and epoxy resin are contained, the content of epoxy resin is 10 to 150 parts with respect to 100 parts of (meth) acrylic monomer, and light The colored resin composition according to any one of (I) to (XVII) above, which contains both a polymerization initiator and a curing accelerator.
(XIX) The colored resin composition according to (XVII) or (XVIII), which contains an epoxy resin represented by the formula (3) as an epoxy resin.
(XX) In Formula (3), R _{1c to} R _19c are each independently any one of a hydrogen atom, a methyl group, an ethyl group, and a methoxy group, and at least any of R _17c , R _18c, and R _19c The colored resin composition as described in (XIX) above, which is also a methyl group.
(XXI) In the above formula (3), in R _{1c to} R _19c , R _17c , R _18c and R _19c are all methyl groups, and the remaining groups are all hydrogen atoms. (IX) to (XX) The coloring resin composition as described in any one of these.
(XXII) Among the R _{1a to} R _20a in the formula (2), R _{1a to} R _5a are ethyl groups, the others are hydrogen atoms, and Z is tristrifluoromethanesulfonylmethide, the above (IX) to (IX) XX) The colored resin composition according to any one of the above.

  Next, a method for preparing a colored cured film from the colored resin composition of the present invention will be described. First, the colored resin composition of the present invention is formed on a substrate such as a glass substrate or a silicon substrate by a method such as a spin coating method, a roll coating method, a slit and spin method, a die coating method, or a bar coating method. It is applied so as to be 1 to 20 μm, preferably 0.5 to 5 μm. Then, if necessary, it is dried under reduced pressure in a vacuum chamber at 23 to 150 ° C. for 1 to 60 minutes, preferably 60 to 120 ° C. for 1 to 10 minutes, and further in a hot plate or a clean oven. Pre-baking is performed to form a film. Next, a general photolithography method is used to irradiate radiation (for example, an electron beam or ultraviolet rays, preferably ultraviolet rays) through a predetermined mask pattern, and a surfactant aqueous solution, an alkaline aqueous solution, or a surfactant and an alkaline agent. Develop with mixed aqueous solution. Examples of the development method include a dip method, a spray method, a shower method, a paddle method, and an ultrasonic development method. Any of these may be combined. After removing the non-irradiated part by development and rinsing with water, it is usually post-baked at 130 to 300 ° C. for 1 to 120 minutes, preferably at 150 to 250 ° C. for 1 to 30 minutes. Get a membrane.

  In the above, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, etc. can be used as the surfactant. Moreover, as an alkali agent, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. can be used. In the present invention, it is preferable to use an aqueous solution containing both an alkali agent and a surfactant. Development is usually performed at 10 to 50 ° C. for 30 to 600 seconds, preferably at 20 to 40 ° C. for 30 to 120 seconds.

  The colored cured film of the present invention is useful as a color filter suitable for a solid-state imaging device used in a liquid crystal display device, an organic EL display, a digital camera or the like, and the color filter was prepared as described above. It is a blue pixel which consists of a colored cured film of this invention.

  The liquid crystal display device of the present invention is produced, for example, with a structure in which a backlight, a polarizing film, a display electrode, a liquid crystal, an alignment film, a common electrode, a color filter of the present invention, a polarizing film, and the like are laminated in this order. The organic EL display is manufactured by forming a color filter on either the upper or lower side of the multilayer organic light emitting element. The solid-state imaging device is manufactured, for example, by providing the color filter layer of the present invention on a silicon wafer provided with transfer electrodes and photodiodes, and then laminating microlenses.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In the following examples, unless otherwise indicated, “part” means “part by mass” and “%” means “% by mass”. The maximum absorption wavelength was measured using an ultraviolet spectrophotometer UV-2450 (manufactured by Shimadzu Corporation).

Example 1 (Synthesis of a dye mainly composed of Compound No. 1-1: a dye for a color filter of the present invention represented by formula (1))
A 300 ml four-necked flask was charged with 5.8 parts of Acid Red 289 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 82.5 parts of dry dimethyl sulfoxide and stirred at room temperature. To this was added 1.7 parts of oily sodium hydride (manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred at room temperature for 1.5 hours, and then iodomethane (manufactured by Tokyo Chemical Industry Co., Ltd.) while cooling the reaction solution in an ice bath. ) 75 parts was added dropwise and stirred at room temperature for 20 hours. The obtained reaction solution was poured into a mixed aqueous solution of 750 parts of water and 50 parts of 35% hydrochloric acid, and 35% hydrochloric acid was added so that the pH became 0.3. The volume after addition of hydrochloric acid was 1000 ml. To this was added 200 parts of sodium chloride, and the precipitated crystals were collected by filtration. The crystals were suspended in 200 parts of 6% hydrochloric acid and stirred at room temperature for 2 hours, and then the wet cake of crystals was collected by filtration. Next, the wet cake was suspended in 100 parts of 6% hydrochloric acid and stirred at room temperature for 1 hour, and then the crystals were collected by filtration and dried. The obtained crystals were washed with diethyl ether and hexane, then collected by filtration and dried, whereby the following compound No. 4.1 parts of the color filter dye of the present invention containing 1-1 as a main component was obtained. The maximum absorption wavelength of the dye was 543 nm (cyclohexanone).

Compound No. 1-1

Example 2 (Synthesis of dye mainly composed of Compound No. 1-3: dye for color filter of the present invention represented by formula (1))
A 300 ml four-necked flask was charged with 108 parts of chloroform and 7.4 parts of dimethylformamide and stirred well in an ice bath. To this was added dropwise 9.7 parts of thionyl chloride so that the liquid temperature was between 7 and 11 ° C., and the mixture was stirred for 30 minutes while maintaining 7 to 11 ° C. Thereafter, 15 parts of Acid Red 289 (manufactured by Tokyo Chemical Industry Co., Ltd.) was added over 10 minutes and stirred at 35 ° C. for 3 hours, and then 1.1 parts of thionyl chloride was added and stirred at 35 ° C. for 1.5 hours. did. After cooling this reaction liquid and dropping 8.9 parts of 2-ethylhexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) at 10 ° C., 23 parts of triethylamine was dropped and stirred at room temperature for 16 hours. Next, the reaction solvent was removed under reduced pressure, 53 parts of methanol was added, and the mixture was concentrated until the liquid volume became about half. To this reaction liquid, 76 parts of methanol and 5.3 parts of acetic acid were added and stirred at room temperature for 30 minutes. The obtained reaction solution was poured into 80 parts of ion-exchanged water, then 300 parts of ion-exchanged water was added, and the precipitated crystals were collected by filtration and washed with 80 parts of 50% methanol water and 50 parts of water. The obtained crystals were suspended and stirred in 100 parts of hot water at 60 ° C., filtered, washed with 50 parts of hot water at 60 ° C. and 50 parts of ion-exchanged water, and dried to obtain intermediate dye No. A crystal of 1-2 was obtained (in compound No. 1-3, a dye mainly composed of a compound in which a hydrogen atom was bonded instead of a methyl group on a nitrogen atom).
Next, intermediate dye No. 4 was added to a 500 ml four-necked flask. 6.9 parts of 1-2 crystals and 82.5 parts of dry dimethyl sulfoxide were charged and stirred at room temperature. To this was added 1.7 parts of oily sodium hydride (Wako Pure Chemical Industries, Ltd.), and the mixture was stirred at room temperature for 1.5 hours. ) 75 parts was added dropwise and stirred at room temperature for 16 hours. The reaction solution was poured into a mixed aqueous solution of 750 parts of water and 57 parts of 35% hydrochloric acid, extracted with dichloromethane, the organic layer was washed with 6% hydrochloric acid, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The obtained solid was washed with diethyl ether and hexane, then collected by filtration and dried, whereby the following compound No. 1.9 parts of the color filter dye of the present invention comprising 1-3 as a main component was obtained. The maximum absorption wavelength of the dye was 542 nm (cyclohexanone).

Compound No. 1-3

Example 3 (Synthesis of dye mainly composed of compound No. 1-4: dye for color filter of the present invention represented by formula (1))
In a 500 ml four-necked flask, 4.1 parts of a sulfofluorane compound of the following formula (100), 312 parts of methanol and 10.7 parts of N-methylaniline were charged and refluxed for 30 hours. The reaction solution was filtered at 60 ° C. to remove insoluble matters, and then the solvent was removed under reduced pressure until the reaction solution was about 70 ml, and the mixture was poured into 200 parts of 6% hydrochloric acid. Next, after adding 600 parts of water and stirring at room temperature for 30 minutes, the wet cake was collected by filtration. The wet cake was suspended in 100 parts of water and stirred at 60 ° C. for 2 hours, and then filtered again, washed with hot water at 60 ° C., and then dried to obtain the following compound No. 2.5 parts of the color filter dye of the present invention comprising 1-4 as a main component was obtained. The maximum absorption wavelength of the dye was 546 nm (cyclohexanone).

Formula (100)

Compound No. 1-4

Synthesis Example 1 (Synthesis of Dye No. 2-1: Dye Represented by Formula (2)))
2 parts of Basic Blue 7 (manufactured by Tokyo Chemical Industry Co., Ltd., decomposition temperature: 217 ° C.) represented by the following formula (101) is dissolved in 150 parts of water and stirred with 30 parts of acetonitrile in 30 parts of tristrifluoromethanesulfonium methide. A solution in which 2.1 parts of cesium salt was dissolved was added. After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried. 1.5 parts of 2-1 (compound in which the chlorine anion in formula (101) was replaced with the tristrifluoromethanesulfonylmethide anion) were obtained. The maximum absorption wavelength of the dye was 610 nm (cyclohexanone).

Formula (101)

Synthesis Example 2 (Synthesis of Dye No. 2-2: Dye Represented by Formula (2))
(I) Synthesis of Intermediate Compound 1 1-bromonaphthalene (10.0 g, 0.05 mol), 2-methylcyclohexylamine (6.0 g, 0.05 mol), sodium t-butoxide (6.5 g, 0.07 mol) ), Pd ₂ (dba) ₃ (manufactured by Tokyo Chemical Industry Co., Ltd., (trisdibenzylideneacetone) dipalladium (0), 0.003 eq. Vs. 1-bromonaphthalene) and BINAP (manufactured by Tokyo Chemical Industry Co., Ltd., (± ) -2,2′-bis (diphenylphosphino) -1,1′-ninaphthyl, 0.008 eq. To 1-bromonaphthalene) was dissolved in 120 ml of toluene and stirred at 80 ° C. for 3 hours. Then, it returned to room temperature, the reaction liquid was column-filtered, and 10.5g of compounds 1 of a following formula were obtained by depressurizingly distilling a filtrate. The yield was 91%.

Compound 1

(Ii) Synthesis of intermediate compound 2

Compound 1 (9.3 g, 0.04 mol), 4,4′-bis (diethylamino) benzophenone (11.50 g, 0.04 mol) and phosphorus oxychloride (6.0 g, 0.04 mol) obtained above were used. It was dissolved in 50 ml of toluene and reacted at 60 ° C. for 3 hours. After returning the reaction solution to room temperature, water was added for liquid separation, and the organic layer was concentrated under reduced pressure to obtain 22.8 g of Compound 2 of the following formula. The yield was 98%.

Compound 2

(Iii) Dye No. Synthesis of 2-2 Compound 2 (3.0 g, 0.005 mol) obtained above was dissolved in a mixed solution of 10 ml of water and 40 ml of methanol, and stirred, and then mixed with 3 ml of DMF and 20 ml of methanol. A solution in which 2.8 g of the cesium salt of methide was dissolved was added. After heating and stirring at 60 ° C. for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried. 3.2 g of 2-2 (compound in which the chlorine anion in compound 2 was replaced with the tristrifluoromethanesulfonylmethide anion) was obtained. The maximum absorption wavelength of the dye was 602 nm (cyclohexanone).

Synthesis Example 3 (Synthesis of epoxy resin E-1: epoxy resin represented by formula (3))
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen while trifunctional phenolic compound (TrisP-PA manufactured by Honshu Chemical Industry Co., Ltd.) 141.5 parts, epichlorohydrin 463 parts and dimethylsulfoxide 95 Part was added and dissolved under stirring, and the temperature was raised to 45 ° C. Next, after adding 41 parts of flaky sodium hydroxide over 90 minutes, the reaction was further carried out at 45 ° C. for 5 hours and at 60 ° C. for 2 hours. After completion of the reaction, the reaction mixture was washed with 500 parts of water and the aqueous layer was removed. Then, excess solvents such as epichlorohydrin were distilled off from the oil layer under reduced pressure using a rotary evaporator. To the residue, 500 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 10 parts of a 30% by weight aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour. The oil layer was washed with water until the water became neutral, and the resulting solution was depressurized using a rotary evaporator. 190 parts of epoxy resin (E-1) was obtained by distilling off methyl isobutyl ketone and the like below. The epoxy equivalent of the obtained epoxy resin is 201 g / eq. The softening point was 59 ° C.
The epoxy equivalent is a value measured according to JIS K-7236, and the softening point is measured by the ring and ball method.

Epoxy resin E-1

Synthesis Example 4 (Binder resin: Synthesis of copolymer (A))
A 500 ml four-necked flask was charged with 160 g of methyl ethyl ketone, 10 g of methacrylic acid, 33 g of benzyl methacrylate and 1 g of α, α′-azobis (isobutyronitrile), and nitrogen gas was allowed to flow into the flask for 30 minutes while stirring. Then, it heated up to 80 degreeC and stirred for 4 hours as it was at 80-85 degreeC. After completion of the reaction, the reaction mixture was cooled to room temperature to obtain a colorless, transparent and uniform copolymer solution. This was precipitated in a 1: 1 mixed solution of isopropyl alcohol and water, filtered, and the solid content was taken out and dried to obtain a copolymer (A). The obtained copolymer (A) had a polystyrene equivalent weight average molecular weight of 18000 and an acid value of 152 (mgKOH / g).

Example 4 (Preparation of colored resin composition 1: Dye No. 1-1)
C. I. Pigment Blue 15: 6 / Disperbyk-2001 (produced by Big Chemie Japan) / Solsperse 5000 / PGMEA (propylene glycol monomethyl ether acetate) = 12.0 / 8.0 / 1.0 / 79.0 (mass ratio) Mixed. Next, 400 g of 0.3 mm zirconia beads were added thereto, treated with a paint shaker for 60 minutes, and filtered to obtain a blue pigment dispersion 1. To 25 g of the blue dispersion liquid, 5.5 g of the copolymer (A) obtained in Synthesis Example 4 as a binder resin, 5.5 g of Kayarad ^RTM DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a photopolymerizable monomer, photopolymerization Irgacure ^RTM 907 (manufactured by BASF Japan) as an initiator, 1.0 g, Irgacure ^RTM OXE-02 (manufactured by BASF Japan) 0.1 g and Kayacure ^RTM DETX-S (manufactured by Nippon Kayaku Co., Ltd.) 0.5 g, Examples No. 1 obtained in dye No. 1 The colored resin composition 1 of the present invention was obtained by mixing 0.5 g of 1-1, 20 g of ethyl lactate as a solvent, and 8.6 g of cyclohexanone.

Example 5 (Preparation of colored resin composition 2: Dye No. 1-3)
Pigment No. 1-1 was changed to dye No. 1 obtained in Example 2. A colored resin composition 2 of the present invention was obtained according to Example 4 except that it was changed to 1-3.

Example 6 (Preparation of colored resin composition 3: Dye No. 1-4)
Pigment No. 1-1 was changed to the dye No. 1 obtained in Example 3. A colored resin composition 3 of the present invention was obtained in the same manner as in Example 4 except that it was changed to 1-4.

Example 7 (Preparation of colored resin composition 4: Dye No. 1-1 + Dye No. 2-1)
Dye No. 1 of Synthesis Example 1 A colored resin composition 4 of the present invention was obtained according to Example 4 except that 0.5 g of 2-1 was further added.

Example 8 (Preparation of colored resin composition 5: Dye No. 1-3 + Dye No. 2-1)
Dye No. 1 of Synthesis Example 1 A colored resin composition 5 of the present invention was obtained according to Example 5 except that 0.5 g of 2-1 was further added.

Example 9 (Preparation of colored resin composition 4: Dye No. 1-4 + Dye No. 2-2)
Dye No. of Synthesis Example 2 A colored resin composition 6 of the present invention was obtained according to Example 6 except that 0.5 g of 2-2 was further added.

Example 10 (Preparation of colored resin composition 7: Dye No. 1-1 + Dye No. 2-1)
5.5 g of copolymer (A) obtained in Synthesis Example 4 as a binder resin, 5.5 g of Kayrad ^RTM DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a photopolymerizable monomer, and Irgacure ^RTM 907 (as a photopolymerization initiator) BASF Japan) 1.0 g, Irgacure ^RTM OXE-02 (BASF Japan) 0.1 g and Kayacure DETX-S (Nippon Kayaku Co., Ltd.) 0.5 g. 1-1, 0.25 g, and dye No. 1 of Synthesis Example 1. 2-1 g of 2-1 and 20 g of ethyl lactate and 8.6 g of cyclohexanone as a solvent were mixed to obtain a colored resin composition 7 of the present invention.

Example 11 (Preparation of colored resin composition 8: Dye No. 1-3 + Dye No. 2-1)
Pigment No. 1-1 was changed to dye No. 1 of Example 2. A colored resin composition 8 of the present invention was obtained according to Example 10 except that it was changed to 1-3.

Example 12 (Preparation of colored resin composition 9: Dye No. 1-4 + Dye No. 2-1)
Pigment No. 1-1 was changed to dye No. 1 of Example 3. A colored resin composition 9 of the present invention was obtained according to Example 10 except that it was changed to 1-4.

Example 13 (Preparation of colored resin composition 10: Dye No. 1-1)
The copolymer (A) obtained in Synthesis Example 4 was changed from 5.5 g to 2.4 g, and 3.0 g of the epoxy resin E-1 obtained in Synthesis Example 3 and 1B2PZ ( A colored resin composition 10 of the present invention was obtained according to Example 4 except that 0.1 g (manufactured by Shikoku Kasei Kogyo Co., Ltd.) was further added.

Comparative Example 1 (Preparation of Comparative Resin Composition 1)
C. I. Pigment Blue 15: 6 / Disperbyk-2001 (manufactured by Big Chemie Japan) / Solsperse 5000 / PGMEA = 12.0 / 8.0 / 1.0 / 79.0 (mass ratio) and then mixed. Blue pigment dispersion 1 was obtained by adding 400 g of 3 mm zirconia beads, treating with a paint shaker for 60 minutes, and filtering. 25 g of the above blue dispersion 1 is 5.5 g of the copolymer (A) obtained in Synthesis Example 4 as a binder resin, 5.5 g of Kayrad ^RTM DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a photopolymerizable monomer, light Irgacure ^RTM 907 (manufactured by BASF Japan) as a polymerization initiator, 1.0 g of Irgacure ^RTM OXE-02 (manufactured by BASF Japan) and 0.5 g of Kayacure ^RTM DETX-S (manufactured by Nippon Kayaku Co., Ltd.), as a solvent 20 g of ethyl lactate and 8.6 g of cyclohexanone were mixed to obtain a comparative resin composition 1.

Comparative Example 2 (Preparation of Comparative Resin Composition 2)
Pigment No. Comparative resin composition 2 was obtained according to Example 4 except that 1-1 was changed to Basic Blue 7 (manufactured by Tokyo Chemical Industry Co., Ltd.).

Comparative Example 3 (Preparation of Comparative Resin Composition 3)
Pigment No. Comparative resin composition 3 was obtained in the same manner as in Example 4 except that 1-1 was changed to Acid Red 289 (manufactured by Tokyo Chemical Industry Co., Ltd.).

Comparative Example 4 (Preparation of Comparative Resin Composition 4)
Pigment No. 1-1 of 0.25 g and No. 1-1. Comparative resin composition 4 was obtained in the same manner as in Example 10 except that 2-1 was changed from 0.25 g to 0.5 g of rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.).

Comparative Example 5 (Preparation of Comparative Resin Composition 5)
Comparative resin composition 5 was obtained according to Comparative Example 4 except that Rhodamine B was changed to Acid Red 289 (manufactured by Tokyo Chemical Industry Co., Ltd.).

Comparative Example 6 (Preparation of Comparative Resin Composition 6)
Rhodamine B was added to the intermediate dye No. 2 of Example 2. A comparative resin composition 6 was obtained in the same manner as in Comparative Example 4 except that it was changed to 1-2.

Comparative Example 7 (Preparation of Comparative Resin Composition 7)
A comparative resin composition 7 was obtained in accordance with Comparative Example 4 except that Rhodamine B was changed to Acid Red 52 (manufactured by Tokyo Chemical Industry).

1. Preparation of evaluation substrate and evaluation of developability, resolution and adhesion to substrate Each of the colored resin compositions 1 to 10 of the present invention obtained above was applied on each glass substrate, and 80 ° C. X Pre-baked under conditions of 100 seconds. Subsequently, the obtained coating film was exposed through the mask which has a pattern, and the exposed part was hardened. Then, it developed with the aqueous alkali solution containing surfactant, rinsed with water, and heat-hardened at 200 degreeC for 5 minute (s). As a result, an evaluation substrate having a colored pattern was obtained.
When the evaluation substrate was used to evaluate developability, resolution, and adhesion to the substrate, the resulting pattern had a resolution of 5 μm square in line and space, and the residue and pixels were peeled off. Etc. were not confirmed. Therefore, it was found that the present invention can also be applied to color filter applications requiring high resolution for solid-state imaging devices.

2. Evaluation of spectral characteristics, heat resistance, contrast and solvent resistance In the preparation of the evaluation substrate described in 1 above, except that the mask exposure was changed to full exposure and development and rinsing were not performed, Similarly, an evaluation substrate was produced. When any one of the colored resin compositions 1 to 10 and the comparative resin compositions 1 to 6 of the present invention was used, a color filter substrate having clear color characteristics was obtained. Each evaluation was performed by the method as described below using these evaluation substrates.
The spectral characteristics were evaluated by measuring the spectral transmittance of the evaluation substrate with a spectrophotometer (Shimadzu Corporation UV-3150) and calculating the chromaticity in the XYZ color system.
The heat resistance was evaluated by measuring the spectral transmittance of the evaluation substrate before and after the heat treatment and calculating the color difference (ΔEab) before and after the heat treatment. The heat treatment was performed by exposing the obtained evaluation substrate to 200 ° C. for 120 minutes.
Contrast was measured with a contrast meter (CT-1 manufactured by Aisaka Electric Co., Ltd.) using a substrate for evaluation, and the luminance value (cd / cm ² ) when the ^two polarizing plates were parallel to each other (cd) / Cm ² ) ratio (luminance value when parallel / luminance value when orthogonal).
For solvent resistance, N-methylpyrrolidone was used as a solvent, the substrate for evaluation was immersed in the solvent, and when 30 seconds, 1 minute, and 3 minutes had elapsed, the spectral transmittance was measured, and before the solvent immersion In comparison with the spectral transmittance of the evaluation substrate, the evaluation was performed visually or by spectral color difference.
Note that N-methylpyrrolidone is used as a solvent for the material of the liquid crystal alignment film, and it is necessary that the spectral transmittance of the color filter does not change even when the color filter is immersed therein.
The spectral chromaticity evaluation results are shown in Table 3, the heat resistance evaluation results in Table 4, the contrast evaluation results in Table 5, and the solvent resistance evaluation results in Table 6, respectively.

  From the results of Table 3, when comparing the Y value, which is an indicator of brightness when the y value is fixed, the colored resin compositions 1 to 3 of the present invention are compared with the comparative resin composition 1 using a pigment as a pigment. Very good results are obtained, and it is also better than a comparative resin composition using a known dye as a pigment. The comparative resin composition 3 using a known dye as a pigment is slightly brighter than the comparative resin compositions 1 and 2, but shows a lower value than the colored resin compositions 1 to 3 of the present invention. The x value is an index of color, but if the x value becomes too large, it becomes reddish and a clear blue characteristic does not appear, so it cannot be said to be sufficient. The colored resin compositions 1 to 3 of the present invention are good because they show high brightness while maintaining a clear blue characteristic.

  From the results in Table 4, the colored resin compositions 1 to 6 of the present invention all have a spectral color difference of 4 or less, indicating good results. On the other hand, the comparative resin compositions 2 and 4 using a known dye as a pigment are remarkably poor in spectral color difference of 22 or more, and are not suitable for color filter applications requiring high reliability. The comparative resin composition 2 had relatively good spectral chromaticity results in Table 2, but the heat resistance was remarkably poor, and lightness and heat resistance were not compatible. The colored resin composition using the coloring matter of the present invention satisfies this.

From the results of Table 5, the contrast of the colored resin compositions 4 to 9 of the present invention is superior to that of the comparative resin composition 1 using a pigment as a pigment, and the comparative resin using a known dye as the pigment. It is significantly superior to compositions 4-7. The present invention is a colored resin composition suitable for next-generation color filters.

  From the results of Table 6, it can be said that the colored resin composition 10 of the present invention is excellent in solvent resistance and has a good performance capable of withstanding the color filter manufacturing process while being a colored resin composition containing a dye. . On the other hand, in Comparative resin composition 2 using a known dye as a pigment, the dye was completely eluted into N-methylpyrrolidone after 1 minute, and the colored film was completely peeled off, so the spectral transmittance was measured. I couldn't.

As described above, the colored resin composition of the present invention using the color filter pigment of the present invention has a clear blue characteristic and excellent color characteristics such as brightness and contrast, and has a color such as heat resistance and solvent resistance. It was found that it has a highly reliable color filter suitability that can withstand the filter manufacturing process. In addition, it was confirmed that even when mixed with a pigment as in Example 7, good performance was exhibited, and as in Example 10, a good contrast was exhibited by a combination with a specific other dye. As shown above, it shows a wide range of applicability, so it was found that it has high industrial value.

Claims (19)

Following formula (1)

(In Formula (1), X ₁ and X ₂ each independently represent a C1-C30 alkyl group. R _{1 to} R ₂₁ each independently represent a hydrogen atom, a C1-C30 alkyl group, or a C1-C30 alkyl group. An alkoxy group, an aromatic hydrocarbon group of C6 to C30, an aromatic heterocyclic group of C3 to C30, a halogen atom, a nitro group, a phenoxy group, a carboxy group, a carboxylic acid ester group, a carboxylic acid group, an alkoxycarbonyl group, a hydroxyl group, Represents a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid group, —SO ₂ NHR ₂₂ group or —SO ₂ NR ₂₃ R ₂₄ group, and at least one of R _{1 to} R ₂₁ is a sulfonic acid group, a sulfonic acid ester group, _{sulfonate, .R} 22 _{to R 24} represent either a -SO 2 _{NHR 22} group or _-SO 2 _NR 23 _{R 24} group is independently C1 Represents a C30 alkyl group. Sulfonate and carboxylate is a salt of a monovalent cation, a monovalent cation is Na ^+, is either K ⁺ or a quaternary ammonium cation.)
A color filter dye represented by The color filter dye according to claim _1, wherein X ₁ and X _{2 in} the formula (1) are methyl groups. R _{1 to} R ₂₁ are each independently a hydrogen atom, a C1-C4 alkyl group, a sulfonic acid group, a sulfonic acid group, a (C2-C8) alkylsulfamoyl group or a di (C1-C4) alkylsulfamoyl group. The color filter dye according to claim 2, wherein at least one of R _{1 to} R ₂₁ is a sulfonic acid group or a sulfonic acid group. Of R _{1 to} R ₂₁ , one is a sulfonic acid group or a sulfonic acid group, and (a) all the remaining groups are hydrogen atoms, or (b) four of the remaining groups are C 1 to C 1. The C4 alkyl group, further one is a sulfonic acid group, a sulfonate group, a C2 to C8 alkylsulfamoyl group or a di (C1 to C4 alkyl) sulfamoyl group, and the remainder is a hydrogen atom. Color filter dye. R _{1 to} R _{21 in} Formula (1) are each independently a hydrogen atom, a C1 to C4 alkyl group, a sulfonic acid group, a sodium sulfonate group, a 2-ethylhexanesulfamoyl group, or a diethylsulfamoyl group, and at least The color filter dye according to claim 2, wherein one is a sulfonic acid group or a sodium sulfonate group. Of R _{17 to} R ₂₁ , one is a sulfonic acid group or a sodium sulfonate group, the remainder is a hydrogen atom, and (i) all of R _{1 to} R ₁₆ are hydrogen atoms, or (ii) R 2 of _{1 to} R ₅ are C1-C4 alkyl groups, the remaining groups are hydrogen atoms, 2 of R _{12 to} R ₁₆ are C1 to C4 alkyl groups, one is a sulfonic acid group, and sulfonic acid The color filter dye according to claim 4, wherein the dye is a sodium group, a 2-ethylhexanesulfamoyl group or a diethylsulfamoyl group, and the remainder is a hydrogen atom.   The color filter which has the resin cured film colored with the pigment | dye for color filters as described in any one of Claims 2-6.   The color filter dye of the formula (1) according to any one of claims 2 to 6 is in a range of 0.5 to 10% by mass relative to the total amount of solids in the color filter resin composition. A resin composition for a color filter.   The coloring resin composition for color filters containing the pigment | dye for color filters as described in any one of Claims 1-6, binder resin, a solvent, a hardening | curing agent, and at least any one of a photoinitiator or a hardening accelerator. object. Following formula (2)

(In Formula (2), R < _1a > -R < _6a > respectively independently represents a hydrogen atom, a C1-C30 alkyl group, a phenyl group, or a benzyl group. R < _7a > -R < _20a > respectively independently represents a hydrogen atom, a halogen atom, or It represents an alkyl group of C1 -C6 .Z ^- represents an alkylsulfonyl methide anion, alkylsulfonyl imide anion, or alkyl sulfonates having higher halogenated alkyl group C1 -C10).
The coloring resin composition for color filters of Claim 9 containing the pigment | dye represented by these. Following formula (3)

(In Formula (3), R _{1c to} R _19c each independently represents a hydrogen atom, a C1 to C12 alkyl group, a C1 to C12 alkoxy group, or a halogen atom.)
The coloring resin composition for color filters of Claim 9 or 10 which contains the epoxy resin represented by these as a hardening | curing agent.   The colored resin composition for a color filter according to any one of claims 9 to 11, comprising a metal phthalocyanine pigment.   A colored cured film for a color filter, which is patterned using the colored resin composition according to any one of claims 9 to 12.   A color filter comprising the colored cured film for a color filter according to claim 13.   The liquid crystal display device and organic electroluminescent display which mount | wear with the color filter of Claim 14.   A solid-state imaging device comprising the color filter according to claim 14. In the formula (1) according to claim 1, X ₁ and X ₂ each represent a methyl group, and R _{1 to} R ₂₁ each independently represent a hydrogen atom, a C1 to C30 alkyl group, or a C1 to C30 alkoxy. Group, C6-C30 aromatic hydrocarbon group, C3-C30 aromatic heterocyclic group, halogen atom, nitro group, phenoxy group, carboxy group, carboxylate group, carboxylate group, alkoxycarbonyl group, hydroxyl group, sulfone Represents an acid group, a sulfonic acid ester group, a sulfonic acid group, —SO ₂ NHR ₂₂ group or —SO ₂ NR ₂₃ R ₂₄ group, and at least one of R _{1 to} R ₂₁ represents a sulfonic acid group, a sulfonic acid ester group, a sulfone group _acid-base, represents one of -SO 2 _{NHR 22} group or _-SO 2 _NR 23 _{R 24 group,} R 22 _{to R 24} are each independently C1~C3 Of an alkyl group, sulfonate and carboxylate groups in these are salts with monovalent cations, monovalent cations Na ^+, dye is either K ⁺ or a quaternary ammonium cation. Of R _{1 to} R ₂₁ , one is a sulfonic acid group or a sulfonic acid group, and (a) all the remaining groups are hydrogen atoms, or (b) four of the remaining groups are C 1 to C 1. A C4 alkyl group, further one is a sulfonic acid group, a sulfonate group, a (C2 to C8) alkylsulfamoyl group or a di (C1 to C4) alkylsulfamoyl group, and the remainder is a hydrogen atom. The dye according to 17,   Use of the dye according to claim 17 or 18 for producing a color filter.