WO2012053201A1

WO2012053201A1 - Colored resin composition for use in color filter, color filter, display device, and solid-state imaging element

Info

Publication number: WO2012053201A1
Application number: PCT/JP2011/005850
Authority: WO
Inventors: 聡小林; 石井　裕; 高明倉田; 秀洋新井; あさ子近藤; 諒寺西
Original assignee: 日本化薬株式会社
Priority date: 2010-10-21
Filing date: 2011-10-19
Publication date: 2012-04-26
Also published as: TW201222151A; JPWO2012053201A1; KR20130132688A

Abstract

The present invention relates to: a colored resin composition for use in a color filter, said colored resin composition containing a color-material compound represented by formula (1) (in which R₁ through R₄ each independently represent a hydrogen atom or a C_1-30 alkyl group, phenyl group, or benzyl group; R₅ through R₁₇ each independently represent a hydrogen atom, a halogen atom, or a C_1-6 alkyl group or substituted or unsubstituted amino group; and the anion Z⁻ represents a halogenoalkylsulfonyl imide anion, a halogenoalkylsulfonyl methide anion, or a halogenoalkylsulfonate anion, with the halogenoalkyl group thereof being a C_1-10 alkyl group substituted with three to six halogen atoms), a binder resin, a solvent, a polymerization initiator, and a hardener; and a color filter that has a layer obtained by curing said colored resin composition. As such, this colored resin composition can provide high-quality blue pixels for use in a color filter that has good contrast characteristics and excellent properties such as heat tolerance.

Description

[Name of invention determined by ISA based on Rule 37.2] Colored resin composition for color filter, color filter, display device and solid-state image sensor

The present invention relates to a colored resin composition for forming a blue pixel, a color filter formed using the same, a liquid crystal display device formed using the color filter, an image sensor (CCD, CMOS), an organic EL display, and the like The present invention relates to an electronic display device.

For colorization of liquid crystal display elements such as liquid crystal displays (LCD) typified by notebook computers, liquid crystal televisions, mobile phones, etc., and image sensors (CCD, CMOS) used as input devices for digital cameras, color copiers, etc. A color filter is required. As a method for producing a color filter used in these liquid crystal display devices and solid-state image sensors, there are a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, and the like. In recent years, the pigment dispersion method has become the 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 a colored ink directly on a substrate without using a mask by an ink jet printer is also performed.

Improvement of color purity, saturation, brightness, and contrast, which are characteristics required for color filters, is particularly important. By improving the brightness, the amount of light of the backlight can be suppressed and the power consumption can be reduced, so this is an environmentally necessary technology. 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, since it is necessary to increase the transmittance in order to improve the brightness, the pigment concentration must be reduced or the film thickness must be reduced. In order to achieve both of these contradictory characteristics, a method of making pigment fine particles has been performed. As micronization progresses, there is a limit to the resistance and dispersion stability, and even if the brightness is improved, the compatibility with the resistance is not achieved.

In order to solve these problems, color filters using dyes are being studied as another approach. If a dye is used, there are merits 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. However, for display bodies that require long-term reliability such as televisions, light resistance and heat resistance are necessary, but in particular, blue dyes are much less resistant than pigments. For example, Patent Documents 1 and 2 below report on color filters using triphenylmethane compounds. However, the ammonium salt of the triphenylmethane compound described therein is extremely inferior in light resistance and heat resistance, and is not at a practical level. Although phthalocyanine dyes are known to be excellent in resistance (Patent Document 3), their color characteristics are not blue, and since they are generally reddish cyan, a clear blue pixel cannot be formed. There is a need for a colored resin composition that includes a clear blue pixel and a highly durable color material that is highly reliable in a color filter, but is currently in practical use. Therefore, there is a need for a high-quality color filter that is vivid blue and excellent in durability as the next generation.

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

An object of the present invention is to provide a blue pixel of a color filter which is excellent in color characteristics such as clear contrast and excellent in heat resistance.

As a result of diligent research to solve the above-mentioned problems, the present inventors have used the above-described colored resin composition containing a specific salt of a specific triphenylmethane compound as a color material compound in a blue pixel of a color filter. The present inventors have found that the problems can be solved and have completed the present invention.

That is, the present invention relates to the inventions described in (1) to (17) below.
(1) Colored resin composition for a color filter containing a colorant compound represented by the following formula (1), a binder resin, a solvent, a polymerization initiator, and a curing agent Formula (1)

(Wherein R ₁ to R ₄ each independently represents a hydrogen atom, a C1-C30 alkyl group, a phenyl group or a benzyl group; R ₅ to R ₁₇ each independently represents a hydrogen atom, a halogen atom, C1-C6) An anion moiety Z ⁻ represents a halogenoalkylsulfonylimide anion, a halogenoalkylsulfonylmethide anion, or a halogenoalkylsulfonate anion, and each halogenoalkyl group independently represents A C1-C10 alkyl group substituted with 3 to 6 halogen atoms).
(2) The colored resin composition for a color filter according to (1), wherein the polymerization initiator is a photopolymerization initiator or a thermal polymerization initiator.
(3) The colored resin composition for a color filter according to the above (1) or (2), wherein Z ⁻ is bistrifluoromethanesulfonylimide anion, tristrifluoromethanesulfonylmethide anion or trifluoromethylsulfonate anion.
(4) The colored resin composition for a color filter according to any one of (1) to (3), wherein at least one of R ₅ to R ₁₇ is a halogen atom.
(5) The colored resin composition for a color filter according to any one of (1) to (3), wherein at least one of R ₅ to R ₁₇ is an alkylamino group.

(6) Further comprising any one or both of a metal phthalocyanine pigment and a colorant compound represented by the following formula (2): (1) to (5), any one of the following (12) and (13) Colored resin composition for color filter according to formula (2)

(Wherein R _1a to R _6a each independently represents a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a nitro group, a carboxy group, or an alkoxycarbonyl group. Y ₁ to Y) ₄ each independently represents a hydrogen atom, a C1-C12 alkyl group or an aryl group, and X ₁ to X ₅ each independently represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen atom, a nitro group, group, a phenoxy group, a carboxy group, an alkoxycarbonyl group, a sulfo group, a sulfamoyl group anion Z ^-. represents a halogenoalkyl imide anion, halogenoalkyl methide anion or halogenoalkyl sulfonate anions, each halogenoalkyl The group is independently 3-6 halogen A C1-C10 alkyl group substituted with an atom).
(7) The colored resin composition for a color filter according to the above (6), which contains a metal phthalocyanine pigment.
(8) The colored resin composition for a color filter according to the above (6), which contains both the metal phthalocyanine pigment and the colorant compound represented by the formula (2).

(9) The cured resin layer of the colored resin composition according to any one of (1) to (5) above or the colored resin for a color filter according to any one of (1) to (5) above A color filter having a cured layer of a colored resin composition for a color filter, which further contains either one or both of a metal phthalocyanine pigment or a colorant compound represented by the following formula (2) in the composition;
Formula (2)

(Wherein R _1a to R _6a each independently represents a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a nitro group, a carboxy group, or an alkoxycarbonyl group. Y ₁ to Y) ₄ each independently represents a hydrogen atom, a C1-C12 alkyl group or an aryl group, and X ₁ to X ₅ each independently represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen atom, a nitro group, group, a phenoxy group, a carboxy group, an alkoxycarbonyl group, a sulfo group, a sulfamoyl group, anion Z ^- is represents halogenoalkyl imide anion, halogenoalkyl methide anion or halogenoalkyl sulfonate anions, each halogenoalkyl The group is independently 3-6 halogen A C1-C10 alkyl group substituted with an atom).
(10) A display device comprising the color filter according to (9).

(11) A solid-state imaging device comprising the color filter according to (9).
(12) In the formula (1), R ₁ to R ₄ are each independently a hydrogen atom or a C1-C4 lower alkyl group, and R ₅ to R ₁₂ are each independently a hydrogen atom or a C1-C4 lower alkyl group, R ₁₃ to R ₁₇ are each independently a hydrogen atom, a halogen atom, or a diC1-C3 alkylamino group, and the C1-C3 alkyl group of the diC1-C3 alkylamino group may be unsubstituted or halogenated The colored resin for a color filter according to the above (2), which may be substituted with an atom or a cyano group, and Z ⁻ is a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion, or a trifluoromethylsulfonate anion Composition.
(13) In the formula (1), at least one of R ₅ to R ₁₂ is a C1-C4 lower alkyl group, the other is a hydrogen atom, at least one of R ₁₃ to R ₁₇ is a halogen atom, and the other is a hydrogen atom The colored resin composition for a color filter according to (12), which is an atom.
(14) The colored resin for a color filter according to any one of (1) to (5), (12) and (13) above, wherein in formula (1), Z 2 ^- is a tristrifluoromethanesulfonylmethide anion. Composition.
Z in (15) (2) ^- is bistrifluoromethanesulfonylimide anion, tris trifluoromethanesulfonyl methide anion or the trifluoromethyl sulfonate anion, (6) - (8), (12) and (13) The coloring resin composition for color filters as described in any one of these.
(16) In formula (2), R _1a to R _6a are each independently a hydrogen atom, Y ₁ to Y ₄ are each independently a hydrogen atom or a C1-C4 alkyl group, and X ₁ to X ₅ are each independently hydrogen. The colored resin composition for a color filter according to the above (15), which is an atom or a carboxy group.
(17) In any one of the above (6) to (8), (12) and (13), Z ⁻ in the formula (1) and the formula (2) is both a tristrifluoromethanesulfonylmethide anion. The colored resin composition for color filters as described.

The colored resin composition for a color filter of the present invention (also referred to as the colored resin composition of the present invention or the resin composition of the present invention) has high contrast quality, high quality for color filters having excellent heat resistance, etc. Blue pixels can be provided.

The colored resin composition of the present invention contains a binder resin, a solvent, a polymerization initiator (for example, a photopolymerization initiator or a thermal polymerization initiator), a curing agent, and a specific color material compound. Various additives such as colorant compounds such as pigments or dyes, surfactants, thermosetting agents, polymerization inhibitors, and ultraviolet absorbers can be contained. It is not limited to these, It can use without a restriction | limiting especially as components other than a specific color material compound.

The pixel manufacturing method using the colored resin composition of the present invention mainly includes a photolithography method and an inkjet method. A photosensitive resin composition having excellent developability using a photopolymerization initiator is used for the former, and a thermosetting resin composition is used for the latter without necessarily requiring a photopolymerization initiator.

The specific color material compound used in the present invention is a specific salt of the triphenylmethane compound represented by the formula (1).
In R ₁ to R ₄ of the above formula (1), examples of the C1-C30 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 1-methylpropyl group (s-butyl group), Isobutyl 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 Group, isotricosyl group, isotetracosyl group, isopentacosyl group, isohexacosyl group, isoheptacosyl group, isooctacosyl group, isononacosyl group, isotriacont Group, 1-methylhexyl group, 1-ethylheptyl group, 1-methylheptyl group, 1-cyclohexylethyl group, 1-heptyloctyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexene Xyl, 2,6-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,3-dimethylcyclo Examples include xyl group, 3,3,5-trimethylcyclohexyl group, 4-t-butylcyclohexyl group, 2-ethylhexyl group, 1-adamantyl group, and 2-adamantyl group.

When R ₁ to R _{4 in} the formula (1) are a phenyl group or a benzyl group, they may have a substituent. Examples of the substituent include (i) methyl group, ethyl group, propyl group, isopropyl group, (ii) (C1-C5) alkyl group such as butyl group, isobutyl group, t-butyl group, pentyl group, and the like (iii) ) Halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, (iv) sulfonic acid group, (v) methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, hexyloxy group, etc. (C1-C6) alkoxy groups, (vi) hydroxy (C1-C5) alkyl groups such as hydroxyethyl groups, hydroxypropyl groups, (vii) methoxyethyl groups, ethoxyethyl groups, ethoxypropyl groups, butoxyethyl groups (C1 -C5) hydroxy (C1-C5) such as alkoxy (C1-C5) alkyl group, (viii) 2-hydroxyethoxy group (X) alkoxy groups such as (ix) 2-methoxyethoxy group and 2-ethoxyethoxy group (C1-C5) alkoxy group, and (x) sulfo groups such as 2-sulfoethyl group, carboxyethyl group and cyanoethyl group, (C1-C3) alkyl group (preferably ethyl group) substituted with a carboxy group or a cyano group.
In R ₁ to R ₄ of the formula (1), examples of a preferable group include a hydrogen atom or a C1-C6 alkyl group, and in a more preferable aspect, both R ₁ and R ₂ are C1. This is the case where each is a —C6 alkyl group, one of which is a hydrogen atom and the other is a C1-C6 alkyl group, and both R ₃ and R ₄ are the same as both R ₁ and R ₂ .

In R ₅ to R ₁₇ of the formula (1), examples of the C1-C6 alkyl group include 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, and a cyclohexyl group. Examples include xyl group, hydroxypropyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group and the like.

In R ₅ to R ₁₇ in the formula (1), examples of the substituted or unsubstituted amino group include an unsubstituted amino group and an alkylamino group. Among these, an alkylamino group is preferable, and either a monoalkylamino group or a dialkylamino group may be used. The alkyl group in the alkylamino group has the same meaning as the alkyl in R ₁ to R ₄ described above, but an unsubstituted C1-C6 alkyl group, a halogeno C1-C6 alkyl group or a cyano C1-C6 alkyl group is preferred. The alkylamino group is preferably a dimethylamino group, a diisobutylamino group or a dicyanoethylamino group.
In R ₅ to R ₁₇ in formula (1), each independently represents a hydrogen atom; a chlorine atom; a C1-C6 alkylamino group which may be substituted with a cyano group (preferably an optionally substituted group with a cyano group). A mono or di C1-C6 lower alkylamino group, more preferably a mono or di C1-C4 lower alkylamino group optionally substituted with a cyano group; or an unsubstituted C1-C6 alkyl group (preferably an unsubstituted C1-C4 lower alkyl group, more preferably methyl group) is preferred.
In R ₅ to R ₁₇ in formula (1), at least one of them is preferably a halogen atom (more preferably a chloro atom) or an alkylamino group. In this case, the remaining group may be any of the above-mentioned groups other than a halogen atom or an alkylamino group, but each independently represents a hydrogen atom or a C1-C4 lower alkyl group, as compared with the case of 7 to 11 hydrogen atoms. preferable.
Among R ₅ to R _{17 in} the formula (1), R ₅ to R ₁₂ are preferably each independently a hydrogen atom or a C1-C4 lower alkyl group, and among R ₅ to R ₁₂ , More preferably, 2 or 4 are C1-C4 lower alkyl groups and the remaining groups are hydrogen atoms. In these cases, R ₁₃ to R ₁₇ are preferably each independently a hydrogen atom, a halogen atom, a C1-C4 lower alkyl group or a mono- or di-C1-C4 lower alkylamino group optionally substituted with a cyano group. More preferably, at least one of R ₁₃ to R ₁₇ is a halogen atom (preferably a chloro atom), and the other is a hydrogen atom.

Examples of the halogen atom in the above formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The anion Z in Formula (1) ^- represents a halogenoalkyl imide anion, halogenoalkyl methide anion or halogenoalkyl sulfonate anions, each halogenoalkyl groups are independently 3-6 halogen atoms A substituted C1-C10 alkyl group; The halogen atom in the group is preferably a fluorine atom.
Preferable examples of Z ⁻ include bistrifluoromethanesulfonylimide anion, tristrifluoromethanesulfonylmethide anion, and trifluoromethylsulfonate anion. Among these, tristrifluoromethanesulfonylmethide anion is more preferable.
As a preferable compound represented by the above formula (1), a compound in which at least one of R ₅ to R ₁₇ (preferably at least one of R ₁₃ to R ₁₇ ) is a halogen atom can be given.
As another preferred compound represented by the above formula (1), at least one of R ₅ to R ₁₇ (preferably at least one of R ₁₃ to R ₁₇ ) is substituted with a cyano group. And a compound that is an alkylamino group (preferably a mono- or di-C1-C4 alkylamino group optionally substituted with a cyano group).
In the preferred compounds of the above formula (1), it is more preferred when Z ⁻ is a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion or a trifluoromethylsulfonate anion.

In the above formula (1), as one of the more preferred compounds, R ₁ to R ₄ are each independently a hydrogen atom or a C1-C4 lower alkyl group (preferably, all of R ₁ to R ₄ are hydrogen atoms, or Any one of R ₁ and R ₂ and R ₃ and R ₄ is a hydrogen atom and the other is a C1-C4 lower alkyl group), R ₅ to R ₁₂ are each independently a hydrogen atom or a C1-C4 lower alkyl group ( Preferably at least one, more preferably 2 or 4 are C1-C4 lower alkyl groups and the others are hydrogen atoms), R ₁₃ to R ₁₇ are each independently a hydrogen atom, a halogen atom (preferably a chloro atom), or A di-C1-C4 lower alkylamino group, wherein the C1-C4 lower alkyl group of the di-C1-C4 lower alkylamino group is unsubstituted or is a halogen atom or a cyano group. Examples of the compound may be substituted, and Z 2 ^- is a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion, or a trifluoromethylsulfonate anion (preferably a tristrifluoromethanesulfonylmethide anion). . In the compound, at least one (preferably 2 or 4) of R ₅ to R ₁₂ is a C1-C4 lower alkyl group, the other is a hydrogen atom, and at least one of R ₁₃ to R ₁₇ is a halogen atom (preferably Is more preferably a compound in which one or two are halogen atoms, more preferably the halogen atom is a chloro atom, and the others are hydrogen atoms.

Further preferred compounds are those in which all of R ₁ to R ₄ are hydrogen atoms, or _one of R ₁ and R ₂ and R ₃ and R ₄ is a hydrogen atom and the other is a C1-C4 lower alkyl group (preferably R ₅ to R ₁₂ are two of R ₅ and R ₁₀ or four of R ₅ , R ₈ , R ₁₀ and R ₁₁ are C1-C4 lower alkyl groups (preferably methyl groups). The other is a hydrogen atom, one or two of R ₁₃ to R ₁₇ are a halogen atom, more preferably a chloro atom, the other is a hydrogen atom, Z ⁻ is a bistrifluoromethanesulfonylimide anion, tristrifluoromethanesulfonylmethide An anion, or a compound that is a trifluoromethylsulfonate anion, preferably a tris trifluoromethanesulfonyl metide anion.
As the most preferred compounds, all of R ₁ to R ₄ are hydrogen atoms, or any _one of R ₁ and R ₂ and R ₃ and R ₄ is a hydrogen atom and the other is an ethyl group, and R ₅ to R ₁₂ are 2 of R ₅ and R ₁₀ or 4 of R ₅ , R ₈ , R ₁₀ and R ₁₁ are methyl groups and the other is a hydrogen atom, 1 or 2 of R ₁₃ to R ₁₇ are chloro atoms, The other is a compound in which a hydrogen atom and Z 2 ⁻ are tristrifluoromethanesulfonylmethide anions.
In the above, when one or two of R ₁₃ to R ₁₇ are a halogen atom (preferably a chloro atom), preferably either one of R ₁₃ or R ₁₇ is a halogen atom (preferably a chloro atom), Alternatively, both R ₁₃ and R ₁₄ or R ₁₃ and R ₁₇ are halogen atoms (preferably chloro atoms).
The most preferred compound is Compound 16 in Table 1 below.

Although the specific example of the color material compound represented by Formula (1) is shown in Table 1, this invention is not limited to these.
Table 1

In Table 1, the numbers in the section of substituent R indicate R ₁ to R ₁₇ respectively, Me is a methyl group, Et is an ethyl group, n-Bu is a normal butyl group, i-Bu is an isobutyl group, EtCN represents a cyanoethyl group, EtCl represents a chloroethyl group, Bz represents a benzyl group, Ph represents a phenyl group, and the substituents on the amino group of the alkylamino group of R ₁₅ are also synonymous. Further, when Z ⁻ is α, it represents a tristrifluoromethanesulfonylmethide anion, when β is bistrifluoromethanesulfonylimide anion, and when γ represents trifluoromethylsulfonate anion.

In the present invention, an embodiment in which the metal phthalocyanine pigment described later together with the color material compound represented by formula (1) is used in combination with the color material compound represented by formula (1) may be preferable in terms of heat resistance. It is one of. There are no particular limitations on the metal phthalocyanine pigment, but copper phthalocyanine pigments such as Pigment Blue 15: 6 and Pigment Violet 23 are preferred because of their good hue and resistance.
Moreover, in this invention, the aspect which uses together the color material compound represented by said Formula (2) with the color material compound of Formula (1), or the color material compound of Formula (1), and the said metal phthalocyanine compound. Is also a preferred embodiment.
In the colorant compound represented by the formula (2), R _1a to R _6a each independently represent a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a nitro group, a carboxy group, An alkoxycarbonyl group is preferred, and all of R _1a to R _6a are preferably hydrogen atoms. Y ₁ to Y ₄ each independently represents a hydrogen atom, a C1-C12 alkyl group or an aryl group, and either Y ₁ and Y ₂ or Y ₃ and Y ₄ or both are C1-C12 alkyl groups (preferably Is preferably a C1-C4 alkyl group. X ₁ to X ₅ are each independently a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen atom, a nitro group, a phenoxy group, a carboxy group, an alkoxycarbonyl group, a carboxamide group, a sulfo group, or a sulfamoyl group. Each of X ₁ to X ₅ may be the same or different. The anion Z ⁻ represents a halogenoalkylsulfonylimide anion, a halogenoalkylsulfonylmethide anion, or a halogenoalkylsulfonate anion, and each halogenoalkyl group is independently 3 to 6 halogen atoms (preferably a fluorine atom). A C1-C10 alkyl group substituted with a 3 to 6 halogen atom (preferably chloro atom) substituted C1-C10 alkylsulfonylmethide anion.

Examples of the halogen atom of the formula (2) include the same ones as described in the formula (1), including preferable ones.
Examples of the alkyl group of the formula (2) include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, t-butyl group, iso-butyl group, n- Examples thereof include C1-C12 alkyl groups such as a pentyl group, an n-hexyl group, an n-octyl group, a 2-ethylhexyl group, and a cyclohexyl group. These alkyl groups may have a substituent, and 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 methoxyethyl group, Examples include ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, carbamoyl group, carboxy group and the like.

Examples of the alkoxy group of the formula (2) include an alkoxy group having the same C1-C12 alkyl group as the above alkyl group, and also an alkoxycarbonyl group having a C1-C12 alkyl group in the case of an alkoxycarbonyl group. Is mentioned.

Examples of the aryl group of the formula (2) include aromatic hydrocarbon residues such as phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, benzopyrenyl group; pyridyl group, pyrazyl group, pyrimidyl group, quinolyl group, An aromatic heterocyclic residue such as an isoquinolyl group, a pyrrolyl group, an indolenyl group, an imidazolyl group, a carbazolyl group, a thienyl group, and a furyl group. These aryl groups may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a sulfo group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, and a cyano group.

The anion moiety Z ⁻ of the colorant compound represented by the formula (2) is the same as described in the formula (1), and specific examples thereof include bistrifluoromethanesulfonylimide anion, tristrifluoromethanesulfonylmethide anion. , Trifluoromethylsulfonate anion, and nonafluorobutylsulfonate anion, and tristrifluoromethanesulfonylmethide anion is particularly preferable.
As the preferred colorant compound represented by the formula (2), all of R _1a to R _6a are hydrogen atoms, and either Y ₁ and Y ₂ or Y ₃ and Y ₄ or both of them are C1-C12. An alkyl group (preferably a C1-C4 alkyl group), and any one of X ₁ to X ₅ is a carboxy group, an alkoxycarbonyl group (preferably a C1-C4 alkoxycarbonyl group) or a carboxamide group (preferably a benzylaminocarbonyl group) or a hydroxy-substituted are also be C1-C4-lower alkylaminocarbonyl group), the other is a hydrogen atom, Z ^- can be exemplified compound is tris trifluoromethanesulfonyl methide anion.
More preferable examples of the colorant compound represented by the formula (2) include that all of R _1a to R _6a are hydrogen atoms, and all of Y ₁ to Y ₄ are C1-C4 alkyl groups (preferably ethyl groups). , X ₁ is a carboxy group, X 2 _~ X ₅ is a hydrogen atom, Z ^- can be exemplified compound is tris trifluoromethanesulfonyl methide anion.

Specific examples of the colorant compound represented by the formula (2) are shown in the following Table 2-1 and Table 2-2, but the present invention is not limited to these.

Table 2-1.

Table 2-2

The coloring material compound represented by the formula (1) or (2) used in the colored resin composition of the present invention is disclosed in, for example, Yutaka Hosoda “Theoretical Manufacturing Dye Chemistry” (pages 373 to 375) published by Gihodo Co., Ltd. is obtained in the described known synthetic methods, anion Z ^- is purchased commercially chlorine anion, can also be synthesized by salt plus the corresponding salt or acid exchange.

When the colorant compound in the present invention is synthesized by salt exchange, for example, the colorant compound in which the anion portion Z ⁻ is a chlorine anion is reacted with a reaction solvent (for example, water, methanol, ethanol, isopropanol, acetone, N, N— Water-soluble polar solvents such as dimethylformamide (hereinafter abbreviated as DMF), N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), and the like. These solvents may be used alone or in combination. It can be easily obtained by adding about 0.5 to 3 equivalents of the corresponding salt or acid, stirring at a predetermined temperature (for example, 0 to 100 ° C.), and collecting the precipitated crystals by filtration.

Included in 100 parts by mass of the total solid content of the colored resin composition of the present invention (referring to the total amount of solid content including a colorant compound, a binder resin, a curing agent, etc. excluding the solvent. The same shall apply hereinafter). The content of the colorant compound represented by the formula (1) is preferably 0.1 to 60 parts by mass, preferably 2 to 30 parts by mass, more preferably 3 to 30 parts by mass. In some cases, the coloring material according to the present invention contains the coloring material compound of the formula (1) in an amount of 2 to 10% by mass, more preferably about 3 to 10% by mass in the total solid content of the colored resin composition of the present invention. A resin composition is more preferable.
When there is too much content of the color material compound represented by said Formula (1), the problem of precipitation or aggregation will generate | occur | produce, or the adhesiveness with a board | substrate will be reduced because of insufficient hardening. When the content is too small, there is a tendency that sufficient color purity cannot be obtained as color characteristics.

When the solubility of the colorant compound represented by the formula (1) in the colored resin composition is low, it is dispersed using a dispersant, a dispersion aid or the like in the same manner as a pigment which is an optional component described later. May be. Two or more colorant compounds represented by the formula (1) may be mixed or used alone.
Further, other dyes and pigments may be mixed. In addition, since the present invention relates to a blue pixel, it is also desirable to use a known blue dye or violet dye, or a combination with a blue pigment or a violet pigment, and particularly, the above-described metal phthalocyanine pigment (preferably a copper phthalocyanine pigment) or / and The colored resin composition of the present invention in which the color material compound represented by the formula (2) is used in combination is one of preferred embodiments. The content of the metal phthalocyanine pigment (preferably copper phthalocyanine pigment) or the color material compound represented by the formula (2) is 0 to 30 in the total solid content of the colored resin composition of the present invention. It is about mass%. The total amount with the colorant compound represented by the formula (1) is usually about 2 to 60% by mass, more preferably about 10 to 30% by mass.
When a metal phthalocyanine pigment (preferably a copper phthalocyanine pigment) is used in combination, the content thereof is usually about 5 to 30% by mass, preferably 7 to 20% by mass in the total solid content of the colored resin composition of the present invention. It is. When the colorant compound of the formula (2) is used in combination, its content is usually about 0.5 to 10% by mass, preferably 1 to 7% in the total solid content of the colored resin composition of the present invention. % By mass.

As the binder resin used in the present invention, a resin having the following properties is preferable.
That is,
(I) to function as a dispersant or a dispersion aid for dispersion stability during dispersion of the pigment or water-insoluble dye;
(Ii) When used in a photolithography method, it is soluble in an alkaline developer used in a development processing step when producing a color filter,
(Iii) Furthermore, in order to form a good fine pattern, a polymerization initiator (for example, a photopolymerization initiator and / or a thermal polymerization initiator) and a curing agent (for example, a polymerizable monomer, etc.) contained in the colored resin composition of the present invention. More specifically, it has excellent curing characteristics together with a photopolymerizable monomer or a thermally polymerizable monomer),
It is.
The colored resin composition of the present invention obtained by blending the binder resin includes a polymerization initiator (for example, a photopolymerization initiator or a thermal polymerization initiator) contained therein, a polymerizable monomer (a photopolymerizable monomer or / and Thermally polymerizable monomer), colorant compound represented by formula (1), compatibility with constituent materials such as pigment dispersions, etc., and not stable so as not to cause precipitation or aggregation during storage or use Don't be.
When the colored resin composition of the present invention is used in the ink jet method, alkali solubility is not particularly required, and therefore a resin having good compatibility with other colorant compounds and additives may be selected.

A known resin can be used as the binder resin. Preferably, a homopolymer of an ethylenically unsaturated monomer having one or more carboxy groups / or hydroxyl groups (hereinafter also referred to as a carboxy group-containing unsaturated monomer or a hydroxyl group-containing unsaturated monomer) described later or the ethylenically unsaturated monomer Copolymerizable copolymer with other ethylenically unsaturated monomer having aromatic hydrocarbon group or aliphatic hydrocarbon group (hereinafter also referred to as other unsaturated monomer), usually copolymer is preferred .
In addition, those having an epoxy group at the side chain or terminal of these polymers, epoxy acrylate resin to which acrylate is added, and the like can also be used.
The above-described monomers used for the production of the binder resin may be used alone or in combination of two or more to form a binder resin.

As the carboxy group-containing unsaturated monomer that can be used in the present invention,
(I) Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
(Ii) unsaturated dicarboxylic acids (anhydrides) such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid;
(Iii) Trivalent or higher unsaturated polycarboxylic acids (anhydrides),
(Iv) 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2-acryloyloxyethyl 2-hydroxyethylphthalic acid, etc. .
These ethylenically unsaturated monomers having a carboxy group can be used alone or in admixture of two or more. Among these, (meth) acrylic acid is more preferable.

Examples of the hydroxyl group-containing unsaturated monomer that can be used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 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-hydroxy Hexyl (meth) acrylate, 4-hydroxyhexyl (meth) acrylate, 5-hydroxy-3-methyl-pentyl (meth) acrylate, cyclohexane-1,4-dimethanol-mono (meth) acrylate, etc. C1-C8 glycol (mono) (meth) acrylate; C3-C6 triol (mono or di) (meth) acrylate such as glycerin monomethacrylate; 2- (2-hydroxyethyloxy) ethyl (meth) acrylate, polyethylene glycol mono ( Hydroxyl-terminated polyalkylene glycol mono (meth) acrylates (preferably poly C1-C4 alkylene glycol mono (meth) acrylates) such as (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) monomethacrylate, etc. And (hydroxy) -containing (meth) acrylates. These ethylenically unsaturated monomers having a hydroxyl group can be used alone or in admixture of two or more. As the ethylenically unsaturated monomer having a hydroxyl group, the above hydroxyl group-containing (meth) acrylate is usually preferable, and hydroxy C1-C6 (meth) acrylate is more preferable.

Examples of the other unsaturated monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, Aromatic vinyl compounds such as 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, benzyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, o-Phenylpheno Unsaturated carboxylic acid esters such as luglycidyl ether (meth) acrylate, o-phenylphenol (meth) acrylate hydroxyethylated product, phenoxyethyl (meth) acrylate (preferably phenyl group-containing C1-C4 alkyl (meth) acrylate, more preferably Is phenyl or phenoxy substituted C1-C4 alkyl (meth) acrylate); cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, norbornylmethyl (meth) acrylate, phenyl Norbornyl (meth) acrylate, cyanonorbornyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, menthyl ( (Meth) acrylate, fentyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, tricyclo [5.2.1.02,6] dec-8-yl = (meth) acrylate, tricyclo [5.2.1.02,6] Deca-4-methyl = (meth) acrylate, cyclodecyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, t-butylcyclohexyl (meth) acrylate and other alicyclic skeleton-containing compounds (preferably C5 -C10 aliphatic ring-containing (meth) acrylate, more preferably C5-C10 aliphatic ring (meth) acrylate);

Methoxy polyethylene glycol monomethacrylate, Lauroxy polyethylene glycol mono (meth) acrylate, Octoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, Nonylphenoxy polyethylene glycol monoacrylate, Nonylphenoxy polypropylene glycol monoacrylate, Allyloxy polyethylene glycol-polypropylene glycol mono Alkyl-terminated polyalkylene glycol mono (meth) acrylates such as (meth) acrylates (preferably C1-C10 alkyl-terminated poly C2-C4 alkylene glycol (meth) acrylates); 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2- Aminopropyl acrylate, 2-aminopropyl methacrylate Unsaturated carboxylic acid aminoalkyl esters such as 3-aminopropyl acrylate and 3-aminopropyl methacrylate (preferably amino C1-C4 alkyl (meth) acrylate); glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meta ) Acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and unsaturated carboxylic acid glycidyl esters such as 4-hydroxybutyl (meth) acrylate glycidyl ether (preferably epoxy group-containing (meth) acrylate, epoxy-containing C1) -C6 aliphatic (meth) acrylate); vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc .; vinyl methyl ether, vinyl ethyl ether, allyl glycol Unsaturated ethers such as sidyl ether and methacryl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide, N-phenylmaleimide, N- Unsaturated amides or unsaturated imides such as cyclohexylmaleimide, N- (meth) acryloylphthalimide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, maleimide; 1,3-butadiene, isoprene Aliphatic conjugated diene compounds such as chloroprene; polystyrene, polymethyl acrylate, polymethyl methacrylate, poly n-butyl acrylate, poly n-butyl methacrylate, polysilico And a macromonomer having a monoacryloyl group or a monomethacryloyl group at the end of a polymer molecular chain such as a polymer. These other unsaturated monomers can be used alone or in admixture of two or more.
Among these, as other unsaturated monomers, preferred are phenyl group-containing C1-C4 alkyl (meth) acrylate, C5-C10 aliphatic ring-containing (meth) acrylate, C1-C10 alkyl-terminated poly C2-C4 alkylene. (Meth) acrylates such as glycol (meth) acrylate, amino C1-C4 alkyl (meth) acrylate, and epoxy group-containing (meth) acrylate. More preferably, it is a C1-C4 alkyl (meth) acrylate optionally substituted with a phenyl group or a C5-C10 aliphatic ring-containing (meth) acrylate, and more preferably C1 optionally substituted with a phenyl group -C4 alkyl (meth) acrylate. Most preferred is benzyl acrylate.

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

The binder resin contained in the colored resin composition of the present invention is a (meth) acrylic acid copolymer resin which is a copolymer of (meth) acrylic acid (preferably methacrylic acid) and a monomer copolymerizable therewith. More preferably, a copolymer ((meth) acrylic acid- (meth) acrylate copolymer) of (meth) acrylic acid (preferably methacrylic acid) and a (meth) acrylate compound (including a hydroxyl group-containing (meth) acrylate) is more preferable. It is also called a polymer). The copolymer as the binder resin is preferably a copolymer having an acid value of 10 to 300 (mgKOH / g) and / or a hydroxyl value of 10 to 200 (mgKOH / g). More preferred is a copolymer having an acid value of about 50 to 250, more preferably about 100 to 200.
The molecular weight only needs to play a role as a binder resin, and the weight average molecular weight (Mw) (polystyrene conversion) is usually about 2000 to 400,000, preferably about 3000 to 100,000, more preferably about 5000 to 70000, More preferably, it is about 8000 to 40,000.
The ratio of both monomers in the (meth) acrylic acid- (meth) acrylate copolymer is not particularly limited, but considering developability, the (meth) acrylic acid: copolymerizable monomer (preferably ( The (meth) acrylate compound) is about 1: 0.5 to 1:10, preferably about 1: 1 to 1: 5.
Examples of the (meth) acrylate compound include the hydroxyl group-containing (meth) acrylate and the other (meth) acrylates described above. As the (meth) acrylate compound, C5-C10 aliphatic ring-containing (meth) acrylate or C1-C4 alkyl (meth) acrylate optionally substituted with the phenyl group is more preferable, and benzyl (meth) acrylate is more preferable. .
More preferable (meth) acrylic acid- (meth) acrylate copolymers include (meth) acrylic acid and a C1-C4 alkyl (meth) acrylate optionally substituted with a phenyl group (preferably benzyl (meth) acrylate). Or a copolymer of (meth) acrylic acid and a C5-C10 aliphatic ring-containing (meth) acrylate, even if it is a copolymer consisting only of both, it is within the range where there is no problem. Other copolymer components may be included (for example, in the range of 0 to 20 mol%, preferably 0 to 10 mol%, more preferably 0 to 5 mol%).
In the present invention, expressions such as “(meth) acrylic acid” are used to mean acrylic acid or methacrylic acid, or both. For example, (meth) acrylate is used in the meaning of acrylate or / and methacrylate.

Generally, when dispersing a pigment, a dispersant and a dispersion aid are used. Therefore, when the resin composition of the present invention contains a pigment, the resin composition of the present invention preferably contains a dispersant, or a dispersant and a dispersion aid.
Examples of the dispersant include a pigment-based dispersant having a good adsorptivity to the pigment, a resin-based dispersant, a surfactant, and the like. In the present invention, when a pigment is used in combination, it is preferable to use them. . For example, as a technique for dispersing a pigment using a dye-based dispersant, a method of mixing a sulfonated pigment or a metal salt thereof as described in Patent Document 4 with a pigment, or a substituted aminomethyl derivative is mixed with a pigment. Methods and the like are known as known techniques. Resin-based dispersants include nonpolar nonionic ones, but polymer resins having acid value, amine value, etc. that give good pigment adsorbability are common, such as acrylic resin, polyurethane resin, polycarboxylic acid Examples include acids, polyamide resins, and polyester resins. Specific examples thereof include ED211 (manufactured by Enomoto Kasei Co., Ltd.), Ajisper ^RTM PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.), Solsperse ^RTM 71000 (manufactured by Avicia Co., Ltd.), and the like.
The content of the dispersant in the resin composition of the present invention is about 0 to 30% by mass, preferably about 0 to 20% by mass, based on the total solid content.

The binder resin (copolymer) used in the present invention can be a commercially available product or can be synthesized.
When manufacturing this binder resin, 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 use ratio of the polymerization initiator is 0.01 to 25 parts by mass with respect to 100 parts by mass in total of all monomers used for the synthesis of the copolymer. When synthesizing a copolymer, it is preferable to use an organic solvent described below. The organic solvent is preferably one having sufficient dissolving power for the monofunctional monomer or polymerization initiator used. The reaction temperature when synthesizing the copolymer is preferably 50 to 120 ° C., particularly preferably 80 to 100 ° C. The reaction time is preferably 1 to 60 hours, more preferably 3 to 20 hours.
The copolymer as the binder resin is preferably a copolymer having an acid value of 10 to 300 (mgKOH / g) and / or a hydroxyl value of 10 to 200 (mgKOH / g).
When the acid value or hydroxyl value is 10 or less, developability is lowered.
The weight average molecular weight (Mw) of the copolymer is preferably from 2,000 to 400,000, more preferably from 3,000 to 100,000. When the weight average molecular weight is 2000 or less, or 400000 or more, sensitivity, developability and the like are lowered.

In this invention, the said binder resin can be used individually or in mixture of 2 or more types.
The content of the binder resin in the present invention is usually 0.5 to 99 parts by mass, preferably 5 to 50 parts by mass, in 100 parts by mass of the total solid content of the colored resin composition. In this case, if the content of the binder resin is less than 0.5 parts by mass, the alkali developability may be lowered, or problems such as scumming or film residue in areas other than the area where pixels are formed may occur. is there.

Examples of the curing agent used in the present invention include a light or thermal polymerization 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 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, dipentaerythritol hexa (Meth) acrylate, glycerol (meth) acrylate, bisphenol-A type epoxy di (meth) acrylate, bisphenol-F type epoxy Sidi (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, Kayrad RP-1040 ( Nippon Kayaku Co., Ltd.), Kayrad DPCA-30 (Nihon Kayaku Co., Ltd.), UA-33H (Shin Nakamura Chemical Co., Ltd.), UA-53H (Shin Nakamura Chemical Co., Ltd.), M 8060 (manufactured by Toagosei Co., Ltd.); TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.), TMMP (manufactured by Sakai Chemical Industry Co., Ltd.), PEMP (manufactured by Sakai Chemical Industry Co., Ltd.), DPMP (Sakai Chemical Industry Co., Ltd.) As an epoxy resin, Nippon Kayaku Co., Ltd. products NC-6000, NC-3000, EOCN-1020, XD-1000, EPPN-501H, BREN-S, NC-7300L, Daicel Chemical Co., Ltd. Celoxite 2021P, EHPE3150, Cyclomer M100, Epolide PB3600, Japan Epoxy Resins Co., Ltd. Epicoat 828, Epicoat YX8000, Epicoat YX4000, Silaace S510 (manufactured by Chisso Corporation), TEPIC (manufactured by Nissan Chemical Industries, Ltd.), etc .; Mela The emissions curing agent and the like methylolated melamine and Mw-30 (manufactured by Sanwa Chemical) is. These can be used individually or in mixture of 2 or more types. As the polymerizable monomer preferable as the curing agent, a polyfunctional (meth) acrylate compound is preferable, and a tri- to hexafunctional (meth) acrylate compound is more preferable. Examples of the tri- to hexa-functional (meth) acrylate compound include pentaerythritol tri- or tetra (meth) acrylate or dipentaerythritol (tri-hexameth) acrylate.
The content thereof is 1 to 80 parts by mass, preferably 10 to 60 parts by mass, more preferably 20 to 60 parts by mass, and optionally 5 to 30 parts per 100 parts by mass of the total solid content of the colored resin composition. A mass part may be sufficient.

The colorant that can be used in combination with the colored resin composition of the present invention preferably has a spectral characteristic suitable for a color filter, and can be appropriately selected from dyes, organic pigments, and inorganic pigments. It can also be used in combination of more than one species. The content thereof is 0 to 60 parts by mass, preferably 0 to 30 parts by mass, and preferably 5 to 30 parts by mass in 100 parts by mass of the total solid content of the colored resin composition. These various pigments and dyes are specifically described below.

The organic pigment that can be used in combination with the present invention is not particularly limited as long as it has spectral characteristics suitable for a color filter. For example, anthraquinone, phthalocyanine, triphenylmethane, benzimidazolone, quinacridone, Azo chelate, azo, isoindoline, isoindolinone, pyranthrone, indanthrone, anthrapyrimidine, dibromoanthanthrone, flavanthrone, perylene, perinone, quinophthalone, thioindigo, dioxazine, Examples include quinacridone-based and xanthene-based pigments; lake pigments obtained by insolubilizing acid dyes, basic dyes, direct dyes, and the like with respective precipitants, and dyed lake pigments. More specifically, the color index, for example, 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, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29 31, 32, 37, 39, 42, 44, 47, 49, 50; Pigment Violet 3, 4, 27, 39, and the like. In particular, metal phthalocyanine pigments such as CI Pigment Blue 15: 6 and CI Pigment Violet 23 are more preferable in terms of hue and resistance.

The inorganic pigment that can be used in combination with the present invention is not particularly limited. For example, composite metal oxide pigments, carbon black, black low-order titanium oxide, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, red rose, ultramarine blue , Bitumen, chromium oxide, antimony white, iron black, red lead, zinc sulfide, cadmium yellow, cadmium red, zinc, manganese purple, cobalt purple, barium sulfate, magnesium carbonate and other metal oxides, metal sulfides, sulfates, Metal hydroxide, metal carbonate, etc. are mentioned.

The dye that can be used in the present invention is not particularly limited, and examples thereof include acid dyes, basic dyes, direct dyes, sulfur dyes, vat dyes, naphthol dyes, reactive dyes, and disperse dyes. Among them, any dye that is soluble in an organic solvent may be used, but even a dye that is insoluble in an organic solvent can be appropriately used by forming a dispersion.

In the above, the dye insoluble in the organic solvent may be modified by a well-known modification method. For example, in the case of an acid dye or a basic dye, an organic amine compound (for example, n-propylamine, ethylhexylpropionate amine, etc.) is reacted to modify the amine salt dye, or the sulfonic acid group is reacted with the organic amine compound. It is known to modify the dye into a dye having a sulfonamide group. These amine-modified dyes can also be used in the colored resin composition of the present invention. The specific dye is a color index, for example, 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.

As the photopolymerization initiator added to the colored resin of the present invention used in the photographic method, those having sufficient sensitivity to ultraviolet rays emitted from an ultra-high pressure mercury lamp generally used as an exposure light source are preferable, and radical polymerization property Photoacid generators or photobase generators used for photo radical initiators and ion curable resins. In photopolymerization, a component of a polymerization accelerator called a sensitizer that can be cured with less exposure energy can be used in combination. The photopolymerization initiator that can be used is not particularly limited. Specific examples include benzyl, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, benzoylbenzoic acid, and benzoylbenzoic acid. Acid esterified product, 4-benzoyl-4'-methyldiphenyl sulfide, benzyldimethyl ketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, isopropylthioxanthone, dimethylthioxanthone, diethylthioxanthone, diisopropyl Thioxanthone, 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, methylbenzoyl formate 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) butan-1-oneoxime-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'-biimi Examples thereof include dazole and diazonaphthoquinone initiators.

Commercial Kayacure ^RTM DMBI, Kayacure ^RTM BDK, Kayacure ^RTM BP-100, Kayacure ^RTM BMBI, Kayacure ^RTM DETX-S, Kayacure ^RTM EPA (all manufactured by Nippon Kayaku Co., Ltd.), Darocure ^RTM 1173, Darocure ^{RTM 11} also manufactured by Merck Japan Co., Ltd.), Irgacure ^RTM 907, Irgacure ^RTM 369 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Irgacure ^RTM 379EG (manufactured by Ciba Specialty Chemicals Co., Ltd.), Irgacure ^RTM OXE-01 (manufactured by Ciba Specialty made Chemicals Co., Ltd.), Irgacure ^RTM OXE-02 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Irgacure ^RTM PAG 03 (Irgacure is manufactured by Ciba Specialty Chemicals Co., Ltd.), TME-triazine (manufactured by Sanwa Chemical Co., Ltd.), biimidazole (manufactured by Kurokin Kasei Co., Ltd.), STR-110, STR-1 (all Chemical Co., Ltd.).

In the case of a thermosetting resin composition used in an inkjet method or the like, a thermal polymerization initiator is generally used, but a photopolymerization initiator may be used in combination as necessary. 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.

These polymerization initiators can be used alone or in combination of two or more as required. The content thereof is 0.5 to 50 parts by mass, preferably 1 to 25 parts by mass, more preferably 1 to 10 parts by mass when the total solid content of the colored resinous composition is 100 parts by mass. Part.

The organic solvent used in the present invention has sufficient dissolving power with respect to the binder resin, photopolymerizable monomer, photopolymerization initiator, and the like, which are components of the colored resin composition, and is a monofunctional compound used for the synthesis of the binder resin. Those having sufficient dissolving power for monomers, polymerization initiators and the like can be used. Moreover, what can maintain dispersion stability can also be used when preparing a pigment dispersion.

The organic solvent used in the present invention is not particularly limited as long as it can be used. Specific examples include benzenes such as benzene, toluene and xylene; cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; methyl cellosolve acetate. Cellosolve acetates such as ethyl cellosolve acetate and butyl cellosolve acetate; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate; methyl methoxypropionate, methoxypropion Propionates such as ethyl acrylate, methyl ethoxypropionate, ethyl ethoxypropionate; methyl lactate, lactic acid Lactic acid esters such as chill and butyl lactate; Diethylene glycols such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; Acetic esters such as methyl acetate, ethyl acetate and butyl acetate; Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane; Examples include ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone; alcohols such as methanol, ethanol, butanol, isopropyl alcohol, and benzyl alcohol.
As a preferable solvent, a combined use of a ketone solvent and an acetate ester is more preferable, and a combined use of a ketone solvent and a propylene glycol monoalkyl ether acetate is more preferable.

You may use these individually or in combination of 2 or more types. The amount of the organic solvent used is preferably 40 to 10,000 parts by mass, more preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the total solid content of the colored resin composition.
An example of a preferred composition ratio of the colored resin composition of the present invention is as follows.
In addition, a content ratio is a mass ratio (%) contained in the total amount (total solid content) of the solid content of the colored resin composition of this invention except a solvent.
The content ratio of the solid content is 3 to 30% of the colorant compound represented by the formula (1), 5 to 50% of the binder resin, 1 to 80% of the curing agent, and the dye 0 other than the colorant compound of the formula (1). -60% and polymerization initiator 1-25%. More preferably, 2 to 10% of the colorant compound represented by the formula (1), 10 to 50% of the binder resin, 20 to 50% of the curing agent, 0 to 60% of the dye other than the colorant compound of the formula (1), and The polymerization initiator is 1 to 10%.
The solvent content in the preferred colored resin composition is about 100 to 1000% by mass (about 1 to 10 times by mass) based on the total amount of solids.
In addition, the viscosity of the colored resin composition of the present invention is about 8 to 20 mP · s, more preferably about 10 to 15 mP · s at 25 ° C. from the viewpoint of convenience of application and the like.

The colored resin composition of the present invention is produced by mixing and stirring the binder resin, curing agent, photopolymerization initiator, specific colorant compound, organic solvent, and the like with a dissolver, a homomixer, or the like. Further, other pigments and dyes can be added as necessary. In the case where what is added is a pigment or a low-solubility dye, an appropriate dispersant is blended in advance, and the pigment or the dye dispersion is prepared by a dispersing machine such as a paint shaker, and then a colored resin composition It is preferable to mix in addition to.

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, and the like. 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.

Next, the preparation method of the color filter which has the hardened | cured material layer from the colored resin composition of this invention is demonstrated.
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. Next, drying is performed in a vacuum chamber or the like as necessary. For example, drying under reduced pressure is performed at a temperature of 23 to 150 ° C. for 1 to 60 minutes, more preferably at a temperature of 60 to 120 ° C. for 1 to 10 minutes. Further, a prebaking process is performed with a hot plate or a clean oven to form a film. Next, radiation (eg, electron beam, ultraviolet ray, preferably ultraviolet ray) is irradiated through a predetermined mask pattern by a general photolithography method, and development is performed with a surfactant aqueous solution, an alkaline aqueous solution, or a mixed aqueous solution of a surfactant and an alkaline agent. To do. Examples of the development method include a dipping method, a spray method, a shower method, a paddle method, and an ultrasonic development method, and any of these methods may be combined. A non-irradiated portion is removed by development, rinsed with water, and then post-baked. The post-bake treatment is performed, for example, under conditions of a temperature of 130 to 300 ° C. for 1 to 120 minutes, more preferably a temperature of 150 to 250 ° C. for 1 to 30 minutes. By the post-baking treatment, a color filter having pixels composed of the colored cured film of the present invention was obtained.

In the above, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, etc. can be used as the surfactant. Examples of the alkali agent include alkali carbonates such as sodium carbonate and potassium carbonate, alkali hydroxides such as sodium hydroxide and potassium hydroxide, diethanolamine, tetramethylammonium hydroxide and the like. In the present invention, it is preferable to use an aqueous solution containing both an alkali agent and a surfactant. Development is usually carried out at a processing temperature of 10 to 50 ° C., preferably 20 to 40 ° C., for a processing time of usually 30 to 600 seconds, preferably 30 to 120 seconds.

The color filter having the cured product layer of the colored resin composition of the present invention is useful as a color filter suitable for a liquid crystal display device, an organic EL display, a solid-state image sensor used in a digital camera, or the like. The color filter has a patterned blue pixel made of a cured product of the colored resin composition of the present invention prepared as described above.

Among the display devices of the present invention, the liquid crystal display device is produced with a structure in which, for example, 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 produced by forming the color filter of the present invention on either the upper or lower side of the multilayer organic light emitting device. The solid-state imaging device is manufactured by, for example, providing the color filter layer of the present invention on a silicon wafer provided with transfer electrodes and photodiodes, and then laminating microlenses.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In Examples, “%” means “% by mass” unless otherwise specified.

Synthesis example 1
5 g of Basic Violet 3 (manufactured by Tokyo Chemical Industry Co., Ltd., decomposition temperature: 205 ° C.) of the following formula (100) is dissolved in 500 g of water, and 1 g of cesium salt of tristrifluoromethanesulfonium metide is dissolved in 10 g of DMF while stirring. Solution was added. After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to obtain 1.2 g of crystalline Compound 2 (the triarylmethane compound of the present invention). Decomposition temperature: 240 ° C. Maximum absorption wavelength 598 nm (cyclohexanone)
Formula (100)

Synthesis example 2
Reaction formula

2,6-dichlorobenzaldehyde (4.2 g, 0.02 mol), 2,6-dimethylaniline (6.4 g, 0.04 mol) and urea (0.3 g, 0.005 mol) were added to 34 ml of 60% aqueous phosphoric acid solution. The mixed solution is reacted at 105 ° C. for 2.5 hours to obtain an intermediate product. To this was added 14 ml of water and chloranil (5.9 g, 0.02 mol), and the mixture was further reacted at 100 ° C. for 6 hours. The product was purified by conventional activated carbon filtration and silica gel filtration to obtain Compound 101 (3.5 g, 36%).

Synthesis example 3
Compound 101 (2.0 g, 0.005 mol) was dissolved in a mixed solution of 150 ml of water and 40 ml of methanol, and a solution obtained by dissolving 2.4 g of a cesium salt of tristrifluoromethanesulfonium metide in 1 ml of DMF was added with stirring. . After 3 hours of heating and stirring at 40 ° C., the precipitated crystals were collected by filtration, washed with water and dried to obtain 2.0 g of crystalline Compound 15 (the triarylmethane compound of the present invention, absorption maximum: 619 nm).

Synthesis example 4
Reaction formula

2-Chlorobenzaldehyde (5.0 g, 0.04 mol), N-ethyl-2-methylaniline (10.1 g, 0.07 mol) and urea (0.4 g, 0.01 mol) were added to 50 ml of 60% aqueous phosphoric acid solution. Then, this mixed solution was reacted at 105 ° C. for 3 hours to synthesize an intermediate product. To this, 16 ml of water and chloranil (8.7 g, 0.04 mol) were added, and further reacted at 100 ° C. for 8 hours. The product was purified by conventional activated carbon filtration and silica gel filtration to obtain Compound 102 (7.4 g, 52%).

Synthesis example 5
Compound 102 (3.0 g, 0.008 mol) was dissolved in a mixed solution of 150 ml of water and 40 ml of methanol, and a solution obtained by dissolving 2.4 g of a cesium salt of tristrifluoromethanesulfonium metide in 1 ml of DMF was added thereto while stirring. . After heating and stirring at 40 ° C. for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to obtain 2.0 g of crystalline Compound 16 (triarylmethane compound of the present invention, absorption maximum: 624 nm).

Synthesis Example 6
Reaction formula

Phosphorus oxychloride (55.4 g, 0.36 mol) is slowly added dropwise to 204.3 g of DMF in ice-cooling, and the mixture is stirred as it is for 30 minutes, and N, N-dicyanoethylaniline (60.0 g, 0.30 mol) is gradually added. Added to. Then, it heated at 90 degreeC and stirred for 4 hours. After completion of the reaction, the reaction solution was poured into ice water for neutralization, and the contents were extracted with ethyl acetate. Thereafter, the solvent was distilled off under reduced pressure to obtain 63.5 g of Compound 103 in a yield of 93%.

Synthesis example 7
Reaction formula

N, N-dibutylaniline (24.64 g, 0.12 mol), urea (1.08 g, 0.06 mol), compound 103 (13.64 g, 0.06 mol), concentrated sulfuric acid (3.6 g, 0.06 mol) Was dissolved in 60 ml of isopropanol and heated to reflux for 10 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain Compound 104.

Synthesis example 8

The compound 104 obtained in Synthesis Example 7 above was added to a solvent consisting of 600 ml of hot water, 100 ml of methanol and concentrated hydrochloric acid (5 ml, 0.16 mol) and stirred at 80 ° C. for a while, then sodium carbonate was added to adjust the pH to 2. While maintaining 0, 150 ml of a 34% aqueous solution of ferric chloride was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, then returned to room temperature, and the precipitated solid was collected by filtration to obtain 44.3 g of a crude yield of Compound 105.

Synthesis Example 9
Compound 105 (3.03 g, 0.0046 mol) obtained in Synthesis Example 8 was dissolved in a mixed solution of 50 ml of water and 40 ml of methanol, and 3.01 g of cesium salt of tristrifluoromethanesulfonium methide was added to 2 ml of DMF while stirring. The dissolved solution was added. After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water and dried to obtain 4.36 g of crystalline Compound 18 (absorption maximum value: 585 nm). Decomposition temperature: 247 ° C

Synthesis Example 10
In a 100 ml beaker, 1 g of rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.) of the following formula (106) and 20 g of water were charged and stirred at room temperature for 30 minutes. A solution prepared by dissolving 1 g of a cesium salt of tristrifluoromethanesulfonium methide (TFSM) in 1 g of DMF was added dropwise thereto and stirred for 3 hours. The precipitated dye was collected by filtration, washed with water and dried to obtain 0.7 g of rhodamine B TFSM salt (compound 2-3). Maximum absorption wavelength: 560 nm (cyclohexanone)
Formula (106)

Synthesis Example 11 (Synthesis of binder resin (copolymer))
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. Thereafter, the temperature was raised to 80 ° C., and the mixture was stirred at 80 to 85 ° C. for 4 hours. 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 resulting copolymer (A) had a polystyrene equivalent weight average molecular weight of 18,000 and an acid value of 152.

Example 1
5.4 g of copolymer (A) as a binder resin, 6 g of Kayrad ^RTM DPHA (trade name, dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) as a photopolymerizable monomer, and Irgacure ^RTM 907 (Ciba) as a photopolymerization initiator・ Specialty Chemicals Co., Ltd.) 1.5 g, Kayacure ^RTM DETX-S (Nippon Kayaku Co., Ltd.) 0.6 g, Compound 2 of Synthesis Example 1 0.6 g, Cyclohexanone 20 g and propylene glycol monomethyl ether acetate as solvent 8.6 g was mixed to obtain a colored resin composition of the present invention.

Examples 2 to 6 were as follows.
Example 2
A colored resin composition of the present invention was obtained in the same manner as in Example 1 except that Compound 2 in Synthesis Example 1 was changed to Compound 15 in Synthesis Example 3.
Example 3
A colored resin composition of the present invention was obtained in the same manner as in Example 1 except that Compound 2 in Synthesis Example 1 was changed to Compound 16 in Synthesis Example 5.
Example 4
A colored resin composition of the present invention was obtained in the same manner as in Example 1 except that Compound 2 in Synthesis Example 1 was changed to Compound 18 in Synthesis Example 9.

Example 5
(I) C.I. I. Pigment Blue 15: 6 / Addisper ^RTM PB821 / Solspers ^RTM 5000 / PGMEA = 15.0 / 6.0 / 1.0 / 78.0 (mass ratio) after mixing at a composition ratio of 0.3 mm zirconia beads 400 g The pigment dispersion liquid 1 was obtained by adding, processing with a paint shaker for 60 minutes, and filtering.
In the above, C.I. I. Pigment Blue 15: 6 is a copper phthalocyanine pigment, Ajisper PB821 (trade name, manufactured by Ajinomoto Fine Techno Co., Ltd.) and Solsperse 5000 (trade name, manufactured by Nihon Lubrizol Co., Ltd.) are dispersing agents, and PGMEA is propylene glycol monomethyl ether. Superscript RTM indicates a registered trademark.
(Ii) 19 g of the pigment dispersion 1 obtained above was further added to the colored resin composition of Example 3 to obtain the colored resin composition of the present invention.
Example 6
To the colored resin composition obtained in Example (ii), 0.6 g of Compound 2-3 (Coloring Material Compound of Formula (2)) of Synthesis Example 10 was further added, and the colored resin composition of the present invention was added. Got.

Comparative Example 1
Compound 2 (0.6 g) was prepared in the same manner as in Example 1 except that 19 g of the pigment dispersion 1 obtained in (i) of Example 5 was used instead of Compound 2 (0.6 g) of Example 1. ), A comparative colored resin composition containing 19 g of the pigment dispersion 1 was obtained.

Comparative Example 2
A colored resin composition for comparison was obtained in the same manner as in Example 1 except that Compound 2 of Synthesis Example 1 was changed to Basic Violet 3 which is a clear violet dye.

Example 7
Each of the colored resin compositions (Examples 1 to 6 and Comparative Examples 1 and 2) obtained above was applied onto each glass substrate to obtain a glass substrate having a coating film of each colored resin composition. . Each glass substrate was pre-baked under conditions of 80 ° C. × 100 seconds, and then exposed through a mask to cure the exposed portion. Next, the exposed area was developed with an aqueous alkali solution containing a surfactant, rinsed with water, and then heated at 200 ° C. to obtain the color filter of the present invention having a cured product layer having the same pattern as the mask. The obtained color filter pattern had a resolution of 5 μm square in line and space, and no residue or peeling of pixels was confirmed.

Evaluation test The color filter for evaluation of heat resistance and contrast (evaluation substrate having a cured product layer) was coated on a glass substrate in the same manner as described above, exposed on the entire surface, and treated at 200 ° C. for 5 minutes after post-baking. And made it. In both cases, a color filter having clear color characteristics was obtained.
Evaluation was performed as follows.
Heat-resistant:
The evaluation substrate obtained above was treated at 200 ° C. for 40 minutes, and the spectral transmittance of the evaluation substrate before and after the treatment was measured with a spectrophotometer “Shimadzu UV-3150”. The color difference (ΔEab) before and after the heat treatment was calculated and evaluated from the chromaticity in the XYZ color system calculated from the measured spectral transmittance.
contrast:
The above evaluation substrate is placed between two polarizing plates of a contrast meter (CT-1 manufactured by Aisaka Electric Co., Ltd.), and the luminance value (cd / cm ² ) when the ^two polarizing plates are parallel to each other is orthogonal. The contrast was calculated from the ratio of luminance values (cd / cm ² ) (luminance value when parallel / luminance value when orthogonal).
Table 3 shows the evaluation results of heat resistance, and Table 4 shows the evaluation results of contrast.

Table 3 Evaluation results of heat resistance

Table 4 Contrast evaluation results

From the evaluation results of Table 3, Examples 1 to 6 of the present invention all showed better results than Comparative Example 2 which is a conventional dye, and the resistance of the colorant compound of the present invention was greatly improved. I understand that. In Examples 5 and 6, a pigment is mixed in the dye of the present invention, and in particular, the insoluble matter is not precipitated and the state is good. This is the wide applicability of the dye-based color material compound of the present invention. It can be said that it suggests. Also, from the contrast evaluation results in Table 4, Examples 2, 3, 5, and 6 all showed better results than the pigment of Comparative Example 1. In particular, Examples 2 and 3 are the result of the dye alone, showing a marked improvement in contrast that is difficult with pigments. Therefore, it was confirmed that the colored resin composition of the present invention has suitability for the next generation color filter.

As described above, the colored resin composition of the present invention using a specific dye-based color material compound is clear, has excellent color filter characteristics (resistance, contrast, etc.), high quality and highly reliable color. A filter pixel can be obtained. In addition, it can be used by being well mixed with pigments depending on the application, and shows wide applicability.

Claims

Colored resin composition for color filter containing a colorant compound represented by the following formula (1), a binder resin, a solvent, a polymerization initiator, and a curing agent Formula (1)

(Wherein R 1 to R 4 each independently represents a hydrogen atom, a C1-C30 alkyl group, a phenyl group or a benzyl group; R 5 to R 17 each independently represents a hydrogen atom, a halogen atom, C1-C6) An anion moiety Z − represents a halogenoalkylsulfonylimide anion, a halogenoalkylsulfonylmethide anion, or a halogenoalkylsulfonate anion, and each halogenoalkyl group independently represents A C1-C10 alkyl group substituted with 3 to 6 halogen atoms).
The colored resin composition for a color filter according to claim 1, wherein the polymerization initiator is a photopolymerization initiator or a thermal polymerization initiator.
Z - is bistrifluoromethanesulfonylimide anion, tris trifluoromethanesulfonyl methide anion or a color filter for the colored resin composition according to claim 2 is trifluoromethyl sulfonate anions.
The colored resin composition for a color filter according to claim 3, wherein at least one of R 5 to R 17 is a halogen atom.
The colored resin composition for a color filter according to claim 3, wherein at least one of R 5 to R 17 is an alkylamino group.
The colored resin composition for a color filter according to any one of claims 1 to 5, and 12 and 13, further comprising one or both of a metal phthalocyanine pigment and a colorant compound represented by the following formula (2): Formula (2)

(Wherein R 1a to R 6a each independently represents a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a nitro group, a carboxy group, or an alkoxycarbonyl group. Y 1 to Y) 4 each independently represents a hydrogen atom, a C1-C12 alkyl group or an aryl group, and X 1 to X 5 each independently represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen atom, a nitro group, group, a phenoxy group, a carboxy group, an alkoxycarbonyl group, a sulfo group, a sulfamoyl group anion Z -. represents a halogenoalkyl imide anion, halogenoalkyl methide anion or halogenoalkyl sulfonate anions, each halogenoalkyl The group is independently 3-6 halogen A C1-C10 alkyl group substituted with an atom).
The colored resin composition for a color filter according to claim 6, comprising a metal phthalocyanine pigment.
The colored resin composition for a color filter according to claim 6, comprising a metal phthalocyanine pigment and a colorant compound represented by the formula (2).
A cured product layer of the colored resin composition according to any one of claims 1 to 5 or a colored resin composition for a color filter according to any one of claims 1 to 5, further comprising a metal phthalocyanine pigment. Or a color filter having a cured layer of a colored resin composition for a color filter containing one or both of the colorant compounds represented by the following formula (2),
Formula (2)

(Wherein R 1a to R 6a each independently represents a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a nitro group, a carboxy group, or an alkoxycarbonyl group. Y 1 to Y) 4 each independently represents a hydrogen atom, a C1-C12 alkyl group or an aryl group, and X 1 to X 5 each independently represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen atom, a nitro group, group, a phenoxy group, a carboxy group, an alkoxycarbonyl group, a sulfo group, a sulfamoyl group, anion Z - is represents halogenoalkyl imide anion, halogenoalkyl methide anion or halogenoalkyl sulfonate anions, each halogenoalkyl The group is independently 3-6 halogen A C1-C10 alkyl group substituted with an atom).
A display device comprising the color filter according to claim 9.
A solid-state imaging device comprising the color filter according to claim 9.
In the formula (1), R 1 to R 4 are each independently a hydrogen atom or a C1-C4 lower alkyl group, R 5 to R 12 are each independently a hydrogen atom or a C1-C4 lower alkyl group, R 13 to R 17 each independently represents a hydrogen atom, a halogen atom, or a diC1-C3 alkylamino group, wherein the C1-C3 alkyl group of the diC1-C3 alkylamino group is unsubstituted, or a halogen atom or cyano The colored resin composition for a color filter according to claim 2, which may be substituted with a group, and Z - is a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion, or a trifluoromethylsulfonate anion.
In the formula (1), at least one of R 5 to R 12 is a C1-C4 lower alkyl group, the other is a hydrogen atom, at least one of R 13 to R 17 is a halogen atom, and the other is a hydrogen atom. The colored resin composition for a color filter according to claim 12.
14. The colored resin composition for a color filter according to any one of claims 1 to 5, 12 and 13, wherein in formula (1), Z − is a tristrifluoromethanesulfonylmethide anion.
Is bistrifluoromethanesulfonylimide anion, tris trifluoromethanesulfonyl methide anion or a color filter for the colored resin composition according to claim 6 is trifluoromethyl sulfonate anion, - Z in the formula (2).
R 1a to R 6a in formula (2) are each independently a hydrogen atom, Y 1 to Y 4 are each independently a hydrogen atom or a C1-C4 alkyl group, and X 1 to X 5 are each independently a hydrogen atom or The colored resin composition for a color filter according to claim 15, which is a carboxy group.
7. The colored resin composition for a color filter according to claim 6, wherein Z − in formula (1) and formula (2) is both a tristrifluoromethanesulfonylmethide anion.