WO2012053211A1 - Colored resin composition for use in color filter, color filter, display device, and solid-state imaging element - Google Patents

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 R₂ and R₁₅ through R₁₈ each independently represent a hydrogen atom or a C_1-30 alkyl group, phenyl group, or benzyl group; R₁ and R₃ through R₁₄ each independently represent a hydrogen atom, a halogen atom, or a C_1-12 alkyl group; and X⁻ 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; a color filter that contains a substance obtained by curing said colored resin composition; and the like. Said colored resin composition has good storage stability, even if a metal-phthalocyanine pigment is contained therein, and can provide color-filter pixels that have vivid color characteristics and excellent 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 conflicting characteristics, a method of making the pigment fine particles has been used, but there are limits to durability and dispersion stability, and at the present time it is not possible to achieve compatibility with resistance even if the brightness is improved. is there.

カ ラ ー As an approach to solve these problems, color filters using dyes are being studied. If a dye is used, there is a merit that the contrast can be improved because the light purity can be suppressed because the color purity and lightness cannot be achieved by a pigment, and the particles are not particles. 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 triphenylmethane compounds described therein are remarkably inferior in light resistance and heat resistance, and are 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. Accordingly, there is a need for a high-quality color filter that has clear color characteristics as the next generation and has excellent durability.

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 color filter having clear color characteristics and excellent heat resistance.

As a result of diligent research 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 for the pixels of the color filter. It came to complete.

That is, the present invention relates to the following (1) to (12).
(1) Colored resin composition for color filter (1) containing a colorant compound represented by the following formula (1), a binder resin, a solvent, a polymerization initiator, and a curing agent

(Wherein R ₂ and R ₁₅ to R ₁₈ each independently represent a hydrogen atom, a C1-C30 alkyl group, a phenyl group or a benzyl group; R ₁ and R ₃ to R ₁₄ each independently represent a hydrogen atom; halogen atom, .X represents an alkyl group of C1-C12 ^- halogenoalkyl imide anion, represent halogenoalkyl methide anion, or halogenoalkyl sulfonate anions, each halogenoalkyl groups are each independently 3-6 A C1-C10 alkyl group substituted with 1 halogen atom).
(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.
Is bistrifluoromethanesulfonylimide anion, tris trifluoromethanesulfonyl methide anion or trifluoromethylsulfonate anion in the above (1) or (2) for color filter colored resin composition according to ^- (3) X of formula (1) object.
(4) In the formula (1), R ₂ and R ₁₅ to R ₁₈ are each independently a C1-C4 alkyl group, and R ₁ and R ₃ to R ₁₄ are all hydrogen atoms. The colored resin composition for a color filter according to any one of (3).

(5) The colored resin composition for a color filter according to any one of (1) to (4), further including 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, an anionic portion X representing a sulfamoyl group ^- represents a halogenoalkyl imide anion, halogenoalkyl methide anion, or halogenoalkyl sulfonate anions, each halogenoalkyl The group is independently 3-6 halogen atoms C1-C10 alkyl group substituted with a child).
(6) The colored resin composition according to the above (5), which contains a metal phthalocyanine pigment.
(7) The colored resin composition for a color filter according to the above (5), comprising a metal phthalocyanine pigment and a colorant compound represented by the formula (2).
(8) In the formula (2), all of R _1a to R _6a are hydrogen atoms, all of Y ₁ to Y ₄ are C1-C4 alkyl groups, X ₁ is a carboxy group, and X ₂ to X ₅ are The colored resin composition for a color filter according to any one of the above (5) to (7), wherein the hydrogen atom, X ⁻ is tristrifluoromethanesulfonylmethide anion.

(9) The colored resin composition according to any one of (1) to (4) above, or a metal phthalocyanine pigment or a colorant compound represented by the following formula (2), or both: A color filter having a cured product layer of the colored resin composition for a color filter according to any one of (1) to (4),
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, an anionic portion X representing a sulfamoyl group ^- represents a halogenoalkyl imide anion, halogenoalkyl methide anion, or halogenoalkyl sulfonate anions, each halogenoalkyl The group is independently 3-6 halogen atoms C1-C10 alkyl group substituted with a child).
(10) In the formula (1), R ₂ and R ₁₅ to R ₁₈ are each independently a C1-C4 alkyl group, R ₁ and R ₃ to R ₁₄ are all hydrogen atoms, and X ⁻ is tris A trifluoromethanesulfonylmethide anion, wherein in Formula (2), all of R _1a to R _6a are hydrogen atoms, all of Y ₁ to Y ₄ are C1-C4 alkyl groups, and X ₁ is a carboxy group, The color filter according to the above (9), wherein X ₂ to X ₅ are hydrogen atoms, and X ⁻ is a tristrifluoromethanesulfonylmethide anion.
(11) A display device equipped with the color filter according to (9) or (10).
(12) A solid-state imaging device equipped with the color filter according to (9) or (10).

The colored resin composition for color filters of the present invention (also referred to as the colored resin composition of the present invention or the resin composition of the present invention) provides a color filter pixel having clear color characteristics and excellent heat resistance. be able to. The colored resin composition for color filters is excellent in storage stability even if it contains a metal phthalocyanine pigment.

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. However, the present invention is not limited to these, and the components other than the specific color material compound can be used without any particular limitation.

The pixel manufacturing method using the colored resin composition of the present invention mainly includes a photolithography method and an inkjet method, and the former uses a photosensitive resin composition having excellent developability using a photopolymerization initiator. The latter does not necessarily require a photopolymerization initiator and a thermosetting resin composition is used.

The specific color material compound used in the present invention is represented by the formula (1).
In R ₂ and R ₁₅ to R ₁₈ in the 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). 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 Group, isononyl group, isodecyl 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, 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. Among these, C1-C6 alkyl Groups are preferred, and in some cases a C1-C4 alkyl group is preferred.

In R ₂ and R ₁₅ to R ₁₈ in the formula (1), the phenyl group or benzyl group may have a substituent, and examples of the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, and butyl. (C1-C5) alkyl groups such as an isobutyl group, a t-butyl group and a pentyl group; halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a sulfonic acid group; a methoxy group, an ethoxy group and a propoxy group (C1-C6) alkoxy groups such as butoxy, t-butoxy and hexyloxy; hydroxy (C1-C5) alkyl such as hydroxyethyl and hydroxypropyl; methoxyethyl, ethoxyethyl and ethoxypropyl A (C1-C5) alkoxy (C1-C5) alkyl group such as a butoxyethyl group; a 2-hydroxyethoxy group Hydroxy (C1-C5) alkoxy groups; alkoxy (C1-C5) alkoxy groups such as 2-methoxyethoxy group and 2-ethoxyethoxy group; substituted ethyl groups such as 2-sulfoethyl group, carboxyethyl group and cyanoethyl group; It is done.
R ₂ and R ₁₅ to R _{18 in the} formula (1) are each independently preferably a C1-C6 alkyl group, and more preferably a C1-C4 alkyl group.

In R ₁ and R ₃ to R ₁₄ in the formula (1), examples of the C1-C12 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, and a hexyl group. Cyclohexyl group, hydroxypropyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group and the like.
R ₁ and R ₃ to R _{14 in the} formula (1) are each independently preferably a hydrogen atom, a chlorine atom, or an unsubstituted C1-C12 alkyl group, more preferably a hydrogen atom. .

As a halogen atom in Formula (1), a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned.
The anion X 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 X ⁻ include bistrifluoromethanesulfonylimide anion, tristrifluoromethanesulfonylmethide anion, and trifluoromethylsulfonate anion. Among these, tristrifluoromethanesulfonylmethide anion is more preferable.

As one of the preferable compounds represented by the formula (1), in the formula (1), R ₂ and R ₁₅ to R ₁₈ are each independently a C1-C4 alkyl group, and R ₁ and R ₃ to R ₁₄ Can be any compound in which each is a hydrogen atom and X ⁻ is a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion or a trifluoromethylsulfonate anion, more preferably X ⁻ is tristrifluoromethane. It is a compound that is a sulfonylmethide anion.

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 the table, substituent R represents R ₁ to R ₁₈ with corresponding numbers, Me represents a methyl group, Et represents an ethyl group, i-Bu represents an isobutyl group, Ph represents a phenyl group, and CH represents a cyclohexyl group. Further, when X ⁻ is α, it represents a tris-trifluoromethanesulfonylmethide anion, when β represents a bistrifluoromethanesulfonylimide anion, and when γ represents a trifluoromethylsulfonate anion.

In the colorant compound represented by the formula (2) that can be used in combination with the compound of the formula (1) in the present invention, R _1a to R _6a are each independently a hydrogen atom, a halogen atom, a C1-C12 alkyl group, C1 —C12 represents an alkoxy group, a nitro group, a carboxy group, or an alkoxycarbonyl group, 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 , Y ₃ and Y ₄ or both are C1-C12 alkyl groups (Preferably a C1-C4 alkyl group) is preferred. X ₁ to X ₅ each independently represents 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 sulfo group or a sulfamoyl group. , X ₁ to X ₅ may be the same or different. The anion part X 2 ^- represents a halogenoalkylsulfonylimide anion, a halogenoalkylsulfonylmethide anion, or a halogenoalkylsulfonate anion, wherein each halogenoalkyl group is independently C1-C10 substituted with 3 to 6 halogen atoms It is an alkyl group.
Examples of the halogen atom of the formula (2) include the same as those described in the formula (1).

Examples of the C1-C12 alkyl group or the C1-C10 alkyl group in the formula (2) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. Examples thereof include a butyl group, an iso-butyl group, an n-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 C1-C12 alkoxy group in the formula (2) include groups in which an oxygen atom is attached to the alkyl group exemplified as the C1-C12 alkyl group to form an alkoxy group. In the case of an alkoxycarbonyl group, there can also be mentioned a group in which an oxycarbonyl group (—OCO— group) is added to the alkyl group exemplified as the C1-C12 alkyl group to form an alkoxycarbonyl group.

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 X ⁻ of the colorant compound represented by formula (1) and formula (2) contained in the colored resin composition of the present invention is a halogenoalkylsulfonylimide anion, a halogenoalkylsulfonylmethide anion, or a halogeno Represents an alkyl sulfonate anion, and each halogenoalkyl group is independently a C1-C10 alkyl group substituted with 3 to 6 halogen atoms. The halogen in the halogenoalkyl group is preferably a fluorine atom. X ^- include Examples of the bistrifluoromethanesulfonylimide anion, tris trifluoromethanesulfonyl methide anion, trifluoromethylsulfonate anion, include nonafluorobutyl sulfonate anion, especially tris trifluoromethanesulfonyl methide anion preferred.
As the coloring material compound represented by the preferred 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 hydrogen atom, X ^- 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, X ^- 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 used in the colored resin composition of the present invention can be obtained, for example, by a known synthesis method described in Yutaka Hosoda, “Theoretical Manufacturing Dye Chemistry” (pp. 373-375) published by Gihodo Co., Ltd. It is also possible to synthesize by purchasing a commercial product in which the anion part X ⁻ is a chlorine anion and adding a corresponding salt or acid to exchange the salt.

When the colorant compound in the present invention is synthesized by salt exchange, for example, the colorant compound in which the anion portion X ⁻ 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.

The total solid content of the colored resin composition of the present invention (referring to the total amount of solid content composed of a colorant compound, a binder resin, a curing agent, etc., excluding the solvent, which is also used synonymously hereinafter) included in 100 parts. The content of the color material compound represented by the formula (1) is preferably 0.1 to 60 parts by mass, preferably 1 to 30 parts, more preferably 3 to 30 parts by mass. In some cases, the coloring material compound of the formula (1) is 1 to 10% by mass, preferably 2 to 10% by mass, more preferably 3 to 10% by mass in the total solid content of the colored resin composition of the present invention. The colored resin composition of the present invention containing about 3%, more preferably about 3-8% by mass is also preferred.
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, and further, other dyes or 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 violet pigment, and in particular, the above-described metal phthalocyanine pigment (preferably copper phthalocyanine content) 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 content) or the colorant compound represented by the formula (2) is 0 to 30% by mass in the total solid content of the colored resin composition of the present invention. Degree. 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 copper phthalocyanine) is used in combination, its content 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. is there. 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 carboxyl groups / or hydroxyl groups (hereinafter also referred to as a carboxyl 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 carboxyl 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 carboxyl 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 Such as hexyl (meth) acrylate, 4-hydroxyhexyl (meth) acrylate, 5-hydroxy-3-methyl-pentyl (meth) acrylate, cyclohexane-1,4-dimethanol-mono (meth) acrylate, etc. 1-C8 glycol (mono) (meth) acrylate; C3-C6 triol (mono or di) (meth) acrylate such as glycerol 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; And hydroxyl group-containing (meth) acrylates such as 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.
The hydroxyl group-containing unsaturated monomer (preferably hydroxyl group-containing (meth) acrylate) may be used as a monomer for copolymerization with the carboxy group-containing unsaturated monomer (preferably (meth) acrylic acid).

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 ester (preferably phenyl group-containing C1-C4 alkyl (meth) acrylate) such as luglycidyl ether (meth) acrylate, o-phenylphenol (meth) acrylate hydroxyethylated product, 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, fentil (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] dec-4-methyl = (meth) acrylate, cyclodecyl ( Alicyclic skeleton-containing compounds such as (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, t-butylcyclohexyl (meth) acrylate (preferably C5-C10 aliphatic ring-containing (meth) acrylate, more preferably Is 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 substituted with a phenyl group or a C5-C10 aliphatic ring-containing (meth) acrylate, and more preferably a C1-C4 alkyl (meth) substituted with a phenyl group. 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 ( (Meth) acrylate) 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 described above 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 with respect to 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 deteriorated, or problems such as scumming or film residue in areas other than the area where pixels are formed may occur. .

The curing agent used in the present invention includes a photo- or thermal polymerization monomer in the case of radical polymerization, an epoxy resin in the case of ion curing, and a melamine curing agent in addition. 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 Examples include acrylate compounds such as acid tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, and 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene. be able to.

Commercially available products include Kayrad ^RTM RP-1040 (Nippon Kayaku Co., Ltd.), Kayarad ^RTM DPCA-30 (Nihon Kayaku Co., Ltd.), UA-33H (Shin Nakamura Chemical Co., Ltd.), UA-53H And (meth) acrylate compounds sold under trade names such as Shin-Nakamura Chemical Co., Ltd. and M-8060 (Toagosei Co., Ltd.).
Examples of the thiol-based polymerization monomer include products such as TEMPIC, TMMP, PEMP, DPMP (manufactured by Sakai Chemical Industry Co., Ltd.).
Epoxy resins include NC-6000, NC-3000, EOCN-1020, XD-1000, EPPN-501H, BREN-S, NC-7300L from Nippon Kayaku Co., Ltd., Celoxide from Daicel Chemical Industries, Ltd. 2021P, EHPE3150, Cyclomer M100, Eporide PB3600, Japan Epoxy Resin Co., Ltd. product Epicoat ^RTM 828, Epicoat ^RTM YX8000, Epicoat ^RTM YX4000, Silaace ^RTM S510 (manufactured by Chisso Corporation), TEPIC (manufactured by Nissan Chemical Industries, Ltd.), etc. Can be listed.
Examples of the melamine curing agent include products such as methylolated melamine and Mw-30 (manufactured by Sanwa Chemical Co., Ltd.). These can be used alone or in admixture of two or more.
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, a metal phthalocyanine pigment exhibiting a blue color such as CI Pigment Blue 15: 6 or CI Pigment Violet 23 is 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, ethylhexylpropionic acid 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 Photo radical initiators, photo acid generators or photo base generators used for 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, -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-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, Azonafutokinon based initiators, also commercially available KAYACURE ^RTM DMBI, KAYACURE ^RTM BDMK, KAYACURE ^RTM BP-100, KAYACURE ^RTM BMBI, Kayacure DETX-S, Kayacure ^RTM EPA (all manufactured by Nippon Kayaku Co., Ltd.), Darocure ^RTM 1173, Darocur 1116 (Iremo Merck Japan Co., Ltd.), Irgacure ^RTM 907, Irgacure ^RTM 369, Irgacure ^RTM 379EG, Irgacure ^RTM OXE-01, Irgacure ^RTM OXE-02, Irgacure ^RTM PAG103 (Irgacure is Ciba Specialty Chemicals) , TME-triazine (manufactured by Sanwa Chemical Co., Ltd.), biimidazole (manufactured by Kurokin Kasei Co., Ltd.), STR-110, STR- (Both less Bae Chemical Co., Ltd.) and the like.

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. It is.

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.

A method for producing a color filter having the cured product layer 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. 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 (for example, 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 to obtain a pixel comprising the colored cured film of the present invention.

In the above, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, etc. can be used as the surfactant. As the alkali agent, alkali carbonate such as sodium carbonate or potassium carbonate, alkali hydroxide such as sodium hydroxide or potassium hydroxide, diethanolamine, tetramethylammonium hydroxide and the like are used. 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
Reaction formula

4,4′-bis (diethylamino) benzophenone (5.0 g, 0.02 mol), 1-methyl-2-phenyl-1H-indole (3.2 g, 0.02 mol), phosphorus oxychloride (4.7 g, 0 0.03 mol) in toluene (10 ml) was heated and stirred at 100 ° C. for 10 hours. After cooling to room temperature, water was added for liquid separation, and the organic layer was concentrated under reduced pressure to obtain Compound 100 (7.5 g, 95%).

Synthesis example 2
While stirring a mixed solution of Compound 100 (1.0 g, 0.003 mol) in 10 ml of water and 50 ml of methanol, a solution of 1.7 g of cesium salt of tristrifluoromethanesulfonium methide in 1 ml of DMF was added. After stirring at room temperature for 3 hours, the precipitated crystals were collected by filtration, washed with water, and dried to obtain crystalline Compound 1 (the triarylmethane compound of the present invention) (1.04 g, 54%).

Synthesis example 3
In a 100 ml beaker, 1 g of rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.) of the following formula (101) 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 ml 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 (101)

Synthesis Example 4 (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) of methacrylic acid and benzyl methacrylate.
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 (as a photopolymerization initiator) 1.5 g of Ciba Specialty Chemicals Co., Ltd.) and 0.6 g of Kayacure ^RTM DETX-S (Nippon Kayaku Co., Ltd.), 0.6 g of Compound 1 of Synthesis Example 2, 20 g of cyclohexanone and propylene glycol monomethyl ether as a solvent Acetate (PGMEA) 8.6g and each were mixed and the colored resin composition of this invention was obtained.

Example 2
C. I. After mixing at a composition ratio of CI Pigment Blue 15: 6 (copper phthalocyanine pigment) / Azisper ^RTM PB821 / Solsperth ^RTM 5000 / PGMEA (solvent) = 15.0 / 6.0 / 1.0 / 78.0 (mass ratio) Then, 400 g of 0.3 mm zirconia beads were added, the mixture was treated for 60 minutes with a paint shaker, the zirconia beads were removed by filtration, and pigment dispersion 1 was obtained. 19 g of the pigment dispersion 1 was added to the colored resin composition of the present invention obtained in Example 1 to obtain a colored resin composition of the present invention containing a copper phthalocyanine pigment.

Example 3
To the colored resin composition obtained in Example 2, 0.6 g of Compound 2-3 (TFSM salt of rhodamine B) obtained in Synthesis Example 3 was further added, and a copper phthalocyanine pigment and a coloring material of the formula (2) were added. A colored resin composition of the present invention containing a compound was obtained.

Comparative Example 1
A colored resin composition of Comparative Example 1 was obtained in the same manner as in Example 1 except that Compound 1 in Example 1 was changed to Basic Blue 7, which is a conventional bright blue dye.

The colored resin compositions obtained above (Examples 1 to 3 and Comparative Example 1) were applied on different glass substrates. The obtained coated substrate was pre-baked at 80 ° C. for 100 seconds, and then exposed through a mask having a pattern to cure the exposed portion. Subsequently, it developed with the aqueous alkali solution containing surfactant, rinsed with water, and heated at 200 degreeC, and the color filter which has a pixel pattern was obtained. The obtained color filter had a resolution of 5 μm square in line and space, and no residue or peeling of pixels was confirmed.

Evaluation of heat resistance The substrate for evaluation of heat resistance was prepared by whole surface exposure without using an exposure mask having a pattern as described below.
That is, in the same manner as described in Example 1, the resin composition of each example and the resin composition of the comparative example were applied to different glass substrates, respectively, and light of the applied resin composition was obtained by overall exposure. Curing was performed. Subsequently, the post-baking process was performed at 200 ° C. for 5 minutes, and each produced a color filter (evaluation substrate) having clear blue characteristics.
Using the obtained evaluation substrate, an evaluation test was performed as follows.
Each of the evaluation substrates obtained above was treated at 200 ° C. for 120 minutes, and the spectral transmittance of the evaluation substrate before and after the treatment was measured with a spectrophotometer “Shimadzu Corporation 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.
Table 3 below shows the evaluation results of heat resistance.

Table 3 Evaluation results of heat resistance

From the evaluation results in Table 3, the color filters obtained in Examples 1 to 3 of the present invention have significantly smaller color differences before and after the heat treatment than the color filter of Comparative Example 1 obtained using a conventional dye. Showed good results.
That is, it can be seen that an excellent color filter with improved heat resistance can be obtained from the resin composition of the present invention containing the colorant compound of formula (1).
Moreover, the color filter using the colored resin composition of Example 2 containing both the coloring material compound of Formula (1) and the copper phthalocyanine pigment is the colored resin composition of Example 1 containing only the coloring material compound of Formula (1). The coloring resin composition of Example 3 which has heat resistance further superior to the color filter using a thing, and also contains the coloring material compound of Formula (1), copper phthalocyanine, and the coloring material compound of Formula (2). It can be seen that the used color filter has further excellent heat resistance.
Further, the colored resin compositions of Examples 2 and 3 contained a copper phthalocyanine pigment, but the storage stability of the resin composition was also good without precipitation of insolubles and the like.
From the above, the colored resin composition of the present invention containing the colorant compound of the dye system formula (1) has wide applicability and is useful as a colored resin composition for next-generation color filters.

As described above, the colored resin composition of the present invention containing the dye-based colorant compound of the formula (1) has characteristics suitable for the next-generation color filter, and the resin composition has high quality. And a highly reliable color filter pixel can be obtained. In addition, the resin composition can be used by being well mixed with the pigment according to the use, and therefore, the resin composition has a wide range of applicability and has high industrial applicability.

Claims (12)

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

   

   (Wherein R ₂ and R ₁₅ to R ₁₈ each independently represent a hydrogen atom, a C1-C30 alkyl group, a phenyl group or a benzyl group; R ₁ and R ₃ to R ₁₄ each independently represent a hydrogen atom; halogen atom, .X represents an alkyl group of C1-C12 ^- halogenoalkyl imide anion, represent halogenoalkyl methide anion, or halogenoalkyl sulfonate anions, each halogenoalkyl groups are each independently 3-6 A C1-C10 alkyl group substituted with 1 halogen atom).
2. 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.
3. Is bistrifluoromethanesulfonylimide anion, tris trifluoromethanesulfonyl methide anion or a color filter for the colored resin composition according to claim 1 is trifluoromethyl sulfonate anion ^- X of the formula (1).
4. _2. The color filter according to claim 1, wherein in the formula (1), R ₂ and R ₁₅ to R ₁₈ are each independently a C1-C4 alkyl group, and R ₁ and R ₃ to R ₁₄ are both hydrogen atoms. Coloring resin composition.
5. Furthermore, the coloring resin composition for color filters as described in any one of Claims 1 thru | or 4 containing any one or both of a metal phthalocyanine pigment or a coloring material compound represented by 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, an anionic portion X representing a sulfamoyl group ^- represents a halogenoalkyl imide anion, halogenoalkyl methide anion, or halogenoalkyl sulfonate anions, each halogenoalkyl The group is independently 3-6 halogen atoms C1-C10 alkyl group substituted with a child).
6. The colored resin composition according to claim 5, comprising a metal phthalocyanine pigment.
7. The colored resin composition for a color filter according to claim 5, comprising a metal phthalocyanine pigment and a colorant compound represented by the formula (2).
8. In the formula (2), all of R _1a to R _6a are hydrogen atoms, all of Y ₁ to Y ₄ are C1-C4 alkyl groups, X ₁ is a carboxy group, X ₂ to X ₅ are hydrogen atoms, 6. The colored resin composition for a color filter according to claim 5, wherein X ⁻ is a tristrifluoromethanesulfonylmethide anion.
9. 5. The colored resin composition according to any one of claims 1 to 4, or a metal phthalocyanine pigment or a colorant compound represented by the following formula (2), or both. A color filter having a cured product layer of the colored resin composition for a color filter according to any one of
   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 -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 or a sulfamoyl group, anion X ^- 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).
10. In the formula (1), R ₂ and R ₁₅ to R ₁₈ are each independently a C1-C4 alkyl group, R ₁ and R ₃ to R ₁₄ are both hydrogen atoms, and X ⁻ is tris (trifluoromethanesulfonyl). In formula (2), all of R _1a to R _6a are hydrogen atoms, all of Y ₁ to Y ₄ are C1-C4 alkyl groups, X ₁ is a carboxy group, X ₂ to The color filter according to claim 9, wherein X ₅ is a hydrogen atom, and X ^- is a tristrifluoromethanesulfonylmethide anion.
11. A display device equipped with the color filter according to claim 9.
12. A solid-state imaging device equipped with the color filter according to claim 9.