JP2014016376A - Color resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter having color characteristics of bright and high definition dye-based color material compound as well as having high reliability with better heat resistance compared to a conventional product.SOLUTION: A coloring resin composition for producing a color filter is easily obtained by using a specific color material compound and in addition blending with such as binder resin, solvent and a hardening agent. The produced color filter has high definition excelling in color characteristic such as contrast and furthermore having high reliability with excellent durability such as heat resistance.

Description

  The present invention relates to a colored resin composition for forming pixels of a color filter, a color filter formed using the same, a liquid crystal display device formed using the color filter, an image pickup device (CCD, CMOS), an organic EL The present invention relates to an electronic display device such as a display.

  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.

  Improvements in color purity, saturation, brightness, and contrast, which are characteristics required for color filters, are 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.

  As an approach for solving these problems, a color filter using a dye is 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 many dyes are significantly inferior in resistance to pigments. For example, in Patent Documents 1 and 2 below, a color filter using a triphenylmethane compound is reported, but the triphenylmethane compound is extremely inferior in light resistance and heat resistance and is not at a practical level. Patent Documents 3 and 4 report color filters using methine dye compounds, but are limited to organic EL applications that do not require resistance such as heat resistance. There is no description of data. Although these dyes are excellent in color characteristics, at present, dye compounds suitable for applications requiring high heat resistance such as liquid crystal display applications have hardly been put into practical use. Accordingly, there is a need for a high-quality color filter that is clear, excellent in color characteristics, and excellent in durability as the next generation.

JP-A-8-94826 Japanese Patent Laid-Open No. 2002-14222 JP 2009-265641 A JP 2009-134906 A JP 63-172772 A

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

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

（式（１）において、Ｒ_１〜Ｒ_６はそれぞれ独立に水素原子、Ｃ１−Ｃ３０のアルキル基、アリール基、ハロゲン原子、アミノ基を表す。Ｒ_１とＲ_２、Ｒ_２とＲ_３、又は、Ｒ_４とＲ_５はそれぞれ独立に／または同時に脂肪族飽和炭化水素系もしくは芳香族系の環状構造を形成できる。Ｙは硫黄原子、酸素原子、アミノ基、置換又は無置換の炭素原子を表す。アニオン部Ｘ⁻はＣ１−Ｃ１０の高次ハロゲン化アルキル基を有するアルキルスルホニルイミドアニオン、アルキルスルホニルメチドアニオン、又はアルキルスルホネートアニオンを表す。）、
（２）式（１）のＸ⁻がビストリフルオロメタンスルホニルイミドアニオン、トリストリフルオロメタンスルホニルメチドアニオンまたはトリフルオロメチルスルホネートアニオンである（１）に記載の着色樹脂組成物、
（３）式（１）のＹが硫黄原子である（１）又は（２）に記載の着色樹脂組成物、
（４）式（１）のＲ_１とＲ_２、Ｒ_２とＲ_３、又は、Ｒ_４とＲ_５がそれぞれ独立に／または同時に芳香族系環状構造を形成した（１）乃至（３）のいずれか一つに記載の着色樹脂組成物、
（５）金属フタロシアニン顔料を含む（１）乃至（４）のいずれか一つに記載の着色樹脂組成物、
（６）（１）乃至(５)のいずれか一つに記載の着色樹脂組成物を用い、パターニングされてなるカラーフィルター用着色硬化膜、
（７）（６）に記載のカラーフィルター用着色硬化膜からなるカラーフィルター、
（８）（７）に記載のカラーフィルターを装着してなる表示装置、
（９）（７）に記載のカラーフィルターを装着してなる固体撮像素子、
に関する。 That is, the present invention
(1) A colored resin composition for a color filter containing a colorant compound represented by the following formula (1), a binder resin, a solvent, a photopolymerization initiator, and a curing agent.

(In Formula (1), R _{1 to} R ₆ each independently represent a hydrogen atom, a C1-C30 alkyl group, an aryl group, a halogen atom, or an amino group. R ₁ and R ₂ , R ₂ and R ₃ , or , R ₄ and R ₅ can independently and / or simultaneously form an aliphatic saturated hydrocarbon or aromatic cyclic structure, and Y represents a sulfur atom, an oxygen atom, an amino group, or a substituted or unsubstituted carbon atom. . anion X ^- represents an alkylsulfonyl imide anion, methide anion, or alkyl sulfonate anion having higher halogenated alkyl group C1-C10),.
(2) The colored resin composition according to (1), wherein X ^{− in the} formula (1) is a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion, or a trifluoromethylsulfonate anion,
(3) The colored resin composition according to (1) or (2), wherein Y in formula (1) is a sulfur atom,
(4) R ₁ and R ₂ , R ₂ and R ₃ , or R ₄ and R _{5 in} formula (1) each independently / or simultaneously formed an aromatic ring structure (1) to (3) The colored resin composition according to any one of the above,
(5) The colored resin composition according to any one of (1) to (4), comprising a metal phthalocyanine pigment,
(6) A colored cured film for a color filter, which is patterned using the colored resin composition according to any one of (1) to (5),
(7) A color filter comprising the colored cured film for a color filter according to (6),
(8) A display device comprising the color filter according to (7).
(9) A solid-state imaging device comprising the color filter according to (7),
About.

  By including a specific color material compound, the colored resin composition of the present invention can provide a highly reliable color filter pixel excellent in heat resistance while being a dye having clear color characteristics.

  The colored resin composition of the present invention contains a binder resin, a solvent, a photopolymerization initiator, a curing agent, and a specific color material compound, and if necessary, a color material compound such as other pigments or dyes, a surface activity. Various additives such as an agent, a thermosetting agent, a polymerization inhibitor, and an ultraviolet absorber can be contained, but are not limited to these, and can be used without particular limitation as components other than the 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, 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 that can be used in the present invention is represented by the formula (1). In R _{1 to} R ₆ 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, 2-adamantyl group, benzyl group and the like.

In R _{1 to} R ₆ of the formula (1), examples of the aryl group include a phenyl group, a naphthyl group, an indolyl group, a quinolyl group, and the like. These may have a substituent, and the substituent is as follows. For example, (C1-C5) alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group; fluorine atom, chlorine atom, bromine atom, iodine atom, etc. Halogen atom: (C1-C6) alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, hexyloxy group; hydroxy (C1-C5) alkyl group such as hydroxyethyl group, hydroxypropyl group ; (C1-C5) alkoxy (C1-C5) such as methoxyethyl group, ethoxyethyl group, ethoxypropyl group, butoxyethyl group; ) Alkyl group; hydroxy (C1-C5) alkoxy group such as 2-hydroxyethoxy group, alkoxy (C1-C5) alkoxy group such as 2-methoxyethoxy group, 2-ethoxyethoxy group; sulfonic acid group, 2-sulfoethyl group Carboxyethyl group, cyanoethyl group, and the like.

R ₁ and R ₂ , R ₂ and R ₃ , or R ₄ and R ₅ in the formula (1) can each independently and / or simultaneously form an aliphatic saturated hydrocarbon or aromatic cyclic structure. Examples include benzene, naphthalene, anthracene, cyclopentane, cyclohexane, cycloheptane and the like, which may have a substituent, and benzene is particularly preferable.

Examples of the amino group in R _{1 to} R ₆ of the formula (1) include a substituted or unsubstituted amino group, and examples of the substituent of the amino group having a substituent include those in R _{1 to} R ₆ described above. The same alkyl group, and specific examples of the alkyl-substituted amino group are particularly preferably a dimethylamino group and a diisobutylamino group.

  As a halogen atom in Formula (1), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

Y in Formula (1) represents a sulfur atom, an oxygen atom, a substituted or unsubstituted amino group, or a substituted or unsubstituted carbon atom. Specific examples of the amino group having a substituent and the substituent of the carbon atom having a substituent include the same alkyl groups as in R _{1 to} R ₆ described above.

表１中、Ｘ⁻がαの場合はトリストリフルオロメタンスルホニルメチドアニオン、βの場合はビストリフルオロメタンスルホニルイミドアニオン、γの場合はトリフルオロメチルスルホネートアニオンをそれぞれ表す。 Although the specific example of the color material compound shown by Formula (1) is shown in Table 1, this invention is not limited to these.
Table 1

In Table 1, X ^- is the case of α each representing tris trifluoromethanesulfonyl methide anion, bistrifluoromethanesulfonylimide anion in the case of beta, trifluoromethyl sulfonate anion in the case of gamma.

The colorant 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" (pages 373-375) issued by Gihodo Co., Ltd. anion wherein X ^- purchased commercially is chlorine anions can be synthesized by salt plus the corresponding salt or acid exchange.

When synthesized by salt exchange colorant compound in the present invention are, for example, anion X ^- reaction solvent is colorant compound is chlorine anions (e.g., water or 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 is 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.

  It is represented by the above formula (1) contained in the total solid content of the colored resin composition of the present invention (referring to the total amount of solid content consisting of a colorant compound, a binder resin, a curing agent, etc., which is also used synonymously hereinafter). The content of the coloring material compound is preferably 0.1 to 60 parts by mass, more preferably 3 to 30 parts by mass. When the content is larger than this range, problems of precipitation and aggregation occur, or the adhesiveness with the substrate is lowered due to insufficient curing. When the content is small, there is no major problem, but there is a tendency that sufficient color purity cannot be obtained as color characteristics.

  The binder resin used in the present invention functions as a dispersant and a dispersion aid because of dispersion stability at the time of pigment dispersion. On the other hand, as a design of a photolithography method, in a development processing step at the time of manufacturing a color filter. It is desirable that it is soluble in the alkaline developer to be used, and further it has sufficient curing characteristics with a photopolymerization initiator, a photopolymerizable monomer, etc. in order to form a good fine pattern. The obtained pigment-dispersed resin composition must have good compatibility with constituent materials such as a photopolymerization initiator, a photopolymerizable monomer, and a pigment dispersion, and be stable so as not to cause precipitation or aggregation. In the case of the inkjet method, alkali solubility is not particularly necessary, 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, but more preferably one or more of the following carboxyl groups or ethylenically unsaturated monomers having a hydroxyl group or other copolymerizable aromatic hydrocarbon groups. And a copolymer such as an ethylenically unsaturated monomer having an aliphatic hydrocarbon group. In addition, those having an epoxy group at the side chain or terminal, and epoxy acrylate resins to which acrylate is added can also be used. These monomers may be used alone or in combination of two or more.

  Examples of the carboxyl group-containing unsaturated monomer that can be used in the present invention include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; maleic acid, anhydrous Unsaturated dicarboxylic acids (anhydrides) such as maleic acid, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid; trivalent or higher unsaturated polycarboxylic acids (anhydrides); Examples include 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl 2-hydroxypropyl phthalate, 2-acryloyloxyethyl 2-hydroxyethyl phthalic acid, and the like. These ethylenically unsaturated monomers having a carboxyl group can be used alone or in admixture of two or more.

  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, 2 Hydroxyl-terminated polyalkylene glycols such as (2-hydroxyethyloxy) ethyl (meth) acrylate, glycerin monomethacrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) monomethacrylate Examples include mono (meth) acrylate. These ethylenically unsaturated monomers having a hydroxyl group can be used alone or in admixture of two or more.

  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, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, 2-hydroxy- 3-phenoxypropyl Unsaturated carboxylic acid esters such as (meth) acrylate, o-phenylphenol glycidyl 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, 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] dec-4-methyl = (meth) acrylate, cyclodecyl (meth) acrylate, 2 -Alicyclic skeletons such as (meth) acryloyloxyethyl hexahydrophthalic acid and t-butylcyclohexyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene Glycol) monohydroxyl-terminated polyalkylene glycol mono (meth) acrylates such as monomethacrylate; methoxypolyethylene glycol monomethacrylate, lauroxypolyethyleneglycol mono (meth) acrylate, octoxypolyethyleneglycol poly Alkyl-terminated polyalkylene glycol mono (meth) acrylates such as propylene glycol mono (meth) acrylate, nonylphenoxypolyethylene glycol monoacrylate, nonylphenoxypolypropylene glycol monoacrylate, allyloxypolyethylene glycol-polypropylene glycol mono (meth) acrylate; Unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate; glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexane Unsaturated carboxylic acid glycidyl esters such as xyl) methyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and the like; vinyl Unsaturated ethers such as methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide; acrylamide, methacrylamide, α- Chloroacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, N- (meth) acryloylphthalimide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxy) Ciethyl) unsaturated amides or unsaturated imides such as methacrylamide and maleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl acrylate, polymethyl methacrylate, poly n-butyl acrylate, Examples thereof include macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of a polymer molecular chain such as poly n-butyl methacrylate and polysilicone. These other unsaturated monomers can be used alone or in admixture of two or more.

  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), ORGA-3060 (manufactured by Osaka Organic Chemical), AX3-BNX02 (manufactured by Nippon Shokubai), UXE-3024 (Nippon Kayaku) Manufactured), UXE-3000 (manufactured by Nippon Kayaku), ZGA-287H (manufactured by Nippon Kayaku), TCR-1338H (manufactured by Nippon Kayaku), ZXR-1722H (manufactured by Nippon Kayaku), ZFR-1401H (manufactured by Nippon Kayaku) And ZCR-1642 (manufactured by Nippon Kayaku) can also be used.

  When the solubility of the colorant compound represented by formula (1) in the colored resin composition is low, it can be dispersed using a dispersant, a dispersion aid or the like in the same manner as the pigment which is an optional component described later. Also good.

  In general, examples of the dispersant and the dispersion aid used when dispersing the pigment include a pigment-based dispersant, a resin-based dispersant, a surfactant, and the like having good adsorptivity to the pigment. Known examples of the dye-based dispersant include a method of mixing a sulfonated pigment or a metal salt thereof described in Patent Document 5 with a pigment, a method of mixing a substituted aminomethyl derivative, and the like. Some resin dispersants are nonpolar nonionic, but polymer resins having an acid value, an amine value, etc. that give good pigment adsorption are common, such as acrylic resins, polyurethane resins, and polycarboxylic acids. , Polyamide resin, polyester resin and the like. Specific examples thereof include ED211 (manufactured by Enomoto Kasei), Ajisper PB821 (manufactured by Ajinomoto Fine Techno), Solsperse 71000 (manufactured by Avicia), and the like.

  When producing the binder resin (copolymer) used in the present invention, 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 benzoylmethyl ethyl ketone peroxide and the like. The content rate of a polymerization initiator is 0.01-25 mass parts with respect to the sum total of all the monomers used for the synthesis | combination of a copolymer. In the case of synthesizing a copolymer, it is preferable to use an organic solvent described below, but a solvent having sufficient dissolving power for the monofunctional monomer and polymerization initiator used is 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, and more preferably 3 to 20 hours. The preferred acid value of the copolymer is 10 to 300 (mgKOH / g), and the preferred hydroxyl value is 10 to 200 (mgKOH / g). When the acid value or hydroxyl value is 10 or less, developability is lowered. As for the weight average molecular weight (Mw) of a copolymer, 2000-400000 are preferable and 3000-100000 are more preferable. When the weight average molecular weight is 2000 or less, or 400000 or more, sensitivity, developability and the like are lowered.

  In this invention, the said binder resin can be used individually or in mixture of 2 or more types. Content of binder resin in this invention is 0.5-99 mass parts normally with respect to 100 mass parts of total solids of a colored resin composition, Preferably it is 5-50 mass parts. 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 photopolymerization monomer in the case of radical polymerization, an epoxy resin in the case of ion curing, and a melamine curing agent. Specific examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethyleneglycol. (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 Di (meth) acrylate, bisphenol-fluorene type epoxy di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanuric Acid tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, Kayrad RP-1040 ( Nippon Kayaku), Kayrad DPCA-30 (Nippon Kayaku), UA-33H (Shin Nakamura Chemical), UA-53H (Shin Nakamura Chemical), M-8060 (Toagosei); Thiol-based polymerization monomer As TEMPIC (manufactured by Sakai Chemical), TMMP (manufactured by Sakai Chemical), PEMP (manufactured by Sakai Chemical), and DPMP (manufactured by Sakai Chemical); as epoxy resins, Nippon Kayaku products NC-6000, NC-3000, EOCN- 1020, XD-1000, EPPN-501H, BREN-S, NC-7300L, Daicel Chemical Product's Celoxite 2021P, EHPE3150, Cyclomer M100, Epolide PB3600, Japan Epoxy Resin Product Epicoat 828, Epicoat YX8000, Epicoat YX4000, Silaace S510 (Chisso), TEPIC (Nissan Chemical Industries), etc .; Examples of melamine curing agents include methylolated melamine and Mw-30 (Sanwa Chemical). These can be used alone or in admixture of two or more. These content is 1-80 mass parts with respect to 100 mass parts of total solids of a colored resin composition, Preferably it is 5-30 mass parts.

  Two or more colorant compounds represented by the formula (1) may be mixed or used alone, but other dyes or pigments may be mixed. The specific color material compound used in the colored resin composition of the present invention can be applied to a blue pixel, a red pixel, a green pixel, and the like depending on its chemical structure, so that it is known blue, red, yellow, green, violet, orange, cyan. , Magenta dyes, or pigments of the same color, for example, blue or violet dyes or pigments for blue pixels, red or yellow dyes or pigments for red pixels, green or yellow dyes or pigments for green pixels Etc. are desirable.

  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. These content is 0-60 mass parts with respect to 100 mass parts of total solid of a colored resin composition, Preferably it is 5-30 mass parts. Specific examples of these various pigments and dyes are shown below.

  The organic pigment that can be used in combination with the colored resin composition for the blue pixel of the present invention is not particularly limited. For example, anthraquinone, phthalocyanine, triphenylmethane, benzimidazolone, quinacridone, azo chelate, azo , Isoindoline, isoindolinone, pyranthrone, indanthrone, anthrapyrimidine, dibromoanthanthrone, flavanthrone, perylene, perinone, quinophthalone, thioindigo, dioxazine, quinacridone, xanthene Examples include pigments such as pigments; lake pigments in which acid dyes, basic dyes, direct dyes and the like are insolubilized with respective precipitants, dyed lake pigments, and the like. 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, 4, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, Pigment Violet 23 and Pigment Blue 15: 6 which is a metal phthalocyanine pigment are particularly preferable because of good hue and resistance.

  The organic pigment that can be used in combination with the colored resin composition of the present invention for the color filter pixels of other colors is not particularly limited. For example, pigment reds 254 and 177 and pigment yellows 150, 139, and 138 are used for red pixels. For green pixels, pigment green 7, 36, 58, pigment yellow 150, 139, 138, etc. are preferably used. Among these, Pigment Red 254 and Pigment Green 36 and 58, which are metal phthalocyanine pigments, are particularly preferable due to good hue and resistance.

  The inorganic pigment that can be used in combination with the colored resin composition of the present invention is not particularly limited. For example, composite metal oxide pigment, carbon black, black low-order titanium oxide, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow Lead, Bengala, ultramarine, 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 Products, sulfates, metal hydroxides, metal carbonates and the like.

  The dye that can be used in combination with the colored resin composition of the present invention is not particularly limited, and examples thereof include acidic 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, dyes that are insoluble in organic solvents are well-known formulations. For example, in the case of acidic dyes or basic dyes, organic amine compounds (for example, n-propylamine, ethylhexylpropionate amine, etc.) are reacted to form amine salt dyes. It is known to modify or to make a dye having a sulfonamide group by reacting the sulfonic acid group with the same organic amine compound. 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; Solvent Violet 8, 9 as violet dye; Violet 4, 5, 14; Basic Violet 10, Basic Red 1, 14, Basic Yellow 1, 19, 21, 40, basic orange 22, 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, ion-curing photo-acid generators or photo-base generators. 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 Dozol, diazonaphthoquinone initiator, and commercially available Kayacure DMBI, Kayacure BDK, Kayacure BP-100, Kayacure BMBI, Kayacure DETX-S, Kayacure EPA (all manufactured by Nippon Kayaku), Darocure 1173, Darocure 1116 (Iremo Merck) Japan)), Irgacure 907, Irgacure 369 (Ciba Specialty Chemicals), Irgacure 379EG (Ciba Specialty Chemicals), Irgacure OX-01 (Ciba Specialty Chemicals), Irgacure OXE- 02 (Ciba Specialty Chemicals), Irgacure PAG103 (Ciba Specialty Chemicals), TME-Triazine (Sanwa Chemical), Biimi Tetrazole (Kurogane Kasei), STR-110, STR-1 (manufactured by less Bae Chemicals any), 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. These contents are 0.5 to 50 parts by mass, preferably 1 to 25 parts by mass when the total solid content of the colored resinous composition is 100 parts by mass.

  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.

  You may use these individually or in combination of 2 or more types. Moreover, 40-10000 mass parts is preferable with respect to 100 mass parts of total solids of a colored resin composition, and, as for the usage-amount of an organic solvent, 100-1000 mass parts is more preferable.

  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. In addition, other pigments and dyes can be added as necessary, but if the pigment or dye has low solubility, a dispersion is obtained by a dispersing machine such as a paint shaker using an appropriate dispersant, In addition to the colored resin composition, it is mixed.

  If necessary, the colored resin composition of the present invention may further contain various additives such as fillers, surfactants, thermal polymerization inhibitors, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, 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, a method for preparing the cured product from the colored resin composition of the present invention will be described. First, the colored resin composition of the present invention is formed on a substrate such as a glass substrate or a silicon substrate by a method such as a spin coating method, a roll coating method, a slit and spin method, a die coating method, or a bar coating method. It is applied so as to be 1 to 20 μm, preferably 0.5 to 5 μm, and if necessary, in a vacuum chamber, under drying conditions, at a temperature of 23 to 150 ° C. for 1 to 60 minutes, more preferably at a temperature of 60 to The film is dried under reduced pressure at 120 ° C. for 1 to 10 minutes, and further pre-baked 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. After removing the unirradiated part by development and rinsing with water, the post-bake treatment and treatment are performed at a temperature of 130 to 300 ° C. for 1 to 120 minutes, more preferably at 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, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, or the like is used. In the present invention, it is preferable to use an aqueous solution containing both an alkali agent and a surfactant. Development is usually performed at 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 cured product 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, etc., and the color filter is as described above. It has the patterned pixel which consists of hardened | cured material of the colored resin composition of this invention prepared in this way.

  Among the display devices of the present invention, the liquid crystal display device is manufactured 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 An organic EL display is produced by forming the color filter of the present invention on either the upper or lower side of a 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.

  EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In Examples, “%” means “% by mass” unless otherwise specified. Further, the spectral transmittance was measured with a spectrophotometer “Shimadzu UV-3150”, the chromaticity in the XYZ color system was calculated, and the resistance of the colored body was evaluated.

１００ｍｌビーカーに、上記式（１００）の化合物１ｇ、水２０ｇを仕込み、常温で３０分間攪拌した。これにＤＭＦ１ｇにトリストリフルオロメタンスルホニウムメチドのセシウム塩１ｇを溶解させた溶液を滴下し、３時間攪拌した。析出物をろ取、水洗、乾燥し、染料（表１の化合物Ｎｏ．１）０．８ｇを得た。分解温度２６０℃、極大吸収波長：６０１ｍ（シクロヘキサノン） Synthesis example 1
A compound represented by the following formula (100) was obtained by the method described in Example 1 of JP-A-52-76329.

In a 100 ml beaker, 1 g of the compound of the above formula (100) 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 metide in 1 g of DMF was added dropwise thereto and stirred for 3 hours. The precipitate was collected by filtration, washed with water and dried to obtain 0.8 g of a dye (Compound No. 1 in Table 1). Decomposition temperature 260 ° C, maximum absorption wavelength: 601m (cyclohexanone)

Synthesis example 2
A 300 ml beaker was charged with 4 parts of Basic Red 14 chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 150 parts of water, and stirred at room temperature for 20 minutes. A solution prepared by dissolving 5.7 parts of a cesium salt of tristrifluoromethanesulfonium methide in 5.7 parts of DMF was added dropwise thereto and stirred for 3 hours. The precipitate was collected by filtration, washed with water, and dried to obtain a dye (Compound No. 5 in Table 1). Maximum absorption wavelength: 532 nm (cyclohexanone)

Synthesis example 3
A 500 ml beaker was charged with 1 part of Basic Orange 22 chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 200 parts of water and stirred at 50 ° C. for 30 minutes. A solution obtained by dissolving 1.4 parts of a cesium salt of tristrifluoromethanesulfonium metide in 1.4 parts of DMF was added dropwise thereto, and the mixture was stirred for 2 hours. The precipitate was collected by filtration, washed with water, and dried to obtain a dye (Compound No. 6 in Table 1). Maximum absorption wavelength: 508 nm (cyclohexanone)

Synthesis example 4
A 500 ml beaker was charged with 5 parts of Basic Yellow 1 chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 parts of water and stirred at 50 ° C. for 20 minutes. A solution prepared by dissolving 9 parts of a cesium salt of tristrifluoromethanesulfonium methide in 9 parts of DMF was added dropwise thereto and stirred for 3 hours. The precipitate was collected by filtration, washed with water, and dried to obtain a dye (Compound No. 7 in Table 1). Maximum absorption wavelength: 419 nm (cyclohexanone)

Synthesis Example 5 (Preparation 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. Then, it heated up to 80 degreeC and stirred at 80-85 degreeC 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 DPHA (manufactured by Nippon Kayaku) as a photopolymerizable monomer, 1.5 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator and Kayacure DETX -S (Nippon Kayaku Co., Ltd.) 0.6 g, Compound No. of Synthesis Example 1 0.6 g of 1 and 20 g of cyclohexanone and 8.6 g of propylene glycol monomethyl ether acetate as a solvent were mixed to obtain a colored resin composition of the present invention.

Example 2
C. I. Pigment Blue 15: 6 / Addisper PB821 / Solsperse 5000 / PGMEA = 15.0 / 6.0 / 1.0 / 78.0 (mass ratio), and then mixed with 400 g of 0.3 mm zirconia beads. The pigment dispersion liquid 1 was obtained by processing for 60 minutes with a paint shaker and filtering. 19 g of pigment dispersion 1 was added to Example 1 to obtain a colored resin composition of the present invention.

Example 3
Compound No. 1 of Synthesis Example 1 was used as the colorant compound. 1 was synthesized as Compound No. 1 of Synthesis Example 2. The composition was the same as in Example 1 except that the composition was changed to 5.

Example 4
C. I. After mixing at a composition ratio of Pigment Red 254 / Azisper PB821 / PGMEA = 15.0 / 10.0 / 75.0 (mass ratio), 400 g of 0.3 mm zirconia beads were added, and the mixture was processed with a paint shaker for 60 minutes. The pigment dispersion 2 was obtained by filtration. 19 g of pigment dispersion 2 was added to Example 3 to obtain a colored resin composition of the present invention.

Example 5
Compound No. 1 of Synthesis Example 1 was used as the colorant compound. 1 is compound No. 1 of Synthesis Example 3. The composition was the same as in Example 1 except that the composition was changed to 6.

Example 6
As a colorant compound, the compound No. 1 of Synthesis Example 2 was used. 5 is compound No. 5 of Synthesis Example 3. The composition was the same as in Example 4 except that the composition was changed to 6.

Example 7
Compound No. 1 of Synthesis Example 1 was used as the colorant compound. 1 is compound No. 1 of Synthesis Example 4. The composition was the same as in Example 1 except that the composition was changed to 7.

Comparative Example 1
Compound No. 1 of Example 1 1 was replaced with the pigment dispersion 1 described in Example 2 to obtain a colored resin composition containing only the pigment as the colorant compound.

Comparative Example 2
Compound No. 1 of Synthesis Example 1 The composition was the same as in Example 1 except that 1 was changed to the colorant compound of the formula (100).

Comparative Example 3
Compound No. 1 of Synthesis Example 1 The composition was the same as in Example 1 except that 1 was changed to Basic Blue 7, which is a conventional dye.

Comparative Example 4
Compound No. 1 of Synthesis Example 1 The composition was the same as in Example 1 except that 1 was changed to Basic Red 14 which is a conventional dye.

Comparative Example 5
Compound No. 1 of Synthesis Example 1 The composition was the same as in Example 1 except that 1 was changed to Basic Orange 22, which is a conventional dye.

  The colored resin composition (Examples 1 to 7) obtained above is applied on the substrate, pre-baked (80 ° C. × 100 seconds), and after curing by exposure through a mask, contains a surfactant. The pattern was obtained by developing with an alkaline aqueous solution, rinsing with water, and heating at 200 ° C. The obtained pattern had a resolution of 5 μm square in line and space, and no residue or peeling of pixels was confirmed.

About Evaluation of Heat Resistance and Contrast A substrate for evaluation of heat resistance and contrast was prepared by coating each composition on a glass substrate in the same manner as described above, and exposing the entire surface and post baking (200 ° C. × 5 minutes). In both cases, a color filter substrate having clear characteristics was obtained. Thereafter, each evaluation was performed as described below.
The heat resistance was evaluated by measuring the spectral transmittance of the evaluation substrate before and after the treatment at 200 ° C. for 120 minutes and calculating the color difference (ΔEab) before and after the heat treatment.
Contrast was measured with a contrast meter (CT-1 manufactured by Osaka Co., Ltd.) using the evaluation substrate, and the luminance value (cd / cm ² ) when the ^two polarizing plates were parallel to each other (cd / cm ² ). The contrast was calculated from the ratio of cm ² ) (brightness value in parallel / brightness value in orthogonal).
The heat resistance evaluation results are shown in Table 2, and the contrast evaluation results are shown in Table 3.

実施例１は吸収極大波長６０１ｎｍで透過率３０％であったのに対し、比較例２は耐熱不足によりポストベーク時に大きく退色して同波長で透過率８０％であったため評価できなかった。実施例３は吸収極大波長５３２ｎｍで透過率３０％であったが、比較例４は透過率９０％であり、実施例５は吸収極大波長５０８ｎｍで透過率１３％であったが、比較例５は透過率７０％であった。すなわち、表２の耐熱性の評価結果から、実施例１〜７は従来の染料である比較例２〜５と比べると、いずれも本発明のトリストリフルオロメタンスルホニウムメチド塩とすることにより耐熱性が顕著に向上することがわかる。また、実施例２、４、６は本発明の色材化合物に顔料を混合しているが、特に不溶分等が析出することもなく状態も良好であり、このことは本発明の色材化合物の幅広い適用性を示唆していると言える。 Table 2 Evaluation results of heat resistance

While Example 1 had a maximum absorption wavelength of 601 nm and a transmittance of 30%, Comparative Example 2 could not be evaluated because it was discolored greatly during post-baking due to insufficient heat resistance and had a transmittance of 80% at the same wavelength. Example 3 had a transmittance of 30% at an absorption maximum wavelength of 532 nm, while Comparative Example 4 had a transmittance of 90%, and Example 5 had a transmittance of 13% at an absorption maximum wavelength of 508 nm. The transmittance was 70%. That is, from the evaluation results of heat resistance in Table 2, Examples 1 to 7 are more heat resistant by using tristrifluoromethanesulfonium methide salt of the present invention as compared with Comparative Examples 2 to 5 which are conventional dyes. It can be seen that is significantly improved. In Examples 2, 4, and 6, the colorant compound of the present invention is mixed with a pigment. In particular, the insoluble matter is not precipitated and the state is good. It can be said that this suggests a wide range of applicability.

Table 3 Contrast evaluation results

  From the contrast evaluation results in Table 3, both Examples 1 and 2 showed better results than the pigment of Comparative Example 1. In particular, Example 1 is the result of the dye alone and shows 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.

  From the above, the colored resin composition of the present invention using a specific color material compound uses a dye having clear color characteristics as the color material compound, but has excellent color filter characteristics (heat resistance, contrast, etc.). Therefore, it is possible to obtain a high-quality and highly reliable color filter. In addition, it can be used by being well mixed with pigments depending on the application, and shows wide applicability.

Claims (9)

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

(In Formula (1), R _{1 to} R ₆ each independently represent a hydrogen atom, a C1-C30 alkyl group, an aryl group, a halogen atom, or an amino group. R ₁ and R ₂ , R ₂ and R ₃ , or , R ₄ and R ₅ can independently and / or simultaneously form an aliphatic saturated hydrocarbon or aromatic cyclic structure, and Y represents a sulfur atom, an oxygen atom, an amino group, or a substituted or unsubstituted carbon atom. . anion X ^- represents an alkylsulfonyl imide anion, methide anion, or alkyl sulfonate anion having higher halogenated alkyl group C1-C10).. The colored resin composition according to claim 1, wherein X ^{− in} formula (1) is a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion, or a trifluoromethylsulfonate anion. The colored resin composition according to claim 1 or 2, wherein Y in formula (1) is a sulfur atom. The R ₁ and R ₂ , R ₂ and R ₃ , R ₄ and R _{5 in the} formula (1) each independently or simultaneously form an aromatic ring structure. Colored resin composition. The colored resin composition according to any one of claims 1 to 4, comprising a metal phthalocyanine pigment. A colored cured film for a color filter, which is patterned using the colored resin composition according to any one of claims 1 to 5. A color filter comprising the colored cured film for a color filter according to claim 6. A display device comprising the color filter according to claim 7. A solid-state imaging device comprising the color filter according to claim 7.