JP2014177567A - Xanthene compound and coloring resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide novel xanthene compounds excellent in heat resistance and fastness and a coloring resin composition which enables production of a red color filter using the compounds as a dye.SOLUTION: Xanthene compounds of formula (1) are provided. In the formula (1), Rto Rare independently H or a 1-4C alkyl group; Ris a carboxylic acid ester group; Rto Rare independently H, a halogen atom, a cyano group, a nitro group or a 1-4C alkyl group; and Ris H, a 1-10C alkyl group or a 5-10C aromatic hydrocarbon group.

Description

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

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

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

As another 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, when a dye having fluorescence is used, it is known that a decrease in contrast occurs due to unpolarized fluorescence emitted from a dye excited by backlight light.
Furthermore, for display applications that require long-term reliability such as those for televisions, excellent light resistance and heat resistance are required, but dyes are generally less resistant than pigments. C. I. Xanthene compounds such as Basic Violet 10 have been used in a wide range of applications such as various paints, water-based inks, oil-based inks, ink-jet inks, and color filters as red to violet dyes. Is different depending on the application, but it is required that the hue is clear, the color is high, and the colored product is robust against light, heat and the like. For example, Patent Document 1 describes a xanthene dye composed of a cation moiety of a xanthene compound, chloride ion, and further zinc chloride. As a result of the study by the present inventors, the xanthene dye described in Patent Document 1 is described. Has insufficient fastness such as light resistance, heat resistance, water resistance, and heat and moisture resistance. Patent Document 2 relates to a xanthene dye having a metal complex having an azo compound as a ligand as a counter ion, but the document does not describe any heat resistance of the color filter. Patent Document 3 relates to a colored photosensitive resin composition containing a xanthene dye having a metal complex having an azo compound as a ligand as a counter ion, but does not describe any heat resistance and contrast of the color filter. Absent. That is, the current state is that a vivid red color filter having excellent reliability and high durability, which is required in the field of liquid crystal display devices and solid-state imaging devices, has hardly been put into practical use.

JP-A-5-271559 JP2012-122007A JP 2012-185383 A

  The present invention relates to a novel xanthene compound excellent in fastness such as heat resistance, a colored resin composition capable of producing a red color filter excellent in heat resistance and contrast using the compound as a dye, and using the same The purpose is to provide a manufactured color filter.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that xanthene compounds having a specific structure drastically improve fastness such as heat resistance as compared with conventional ones, and include the xanthene compounds. The present inventors have found that the above problems can be solved by using a colored resin composition, and have completed the present invention.

That is, the present invention
(1) Xanthene compound represented by formula (1)

(In Formula (1), R ^{1 to} R ⁶ are each independently a hydrogen atom; a substituent selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, a cyano group, a carboxyl group, an amide group, a sulfonamide group, and a sulfo group. Represents an alkyl group having 1 to 4 carbon atoms or an unsubstituted alkyl group having 1 to 4 carbon atoms, R ⁷ represents a carboxylic acid ester group, R ^{8 to} R ¹¹ are each independently a hydrogen atom; Cyano group; nitro group; an alkyl group having 1 to 4 carbon atoms or an unsubstituted alkyl group having 1 to 4 carbon atoms having a substituent selected from the group consisting of a halogen atom, an alkoxy group, a cyano group, and a nitro group; .R ¹² is a hydrogen atom, a halogen atom, hydroxy group, an alkoxy group, a cyano group, a carboxyl group, the group consisting of an amido group, a sulfonamido group, and a sulfo group An alkyl group having 1 to 10 carbon atoms having a selected substituent; an unsubstituted alkyl group having 1 to 10 carbon atoms; a halogen atom, a hydroxy group, an alkoxy group, a cyano group, a carboxyl group, an amide group, a sulfonamide group, and A C5-C10 aromatic hydrocarbon group or an unsubstituted C5-C10 aromatic hydrocarbon group having a substituent selected from the group consisting of sulfo groups).
(2) R ^{1 to} R ⁶ in Formula (1) are each independently a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms, R ⁸ , R ⁹ and R ¹¹ are hydrogen atoms, and R ¹⁰ Wherein x is a halogen atom, a cyano group or a nitro group, and R ¹² is a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms,
(3) R ^{1 to} R ⁴ in Formula (1) are ethyl groups, R ^{5 to} R ⁶ are hydrogen atoms, R ¹⁰ is a nitro group, and R ¹² is an unsubstituted C 1-5. The xanthene compound according to (2), which is an alkyl group,
(4) A colored resin composition for a color filter containing the xanthene compound according to any one of (1) to (3), a binder resin, a curing agent, a photopolymerization initiator, and / or a curing accelerator,
(5) The colored resin composition according to (4), further containing a pigment,
(6) The pigment is C.I. I. Pigment red 177, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment yellow 150 and C.I. I. The colored resin composition according to (5), which is one or more selected from the group consisting of CI Pigment Yellow 138,
(7) A colored cured film for a color filter, which is patterned using the colored resin composition according to any one of (4) to (6),
(8) A color filter comprising the colored cured film for a color filter according to (7),
(9) A liquid crystal display device equipped with the color filter according to (8),
(10) An organic EL display equipped with the color filter according to (8),
(11) A solid-state imaging device equipped with the color filter according to (8),
About.

  The xanthene compound of the present invention is excellent in sharpness and color developability, and a colored cured film formed using a colored resin composition containing the compound has characteristics excellent in heat resistance and contrast. That is, the compound of the present invention can be applied to a wide range of uses such as color filter inks and inkjet inks.

The xanthene compound of the present invention is represented by the formula (1).
In formula (1), R ^{1 to} R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group having 1 to 4 carbon atoms is an alkyl group having 1 to 4 carbon atoms. It is not limited to either linear or branched. The alkyl group may have a substituent.
Specific examples of the alkyl group having 1 to 4 carbon atoms in R ^{1 to} R ⁶ of the formula (1) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso-butyl group. , Sec-butyl group and t-butyl group.

Examples of the substituent that the alkyl group represented by R ^{1 to} R ^{6 in} Formula (1) may have include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a hydroxy group, and an alkoxy group (for example, , Methoxy group, ethoxy group, iso-butoxy group, etc.), cyano group, carboxyl group, amide group (eg, acetamide group), sulfonamide group (eg, methanesulfonamide group, ethanesulfonamide group, propanesulfonamide group) Etc.) or a sulfo group.

R ^{1 to} R ⁶ in formula (1) are each independently a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms (an unsubstituted alkyl group is a substituent composed of only a carbon atom and a hydrogen atom) In the following, the term “unsubstituted” is preferably used in the same meaning).
More specifically, as R ^{1 to} R ⁴ in Formula (1), an unsubstituted alkyl group having 2 to 4 carbon atoms is preferable, and an ethyl group is more preferable.
Moreover, as R < ⁵ > -R < ⁶ > in Formula (1), it is preferable that they are a hydrogen atom or a methyl group, and it is more preferable that it is a hydrogen atom.

In formula (1), R ⁷ represents a carboxylic acid ester group.
Specific examples of the carboxylic acid ester group in R ⁷ of the formula (1) include a methyl ester group, an ethyl ester group, an n-propyl ester group, an iso-propyl ester group, an n-butyl ester group, an iso-butyl ester group, Examples include sec-butyl ester group, t-butyl ester group, pentyl ester group, cyclopentyl ester group, hexyl ester group, cyclohexyl ester group, and benzyl ester group.

R ⁷ in formula (1) is preferably a methyl ester group, an ethyl ester group or a benzyl ester group, and more preferably a methyl ester group.

In formula (1), R ^{8 to} R ¹¹ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, or an alkyl group having 1 to 4 carbon atoms, and the alkyl group having 1 to 4 carbon atoms has If it is 1-4 alkyl groups, it will not be limited to either a linear form or a branched structure. The alkyl group may have a substituent.

Specific examples of the alkyl group having 1 to 4 carbon atoms in R ^{8 to} R ¹¹ in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso-butyl group. , Sec-butyl group and t-butyl group.

Examples of the substituent that the alkyl group represented by R ^{8 to} R ^{11 in} Formula (1) may have include, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxy group (for example, a methoxy group) Ethoxy group, iso-butoxy group, etc.), cyano group or nitro group.

R ^{8 to} R ⁹ and R ¹¹ in Formula (1) are preferably hydrogen atoms.

R ¹⁰ in formula (1) is preferably a halogen atom, a cyano group or a nitro group, more preferably a halogen atom or a nitro group, and still more preferably a nitro group.

In the formula (1), R ¹² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is not limited to any of linear, branched or cyclic as long as the alkyl group has 1 to 10 carbon atoms. Moreover, this C1-C10 alkyl group and this C5-C10 aromatic hydrocarbon group may have a substituent.

Specific examples of the alkyl group having 1 to 10 carbon atoms in R ¹² of the formula (1) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, sec- Butyl group, t-butyl group, n-pentyl group, iso-pentyl group, t-pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cyclopentyl group, cyclohexyl group, vinyl group, allyl group, Propenyl, pentynyl, butenyl, hexenyl, hexadienyl, isopropenyl, isohexenyl, cyclohexenyl, cyclopentadienyl, ethynyl, propynyl, hexynyl, isohexynyl and cyclo A hexynyl group etc. are mentioned.

Specific examples of the aromatic hydrocarbon group having 5 to 10 carbon atoms in R ¹² of the formula (1) include a phenyl group, a naphthyl group, and an azulenyl group.

  Examples of the substituent that the alkyl group having 1 to 10 carbon atoms and the aromatic hydrocarbon group having 5 to 10 carbon atoms may have include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom). , Hydroxy group, alkoxy group (eg methoxy group, ethoxy group, iso-butoxy group etc.), cyano group, carboxyl group, amide group (eg acetamide group etc.), sulfonamide group (eg methanesulfonamide group, ethane) A sulfonamide group, a propanesulfonamide group, etc.) or a sulfo group.

R ¹² in Formula (1) is preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms, more preferably an unsubstituted alkyl group having 1 to 5 carbon atoms, n- More preferably, it is a butyl group.
The xanthene compounds represented by the formula (1) of the present invention, more preferably a combination of the above R ¹ to R ¹² each preferred, more preferably a combination of more preferable ones.

  The xanthene compound represented by the formula (1) of the present invention is, for example, a condensation synthesized according to a known method described in Yutaka Hosoda, “Theoretical Manufacturing Dye Chemistry” (pages 373-375) published by Gihodo Co., Ltd. The product can be synthesized by salt exchange using a commercially available corresponding salt. That is, a xanthene compound obtained by condensing phthalic anhydride, the corresponding N, N-dialkylphenol, and a phthalic acid derivative can be obtained by salt exchange using a metal complex salt having an azo compound as a ligand. it can. Moreover, it can synthesize | combine by purchasing the commercially available xanthene compound whose counter ion is a chlorine ion etc., adding a corresponding salt, and carrying out salt exchange.

  The salt of the metal complex having the azo compound represented by the formula (1) of the present invention as a ligand can be obtained by various methods. For example, “Theoretical production dye” by Yutaka Hosoda published by Gihodo Co., Ltd. It can be synthesized according to a known method described in “Chemistry” (page 601). That is, a salt of a metal complex having an azo compound as a ligand can be synthesized by allowing an organic cobalt salt to act on an azo compound obtained by diazo coupling of an o-aminophenol compound and a pyridone compound.

  Specific examples of the compound represented by the above formula (1) are shown below, but the present invention is not limited thereto.

The color filter resin composition of the present invention contains a xanthene compound represented by the above formula (1), a binder resin, a curing agent, a photopolymerization initiator and / or a curing accelerator.
The content of the xanthene compound represented by formula (1) in the colored resin composition for color filters of the present invention is the total solid content of the colored resin composition of the present invention (compound represented by formula (1), binder resin) The total amount of solids other than the organic solvent, such as a curing agent, etc. is also used synonymously hereinafter.) For 100 parts by mass, usually 0.01 to 50 parts by mass, preferably 0.5 to 30 parts by mass, More preferably, it is 1-10 mass parts. When the content is larger than this range, precipitation or aggregation may occur, or adhesion with the substrate may decrease due to insufficient curing. On the other hand, when the content is small, there is a possibility that sufficient color purity cannot be obtained as color characteristics.

  The binder resin contained in the colored resin composition for a color filter of the present invention includes a dispersant and a dispersion aid because of dispersion stability during dispersion of a colorant compound such as a xanthene compound or a pigment represented by the formula (1). However, when the colored resin composition is used in a photolithography method, it is desirable that the colored resin composition is soluble in an alkaline developer used in a development processing step when producing a color filter. In order to form a good fine pattern, it is desirable that the binder resin has sufficient curing characteristics with a photopolymerization initiator, a photopolymerizable monomer, etc., and the binder resin is represented by the formula (1). Good compatibility with constituent materials such as colorant compounds such as xanthene compounds, photopolymerization initiators, photopolymerizable monomers, pigment dispersions, and the like so long as the colored resin composition does not cause precipitation or aggregation Don't be. When the colored resin composition is used in the ink jet method, alkali solubility is not particularly required, and therefore a binder resin having good compatibility with other constituent materials may be selected.

  As the binder resin, known resins can be used, but more preferably, one or more of the following carboxyl groups, ethylenically unsaturated monomers having a hydroxyl group, or other copolymerizable aromatic hydrocarbon groups, A copolymer such as an ethylenically unsaturated monomer having an aliphatic hydrocarbon group is desirable. 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 as a raw material for the binder resin include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; Unsaturated dicarboxylic acids (anhydrides) such as acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid; trivalent or higher unsaturated polycarboxylic acids (anhydrides) ), 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl 2-hydroxypropyl phthalate, 2-acryloyloxyethyl 2-hydroxyethylphthalic 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 as a raw material for the binder resin 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-hydroxyhexyl (meth) acrylate, 4-hydroxyhexyl (meth) acrylate, 5-hydroxy-3-methyl-pentyl (meth) acrylate, cyclohexane-1,4-dimethanol-mono (meth) Hydroxyl groups such as acrylate, 2- (2-hydroxyethyloxy) ethyl (meth) acrylate, glycerin monomethacrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and poly (ethylene glycol-propylene glycol) monomethacrylate Examples include terminal polyalkylene glycol mono (meth) acrylate. These ethylenically unsaturated monomers having a hydroxyl group can be used alone or in admixture of two or more.

Examples of unsaturated monomers other than those that can be used as a raw material for the binder resin include, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m- Aromatic vinyl compounds such as chlorostyrene, p-chlorostyrene, p-methoxystyrene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (Meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, paracumylphenoxyethylene glycol ( (Meth) acrylate, Unsaturated carboxylic acid esters such as hydroxy-3-phenoxypropyl (meth) acrylate, o-phenylphenol glycidyl ether (meth) acrylate, o-phenylphenol (meth) acrylate hydroxyethylated product and phenoxyethyl (meth) acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, norbornylmethyl (meth) acrylate, phenylnorbornyl (meth) acrylate, cyanonorbornyl (meth) acrylate , Isobornyl (meth) acrylate, bornyl (meth) acrylate, menthyl (meth) acrylate, fentyl (meth) acrylate, adamantyl ( (Meth) acrylate, dimethyladamantyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] dec-8-yl = (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] deca Alicyclic skeletons such as 4-methyl = (meth) acrylate, cyclodecyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid and t-butylcyclohexyl (meth) acrylate; polyethylene glycol mono (meth) Hydroxyl-terminated polyalkylene glycol mono (meth) acrylates such as acrylate, polypropylene glycol mono (meth) acrylate and poly (ethylene glycol-propylene glycol) monomethacrylate; methoxypolyethylene glycol monomethacrylate, lauroxypolyethyleneglycol Alkyl-terminated polyalkylenes such as rumono (meth) acrylate, octoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, nonylphenoxypolyethylene glycol monoacrylate, nonylphenoxypolypropylene glycol monoacrylate and allyloxypolyethylene glycol-polypropylene glycol mono (meth) acrylate Glycol mono (meth) acrylates; unsaturated amino acids such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 3-aminopropyl acrylate and 3-aminopropyl methacrylate Alkyl esters; glycidyl acrylate, glycidyl methacrylate, , 4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ethers and other unsaturated carboxylic acid glycidyl esters; vinyl acetate, vinyl propionate Carboxylic acid vinyl esters such as vinyl butyrate and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and methallyl glycidyl ether; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and cyanide Vinyl cyanide compounds such as vinylidene chloride; acrylamide, methacrylamide, α-chloroacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, N- (meth) acryloyl Unsaturated amides or unsaturated imides such as tarimide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide and maleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene And macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly n-butyl acrylate, poly n-butyl methacrylate and polysilicone. Can be mentioned. These unsaturated monomers can be used alone or in admixture of two or more.

  When manufacturing binder resin (copolymer), 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 usage-amount of a polymerization initiator is 0.01-25 mass parts with respect to 100 mass parts of all the monomers used for the synthesis | combination of a copolymer. In the case of synthesizing a copolymer, it is preferable to use an organic solvent, but one having sufficient dissolving power for the monofunctional monomer and polymerization initiator to be used is used. As an organic solvent which can be used for manufacture of binder resin, the thing similar to the organic solvent which the colored resin composition of this invention mentioned later contains is mentioned.

The reaction temperature when synthesizing the copolymer is preferably 50 to 120 ° C., particularly preferably 80 to 100 ° C. Moreover, it is preferable that reaction time is 1 to 60 hours, More preferably, it is 3 to 20 hours. The preferred acid value of the copolymer is 10 to 300 (mgKOH / g), and the preferred hydroxyl value is 10 to 200 (mgKOH / g). 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 the present invention, the acid value is a value measured by a method according to JIS K-2501, and the hydroxyl value is a value measured by a method according to JIS K-1557, and the weight average molecular weight is GPC (gel permeation chromatography). Based on the measurement result, it means a value calculated in terms of polystyrene.

  A polymer in which an unsaturated double bond is further introduced into the side chain of the copolymer is also useful as a binder resin. For example, 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 a copolymer of acrylic acid or an acrylate ester 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-1642H (manufactured by Nippon Kayaku) can also be used as the binder resin.

  Binder resin can be used individually or in mixture of 2 or more types in the colored resin composition of this invention. Content of the binder resin in the colored resin composition of 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. When the content of the binder resin is less than 0.5 parts by mass, the alkali developability is deteriorated, and problems such as background contamination and film residue in areas other than the area where pixels are formed may occur.

  Examples of the curing agent contained in the colored resin composition for a color filter of the present invention include a photopolymerization monomer in the case of radical polymerization, an epoxy resin in the case of ion curing, and a melamine curing agent. Specific examples of these curing agents include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Triethyleneglycol (meth) acrylate, tetraethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, 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, ethoxy 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) and M-8060 (Toagosei) Me ) Acrylate monomer; thiol polymerization monomers such as TEMPIC (manufactured by Sakai Chemical), TMMP (manufactured by Sakai Chemical), PEMP (manufactured by Sakai Chemical) and DPMP (manufactured by Sakai Chemical); NC-6000 and NC-6300 of Nippon Kayaku products NC-6300H, NC-3000, EOCN-1020, XD-1000, EPPN-501H, BREN-S, NC-7300L, Daicel Chemicals' Celoxite 2021P, EHPE3150, Cyclomer M100, Epolide PB3600, Japan Epoxy Resin Epicoat 828, Epicoat YX8000, Epicoat YX4000, Printec product VG-3101L, Silaace S510 (Nisso), TEPIC (Nissan Chemical Industries) and other epoxy resins; and methylolated melamine and Mw-30 (three Melamine curing agents such as Japanese Chemical), but are not limited thereto.

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

  The colored resin composition for a color filter of the present invention contains a photopolymerization initiator and / or a curing accelerator. As the photopolymerization initiator that can be contained in the colored resin composition, those having sufficient sensitivity to ultraviolet rays emitted from an ultra-high pressure mercury lamp generally used as an exposure light source are preferable, radical polymerizable photoradical initiators, Either an ion curable photoacid generator or a photobase generator can be used. Moreover, in order to harden | cure with less exposure energy, the component of the polymerization accelerator called a sensitizer can also be used in combination. Specific examples of the photopolymerization initiator include benzyl, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, benzoylbenzoic acid, esterified benzoylbenzoic acid, 4-benzoyl -4′-methyldiphenyl sulfide, benzyldimethyl ketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, isopropylthioxanthone, dimethylthioxanthone, diethylthioxanthone, diisopropylthioxanthone, dimethylaminomethylbenzoate, 1 -(4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl Phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 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 (tribromo Methyl) -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, diazonaphthoquinone System initiators, and commercially available Kayacure DMBI, Kayacure BDK, Kayacure BP-100, Kayacure BMBI, Kayacure DETX-S, Kayacure EPA (all manufactured by Nippon Kayaku), Darocur 1173, Darocure 1116 (Iremo Merck Japan), Irgacure 907 (made by BASF Japan), Irgacure 369 (made by BASF Japan), Irgacure 379EG (made by BASF Japan), Irgacure OXE-01 (made by BASF Japan), Irgacure OXE-02 (made by BASF Japan), Irga Cure PAG103 (manufactured by BASF Japan), TME-triazine (manufactured by Sanwa Chemical), biimidazole (manufactured by Kurokin Kasei), STR-110, STR-1 (all manufactured by Respe Chemical) It is, but not limited thereto.

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

  The curing accelerator that can be contained in the colored resin composition for a color filter of the present invention is a reaction catalyst that promotes ion curing, such as N-containing heterocyclic compounds such as primary to tertiary amines and imidazoles, acids, and the like. An anhydride etc. are mentioned.

  Specific examples of amines include triethylamine, triethanolamine, Nippon Kayaku products Kayahard A-A, Kayabond C-100, Kayabond C-200S, Kayabond C-300S, and the like.

  Specific examples of imidazole include Shikoku Kasei Kogyo Co., Ltd. Cureazole 2MZ-H, Cureazole C11Z, Curesol C17Z, Cureazole 1,2DMZ, Curesol 2E4MZ, Cureazole 2PZ, Cureazole 2P4MZ, Cureazole 1B2MZ, Cureazole 1B2PZ, Cureazole 2MZ-CN, Cureazole 2MZ-CN CN, Curezol 2E4MZ-CN, Curezol 2PZ-CN, Curezol C11Z-CNS, Curezol 2PZCNS-PW, Curezol 2MZ-A, Curezol C11Z-A, Curezol 2E4MZ-A, Curezol 2MA-OK, Curezol 2PZ-OKZ PW, Curezol 2P4MHZ-PW, Curezol TBZ, Curezol 2PZL-T, Ki Azole VT, Curesol SFZ, and the like.

  Specific examples of the acid anhydride include maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic dianhydride, Kayahard MCD of Nippon Kayaku products, and the like. Among these, imidazoles are preferable as the curing accelerator, and Curezol 1B2PZ, Curezol 2PZ, Curezol 1B2MZ and Curezol 2E4MZ are more preferable from the viewpoint of reactivity.

  Content of a hardening accelerator is 0.01-50 mass parts normally with respect to 100 mass parts of total solids of a colored resin composition, Preferably it is 0.05-20 mass parts. When there is less content of a hardening accelerator than 0.01 mass part, there exists a possibility that sclerosis | hardenability may fall, and when it exceeds 50 mass parts, there exists a possibility that storage stability may worsen.

  In the colored resin composition for a color filter of the present invention, a dye other than the xanthene compound represented by the above formula (1) may be used in combination as an optional component. The pigment that can be used in combination as an optional component may be appropriately selected from dyes, organic pigments, and inorganic pigments, and may be used alone or in combination of two or more. Since an object relates to a red pixel, it is preferable to use a known red dye or yellow dye, or a red pigment or yellow pigment. When the pigment as an optional component is used in combination, the total content of the xanthene compound as an essential component and the pigment as an optional component with respect to 100 parts by mass of the total solid content of the colored resin composition of the present invention is usually It will not be specifically limited if it exists in the range of 0.01-70 mass parts, Preferably it is 0.5-50 mass parts, More preferably, it is 1.0-40 mass parts.

Moreover, as a pigment | dye which can be used together with the xanthene compound represented by Formula (1), a pigment is also preferable.
There is no particular limitation on the organic pigment that can be used in combination with the colored resin composition of the present invention. Specific examples of the pigment include C.I. I. Pigment Red 2, 5, 17, 31, 32, 41, 122, 123, 144, 149, 166, 168, 170, 171, 175, 176, 177, 178, 179, 180, 185, 187, 202, 206, Red pigments such as C. 207, 209, 214, 220, 221, 224, 242, 243, 254, 255, 262, 264, 272; I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc., yellow pigments, C.I. I. Examples include orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73. Of these, C.I. I. Pigment red 177, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment yellow 138 and C.I. I. It is preferable to use at least one selected from the group consisting of CI Pigment Yellow 150.

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

  The content of these pigments in the colored resin composition for a color filter of the present invention is the content of the xanthene compound represented by the formula (1) which is an essential component of the colored resin composition of the present invention and the content of the pigment which is an optional component. The total is usually 0.01 to 70 parts by weight, preferably 0.5 to 50 parts by weight, more preferably 1.0 to 40 parts by weight with respect to 100 parts by weight of the total solid content of the colored resin composition of the present invention. However, the content of the pigment alone is preferably 0.01 to 60 parts by mass with respect to 100 parts by mass of the total solid content of the colored resin composition of the present invention. More preferably, it is 1-50 mass parts, and it is still more preferable that it is 1.0-40 mass parts. When there is more content than this range, there exists a possibility that adhesiveness with a board | substrate may fall because hardening is inadequate.

There is no restriction | limiting in particular in the dye which can be used together with the colored resin composition of this invention, Acid dye, basic dye, direct dye, sulfur dye, vat dye, naphthol dye, reactive dye, disperse dye, etc. are mentioned. These dyes are not limited to those that are soluble in an organic solvent, and dyes that are insoluble in an organic solvent can be used as a dispersion.
The content of these dyes in the colored resin composition for a color filter of the present invention is the content of the xanthene compound represented by the formula (1) which is an essential component of the colored resin composition of the present invention and the content of the dye which is an optional component. The total is usually 0.01 to 70 parts by weight, preferably 0.5 to 50 parts by weight, more preferably 1.0 to 40 parts by weight with respect to 100 parts by weight of the total solid content of the colored resin composition of the present invention. If it is in the range, it will not specifically limit.

  The colored resin composition for a color filter of the present invention may be used in combination with an organic solvent for the purpose of reducing the viscosity of the colored resin composition and improving workability when the colored resin composition is applied. As an organic solvent, it has sufficient dissolving power with respect to the binder resin, photopolymerization initiator, etc., which are constituents of the colored resin composition, and with respect to the monofunctional monomer and polymerization initiator used for the synthesis of the binder resin. However, those having sufficient dissolving power can be preferably used. Moreover, what can maintain dispersion stability can also be preferably used when preparing a pigment dispersion.

  Specific examples of the organic solvent contained in the colored resin composition of the present invention include benzenes such as benzene, toluene and xylene; cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; methyl cellosolve acetate, ethyl cellosolve acetate and butyl cellosolve acetate. Cellosolve acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monoalkyl ether acetates such as propylene glycol monobutyl ether acetate; methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate , Propionic acid esters such as ethyl ethoxypropionate; methyl lactate, ethyl lactate and milk Lactic acid esters such as butyl; diethylene glycols such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; acetates such as methyl acetate, ethyl acetate and butyl acetate; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane; acetone, methyl ethyl ketone , Ketones such as methyl butyl ketone and cyclohexanone; and alcohols such as methanol, ethanol, butanol, isopropyl alcohol, diacetone alcohol and benzyl alcohol, but are not limited thereto.

  The organic solvent can be used alone or in combination of two or more in the colored resin composition of the present invention. The usage-amount of the organic solvent in the colored resin composition of this invention is normally 10000 mass parts or less with respect to 100 mass parts of total solids of a colored resin composition, Preferably it is 100-1000 mass parts.

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

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

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

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

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

  For example, when using the colored resin composition of this invention by the inkjet method etc., you may use a thermal polymerization initiator together with a photoinitiator. Examples of the thermal polymerization initiator include azo compounds and organic peroxides, such as 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), Examples include 2,2′-azobis (2-methylbutyronitrile), di-t-butyl peroxide, dibenzoyl peroxide, cumylperoxyneodecanoate, and the like.

  In addition, when using a thermal polymerization initiator together, what is necessary is just to use the quantity from which the sum total of a photoinitiator and a thermal polymerization initiator becomes in the range of content of said photoinitiator.

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

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

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

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In Examples, the maximum absorption wavelength, heat resistance, etc. of the compound obtained by the synthesis were determined by measuring the chromaticity (L value, a value, b value) of the dye-colored product with a spectrophotometer “UV-3150 manufactured by Shimadzu Corporation”. ”Was measured and evaluated.

Example 1 (Synthesis of xanthene compound of compound No. 2 in Table 1)
(Step 1-1)
A 300 ml four-necked flask was charged with 38.4 g of rhodamine B (Tokyo Kasei Kogyo), 200 g of water, and 11.4 g of a 28% aqueous sodium hydroxide solution and adjusted to pH 7 using a 25% aqueous sodium hydroxide solution. Further, the pH was adjusted to 10.3 using sodium carbonate. 30 g of dimethyl sulfate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto and stirred at 25-30 ° C. for 2 hours. The reaction solution was transferred to a 2000 ml beaker, 940 g of hot water at 50 ° C. was added, 98% sulfuric acid was added dropwise to adjust to pH 2.7, and the mixture was stirred at 60 ° C. for 2 hours. 800 g of water was added thereto, 11.2 g of zinc chloride (manufactured by Kanto Chemical Co., Inc.) and 20 g of sodium chloride were added, and the mixture was vigorously stirred for 45 minutes while maintaining at 40 ° C. Further, 120 g of sodium chloride was added to the reaction solution little by little and stirred for 30 minutes, and then the precipitated crystals were collected by filtration and washed with a small amount of water to obtain 40 g of a dye intermediate of the following formula (100).

(Step 1-2)
A 500 ml beaker was charged with 23.3 g of 2-amino-4-nitrophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 160 g of water, and 30% aqueous hydrochloric acid was added dropwise to adjust the pH to 1.0 or less. 28.8 g of 40% sodium nitrite aqueous solution was dropped at a liquid temperature of 10 ° C. or lower, and the mixture was stirred at 10 ° C. or lower for 1 hour. Next, this reaction solution was maintained at 10 ° C. or lower and pH 8.5 to 9.0 in a mixed solution of 33.5 g of the pyridone compound represented by the following formula (101), 360 g of water, and 57 g of 25% aqueous sodium hydroxide solution. While dripping. After completion of dropping, the reaction solution was stirred overnight. Subsequently, this reaction liquid was stirred while maintaining the pH at 6 to 7 at 60 to 70 ° C., and the precipitated crystals were collected by filtration and dried to obtain 37.3 g of a dye intermediate of the following formula (102).

(Step 1-3)
A 100 ml four-necked flask was charged with 2.5 g of the intermediate obtained in Step 1-2, 40 ml of acetonitrile, and 0.8 g of cobalt acetate tetrahydrate (manufactured by Kanto Chemical Co., Inc.), and stirred at 65 ° C. for 30 minutes. . Next, 0.84 g of triethylamine (manufactured by Junsei Kagaku Co., Ltd.) was added dropwise, and the reaction solution obtained by stirring at the same temperature for 1 hour was filtered, and then the filtrate was concentrated under reduced pressure to obtain the following formula. 2.1 g of the dye intermediate of (103) was obtained.

(Step 1-4)
In a 300 ml eggplant flask, 0.92 g of the intermediate of the above formula (100) obtained in step 1-1 and 162 g of water were charged and stirred. A solution prepared by dissolving 1.5 g of the intermediate of the above formula (103) obtained in Step 1-3 in 11 g of DMF was dropped into this reaction solution, and the mixture was stirred at room temperature for 1 hour. The precipitated dye was collected by filtration and dried to obtain 2 g of the xanthene compound of the present invention. The maximum absorption wavelength of the xanthene compound was 554 nm (methanol).

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

Example 2
0.48 g of the xanthene compound of the present invention obtained in Example 1, 5 g of the copolymer (A) obtained in Synthesis Example 1 as a binder resin, Kayrad DPCA-60 (Nippon Kayaku Co., Ltd.) as a photopolymerizable monomer 5 g), Irgacure 907 (BASF Japan) 1.0 g as a photopolymerization initiator, 0.5 g Kayacure DETX-S (Nippon Kayaku) and 44.9 g propylene glycol monomethyl ether acetate are mixed. Thus, a colored resin composition 1 of the present invention was obtained.

Example 3
C. I. Pigment Red 254 / Disperbyk-2001 (manufactured by Big Chemie Japan) / PGMEA (propylene glycol monomethyl ether acetate) = 15.0 / 7.0 / 78.0 (mass ratio) after mixing at a composition ratio of 0.3 mm zirconia 400 g of beads were added, treated with a paint shaker, and filtered to obtain a red pigment dispersion. 0.58 g of the xanthene compound of the present invention obtained in Example 1 was added to 35.5 g of the above red dispersion, 5.0 g of the copolymer (A) obtained in Synthesis Example 1 as a binder resin, and photopolymerizable. 5 g of Kayrad DPCA-60 (manufactured by Nippon Kayaku) as a monomer, 1.0 g of Irgacure 907 (manufactured by BASF Japan) as a photopolymerization initiator, 0.1 g of Irgacure OXE-02 (manufactured by BASF Japan), Kayacure DETX 0.5 g of —S (manufactured by Nippon Kayaku) and 34 g of cyclopentanone were mixed to obtain a colored resin composition 2 of the present invention.

Comparative Example 1
The xanthene compound of the present invention obtained in Example 1 is represented by C.I. represented by the following formula (104). I. A comparative colored resin composition 1 was obtained in the same manner as in Example 2 except that the basic violet 10 was used.

Comparative Example 2
The compound of the present invention obtained in Example 1 was converted to C.I. represented by the above formula (104). I. A comparative colored resin composition 2 was obtained in the same manner as in Example 3 except that the basic violet 10 was used.

  The colored resin compositions 1 and 2 of the present invention obtained above and the comparative colored resin compositions 1 and 2 are applied on a glass substrate, pre-baked at 80 ° C. for 100 seconds, and then exposed through a mask. Was cured with an alkaline aqueous solution containing a surfactant, rinsed with water, and then heat-cured at 200 ° C. for 20 minutes to obtain a red colored cured film. The obtained colored cured film had a resolution of 5 μm square in line and space, and no residue, peeling of pixels, etc. were confirmed.

(Contrast evaluation)
Using the colored cured film obtained above, the contrast value (cd / cm ² ) of the two polarizing plates and the brightness value (cd) at the right angle of the two polarizing plates using a contrast meter (CT-1 manufactured by Osaka Co., Ltd.) / Cm ² ) (the luminance value when parallel / the luminance value when orthogonal), the contrast was calculated.
(Heat resistance evaluation)
The colored cured film obtained above was subjected to heat treatment at 230 ° C. for 180 minutes, the spectral transmittance of the evaluation substrate before and after the treatment was measured, and the color difference (ΔEab) before and after the heat treatment was measured. Table 1 shows the results of contrast and heat resistance evaluated when ΔEab is less than 3.0, evaluated as ３．０, when 3.0 or more and less than 5.0, and when it is 5.0 or more.

Table 1
Contrast ratio Heat resistance Colored resin composition 1 13000 ◎
Colored resin composition 2 4000 ○
Comparative resin composition 1 50 ×
Comparative resin composition 2 1500 ×

  From the result of Table 1, the colored resin compositions 1-2 of this invention showed favorable contrast and heat resistance compared with the colored resin compositions 1-2 for comparative examples.

  As described above, the xanthene compound of the present invention, the colored resin composition for color filter prepared using the compound, and the color filter obtained using the colored resin composition for color filter have high heat resistance and contrast. Therefore, it is useful as a highly reliable color filter that can withstand the manufacturing process of a color filter that requires heat resistance.

By using a novel xanthene compound excellent in fastness such as heat resistance of the present invention, and a colored resin composition for a color filter prepared by using the compound, it has high contrast, excellent heat resistance, high quality and high reliability. A red pixel of the color filter can be provided.

Claims (11)

Xanthene compound represented by formula (1)

(In Formula (1), R ^{1 to} R ⁶ are each independently a hydrogen atom; a substituent selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, a cyano group, a carboxyl group, an amide group, a sulfonamide group, and a sulfo group. Represents an alkyl group having 1 to 4 carbon atoms or an unsubstituted alkyl group having 1 to 4 carbon atoms, R ⁷ represents a carboxylic acid ester group, R ^{8 to} R ¹¹ are each independently a hydrogen atom; Cyano group; nitro group; an alkyl group having 1 to 4 carbon atoms or an unsubstituted alkyl group having 1 to 4 carbon atoms having a substituent selected from the group consisting of a halogen atom, an alkoxy group, a cyano group, and a nitro group; .R ¹² is a hydrogen atom, a halogen atom, hydroxy group, an alkoxy group, a cyano group, a carboxyl group, the group consisting of an amido group, a sulfonamido group, and a sulfo group An alkyl group having 1 to 10 carbon atoms having a selected substituent; an unsubstituted alkyl group having 1 to 10 carbon atoms; a halogen atom, a hydroxy group, an alkoxy group, a cyano group, a carboxyl group, an amide group, a sulfonamide group, and Represents an aromatic hydrocarbon group having 5 to 10 carbon atoms or an unsubstituted aromatic hydrocarbon group having 5 to 10 carbon atoms having a substituent selected from the group consisting of a sulfo group. R ^{1 to} R ⁶ in formula (1) are each independently a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms, R ⁸ , R ⁹ and R ¹¹ are hydrogen atoms, and R ¹⁰ is a halogen atom. The xanthene compound according to claim 1, which is a cyano group or a nitro group, and R ¹² is a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms. In Formula (1), R ^{1 to} R ⁴ are ethyl groups, R ^{5 to} R ⁶ are hydrogen atoms, R ¹⁰ is a nitro group, and R ¹² is an unsubstituted alkyl group having 1 to 5 carbon atoms. The xanthene compound according to claim 2. The coloring resin composition for color filters containing the xanthene compound as described in any one of Claims 1-3, binder resin, a hardening | curing agent, a photoinitiator, and / or a hardening accelerator. Furthermore, the colored resin composition of Claim 4 containing a pigment. The pigment is C.I. I. Pigment red 177, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment yellow 150 and C.I. I. The colored resin composition according to claim 5, which is one or more selected from the group consisting of CI Pigment Yellow 138. A colored cured film for a color filter, which is patterned using the colored resin composition according to any one of claims 4 to 6. A color filter comprising the colored cured film for a color filter according to claim 7. A liquid crystal display device equipped with the color filter according to claim 8. An organic EL display equipped with the color filter according to claim 8. A solid-state imaging device equipped with the color filter according to claim 8.