JP2014153441A - Colored resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored resin composition which enables the production of a red color filter having excellent brightness and heat resistance with high quality and high reliability, and a color filter produced using the same.SOLUTION: A colored resin composition for a color filter comprises a cyanine compound represented by the formula (1) below, a binder resin, a curing agent and a photopolymerization initiator and/or a curing accelerator. In the formula (1), Y each independently represents a hydrogen atom or a chlorine atom, B represents a 1-4C linear alkylene group, Zrepresents a sulfonate anion or a carboxylate anion, and A represents any substituted group of a specific formula.

Description

  The present invention relates to a colored resin composition used when forming a red pixel of a color filter, a color filter formed using the colored resin composition, a liquid crystal display device formed using the color filter, and imaging The present invention relates to an electronic display device such as an element (CCD, CMOS) and an organic EL display.

  Liquid crystal display devices such as notebook computers, liquid crystal televisions, mobile phones, and other liquid crystal displays (LCD), organic EL displays, and image sensors (CCD, CMOS) used as input devices for digital cameras, color copiers, etc. A color filter is required for colorization. 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, on the other hand, for display applications that require long-term reliability for TVs and the like, excellent light resistance and heat resistance are required, but dyes are generally less resistant than pigments. is there. For example, Patent Document 1 relates to a blue color filter in which a cyanine compound and a resin are combined, but the document does not describe any heat resistance of the color filter. Patent Document 2 relates to a colored photosensitive resin composition containing a cyanine compound having excellent heat resistance, but does not describe anything about brightness and chromaticity. Moreover, as described in Patent Document 3, it is known that a colored photosensitive resin composition using a dye generally lowers exposure sensitivity and cannot sufficiently cure a coating film. In other words, the clear red color filter with high sensitivity, excellent reliability, and high durability, which is required in the field of liquid crystal display devices and solid-state image sensors, is hardly put into practical use.

JP 2012-233160 A JP 2012-212089 A JP 2012-103586 A

  An object of the present invention is to provide a colored resin composition capable of producing a high-quality, high-reliability and high-sensitivity red color filter excellent in lightness and heat resistance, and a color filter produced using the same. .

  As a result of intensive studies to solve the above problems, the present inventor, as a color filter pixel, as a pigment, at least a cyanine skeleton-containing compound represented by the following formula (1) (hereinafter referred to as a cyanine skeleton-containing compound) The present inventors have found that the above-described problems can be solved by using a colored resin composition containing the present invention, and have completed the present invention.

That is, the present invention
(1) The following formula (1)

(In Formula (1), Y represents a hydrogen atom or a chlorine atom each independently, B represents a C1-C4 linear alkylene group, Z < ^- > represents a sulfonate anion or a carboxylate anion, and A represents Following formula (2)-(4)

(In formula (2), n represents an integer of 0 to 3, and in formula (4), m represents an integer of 0 to 3). A colored resin composition for a color filter containing a cyanine compound, a binder resin, a curing agent and a photopolymerization initiator and / or a curing accelerator,
(2) The colored resin according to (1), wherein Y is a chlorine atom, B is an n-propylene group, Z is a sulfonate anion, and A is a substituent represented by the formula (2). Composition,
(3) Further, the following formula (5)

(In Formula (5), R ¹ represents a hydrogen atom or a chlorine atom, R ² and R ⁴ each independently represents a hydrogen atom; a carbon number having a substituent selected from the group consisting of a halogen atom, a hydroxy group and an alkoxy group) Represents an alkyl group having 1 to 12 carbon atoms or an unsubstituted alkyl group having 1 to 12 carbon atoms, and R ³ represents an alkyl group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, and a carbon number 1 to 6 represents a phenyl group having a substituent selected from the group consisting of an alkoxy group and a cyano group or an unsubstituted phenyl group, R ^{5 to} R ⁸ each independently represents a hydrogen atom or a halogen atom, and M ⁻ represents A methine compound represented by bis (trifluoromethanesulfonyl) imide anion or tris (trifluoromethanesulfonyl) methide anion). Colored resin composition according to (1) or (2),
(4) R ¹ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms, R ² and R ⁴ are each independently a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms; The colored resin composition according to the above (3), wherein ³ is a methyl group or an unsubstituted phenyl group,
(5) The colored resin composition according to any one of (1) 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 at least one selected from the group consisting of CI Pigment Yellow 138,
(7) A colored cured film for a color filter that is patterned using the colored resin composition according to any one of (1) to (6) above,
(8) A color filter comprising the colored cured film for a color filter according to (7) above,
(9) A liquid crystal display device equipped with the color filter according to (8) above,
(10) An organic EL display equipped with the color filter according to (8) above,
(11) A solid-state imaging device equipped with the color filter according to (8) above,
About.

  By using the colored resin composition for a color filter of the present invention, it is possible to provide a red pixel of a high-quality and highly reliable color filter excellent in lightness and heat resistance.

The colored resin composition for color filters of the present invention (hereinafter also simply referred to as “colored resin composition”) contains a cyanine compound represented by the formula (1).

In formula (1), A represents a substituent of any one of formulas (2) to (4), and is preferably a substituent of formula (2) or formula (3). More preferably, it is a group.

In formula (1), Y represents a hydrogen atom or a chlorine atom each independently, Preferably it is a chlorine atom.
In formula (1), B represents a linear alkylene group having 1 to 4 carbon atoms, and specific examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, and an n-butylene group. The alkylene group is preferably an ethylene group or an n-propylene group, and more preferably an n-propylene group. Z ⁻ represents a sulfonate anion or a carboxylate anion, and preferably a sulfonate anion.

In formula (2), n represents an integer of 0 to 3, preferably 0 to 1, more preferably 0. Moreover, in Formula (4), m represents the integer of 0-3, Preferably it is 0.

As the cyanine compound represented by the formula (1) contained in the colored resin composition of the present invention, a compound obtained by combining preferable ones for each of the above A, Y, B, Z ⁻ , n, and m is preferable. The compound which combined the preferable thing is more preferable. The same applies to combinations of preferable and more preferable ones.

The cyanine compound represented by the formula (1) contained in the colored resin composition of the present invention is produced by various methods. For example, it is produced by the following method with reference to the method described in Japanese Patent No. 3626892. can do. In the following formulas (AA) to (C), A, Y, B, Z ⁻ , n, and m each have the same meaning as in the above formula (1).

  First, a commercially available product represented by the following formula (AA) is converted into a sulfoalkylating agent such as 1,3-propane sultone or 1,4-butane sultone, or bromoacetic acid, 3-bromopropionic acid, or acrylic. The compound is converted into a derivative represented by the following formula (B) by reacting with a carboxyalkylating agent such as an acid.

Next, a cyanine compound represented by the above formula (1) is obtained by reacting a formyl derivative represented by the following formula (C), which can be synthesized by a conventional method, with a compound represented by the above formula (B). Can do.

Specific examples of the cyanine compound represented by the above formula (1) are shown in the following Tables 1 and 2, but the present invention is not limited to these specific examples.

  The content of the cyanine 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) It means all components other than organic solvents, such as resin, curing agent, etc. It is used synonymously hereinafter.) 0.01 to 50 parts by mass, preferably 0.5 to 30 parts by mass with respect to 100 parts by mass More preferably, it is 3-10 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 cyanine compound represented by the formula (1) and a colorant compound such as a methine compound and a pigment represented by the formula (5) added as necessary. It functions as a dispersant and a dispersion aid for dispersion stability during dispersion, but when the colored resin composition is used in a photolithography method, it is used as an alkaline developer used in the development processing step during color filter production. It is desirable to be soluble. In order to form a 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 cyanine compounds, photopolymerization initiators, photopolymerizable monomers, pigment dispersions, etc., and the colored resin composition must be stable so as not to cause precipitation or aggregation Don't be. When the colored resin composition is used in the ink jet method, alkali solubility is not particularly required, and therefore a binder resin having good compatibility with other constituent materials may be selected.

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 unsaturated monomer having a carboxyl group 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 maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; Products), 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 unsaturated monomer having a hydroxyl group 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-hydroxy. Butyl (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 ( Acrylate), 2- (2-hydroxyethyloxy) ethyl (meth) acrylate, glycerin monomethacrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) monomethacrylate, etc. And hydroxyl group-terminated polyalkylene glycol mono (meth) acrylates. These ethylenically unsaturated monomers having a hydroxyl group can be used alone or in admixture of two or more.

Examples of unsaturated monomers other than those 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 addition, in this invention, an acid value means the value measured by the method based on JIS K-2501 and hydroxyl value JIS K-1557, and a weight average molecular weight is GPC (gel permeation chromatography). It means a value calculated in terms of polystyrene based on the measurement result.

  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. The content of the binder resin in the colored resin composition of the present invention is usually 0.5 to 99 parts by mass, preferably 5 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the colored resin composition. . 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, methylbenzoylformate, 2-methyl- 1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4-bis (trichloromethyl)- 6- (4-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-s-triazine, 2,4-bis (tribromomethyl) ) -6- (4′-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (tribromomethyl) -1,3,5-s-triazine, 2 4-bis (trichloromethyl) -6- (1,3-benzodioxolan-5-yl) -1,3,5-s-triazine, benzophenone, benzoylbenzoic acid, 1- (4-phenylsulfanylphenyl) butane- 1,2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4-methylsulfanylphenyl) butane -1-one oxime-O-acetate, 4,4′-bis (diethylamino) benzophenone, P-dimethylaminobenzoic acid isoamyl ester, P-dimethylaminobenzoic acid ethyl ester, 2,2′-bis (O-chlorophenyl)- 4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, diazonaphthoquinone initiator, 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 ( BASF Japan), Irgacure 369 (BASF Japan), Irgacure 379EG (BASF Japan), Irgacure OXE-01 (BASF Japan), Irgacure OXE-02 (BASF Japan), Irgacure PAG103 (BASF) Japan)), TME-triazine (manufactured by Sanwa Chemical), biimidazole (manufactured by Kurokin Kasei), STR-110, STR-1 (all manufactured by Respe Chemical), etc. The present invention is not limited to these.

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

The curing accelerator 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 the content of the curing accelerator is less than 0.01 parts by mass, the curability may be lowered, and when it is more than 50 parts by mass, the storage stability may be deteriorated.

In the colored resin composition for a color filter of the present invention, a dye other than the cyanine 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 content is usually the sum of the content of the cyanine 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. 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.

The dye that can be used in combination with the cyanine compound represented by the formula (1) is preferably a methine compound represented by the above formula (5).
In Formula (5), R ¹ represents a hydrogen atom or a chlorine atom, and is preferably a hydrogen atom.

In formula (5), R ² and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and the alkyl group has 1 to 12 carbon atoms, linear, branched or It is not limited to any ring shape. The alkyl group may have a substituent selected from the group consisting of a halogen atom, a hydroxy group and an alkoxy group.

In the formula (5), specific examples of the alkyl group having 1 to 12 carbon atoms represented by R ² and R ⁴ include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso- Butyl, sec-butyl, t-butyl, n-pentyl, iso-pentyl, t-pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, cyclopentyl, cyclohexyl Group, vinyl group, allyl group, propenyl group, pentynyl group, butenyl group, hexenyl group, hexadienyl group, isopropenyl, isohexenyl group, cyclohexenyl group, cyclopentadienyl group, ethynyl group, propynyl group, hexynyl Group, isohexynyl group, cyclohexynyl group and the like.

In formula (5), the alkyl group having 1 to 12 carbon atoms represented by R ² and R ⁴ is preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms, among which a hydrogen atom, a methyl group, An ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso-butyl group are more preferable, a hydrogen atom or a methyl group is further preferable, and a methyl group is particularly preferable.

In Formula (5), R ³ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and the phenyl group is an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or an alkoxy group having 1 to 6 carbon atoms. And may have a substituent selected from the group consisting of a cyano group.

In the formula (5), specific examples of the alkyl group having 1 to 6 carbon atoms represented by R ³ 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, cyclopentyl group, cyclohexyl group, vinyl group, allyl group, propenyl group, pentynyl group, butenyl group, hexenyl Group, hexadienyl group, isopropenyl, isohexenyl group, cyclohexenyl group, cyclopentadienyl group, ethynyl group, propynyl group, hexynyl group, isohexynyl group, cyclohexynyl group and the like.

In the formula (5), specific examples of the substituent that the phenyl group represented by R ³ may have include an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an iso- Propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc.), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) , Hydroxy group, alkoxy group (for example, methoxy group, ethoxy group, propoxy group and the like), and cyano group.

In Formula (5), R ³ is more preferably an unsubstituted linear alkyl group having 1 to 6 carbon atoms or an unsubstituted phenyl group, and particularly preferably a methyl group or an unsubstituted phenyl group. preferable.

In formula (5), R ^{5 to} R ⁸ each independently represents a hydrogen atom or a halogen atom, and particularly preferably a hydrogen atom.

In formula (5), M ⁻ represents a bis (trifluoromethanesulfonyl) imide anion or a tris (trifluoromethanesulfonyl) methide anion, and particularly preferably a tris (trifluoromethanesulfonyl) methide anion.

  The methine compound represented by the formula (5) is obtained, for example, by a known synthesis method described in Yutaka Hosoda “Theoretical Manufacturing Dye Chemistry” (pages 396 to 402) published by Gihodo Co., Ltd. It can also be synthesized by purchasing a commercial product which is a chlorine anion and adding the corresponding salt or acid to exchange the salt.

  When the methine compound contained in the colored resin composition of the present invention as an optional component is synthesized by salt exchange, a compound whose anion portion is a chlorine anion is reacted with a reaction solvent (for example, water, methanol, ethanol, isopropanol, acetone, Examples thereof include water-soluble polar solvents such as N, N-dimethylformamide (hereinafter abbreviated as DMF) and N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), and these solvents may be used alone or in combination. ), The corresponding salt or acid is added in an amount of about 0.5 to 3 equivalents, and it is easily synthesized by stirring at a predetermined temperature (for example, 0 to 100 ° C.), and the precipitated crystals are collected by filtration. can get.

The content of the methine compound represented by the formula (5) in the colored resin composition for a color filter of the present invention is the cyanine compound represented by the formula (1) which is an essential component of the colored resin composition of the present invention. Although it will not specifically limit if the sum total of content with the pigment | dyes used together including the methine compound represented by Formula (5) which is an arbitrary component is in the range of 0.01-70 mass parts, Formula (5) It is preferable that content of the methine compound single represented by this is 0.01-50 mass parts with respect to 100 mass parts of total solid of the colored resin composition of this invention, and 0.1-40 masses Part is more preferable, and 1.0 to 30 parts by mass is even more preferable. When the content is larger than this range, precipitation or aggregation may occur, or adhesion with the substrate may decrease due to insufficient curing.

Moreover, as a pigment | dye which can be used together with the cyanine 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 combined use including the cyanine compound represented by the formula (1), which is an essential component of the colored resin composition of the present invention, and the optional pigment. The total content of the pigments to be used is not particularly limited as long as it is in the range of 0.01 to 70 parts by mass, but the content of the pigment alone is 100 parts by mass of the total solid content of the colored resin composition of the present invention. Is preferably 0.01 to 70 parts by mass, more preferably 0.1 to 50 parts by mass, and still more preferably 1.0 to 40 parts by mass. 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 a combined use including the cyanine compound represented by the formula (1) which is an essential component of the colored resin composition of the present invention and a dye which is an optional component. If the sum total of content with the pigment | dyes to be performed exists in the range of 0.01-70 mass parts, 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 the workability at the time of applying the colored resin composition. 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.

In the case where the solubility of the cyanine compound represented by the formula (1) and optionally used pigments in the resin component is low, a dispersant or a dispersion aid may be used in combination and 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 cyanine compound represented by the formula (1), the binder resin, the curing agent, the photopolymerization initiator and / or the curing accelerator with a dissolver, a homomixer, or the like. 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 The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples. Unless otherwise specified, “part” and “%” in the text are based on mass, and the reaction temperature is the internal temperature. Among the synthesized compounds, those for which λmax (maximum absorption wavelength) was measured were measured with an ultraviolet-visible spectrophotometer UV-3150 (manufactured by Shimadzu Corporation) in methanol unless otherwise specified.

Synthesis Example 1 (Synthesis of cyanine compound of compound number 3 in Table 1)
(Process 1)
It is represented by the following formula (6) by adding 7.8 g of 5-chloro-2,3,3-trimethylindolenine and 5.9 g of propane sultone to 20 g of N-methylpyrrolidone and stirring at 120 ° C. for 6 hours. A reaction solution containing the compound was obtained. The obtained reaction solution was used as it was in the next step.

(Process 2)
To 30 g of acetic acid and 30 g of acetic anhydride, 4.7 g of a formyl derivative represented by the following formula (7) and a reaction solution containing the compound represented by formula (6) obtained in Synthesis Example 1 (Step 1) were added. , And stirred at 100 ° C. for 8 hours. The obtained liquid was cooled to room temperature, poured into 200 g of water and stirred for 30 minutes, and then the precipitated solid was collected by filtration, washed with water and dried to dry the cyanine compound (λmax: 6.0 g of 554 nm (cyanine compound of compound number 3 in Table 1) was obtained.

Synthesis Example 2 (Synthesis of a cyanine compound for comparison)
(Process 1)
20 g of 5-chloro-2,3,3-trimethylindolenine and 17 g of iodomethane were added to 70 g of N, N-dimethylformamide, and the mixture was stirred at 100 ° C. for 6 hours. After cooling to room temperature, 100 g of toluene was added to the obtained liquid, and the precipitated solid was filtered off to obtain 25 g of a compound represented by the following formula (9).

(Process 2)
To 100 g of pyridine, 13.4 g of the compound represented by the formula (9) obtained in Synthesis Example 2 (Step 1), 2.8 g of triethyl orthoformate, and 12 g of tris (trifluoromethanesulfonyl) methanide potassium are added. Stir at 8 ° C. for 8 hours. The obtained liquid was cooled to room temperature, poured into 100 g of water and stirred for 30 minutes, and then the precipitated solid was collected by filtration and dried to obtain a cyanine compound (λmax: 563 nm) represented by the following formula (10). 7.8 g was obtained.

Synthesis Example 3 (R ¹ and R ^{5 to} R ^{8 in} Formula (5) are hydrogen atoms, R ² and R ⁴ are methyl groups, R ³ is a phenyl group, and M ⁻ is tris (trifluoromethanesulfonyl). ) Synthesis of methine compounds that are methide anions)
In a 2000 ml beaker, 10 g of Astrazone Orange R (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1000 g of water were charged and stirred at 50 ° C. for 30 minutes. A solution prepared by dissolving 12.7 g of a cesium salt of tristrifluoromethanesulfonylmethide (manufactured by Central Glass Co., Ltd.) in 13 g of DMF was added dropwise thereto and stirred at room temperature for 2 hours. The precipitated dye was collected by filtration, washed with water and dried to obtain 16.6 g of a methine compound (λmax: 508 nm) represented by the following formula (11).

Synthesis Example 4 (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 1
C. I. Pigment Red 254 / Cyanine compound represented by Formula (8) obtained in Synthesis Example 1 / Disperbyk-2001 (manufactured by Big Chemie Japan) / PGMEA (propylene glycol monomethyl ether acetate) = 14.3 / 0.7 / 4 After mixing at a composition ratio of 0.0 / 81.0 (mass ratio), 400 g of 0.3 mm zirconia beads were added, treated for 240 minutes with a paint shaker, and filtered to obtain red dispersion 1. 3. 31.3 g of the red dispersion 1, 5.0 g of the copolymer (A) obtained in Synthesis Example 4 as a binder resin, and Kayrad DPCA-60 (manufactured by Nippon Kayaku) as a photopolymerizable monomer. 0 g, 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), and 40 g of PGMEA are mixed to give the colored resin composition 1 of the present invention. Obtained.

Example 2
Cyanine compound represented by formula (8) obtained in Synthesis Example 1 / Disperbyk-2001 (manufactured by Big Chemie Japan) / PGMEA (propylene glycol monomethyl ether acetate) = 8.0 / 4.0 / 88.0 (mass) After mixing at a composition ratio of 400), 400 g of 0.3 mm zirconia beads were added, treated for 240 minutes with a paint shaker, and filtered to obtain a red dispersion 2. 5.5 g of the red dispersion liquid 2, 2.4 g of the methine compound represented by the formula (11) obtained in Synthesis Example 3, and the copolymer (A) obtained in Synthesis Example 4 as a binder resin 5.0 g, 5.0 g Kayrad DPCA-60 (Nippon Kayaku Co., Ltd.) as a photopolymerizable monomer, 1.0 g Irgacure 907 (BASF Japan) as a photopolymerization initiator, Irgacure OXE-02 (BASF Japan) 0.1 g) and 57 g of PGMEA were mixed to obtain a colored resin composition 2 of the present invention.

Comparative Example 1
C. I. Pigment red 254 / C.I. I. After mixing at a composition ratio of CI Pigment Red 177 / Disperbyk-2001 (by Big Chemie Japan) / PGMEA (propylene glycol monomethyl ether acetate) = 7.5 / 7.5 / 4.0 / 81.0 (mass ratio), 400 g of 0.3 mm zirconia beads were added, treated for 60 minutes with a paint shaker, and filtered to obtain red dispersion 3. 25 g of the red dispersion liquid 3, 5.5 g of the copolymer (A) obtained in Synthesis Example 4 as a binder resin, 5.5 g of Kayrad DPCA-60 (manufactured by Nippon Kayaku) as a photopolymerizable monomer, As a photopolymerization initiator, 1.0 g of Irgacure 907 (manufactured by BASF Japan), 0.1 g of Irgacure OXE-02 (manufactured by BASF Japan), and 30 g of propylene glycol monomethyl ether acetate were mixed, and a comparative resin composition 1 Obtained.

Comparative Example 2
A comparative resin composition 2 was obtained according to Example 1 except that the cyanine compound represented by formula (8) was changed to the cyanine compound represented by formula (10) obtained in Synthesis Example 2. .

(Evaluation of developability, resolution and adhesion to the substrate)
After applying the colored resin compositions 1 and 2 of the present invention obtained above on a glass substrate, prebaking under conditions of 80 ° C. × 100 seconds, curing by exposure through a mask, and containing a surfactant The resultant was developed with an aqueous alkaline solution, rinsed with water, and then heat-cured at 200 ° C. for 20 minutes to obtain a colored pattern. The obtained pattern had a resolution of 5 μm square in line and space, and no residue or peeling of pixels was confirmed. Therefore, it was found that the present invention can also be applied to color filter applications requiring high resolution for solid-state imaging devices.

  When the substrate for evaluation was prepared in the same manner as in the evaluation of the developability except that the mask exposure was changed to the whole surface exposure and the development and the rinse treatment were not performed, the colored resin compositions 1 to 2 of the present invention and When any of the comparative resin compositions 1 and 2 was used, a color filter substrate having clear color characteristics was obtained. Each evaluation was performed by the method as described below using these evaluation substrates.

(Lightness evaluation)
About the color filter board | substrate obtained using the colored resin composition 1-2 of this invention, and the resin composition 1 for a comparison, the spectral transmittance | permeability of the board | substrate for evaluation with a spectrophotometer (UV-2450: Shimadzu Corporation) Were measured, and x, y, chromaticity coordinates and brightness Y in the CIE XYZ color system of the C light source were evaluated. The results are shown in Table 5.

Table 5 Brightness evaluation results of colored resin composition
x y Y
Colored resin composition 1 0.655 0.321 18.7
Colored resin composition 2 0.655 0.321 19.3
Comparative resin composition 1 0.655 0.321 18.0

From the result of Table 5, the colored resin compositions 1-2 of this invention showed the favorable brightness compared with the resin composition 1 for a comparison of a pigment alone.

(Heat resistance evaluation)
The color filter substrate obtained using the colored resin composition 1 of the present invention and the comparative colored resin composition 1 is subjected to heat treatment at 220 ° C. for 120 minutes, and the spectral transmittance of the evaluation substrate before and after the treatment is measured. The color difference (ΔEab) before and after the heat treatment was calculated and evaluated according to the following criteria. The results are shown in Table 6.
○: Color difference (ΔEab) is 1.0 or more and less than 5.0 ×: Color difference (ΔEab) is 5.0 or more

Table 6 Heat resistance evaluation results of colored resin composition
(ΔEab *)
Colored resin composition 1 ○
Comparative resin composition 1 ○

From the results shown in Table 6, the heat resistance of the colored resin composition 1 of the present invention was equivalent to that of the comparative resin composition 1, and ΔEab * was 5 or less, which was a level with no practical problem.

(Sensitivity evaluation)
The colored resin composition 1 of the present invention and the comparative colored resin composition 2 were applied on a glass substrate, prebaked under conditions of 80 ° C. × 100 seconds, and then exposed without passing through a mask. Next, after developing with an alkaline aqueous solution containing a surfactant and rinsing with water, the thickness of the colored pattern obtained by heating and curing at 200 ° C. for 20 minutes was measured. Further, the thickness of the colored pattern obtained by the same procedure as described above was measured except that the development treatment was not performed.
Measure the film thickness of the colored resin pattern obtained by performing the development process in the same manner as described above, and the color pattern obtained without performing the development process, and perform the development process at the same exposure amount. Based on the minimum exposure amount at which the film thickness of the colored pattern obtained was 90% or more of the film thickness of the colored pattern obtained without performing development (film loss was less than 10%), The sensitivity was evaluated based on the following criteria. The results are shown in Table 7.
○: A pattern with a film loss of less than 10% was obtained with an exposure dose of less than 50 mJ / cm ² ×: A pattern with a film loss of less than 10% was obtained with an exposure dose of 50 mJ / cm ² or more

Table 7 Results of sensitivity evaluation of colored resin composition Colored resin composition 1 ○
Comparative resin composition 2 ×

  From the results in Table 7, it is clear that the colored resin composition 1 of the present invention has higher sensitivity than the comparative resin composition 2.

As described above, the color filter obtained using the colored resin composition for a color filter of the present invention has lightness equivalent to or higher than that of a color filter obtained using a conventional pigment-dispersed colored resin composition. In addition, since it has high sensitivity and high heat resistance, 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 the colored resin composition for a color filter of the present invention, it is possible to provide a red pixel of a color filter with high brightness, excellent heat resistance, high quality, high reliability, and high sensitivity.

Claims (11)

Following formula (1)

(In Formula (1), Y represents a hydrogen atom or a chlorine atom each independently, B represents a C1-C4 linear alkylene group, Z < ^- > represents a sulfonate anion or a carboxylate anion, and A represents Following formula (2)-(4)

(In formula (2), n represents an integer of 0 to 3, and in formula (4), m represents an integer of 0 to 3). A colored resin composition for a color filter containing a cyanine compound represented by (II), a binder resin, a curing agent, a photopolymerization initiator, and / or a curing accelerator. The colored resin composition according to claim 1, wherein Y is a chlorine atom, B is an n-propylene group, Z is a sulfonate anion, and A is a substituent represented by formula (2). Further, the following formula (5)

(In Formula (5), R ¹ represents a hydrogen atom or a chlorine atom, R ² and R ⁴ each independently represents a hydrogen atom; a carbon number having a substituent selected from the group consisting of a halogen atom, a hydroxy group and an alkoxy group) Represents an alkyl group having 1 to 12 carbon atoms or an unsubstituted alkyl group having 1 to 12 carbon atoms, and R ³ represents an alkyl group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, and a carbon number 1 to 6 represents a phenyl group having a substituent selected from the group consisting of an alkoxy group and a cyano group or an unsubstituted phenyl group, R ^{5 to} R ⁸ each independently represents a hydrogen atom or a halogen atom, and M ⁻ represents A methine compound represented by bis (trifluoromethanesulfonyl) imide anion or tris (trifluoromethanesulfonyl) methide anion). Colored resin composition according to claim 1 or 2. R ¹ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms, R ² and R ⁴ are each independently a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms, and R ³ is methyl The colored resin composition according to claim 3, which is a group or an unsubstituted phenyl group. Furthermore, the colored resin composition as described in any one of Claims 1 thru | or 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 at least one 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 1 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.