JP2020111625A - Colored resin composition - Google Patents

Abstract

To provide a colored resin composition capable of producing a high-quality and high performance color filter having excellent durability and contrast and to provide a color filter produced using the same.SOLUTION: There is provided a colored resin composition which comprises an aminoxanthene-based compound, an azo-based compound represented by the formula (2), a binder resin, a solvent and a curing agent. (R6 represents an alkyl group having 1 to 4 carbon atoms or a nitro group; R7 represents H or an alkyl group having 1 to 4 carbon atoms; R8 represents H or a halogen atom; and R9 represents an alkyl group having 1 to 10 carbon atoms.)SELECTED DRAWING: None

Description

The present invention uses a colored resin composition containing a xanthene-based compound and an azo compound used when forming a red pixel of a color filter, a color filter formed using the colored resin composition, and the color filter. The present invention relates to an electronic display device such as a liquid crystal display device, an image sensor (CCD, CMOS), and an organic EL display that are formed as described above.

A liquid crystal display device such as a liquid crystal display (LCD) and an organic EL display represented by a notebook computer, a liquid crystal television, a mobile phone, a smart phone, etc., and an image pickup device (CCD, A color filter is necessary for colorization of CMOS. Examples of a method for manufacturing a color filter used in these liquid crystal display devices and solid-state image pickup devices include a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, and the like. In recent years, a pigment dispersion method using a patterning method is used. It is the mainstream. A typical patterning method is a photolithography method in which a color filter is formed by using a mixture of a photosensitive resin composition and a pigment dispersion, but recently, a colored ink is formed by an inkjet printer without using a mask. There is also a method of forming a color filter by directly coating on a substrate.

It is particularly important to improve various characteristics required for a color filter, such as color purity, saturation, brightness and contrast. For example, if the brightness is improved, it is possible to reduce the amount of light of the backlight, and as a result, the power consumption is reduced, which is an environmentally necessary technique.
In order to improve the brightness, it is necessary to increase the transmittance by reducing the pigment concentration or decreasing the film thickness, while increasing the content of the coloring pigment in order to improve the color purity of the color filter. Alternatively, it is necessary to select a pigment having a better spectral waveform. In order to achieve these contradictory characteristics, a method of forming fine particles of a pigment has been carried out, but the dispersion stability of the colored resin composition, and various characteristics such as the resistance of the color filter to light, heat or solvent, and contrast. It is necessary to maintain the balance of the above, and it is the current situation that compatibility with resistance cannot be achieved even if the brightness is improved.

As another approach for solving these problems, a color filter using a dye is being studied. When a dye is used, there is an advantage that both color purity and lightness, which cannot be achieved by a pigment, can be achieved, and light scattering can be suppressed because it is not a particle, so that the contrast can be improved. However, when a fluorescent dye is used, it is known that unpolarized fluorescence emitted from the dye excited by backlight light causes a reduction in contrast.

C. I. Xanthene compounds such as Basic Violet 10 have been applied as a dye having a color tone in the red to violet region in various applications such as various paints, water-based inks, oil-based inks, inkjet inks, and color filters.
A xanthene compound is a compound having strong fluorescence, although it is generally excellent in various properties such as a clear hue required for a dye, a high coloring property, and a colored product that is fast against light and heat. And is not necessarily useful as a dye for a color filter.
Patent Document 1 describes a xanthene-based compound composed of a cation site of xanthene, a chlorine ion, and zinc chloride. However, as a result of studies by the present inventors, the xanthene-based compound described in Patent Document 1 Robustness such as light resistance, heat resistance, water resistance, and moist heat resistance was insufficient. Patent Document 2 relates to a xanthene compound, but the document does not describe the contrast of a color filter. Patent Documents 3 and 4 describe high-contrast color filters using a salt-forming compound of a xanthene-based compound and an azo-containing compound. As a result of the study by the present inventors, the composition of the same document was disclosed. Had a large amount of azo metal compound, and had a problem in curability.
In other words, the clear red color filter with excellent reliability and high durability, which is required in the fields of liquid crystal display devices and solid-state image pickup devices, has not been put into practical use at present.

Japanese Patent Application Laid-Open No. 5-2715959 JP, 2016-60828, A JP, 2017-57400, A JP, 2016-199635, A

It is an object of the present invention to provide a colored resin composition capable of producing a color filter having excellent durability and contrast, and a color filter produced using the same.

In order to solve the above problems, the inventors of the present invention have conducted extensive studies, and use a colored resin composition containing a xanthene compound having a specific structure, an azo compound having a specific structure, a binder resin, a solvent and a curing agent. The inventors have found that the above problems can be solved by the above and have completed the present invention.

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

(In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group or an aryl group, R ³ is a hydrogen atom or a methyl group, R ⁴ is a substituent, and X ⁻ is trifluoromethanesulfonic acid. An anion, a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonylmethide anion).
Formula (2) below

(In the formula (2), R ⁶ represents an alkyl group having 1 to 4 carbon atoms or a nitro group. R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁸ represents a hydrogen atom or a halogen atom. R ⁹ represents an alkyl group having 1 to 10 carbon atoms), a colored resin composition containing an azo compound represented by the formula, a binder resin, a solvent and a curing agent.
(2) The colored resin composition according to the above item (1), wherein R ⁴ is a substituent represented by —COOR ⁵ , and R ⁵ is a hydrogen atom or an alkyl group which may have a substituent.
(3) The colored resin composition according to the above item (1) or (2), wherein R ¹ and R ² are linear alkyl groups having 2 to 6 carbon atoms, and R ³ is a hydrogen atom.
(4) The colored resin composition according to any one of the above items (1) to (3), wherein X ⁻ is a trifluoromethanesulfonate anion or a bistrifluoromethanesulfonylimide anion.
(5) The colored resin composition according to any one of the above items (1) to (4), wherein R ⁶ is a nitro group.
(6) The colored resin composition according to any one of the above items (1) to (5), wherein R ⁷ is an alkyl group having 1 to 4 carbon atoms,
(7) The colored resin composition according to any one of the above items (1) to (6), wherein R ⁸ is a hydrogen atom,
(8) The colored resin composition according to any one of the above items (1) to (7), wherein R ⁹ is a 2-ethylhexyl group,
(9) A color filter obtained by using the colored resin composition according to any one of (1) to (8) above, and (10) a liquid crystal display device equipped with the color filter according to (9) above. , An organic EL display or a solid-state image sensor,
Regarding

By using the colored resin composition of the present invention, a color filter having excellent durability and contrast can be provided.

The colored resin composition of the present invention contains the xanthene compound represented by the above formula (1).
In formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group.
Examples of the alkyl group represented by R ¹ and R ^{2 in} the formula (1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a pentyl group, a cyclopentyl group, Examples thereof include an alkyl group having 1 to 6 carbon atoms such as a hexyl group and a cyclohexyl group, an alkyl group having 2 to 6 carbon atoms is preferable, a linear alkyl group having 2 to 6 carbon atoms is more preferable, and an alkyl group having 2 to 4 carbon atoms. The linear alkyl group of is more preferable.
These alkyl groups may have a substituent, and the substituent is not particularly limited, and examples thereof include hydroxyalkyl groups such as hydroxyethyl group, hydroxypropyl group and hydroxybutyl group; 2-sulfoethyl group; Carboxyethyl group; cyanoethyl group; alkoxyalkyl group such as methoxyethyl group, ethoxyethyl group and butoxyethyl group; halogenated alkyl group such as trifluoromethyl group and pentafluoroethyl group; carbamoyl group; and carboxy group ..

Examples of the aryl group represented by R ¹ and R ^{2 in} the formula (1) include aromatic hydrocarbon residues such as phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group and benzopyrenyl group; and pyridyl group, pyrazyl group. And aromatic heterocyclic groups such as pyrimidyl group, quinolyl group, isoquinolyl group, pyrrolyl group, indolenyl group, imidazolyl group, carbazolyl group, thienyl group and furyl group.
These aryl groups may further have a substituent, and the substituent is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and t. -Alkyl group such as butyl group, i-butyl group and pentyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group and hexyl group Alkoxy group such as oxy group; hydroxyalkyl group such as hydroxyethyl group and hydroxypropyl group; alkoxyalkyl group such as methoxyethyl group, ethoxyethyl group, ethoxypropyl group and butoxyethyl group; hydroxyalkoxy group such as 2-hydroxyethoxy group Group; an alkoxyalkoxy group such as a 2-methoxyethoxy group and a 2-ethoxyethoxy group; a 2-sulfoethyl group; a carboxyethyl group; a cyanoethyl group; and a sulfonic acid group.

As R ¹ and R ^{2 in} formula (1), each independently an alkyl group is preferable, and it is more preferable that R ¹ and R ^{2 at} four positions are the same alkyl group.
In formula (1), R ³ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
In formula (1), R ⁴ represents a substituent.

Examples of the substituent represented by R ^{4 in} formula (1) include an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group, a heterocyclic oxy group, Aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, heterocyclic sulfonyloxy group , Sulfamoyl group, aliphatic sulfonamide group, aryl sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group , Heterocyclic oxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxy group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino Group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphosphinyl group, diaryloxyphosphinyl group, and the like, aliphatic oxycarbonyl group or carboxy group. A group is preferable, and an alkoxycarbonyl group or a carboxy group, that is, a substituent represented by —COOR ⁵ and R ⁵ is a hydrogen atom or an alkyl group is more preferable.

Examples of the alkyl group represented by R ⁵ include an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group and a cyclohexyl group. , An alkyl group having 1 to 4 carbon atoms is preferable, an alkyl group having 1 or 2 carbon atoms is more preferable, and a methyl group is still more preferable.
These alkyl groups may have a substituent, and the substituent is not particularly limited, and examples thereof include hydroxyalkyl groups such as hydroxyethyl group, hydroxypropyl group and hydroxybutyl group; 2-sulfoethyl group; Carboxyethyl group; cyanoethyl group; alkoxyalkyl group such as methoxyethyl group, ethoxyethyl group and butoxyethyl group; halogenated alkyl group such as trifluoromethyl group and pentafluoroethyl group; carbamoyl group; carboxy group; and aryl group, etc. And an aryl group is preferable, and a phenyl group is more preferable.

In formula (1), X ⁻ represents a trifluoromethanesulfonic acid anion, a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonylmethide anion, preferably a trifluoromethanesulfonic acid anion or a bistrifluoromethanesulfonylimide anion, and a bistrifluoromethane. The sulfonylimide anion is more preferred.

As the xanthene compound represented by the formula (1), a combination of the preferable ones of R ^{1 to} R ⁵ and X ⁻ is more preferable, and a combination of the more preferable ones is further preferable.

The xanthene compound used in the colored resin composition of the present invention can also be obtained by a known synthesis method described in, for example, Yutaka Hosoda, "Theoretical Manufacturing Dye Chemistry" (pages 373-375), published by Gihodo. Are commercially available C.I. I. Basic Violet 10 can be purchased and synthesized by the following method.
Specifically, first, C.I. represented by the following formula (AA), which is commercially available, is used. I. Basic Violet 10 is converted to a derivative represented by the following formula (B) by reacting with benzyl bromide, and further, salt exchange reaction is carried out by referring to the method described in Japanese Patent No. 5800393, and the above formula ( It is possible to obtain a xanthene-based compound in which R ¹ and R ² in 1) are ethyl groups, R ³ is a hydrogen atom, and R ⁴ is a methoxycarbonyl group having a phenyl group as a substituent.

The above-mentioned C.I. I. The reaction temperature in the condensation step of Basic Violet 10 and benzyl bromide is preferably 50 to 150°C, more preferably 70 to 120°C. In the condensation step, a condensing agent may be used if necessary, and as the condensing agent that can be used, for example, zinc chloride, magnesium chloride, aluminum chloride or the like is preferably used. When a condensing agent is used, it is preferably contained in an amount of 0.5 to 2.0 molar equivalents with respect to the xanthene-based compound (CI Basic Violet 10 in the above case) as a raw material.

When the xanthene compound represented by the formula (1) is synthesized by salt exchange, for example, a dye in which X ⁻ is a chlorine anion is used as a reaction solvent (for example, water, or methanol, ethanol, isopropanol, acetone, N, N). -A water-soluble polar solvent such as dimethylformamide (hereinafter abbreviated as DMF), N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), and the like, and these solvents may be used alone or may be mixed. Then, about 0.5 to 3 equivalents of the corresponding salt or acid is added to the dye, the mixture is stirred at a predetermined temperature (for example, 0 to 100° C.), and the precipitated crystals may be collected by filtration.

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

Included in the total solid content of the colored resin composition of the present invention (refers to the total amount of solid content consisting of a xanthene compound excluding a solvent, a binder resin, a curing agent, a quencher, and the like. The same applies hereinafter). The content of the xanthene compound represented by the formula (1) is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 20 parts by mass. By setting the content of the xanthene compound represented by the formula (1) within this range, there is no problem of precipitation or aggregation, curability is good, adhesion to the substrate is excellent, and sufficient color characteristics are obtained. A color filter having excellent color purity can be obtained.

The colored resin composition of the present invention contains the azo compound represented by the formula (2).
In the formula (2), R ⁶ represents an alkyl group having 1 to 4 carbon atoms or a nitro group.
Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁶ in the formula (2) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group and t-. A butyl group is mentioned.
R ^{6 in the} formula (2) is preferably a nitro group.

In the formula (2), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁷ in the formula (2) include the same ones as the alkyl group having 1 to 4 carbon atoms represented by R ^{6 in} the formula (2).
R ^{7 in the} formula (2) is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

In formula (2), R ⁸ represents a hydrogen atom or a halogen atom.
Examples of the halogen atom represented by R ^{8 in the} formula (2) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
R ^{8 in} formula (2) is preferably a hydrogen atom.

In the formula (2), R ⁹ represents an alkyl group having 1 to 10 carbon atoms.
The alkyl group having 1 to 10 carbon atoms represented by R ^{9 in the} formula (2) is not limited to linear, branched or cyclic as long as it is an alkyl group having 1 to 10 carbon atoms, and specific examples thereof As, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl Group, 3-methylbutyl group, 2-ethylhexyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, hexyl group, 1-methylpentyl group , 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group , 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethyl-1-methylpropyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group, etc. And a 2-ethylhexyl group is preferred.

As the azo compound represented by the formula (2), a combination of the preferable ones of R ^{6 to} R ⁹ is more preferable, and a combination of the more preferable ones is further preferable.

As the azo compound of the present invention, a commercially available azo compound such as Solvent Orange 56 can be purchased and used, or can be synthesized by the following method, for example. In the formulas (C) to (F) below, R ^{6 to} R ⁹ have the same meanings as in the formula (2).
First, a compound represented by the following formula (C) is diazotized by a conventional method, and the obtained diazo compound and a compound represented by the following formula (D) are subjected to a coupling reaction by a conventional method to obtain a compound represented by the following formula (E) A compound represented by Then, the compound represented by the following formula (F) can be synthesized by subjecting the obtained compound of the following formula (E) to a condensation reaction with a corresponding chromium compound or cobalt compound.
Finally, if necessary, the compound of the following formula (F) is reacted with the corresponding alkylamine compound (G) to obtain the azo compound represented by the above formula (2).

Specific examples of the azo compound represented by the above formula (2) are shown below, but the azo compound represented by the formula (2) contained in the colored resin composition of the present invention is not limited thereto.

The content of the azo compound represented by the formula (2) contained in the total solid content of the colored resin composition of the present invention is preferably 0.5 to 50% by mass, more preferably 1 to 30% by mass. Is. By setting the content of the azo compound represented by the formula (2) within this range, it is possible to form a colored resin composition having excellent contrast without inhibiting the curability of the present colored resin compound.

The colored resin composition of the present invention contains a binder resin.
The binder resin contained in the colored resin composition is not particularly limited, and a conventionally known binder resin can be used, but when the colored resin composition of the present invention is used in the method of photolithography, one or more of the following are listed. A copolymer of an ethylenically unsaturated monomer having a carboxy group or a hydroxyl group or another copolymerizable ethylenically unsaturated monomer having an aromatic hydrocarbon group or an aliphatic hydrocarbon group Is desirable. Further, those having an unsaturated double bond or an epoxy group at the side chain or terminal of these copolymers, or an epoxy acrylate resin can also be used. These monomers and the like may be used alone or in combination of two or more kinds in the copolymer.

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

Specific examples of the ethylenically unsaturated monomer having a hydroxyl group that can be used in the present invention include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxypropyl (meth)acrylate. 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)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. Examples thereof include glycol mono(meth)acrylate, and these can be used alone or in combination of two or more kinds.

Examples of the other ethylenically unsaturated monomer having a copolymerizable aromatic hydrocarbon group or aliphatic hydrocarbon group described above include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, Aromatic vinyl compounds such as p-vinyltoluene, o-chlorostyrene, m-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, 2-hydroxy-3-phenoxypropyl (meth)acrylate, o-phenylphenol glycidyl ether (meth)acrylate, o-phenylphenol (meth)acrylate hydroxyethyl Compounds, unsaturated carboxylic acid esters such as 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, dimethyl Adamantyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]dec-8-yl=(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]dec-4-methyl=( Alicyclic skeletons such as (meth)acrylate, cyclodecyl (meth)acrylate, 2-(meth)acryloyloxyethylhexahydrophthalic acid, t-butylcyclohexyl (meth)acrylate; polyethylene glycol mono(meth)acrylate, polypropylene glycol mono Hydroxyl-terminated polyalkylene glycol mono(meth)acrylates such as (meth)acrylate and poly(ethylene glycol-propylene glycol) monomethacrylate; methoxy polyethylene glycol monomethacrylate Rate, lauroxy polyethylene glycol mono(meth)acrylate, octoxy polyethylene glycol polypropylene glycol mono(meth)acrylate, nonylphenoxy polyethylene glycol monoacrylate, nonylphenoxy polypropylene glycol monoacrylate, allyloxy polyethylene glycol-polypropylene glycol mono(meth)acrylate Alkyl-terminated polyalkylene glycol mono(meth)acrylates such as; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, etc. Unsaturated carboxylic acid aminoalkyl esters; glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl Unsaturated carboxylic acid glycidyl esters such as ethers; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidyl ether, etc. Unsaturated ethers; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, N-(meth ) Unsaturated amides or unsaturated imides such as acryloylphthalimide, N-(2-hydroxyethyl)acrylamide, N-(2-hydroxyethyl)methacrylamide, maleimide; aliphatic such as 1,3-butadiene, isoprene, chloroprene Conjugated dienes; polystyrene, polymethyl acrylate, polymethyl methacrylate, poly n-butyl acrylate, poly n-butyl methacrylate, polysilicones, etc. Macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain, etc. These can be used alone or in admixture of two or more.

Further, a polymer in which an unsaturated double bond is further introduced into the side chain of the copolymer is also useful. For example, styrene having an alcoholic hydroxyl group such as hydroxyethyl acrylate or the like in the maleic anhydride portion of a copolymer with styrene, vinylphenol, acrylic acid, acrylic acid 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 with half-esterification, and acrylic acid, or a copolymer of an acrylic ester and an acrylate having an alcoholic hydroxyl group such as hydroxyethyl acrylate. Examples include reacted compounds. Further, 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 (manufactured by Nippon Kayaku). ), UXE-3000 (Nippon Kayaku), ZGA-287H (Nippon Kayaku), TCR-1338H (Nippon Kayaku), ZXR-1722H (Nippon Kayaku), ZFR-1401H (Nippon Kayaku) ) And ZCR-1642 (manufactured by Nippon Kayaku) can also be used.

When the binder resin (copolymer) contained in the colored resin composition of the present invention is produced, a polymerization initiator is used.
Specific examples of the polymerization initiator include α,α′-azobis(isobutyronitrile), 2,2′-azobis(2-methylbutyronitrile), t-butyl peroctoate, di-t-butyl peroxide. Oxide peroxide such as benzoyl methyl ethyl ketone peroxide can be mentioned. The amount of the polymerization initiator used is preferably 0.01 to 25 parts by mass with respect to the total amount of all the monomers used for the synthesis of the copolymer.
When synthesizing the copolymer, it is preferable to use an organic solvent having a sufficient dissolving power for the monofunctional monomer, the polymerization initiator and the like used in the synthesis. The organic solvent used for the synthesis may be selected from the specific examples of the solvent contained in the colored resin composition of the present invention to be described later in consideration of the dissolving power for the monomer and the polymerization initiator.
The reaction temperature when synthesizing the copolymer is preferably 50 to 120°C, particularly preferably 80 to 100°C. The reaction time is preferably 1 to 60 hours, more preferably 3 to 20 hours.
The preferred acid value of the copolymer is 10 to 300 (mgKOH/g), and the preferred hydroxyl value is 10 to 200 (mgKOH/g). By using a copolymer having an acid value or a hydroxyl value within the above range, a colored resin composition having excellent developability can be obtained.
The weight average molecular weight (Mw) of the copolymer is preferably 2,000 to 400,000, more preferably 3,000 to 100,000. By using a copolymer having a weight average molecular weight within the above range, a photosensitive resin composition having excellent sensitivity and developability can be obtained.

The binder resin (copolymer) may be used alone or in admixture of two or more with the colored resin composition of the present invention. The content of the binder resin in the colored resin composition of the present invention is usually 1 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.

The colored resin composition of the present invention contains a solvent.
The solvent is, for example, an oil-soluble organic solvent, a water-soluble organic solvent and solvents such as water, and further, one or more kinds in which these solvents are combined, particularly limited according to the use and usage of the colored resin composition. Can be used without.

Specific examples of the oil-soluble organic solvent include alcohols such as ethanol, pentanol, octanol, cyclohexanol, benzyl alcohol, tetrafluoropropanol and diacetone alcohol; ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Glycol derivatives such as propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol diacetate, propylene glycol monomethyl ether acetate and propylene glycol diacetate; methyl ethyl ketone and cyclohexanone Ketones; butyl phenyl ether, benzyl ether, hexyl ether, and other ethers; methyl acetate, ethyl acetate, butyl acetate, ethyl benzoate, butyl benzoate, ethyl laurate, butyl laurate, and other esters; acetonitrile, DMF And polar organic solvents such as dimethyl sulfoxide, sulfolane, N-methylpyrrolidone and 2-pyrrolidone.

Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol and benzyl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol. Polypropylene glycol, glycerin, trimethylolpropane, 1,3-pentanediol, 1,5-pentanediol and other polyhydric alcohols; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, tri Glycol derivatives such as ethylene glycol monoethyl ether, triethylene glycol monobutyl ether and dipropylene glycol monomethyl ether; amines such as ethanolamine, diethanolamine, triethanolamine and morpholine; 2-pyrrolidone; N-methylpyrrolidone; 1,3- Examples thereof include dimethyl-imidazolidinone.

These solvents may be used alone or in combination of two or more. When the solvent is used, the amount used is preferably 40 to 10000 parts by mass, more preferably 100 to 1000 parts by mass, based on 100 parts by mass of the total solid content of the colored resin composition.

The colored resin composition of the present invention contains a curing agent.
Examples of the curing agent include a photopolymerizable monomer in the case of radical polymerization, an epoxy resin in the case of ionic curing, and a melamine curing agent. Specific examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol. (Meth)acrylate, tetraethylene glycol (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa (Meth)acrylate, glycerol (meth)acrylate, bisphenol A type epoxy di(meth)acrylate, bisphenol F type epoxy di(meth)acrylate, bisphenol fluorene type epoxy di(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxy Trimethylolpropane tri(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, 9, 9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, Kayarad RP-1040 (manufactured by Nippon Kayaku), Kayarad DPCA-30 (manufactured by Nippon Kayaku), UA-33H (manufactured by Shin-Nakamura Chemical), UA. -53H (manufactured by Shin-Nakamura Chemical), M-8060 (manufactured by Toagosei); TEMPIC (manufactured by Sakai Chemical), TMMP (manufactured by Sakai Chemical), PEMP (manufactured by Sakai Chemical), DPMP (manufactured by Sakai Chemical) ); As the epoxy resin, Nippon Kayaku products NC-6000, NC-3000, EOCN-1020, XD-1000, EPPN-501H, BREN-S, NC-7300L, Daicel chemical products Celoxite 2021P, EHPE3150, Cyclo. Mar M100, Epolide PB3600, Epicord 828 of Japan epoxy resin products, Epicort YX8000, Epicort YX4000, Sila Ace S510 (manufactured by Chisso), TEPIC (manufactured by Nissan Chemical Industries, Ltd.), etc. Wa Chemical Co., Ltd.) and the like. These may be used alone or in combination of two or more. The content of these is usually 80 parts by mass or less, preferably 5 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the colored resin composition.

Other components that can be used in combination with the colored resin composition of the present invention include, for example, organic pigments, dyes, dispersants, resins, photopolymerization initiators, thermal polymerization initiators, surface modifiers, antifoaming agents, and antiseptic agents. Examples thereof include a fungicide, a pH adjuster, a dye other than the xanthene compound represented by the above formula (1), and a dye other than the azo compound represented by the above formula (2).

The dispersant that can be used in combination with the colored resin composition of the present invention is not particularly limited, but selecting a dispersant according to the type of solvent is effective for improving the dispersion stability of the colored resin composition. ..
Dispersants preferably used in combination with oil-soluble organic solvents include sodium dodecylbenzene sulfonate, sodium laurate, formalin condensate of naphthalene sulfonic acid, formalin condensate of alkylnaphthalene sulfonic acid, and formalin of creosote oil sulfonic acid. Condensates, ammonium salts of polyoxyethylene alkyl ether sulphates, ammonium salts of polyoxyethylene alkylphenyl ether sulphates, polyoxyalkyl ether phosphate salts, etc. Known anionic surfactants, vinylnaphthalene derivatives, α, β-ethylenic Aliphatic alcohol ester of saturated carboxylic acid, styrene, styrene derivative, acrylic acid, acrylic acid derivative, methacrylic acid, methacrylic acid derivative, maleic acid, maleic acid derivative, maleic anhydride, maleic anhydride derivative, itaconic acid, itaconic acid Examples thereof include block copolymers composed of at least two monomers selected from derivatives, fumaric acid, fumaric acid derivatives and the like, random copolymers, and polymer dispersants such as salts thereof.

As the dispersant preferably used in combination with the water-soluble organic solvent or water, a polymer dispersant can be preferably used in addition to the surfactant. Specific examples of the polymer dispersant include polyvinyl alcohols, polyvinylpyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymers, acrylate-acrylonitrile copolymers, vinyl acetate-acrylic acid ester copolymers. Acrylic resin such as acrylic acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene -Styrene-acrylic resin such as acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, isobutylene-malein Acid resin, rosin-modified maleic acid resin, vinylnaphthalene-acrylic acid copolymer, vinylnaphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinylethylene copolymer, vinyl acetate-maleic acid Examples thereof include vinyl acetate-based copolymers such as acid ester copolymers, vinyl acetate-crotonic acid copolymers, vinyl acetate-acrylic acid copolymers, and salts thereof.

Examples of other resin-based dispersants include polyurethane resin-based, polycarboxylic acid-based, polyamide resin-based and polyester resin-based dispersants. Specific examples of the resin-based dispersant include ED211 (produced by Kusumoto Kasei) and Azisper PB821 (produced by Ajinomoto Fine-Techno Co., Ltd.) Sols Perth 71000 (produced by Avicia).

These dispersants include a xanthene compound represented by the above formula (1), an azo compound represented by the above formula (2), and a dye that can be optionally contained in the colored resin composition of the present invention. The total amount is usually 500% by mass or less, preferably 10 to 450% by mass, more preferably 100 to 400% by mass.

Examples of resins that can be used in combination with the colored resin composition of the present invention include polyamide-based, polyurethane-based, polyester-based, epoxy-based, and polyacrylic-based resins.
The polyamide resin, polyurethane resin, polyester resin, epoxy resin and polyacrylic resin that can be contained in the colored resin composition of the present invention are not particularly limited, and conventionally known ones can be mentioned.

The photopolymerization initiator that can be used in combination with the colored resin composition of the present invention is preferably a photopolymerization initiator that has sufficient sensitivity to ultraviolet rays emitted from an ultra-high pressure mercury lamp that is generally used as an exposure light source, and radical-polymerizable photoradical initiation Agents, ion-curable photoacid generators or photobase generators, and the like. A polymerization accelerator component called a sensitizer may be used in combination in order to achieve a light effect with less exposure energy.
The photopolymerization initiator that can be used in combination with the colored resin composition of the present invention is not particularly limited, and examples thereof include benzyl, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, Benzoylbenzoic acid, esterified product of benzoylbenzoic acid, 4-benzoyl-4′-methyldiphenyl sulfide, benzyldimethylketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, isopropylthioxanthone, dimethyl Thioxanthone, diethylthioxanthone, diisopropylthioxanthone, methylaminomethylbenzoate, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl 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-benzo Art, 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 type initiator, and commercially available Kayacure DMBI, Kayacure BDMK, Kayacure BP-100, Kayacure BMBI, Kayacure DETX-S, Kayacure EPA (all manufactured by Nippon Kayaku), Darocur 1173, Darocur. 1116 (all manufactured by Merck Japan), Irgacure 907 (manufactured by BASF Japan), Irgacure 369 (manufactured by BASF Japan), Irgacure 379EG (manufactured by BASF Japan), Irgacure OXE-01 (manufactured by BASF Japan), Irgacure OXE. -02 (manufactured by BASF Japan), Irgacure PAG103 (manufactured by BASF Japan), TME-triazine (manufactured by Sanwa Chemical), biimidazole (manufactured by Kurogane Kasei), STR-110, STR-1 (all manufactured by Respe Chemical). Etc.

Examples of the thermal polymerization initiator that can be used in combination with the colored resin composition of the present invention include azo compounds and organic peroxides, and specific examples thereof include 2,2′-azobisisobutyronitrile and 2,2′-azobisisobutyronitrile. 2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), di-t-butyl peroxide, dibenzoyl peroxide, cumylperoxy neodecanoate, etc. Are listed.

These photopolymerization initiators and thermal polymerization initiators can be used alone or in combination of two or more, if necessary. The content of these initiators is usually 50 parts by mass or less, and preferably 1 to 25 parts by mass with respect to 100 parts by mass of the solid content of the colored resin composition.

Examples of the surface modifier that can be used in combination with the colored resin composition of the present invention include known polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, copolymers of ethylene oxide and propylene oxide, and the like. Examples thereof include nonionic, polysiloxane-based, or polydimethylsiloxane-based surfactants.
Examples of the defoaming agent that can be used in combination with the colored resin composition of the present invention include known defoaming agents of silicone type and acetylene type.
Examples of antiseptic/antifungal agents that can be used in combination with the colored resin composition of the present invention include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2-benzisothiazoline- Known antiseptic and antifungal agents such as amine salts of 3-one and 1-benzisothiazolin-3-one can be mentioned.
Examples of the pH adjusting agent that can be used in combination with the colored resin composition of the present invention include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, triethanolamine, diethanolamine, dimethylethanolamine and diethylethanolamine. Known pH adjusting agents such as tertiary amines may be mentioned.

In the colored resin composition of the present invention, as a dye other than the xanthene compound represented by the above formula (1), an organic pigment, an inorganic pigment, a dye or the like may be used in combination.

The organic pigment that can be used in combination with the colored resin composition of the present invention is not particularly limited, and examples thereof include anthraquinone type, phthalocyanine type, triphenylmethane type, benzimidazolone type, quinacridone type, azo chelate type, azo type, isoindoline type. , Isoindolinone-based, pyranthrone-based, indathuron-based, anthrapyrimidine-based, dibromoanzanthuron-based, flavanthuron-based, perylene-based, perinone-based, quinophthalone-based, thioindigo-based, dioxazine-based, quinacridone-based, xanthene-based pigments; Examples thereof include lake pigments obtained by insolubilizing acid dyes, basic dyes, direct dyes and the like with respective precipitants, dye lake pigments and the like.
Specific examples of these pigments include Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, by color index. 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79; Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50; Pigment Violet 3, 4, 27, 39; Pigment Red 7, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 81:5, 122, 146, 168, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264270, 272, 279; Pigment Orange 43, 71, 73; Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 15, 16. 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, Pigment Green 7, 36, 58, and the like.

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

The dye that can be used in combination with the colored resin composition of the present invention is not particularly limited, and examples thereof include acid dyes, basic dyes, direct dyes, sulfur dyes, vat dyes, naphthol dyes, reactive dyes and disperse dyes. When an organic solvent is used in combination, a dye soluble in the organic solvent is preferable, but a dye insoluble in the organic solvent can be appropriately used by forming a dispersion. A dye that is insoluble in an organic solvent has a well-known formulation, for example, in the case of an acid dye, an organic amine compound (for example, n-propylamine, ethylhexylpropionate amine, etc.) is reacted to modify it into an amine salt dye, or It is known that a sulfonic acid group is reacted with the same organic amine compound to be modified into a dye having a sulfonamide group. These amine-modified dyes can also be used in the colored resin composition of the present invention.
Specific examples of these dyes include C.I. I. Numbers Basic Blue 7, Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 249, 256, 259, 267, 278, 280, 285, 290, 296. 315, 324, 335, 340; Basic Blue 7, 11, 15, 26; Solvent Blue 2, 3, 4, 5, 6, 23, 25, 35, 37, 38, 43, 55, 59, 67, 72, 124; Basic Violet 10; Acid Violet 17, 49; Solvent Violet 4, 5, 14; Basic Red 1, 10, 29; Acid Red 91, 92, 97, 114, 138, 151, 289; Solvent Red 45, 49, 127; Acid Yellow 17, 23, 25, 29, 38, 40, 42, 76; Solvent Yellow 4, 14, 15, 24, 76, 81, 82, 94, 98, 162; Solvent Orange 2, 7, 11, 15, 26, 56; Acid Orange 16, 86, and the like.

The colored resin composition of the present invention is produced by mixing and stirring the xanthene-based compound represented by the formula (1), other essential components, and optional components that are added as necessary with a dissolver or a homomixer. When a pigment or a dye having low compatibility with the essential components of the colored resin composition of the present invention is used in combination, a dispersion obtained by a disperser such as a paint shaker using an appropriate solvent and dispersant for these components is used. It may be mixed in addition to the colored resin composition, and may be subjected to microfiltration with a filter or the like in order to remove foreign matters and the like from the prepared colored resin composition.

The colored resin composition of the present invention is used for various paints, water-based inks, oil-based inks, inkjet inks, and colored resin compositions for color filters. Specific applications of the colored resin composition for color filters include liquid crystal display. Examples thereof include color filters for devices, organic EL displays, solid-state imaging devices used in digital cameras and the like.
Examples of the material to be colored using the colored resin composition of the present invention include, but are not limited to, plain paper, coated paper, plastic film, and plastic substrate. Examples of the method for applying the colored resin composition of the present invention to the material to be colored include various printing methods such as offset printing, letterpress printing, flexographic printing, and inkjet printing, or coating methods using a spin coater, a roll coater, or the like. ..

Next, a method for preparing a cured product of the colored resin composition of the present invention will be described. However, the method for preparing a cured product from the colored resin composition of the present invention is not limited to this. First, the colored resin composition of the present invention is applied onto 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, a bar coating method, etc. 1 to 20 μm, preferably 0.5 to 5 μm, and if necessary, in a vacuum chamber under drying conditions at a temperature of 23 to 150° C. for a time of 1 to 60 minutes, more preferably a temperature of 60. Drying is carried out under reduced pressure at a temperature of from 120° C. to 120° C. for a time of from 1 to 10 minutes, and a pre-baking treatment is further carried out with a hot plate or a clean oven to form a film. Next, by a general photolithography method, radiation (eg, electron beam, ultraviolet ray, preferably ultraviolet ray) is irradiated through a predetermined mask pattern, and development is performed with a surfactant aqueous solution, an alkaline aqueous solution, or a mixed aqueous solution of a surfactant and an alkaline agent. To do. Examples of the developing method include a dipping method, a spray method, a shower method, a paddle method, an ultrasonic developing method, and the like, and any of these may be combined. After removing the non-irradiated portion by development and rinsing with water, post-baking treatment is performed, for example, at a temperature of 130 to 300° C. for 1 to 120 minutes, more preferably at 150 to 250° C. for 1 to 30 minutes. Under the conditions described above, a pixel comprising the colored cured film of the present invention is obtained.

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

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

Among the display devices of the present invention, the liquid crystal display device is manufactured, for example, with a structure in which a backlight, a polarizing film, a display electrode, a liquid crystal, an alignment film, a common electrode, the color filter of the present invention, a polarizing film, etc. are laminated in this order. .. The organic EL display is manufactured by forming the color filter of the present invention on either one of the top and bottom of the multilayer organic light emitting device. Further, 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 a transfer electrode and a photodiode, and then laminating a microlens.

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the examples. Unless otherwise specified, "part" in the text is based on mass, and the reaction temperature is the internal temperature. Of the synthesized compounds, those having a measured λmax (maximum absorption wavelength) are UV-visible absorption spectra measured in methanol using UV-visible spectrophotometer UV-3150 (manufactured by Shimadzu Corporation) unless otherwise specified. It is the value of the maximum absorption wavelength in the measurement result of.
The measurement conditions of the UV-visible absorption spectrum are as follows.
Measuring instrument: spectrophotometer "Shimadzu Corporation, trade name UV-3150"
Wavelength range: 300 to 800 nm
Scan speed: Medium speed Sampling pitch: 0.5 nm
Measurement mode: Single Photometric value:: Absorbance Slit width: 2.0 nm
Light source switching wavelength: 360.0 nm
S/R switching: Standard

Synthesis example 1 (synthesis of xanthene compound represented by compound No. 3 in the above specific example)
(Step 1-1)
In a 200 ml four-necked flask, 9.6 parts of Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.), 32 parts of DMF, 10 parts of benzyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.3 parts of potassium carbonate were put, and 2 at 90°C. Stir for hours. After cooling the reaction solution, 6.4 parts of potassium salt of bistrifluoromethanesulfonylimide (manufactured by Morita Chemical Industry Co., Ltd.) was further stirred for 1 hour. The obtained reaction solution was poured into water, and the precipitated crystals were collected by filtration, washed, and dried to give No. 1 of the above specific examples. 20 parts of the xanthene compound represented by 3 was obtained. The maximum absorption wavelength of the xanthene compound was 559 nm (methanol).

Synthesis example A (synthesis of binder resin)
A 500 ml four-necked flask was charged with 160 parts of methyl ethyl ketone, 10 parts of methacrylic acid, 33 parts of benzyl methacrylate and 1 part of α,α′-azobis(isobutyronitrile), and nitrogen gas was introduced into the flask for 30 minutes while stirring. did. Then, the temperature was raised to 80° C. and the mixture was stirred at 80 to 85° C. for 4 hours as it was. After completion of the reaction, the 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 binder resin. The obtained binder resin weight average molecular weight (calculated in terms of polystyrene based on the measurement result of gel permeation chromatography) was 18,000, and the acid value measured according to JIS K2501 was 152 (mgKOH/g). there were.

Example 1 and Comparative Example 1 (Preparation of colored resin composition)
Compound No. obtained in Synthesis Example 1 3, an azo compound represented by the following formula (102), a binder resin obtained in Synthesis Example A as a binder resin, cyclopentanone as a solvent, and a photopolymerizable monomer DPHA( as a curing agent. (Nippon Kayaku Co., Ltd.) and a photopolymerization initiator Irgacure 907 (manufactured by BASF) are mixed at the compounding amounts (parts) shown in Table 1 and then treated by an ultrasonic device for 10 minutes to dissolve the resin. Composition 1 and comparative colored resin composition 1 were prepared.

Example 2 and Comparative Example 2 (Preparation of dye-colored body (color filter))
The colored resin composition 1 and the comparative colored resin composition 1 obtained in Example 1 and Comparative Example 1 were spin-coated on a glass substrate and dried at 80° C. for 10 minutes to obtain a dye coloring body 1 and a comparative dye. Colored bodies 1 were produced respectively.

(Evaluation of fluorescence intensity)
Using a fluorescence spectrophotometer (Hitachi High-Tech Science Co., Ltd., trade name F-7000), the fluorescence intensity of each dye-colored body obtained in Example 2 and Comparative Example 2 was measured. The smaller the fluorescence intensity is, the weaker the fluorescence is, and the better the contrast of the dye-colored body obtained from the colored resin composition is. The results are shown in Table 2.
The measurement and conditions of the fluorescence spectrophotometer are as follows.
Measuring instrument: Fluorescence spectrophotometer "Hitachi High-Tech Science Co., Ltd., trade name F-7000"
Excitation wavelength: 559 nm
Observation wavelength range: 500 to 850 nm
Scan speed: 240nm/min
Sampling pitch: 1 nm
Measurement mode: Fluorescence Slit width: 5.0 nm

From the results in Table 2, it is clear that the dye-colored body produced using the colored resin composition 1 of the present invention has a lower fluorescence intensity than the dye-colored body produced using the comparative colored resin composition 1. Is.

As described above, the dye-colored product obtained by using the colored resin composition of the present invention containing the xanthene compound represented by the formula (1) and the azo compound represented by the formula (2) has a small fluorescence. Since it exhibits strength, it has high contrast and can be used in a wide range of applications that require high robustness such as color filter inks and inkjet inks, and it is clear that it has high industrial value. It was

By using the colored resin composition for a color filter of the present invention containing the xanthene compound having the specific structure represented by the formula (1) and the azo compound having the specific structure represented by the formula (2), excellent contrast was obtained. It is possible to provide a red pixel of a high quality and highly reliable color filter.

Claims (10)

Formula (1) below

(In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group or an aryl group, R ³ is a hydrogen atom or a methyl group, R ⁴ is a substituent, and X ⁻ is trifluoromethanesulfonic acid. Represents an anion, bistrifluoromethanesulfonylimide anion or tristrifluoromethanesulfonylmethide anion.)
A xanthene compound represented by
Formula (2) below

(In the formula (2), R ⁶ represents an alkyl group having 1 to 4 carbon atoms or a nitro group. R ⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁸ represents a hydrogen atom or a halogen atom. R ⁹ represents an alkyl group having 1 to 10 carbon atoms.)
An azo compound represented by
A colored resin composition containing a binder resin, a solvent and a curing agent. The colored resin composition according to claim 1, wherein R ⁴ is a substituent represented by —COOR ⁵ , and R ⁵ is a hydrogen atom or an alkyl group which may have a substituent. The colored resin composition according to claim 1, wherein R ¹ and R ² are linear alkyl groups having 2 to 6 carbon atoms, and R ³ is a hydrogen atom. The colored resin composition according to claim 1, wherein X ⁻ is a trifluoromethanesulfonate anion or a bistrifluoromethanesulfonylimide anion. The colored resin composition according to any one of claims 1 to 4, wherein R ⁶ is a nitro group. The colored resin composition according to any one of claims 1 to 5, wherein R ⁷ is an alkyl group having 1 to 4 carbon atoms. The colored resin composition according to any one of claims 1 to 6, wherein R ⁸ is a hydrogen atom. The colored resin composition according to any one of claims 1 to 7, wherein R ⁹ is a 2-ethylhexyl group. A color filter obtained using the colored resin composition according to claim 1. A liquid crystal display device, an organic EL display, or a solid-state imaging device equipped with the color filter according to claim 9.