JP2020027303A - Colored resin composition - Google Patents

Abstract

To provide a color filter which has an excellent brightness and contrast, etc. and also exhibits a higher durability and reliability than an existing color filter.SOLUTION: The colored resin composition for a color filter includes a triarylmethane-based dye and a xanthene-based dye with a betaine structure, as expressed by the formula (1).SELECTED DRAWING: None

Description

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

  For the colorization of liquid crystal display devices such as liquid crystal displays (LCD) represented by notebook computers, liquid crystal televisions, and mobile phones, and imaging devices (CCD, CMOS) used as input devices such as digital cameras and color copiers. A color filter is required. As a method of manufacturing a color filter used in these liquid crystal display devices and solid-state imaging devices, a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, and the like are known. In recent years, the pigment dispersion method has become mainstream. I have. A photolithography method is typical as a patterning method, and a color filter is formed using a mixture of a photosensitive resin composition and a pigment dispersion. Recently, a method of forming a color filter by applying a colored ink directly onto a substrate by using an inkjet printer without using a mask has been used.

  It is particularly important to improve the color purity, saturation, brightness, and contrast, which are the characteristics required for a color filter. By improving the brightness, the amount of light from the backlight can be reduced, and the power consumption can be reduced. This is an environmentally necessary technique. In order to improve the color purity of the color filter, it is necessary to increase the content of the coloring pigment or to select a pigment having a better spectral waveform. On the other hand, in order to improve the lightness, it is necessary to increase the transmittance, and conversely, the pigment concentration must be reduced or the film thickness must be reduced. In order to balance these contradictory properties, a method of making pigment fine particles has been studied.However, there is a limit to resistance and dispersion stability even in fine particles, and even if lightness is improved, compatibility with resistance cannot be achieved. is the current situation.

In order to solve these problems, a color filter using a dye has been studied as another approach. The use of a dye has the advantages of achieving both color purity and lightness that cannot be achieved with a pigment, and the ability to suppress light scattering because it is not a particle, thereby improving the contrast. However, light resistance and heat resistance are required for display devices requiring long-term reliability, such as televisions, and particularly, blue dyes are often much less resistant than pigments.
For example, Patent Documents 1 and 2 report a color filter using a triphenylmethane-based compound, but the triphenylmethane-based compound has extremely poor light resistance and heat resistance, and is not at a practical level.
Patent Document 3 discloses that xanthene-based compounds are excellent in brightness, but does not disclose a resistance aspect. That is, a colored resin composition containing a coloring material compound having excellent resistance is required for a color filter requiring high reliability, but it is hardly practically used at present.
Patent Document 4 reports a color filter using both a xanthene-based compound and a triphenylmethane-based compound, and describes that the color filter is excellent in heat resistance and contrast, but does not describe light resistance. Therefore, a high-quality color filter having excellent brightness, contrast, and durability is demanded as a next-generation product.

JP-A-8-94826 JP-A-2002-14222 JP-A-60-249102 JP 2012-83651 A JP, 2018-521156, A

  An object of the present invention is to provide a color filter having excellent heat resistance and high brightness.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by using a colored resin composition containing a specific coloring material compound to produce a pixel of a color filter. Thus, the present invention has been completed.
That is, the present invention.
(1) The following equation (1)

(In the formula (1), R _{1 to} R ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group. R _{7 to} R ₂₀ each independently represent a hydrogen atom, Represents an alkyl group or a halogen atom having 1 to 6 carbon atoms, and X ⁻ represents bistrifluoromethanesulfonylimide anion or tristrifluoromethanesulfonylmethide anion.), A xanthene having a betaine structure Colored resin composition for a color filter containing a system dye, a binder resin, a solvent and a curing agent,
(2) The triarylmethane dye represented by the formula (1-1)

(In the formula (1-1), X ⁻ represents a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonylmethide anion.)
The colored resin composition according to the above (1), which is a compound represented by the formula:
(3) The xanthene dye having a betaine structure is represented by the following formula (2)

(In the formula (2), R _{21 to} R ₂₆ each independently represent a hydrogen atom, a deuterium, a halogen atom, a nitro group, a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms. A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted monocyclic group having 2 to 30 carbon atoms or One of R _{27 to} R ₃₁ , R ₃₅ and R ₃₆ represents an anionic group, and the remaining six independently represent a hydrogen atom, deuterium, hydroxy, A substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted carbon group Represents a monocyclic or polycyclic heteroaryl group having a number of 2 to 30. R ₃₅ and R ₃₆ are bonded to each other to be substituted or unsubstituted, a monocyclic or polycyclic aromatic hydrocarbon having 6 to 30 carbon atoms. A ring or a substituted or unsubstituted monocyclic or polycyclic heterocyclic ring having 2 to 30 carbon atoms may be formed, R _{32 to} R ₃₄ each independently represent a hydrogen atom, deuterium, substituted or unsubstituted L1 represents a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms, or a dianhydride group containing a nitrogen atom. And L2 each independently represent a direct bond or a divalent linking group.)
The colored resin composition according to the above (1) or (2), comprising a compound represented by the formula:
(4) The xanthene dye having a betaine structure is represented by the following formula (2-1)

(In the formula (2-1), R ₃₃ and R ₃₄ each independently represent a hydrogen atom, deuterium, a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, substituted or unsubstituted Represents a monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms, or a dianhydride group containing a nitrogen atom, and L1 and L2 each independently represent a direct bond or a divalent linking group. )
The colored resin composition according to any one of the above items (1) to (3), which contains a compound represented by the formula:
(5) The colored resin composition according to any one of (1) to (4), further including a metal phthalocyanine pigment,
(6) The colored resin composition according to any one of the above items (1) to (5), wherein X ^{− in the} formula (1) is a bistrifluoromethanesulfonylimide anion.
(7) a colored cured film for a color filter, which is patterned using the colored resin composition according to any one of the above items (1) to (6);
(8) a color filter comprising the colored cured film for a color filter according to the above (7),
(9) a liquid crystal display device, an organic EL display or a solid-state imaging device equipped with the color filter according to (8),
About.

  By using the colored resin composition of the present invention containing a specific coloring material compound, a high-quality color filter having excellent light resistance and high brightness can be provided.

The colored resin composition for a color filter of the present invention (hereinafter, also simply referred to as “the colored resin composition of the present invention”) contains the triarylmethane dye represented by the formula (1).
In the formula (1), R _{1 to} R ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group. R _{7 to} R ₂₀ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom. X ^- represents an bistrifluoromethanesulfonylimide anion or tris trifluoromethanesulfonyl methide anion.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R _{1 to} R _{20 in} the formula (1) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and a sec-butyl group. , T-butyl group, iso-butyl group, n-pentyl group, neopentyl group, isoamyl group, n-hexyl group and the like.
Examples of the halogen atom represented by R _{7 to} R _{20 in} the formula (1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Preferably, R _{1 to} R ₆ in the formula (1) are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Is more preferable, and it is further preferable that each is independently a hydrogen atom or an ethyl group. Further, R _{1 to} R ₅ are preferably an alkyl group having 1 to 6 carbon atoms and R ₆ is preferably a hydrogen atom, and R _{1 to} R ₅ are an alkyl group having 1 to 4 carbon atoms and R ₆ is More preferably, it is a hydrogen atom.
Preferably, R _{7 to} R ₂₀ in the formula (1) are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Is more preferably independently a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and particularly preferably all are hydrogen atoms. In the formula (1), X ⁻ is bistrifluoromethanesulfonylimide Anions are preferred.
As the triarylmethane dye represented by the formula (1), a compound represented by the above formula (1-1) is more preferable.
In the formula (1-1), X ⁻ represents a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonylmethide anion.

  Specific examples of the cation moiety of the compound represented by the above formula (1) are shown in Tables 1-1 to 1-3 below, but the present invention is not limited thereto. In the following Tables 1-1 to 1-3, Me represents a methyl group, Et represents an ethyl group, n-Pr represents a normal propyl group, i-Pr represents an isopropyl group, and n-Bu represents a normal butyl group. , I-Bu represents an isobutyl group, t-Bu represents a tert-butyl group, n-Pn represents a normal pentyl group, and n-Hex represents a normal hexyl group.

The colored resin composition of the present invention contains a xanthene dye having a betaine structure.
The betaine structure here means that a positive charge and a negative charge are located at non-adjacent positions in the same molecule, and dissociable hydrogen atoms are not bonded to the positively charged atoms. It is a compound that does not have (inner salt). The positive charge exists on the xanthene skeleton, and the negative charge is an anion of a substituent substituted on the xanthene skeleton. As the anion, COO ⁻ and SO ₃ ⁻ are preferable, and SO ₃ ⁻ is more preferable. Also. A xanthene-based dye is a dye (compound) having a xanthene skeleton.
The xanthene dye having a betaine structure contained in the colored resin composition of the present invention is not particularly limited as long as it is a dye (compound) having both a betaine structure and a xanthene skeleton, but is represented by the formula (2). Compounds are preferred.

In the formula (2), R _{21 to} R ₂₆ each independently represent a hydrogen atom, a deuterium, a halogen atom, a nitro group, a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted monocyclic or polycyclic group having 2 to 30 carbon atoms Represents a ring heteroaryl group. One of R _{27 to} R ₃₁ , R ₃₅ and R ₃₆ represents an anionic group, and the remaining six each independently represent a hydrogen atom, a deuterium, a hydroxy group, a substituted or unsubstituted carbon number. A linear or branched alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted monocyclic or polycyclic having 2 to 30 carbon atoms; Represents a ring heteroaryl group. R ₃₅ and R ₃₆ are bonded to each other to form a substituted or unsubstituted monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms, or a substituted or unsubstituted monocyclic or polycyclic aromatic hydrocarbon ring having 2 to 30 carbon atoms, It may form a polycyclic heterocycle. R _{32 to} R ₃₄ each independently represent a hydrogen atom, deuterium, a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted monocyclic monocyclic ring having 2 to 30 carbon atoms. Alternatively, it represents a polycyclic heteroaryl group or a dianhydride group containing a nitrogen atom. L1 and L2 each independently represent a direct bond or a divalent linking group.

Examples of the halogen atom represented by R _{21 to} R _{26 in} the formula (2) include the same halogen atom as that represented by R _{7 to} R _{20 in} the formula (1).
Examples of the linear or branched alkyl group having 1 to 30 carbon atoms represented by R _{21 to 31} , R ₃₅ and R _{36 in the} formula (2) include, for example, a carbon atom 1 represented by R _{1 to} R _{20 in} the formula (1). And a known linear or branched alkyl group having 7 to 30 carbon atoms.
The substituent which the linear or branched alkyl group having 1 to 30 carbon atoms represented by R _{21 to} R ₃₁ , R ₃₅ and R _{36 in the} formula (2) may have is a known substituent. There is no particular limitation, and the number and substitution position of the substituents are not particularly limited.

Examples of the alkyl group of the alkoxy group having 1 to 30 carbon atoms represented by R _{21 to} R ₂₆ in Formula (2) include those having 1 to 30 carbon atoms represented by R _{21 to 31} and R _{35 to} R ₃₆ in Formula (2). The same as the linear or branched alkyl group can be used.
The substituent which the alkoxy group having 1 to 30 carbon atoms represented by R _{21 to} R _{26 in} the formula (2) may have is not particularly limited as long as it is a known substituent, and the number and position of the substituents Is not particularly limited.

Specific examples of the monocyclic or polycyclic aryl group having 6 to 30 carbon atoms represented by R _{21 to} R _{36 in} the formula (2) include, for example, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group And a fluorenyl group.
The substituent which the monocyclic or polycyclic aryl group having 6 to 30 carbon atoms represented by R _{21 to} R _{36 in} the formula (2) may have is not particularly limited as long as it is a known substituent. The number of groups and the substitution position are not particularly limited.
Specific examples of the monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms represented by R _{21 to} R _{36 in} the formula (2) include, for example, thiophene group, furanyl group, pyrrole group, imidazole group, thiazole group, oxazole Group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, triazinyl group, acrylidyl group, pyridazinyl group, quinolinyl group, isoquinolyl group, indole group, carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzo Examples include a carbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a dibenzofuran group, and the like.
The substituent which the monocyclic or polycyclic heteroaryl group having 6 to 30 carbon atoms represented by R _{21 to} R _{36 in} the formula (2) may have is not particularly limited as long as it is a known substituent. The number and position of the substituents are not particularly limited.

Examples of the anionic group represented by R _{27 to} R ₃₁ , R ₃₅ and R _{36 in the} formula (2) include COO ⁻ , SO ₃ ⁻ , PO ₄ ^{− and the} like.
The dianhydride groups containing a nitrogen atom represented by R ₃₂ to R ₃₄ of formula (2), for example a succinimide group, maleimide group, and a phthalimide group, and naphthalimide group.

Examples of the monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms which may be formed by combining R ₃₅ and R ₃₆ of the formula (2) include a phenyl group, a naphthyl group, an anthryl group and And a phenanthryl group.
R ₃₅ and R ₃₆ of the formula (2) which may be formed by bonding to each other and which may have a monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms are known substituents. The substituent is not particularly limited as long as it is a substituent, and the number and position of the substituent are not particularly limited.
Examples of the monocyclic or polycyclic heterocyclic ring having 2 to 30 carbon atoms which may be formed by combining R ₃₅ and R ₃₆ of the formula (2) include a thiophene group, a furanyl group, a pyrrole group, an imidazole group, Examples include a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, and a bipyridyl group.
The substituent that may be formed on the monocyclic or polycyclic heterocyclic ring having 2 to 30 carbon atoms which may be formed by combining R ₃₅ and R ₃₆ with each other in the formula (2) is a known substituent. There is no particular limitation as long as it is present, and the number and substitution position of the substituents are not particularly limited.

R _{21 to} R ₂₆ in Formula (2) are each independently preferably a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an anionic group, a methyl group, an ethyl group, a propyl group, or an isopropyl group, and are preferably a hydrogen atom or A methyl group is more preferred.
As R _{27 to} R ₃₁ in the formula (2), each independently is preferably a hydrogen atom, a hydroxy group, an anionic group, a methyl group, an ethyl group, a propyl group or an isopropyl group (however, among R _{27 to} R ₃₁ ) At least one is an anionic group), and a hydrogen atom is more preferred.
R ₃₂ in the formula (2) is independently a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted monocyclic or polycyclic aryl group having 2 to 30 carbon atoms. A heteroaryl group or a dianhydride group containing a nitrogen atom is preferable, and an N-alkylphthalimide group is more preferable.

R ₃₃ and R ₃₄ in the formula (2) each independently represent a hydrogen atom, a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted 2 to 30 carbon atoms. A monocyclic or polycyclic heteroaryl group or a dianhydride group containing a nitrogen atom is preferable, and a phenyl group substituted with at least one selected from the group consisting of a hydrogen atom, a methyl group and an anionic group is preferred. More preferred is a 2,6-dimethylanilino group.
As R ₃₅ and R ₃₆ in the formula (2), R ₃₅ and R ₃₆ may be bonded to each other to form a substituted or unsubstituted monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms. preferable.

  Examples of the divalent linking group represented by L1 and L2 in Formula (2) include an alkylene group having 1 to 4 carbon atoms, a phenylene group, a piperazine group, and an alkylenediamino group having 1 to 4 carbon atoms. 1-4 alkylene groups are preferred.

As the compound represented by the formula (2), a compound represented by the above formula (2-1) is preferable, and compounds represented by the following formulas (2-2) to (2-5) are more preferable. Incidentally, _R 33 in the formula _(2-1), R 34, _{L 1} and _{L 2} represent the same meaning as _{R 33, R 34, L 1} and _{L 2} corresponding in formula (2), preferred it is also Is the same.

The coloring material compounds of the formulas (1) and (2) used in the colored resin composition of the present invention are described, for example, in Yuho Hosoda, published by Gihodo Co., Ltd., “Theoretical Manufacturing Dye Chemistry” (pp. 373 to 375). It can be synthesized by purchasing a commercially available product in which X ⁻ is a chloride anion and adding the corresponding salt or acid to effect salt exchange.

When the coloring material compound in the present invention is synthesized by salt exchange, for example, a coloring material compound in which X ⁻ is a chlorine anion is reacted with a reaction solvent (for example, water, methanol, ethanol, isopropanol, acetone, N, N-dimethylform). Water-soluble polar solvents such as amides (hereinafter abbreviated as DMF) and N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) are mentioned, and these solvents may be dissolved alone or in a mixture. A salt or an acid is added in an amount of about 0.5 to 3 equivalents, the mixture is stirred at a predetermined temperature (for example, 0 to 100 ° C.), and the precipitated crystals are easily collected by filtration.

  In the colored resin composition of the present invention, the coloring material compound represented by the above formula (1) is referred to as a total solid (total amount of solids composed of the coloring material compound, the binder resin, the curing agent, and the like. ) Is preferably 1 to 60 parts by mass, more preferably 5 to 30 parts by mass. If the content is larger than this range, problems such as precipitation and aggregation occur, and the adhesion to the substrate is reduced due to insufficient curing. When the content is small, there is no major problem, but sufficient color purity may not be obtained as color characteristics.

  When the solubility of the coloring material compound represented by the formula (1) in the colored resin composition is low, the coloring material compound may be used after being dispersed using a dispersing agent, similarly to the optional component pigment described below. Good. The coloring material compounds represented by the formula (1) may be used alone or in combination of two or more, but may be mixed with other dyes or pigments. Since the present invention mainly relates to a blue pixel or a red pixel, if necessary, a known blue dye, a violet dye, a red dye or a yellow dye, or a blue pigment, a violet pigment, a red pigment or a yellow pigment can be mixed. .

The coloring composition of the present invention contains a binder resin.
The binder resin is desirably soluble in an alkaline developing solution used in a development processing step in the production of a color filter on the design of a photolithography method, and furthermore, a photopolymerization initiator for forming a good fine pattern. And those having sufficient curing properties with a photopolymerizable monomer or the like. The pigment-dispersed resin composition must also have good compatibility with constituent materials such as a photopolymerization initiator, a photopolymerizable monomer, and a pigment dispersion, and must be stable so as not to cause precipitation or aggregation. In the case of the ink jet method, alkali solubility is not particularly necessary, and therefore, a resin having good compatibility with other coloring materials and additives may be selected.

  Known resins can be used as the binder resin, but more preferably one or more of the following carboxyl groups, or an ethylenically unsaturated monomer having a hydroxyl group, or another copolymerizable aromatic hydrocarbon group: And a copolymer such as an ethylenically unsaturated monomer having an aliphatic hydrocarbon group. Further, those having an epoxy group on the side chain or terminal thereof, or epoxy acrylate resin further added with acrylate can also be used. These monomers and the like may be used alone or in combination of two or more.

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

  Generally, when dispersing a pigment, a dispersant and a dispersing aid are used. There are a dye-based dispersant, a resin-based dispersant, and a surfactant, which have good adsorptivity to pigment. For example, as a pigment dispersant, a method of mixing a sulfonated product of a pigment or a metal salt thereof with a pigment, a method of mixing a substituted aminomethyl derivative, and the like as described in Patent Document 4 are known as known techniques. . As the resin-based dispersant, there is also a non-polar nonionic one, but a polymer resin having an acid value, an amine value, and the like that imparts good pigment adsorbability is generally used, and an acrylic resin, a polyurethane resin, and a polycarboxylic acid are used. , Polyamide resins, polyester resins and the like. Specific examples thereof include, for example, ED211 (manufactured by Kusumoto Kasei), Azispar PB821 (manufactured by Ajinomoto Fine Techno), Solsperse 71000 (manufactured by Avicia), and the like.

  Specific examples of the hydroxyl group-containing ethylenically unsaturated monomer that can be used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 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 (meth) acyl Rate, 2- (2-hydroxyethyloxy) ethyl (meth) acrylate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono ( Examples thereof include hydroxyl-terminated polyalkylene glycol mono (meth) acrylates such as (meth) acrylate, and these can be used alone or in combination of two or more.

Examples of the other copolymerizable ethylenically unsaturated monomers include, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, and m-chlorostyrene. Aromatic vinyl compounds such as styrene, p-chlorostyrene, and 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 Unsaturated carboxylic acid esters such as 3-phenoxypropyl (meth) acrylate, o-phenylphenol glycidyl ether (meth) acrylate, o-phenylphenol (meth) acrylate hydroxyethylate, phenoxyethyl (meth) acrylate; cyclopentyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, norbornylmethyl (meth) acrylate, phenylnorbonyl (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 ] dec-4- Alicyclic skeletons such as methyl = (meth) acrylate, cyclodecyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, t-butylcyclohexyl (meth) acrylate; polyethylene glycol mono (meth) acrylate; Hydroxyl-terminated polyalkylene glycol mono (meth) acrylates such as polypropylene glycol mono (meth) acrylate and poly (ethylene glycol-propylene glycol) mono (meth) acrylate; methoxy polyethylene glycol mono (meth) acrylate, lauroxy polyethylene glycol Mono (meth) acrylate, octoxypolyethylene glycol polypropylene glycol mono (meth) acrylate, nonylphenoxypolyethylene glycol mono (meth) acrylate, nonylphenoxypolypropylene glycol mono (meth) acrylate, allyloxypolyethylene 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 meta Unsaturated carboxylic acid glycidyl esters such as acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate glycidyl ether; vinyl acetate; Carboxylic acid vinyl esters such as vinyl propionate, 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-chloro Vinyl cyanide compounds such as acrylonitrile and vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, N- (meth) acrylo Unsaturated amides or unsaturated imides such as ruphthalimide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide and maleimide; aliphatic conjugates such as 1,3-butadiene, isoprene and chloroprene Dienes; macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of a polymer molecular chain, such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly n-butyl acrylate, poly n-butyl methacrylate, and polysilicone. These can be used alone or in combination of two or more.

  Further, a polymer in which an unsaturated double bond is further introduced into a side chain of the copolymer is also useful. For example, styrene copolymerizable with maleic anhydride, styrene, vinyl phenol, acrylic acid, acrylic acid ester, acrylate having an alcoholic hydroxyl group such as hydroxyethyl acrylate in the maleic anhydride portion of the copolymer with acrylamide, etc. Acrylic acid is added to the hydroxyl group of a copolymer of an acrylate having an epoxy group such as glycidyl methacrylate and half-esterified, and a copolymer of acrylic acid, an acrylate ester and an acrylate having an alcoholic hydroxyl group such as hydroxyethyl acrylate. Compounds reacted are listed. In addition, urethane resin, polyamide, polyimide resin, polyester resin, commercially available ACA-200M (manufactured by Daicel), ORGA-3060 (manufactured by Osaka Organic Chemicals), 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) ), ZCR-1642 (Nippon Kayaku) can also be used.

  When producing the binder resin (copolymer) used in the present invention, a polymerization initiator is used. Here, specific examples of the polymerization initiator used when synthesizing the copolymer include α, α′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), t-butyl peroctoate, di-t-butyl peroxide, benzoyl methyl ethyl ketone peroxide, and the like. The usage ratio of the polymerization initiator is 0.01 to 25 parts by mass based on the total of all the monomers used for synthesizing the copolymer. In the case of synthesizing a copolymer, it is preferable to use an organic solvent described below, but one having a sufficient dissolving power for a monofunctional monomer or a polymerization initiator to be used is used. The reaction temperature when synthesizing the copolymer is preferably from 50 to 120 ° C, particularly preferably from 80 to 100 ° C. Further, 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 (mg KOH / g), and the preferred hydroxyl value is 10 to 200 (mg KOH / g). When the acid value or the hydroxyl value is 10 or less, the developability decreases. The weight average molecular weight (Mw) of the copolymer is preferably from 2,000 to 400,000, more preferably from 3,000 to 100,000. When the weight average molecular weight is 2,000 or less, or 400,000 or more, sensitivity, developability and the like are reduced.

  In the present invention, the binder resins may be used alone or in combination of two or more. The content of the binder resin in the present invention is usually 0.5 to 99 parts by mass, preferably 5 to 50 parts by mass based on 100 parts by mass of the total solid content of the colored resin composition. In this case, when the content of the binder resin is less than 0.5 parts by mass, there is a possibility that problems such as a decrease in alkali developability and a background stain or film residue in a region other than a portion where a pixel is formed may occur. is there.

The colored resin composition of the present invention contains a solvent (preferably an organic solvent).
The organic solvent used in the present invention has a sufficient dissolving power for a binder resin and a curing agent that are components of the colored resin composition, and for a monofunctional monomer or a polymerization initiator used for the synthesis of the binder resin. However, those having a sufficient dissolving power can be used.

  The organic solvent used in the present invention is not particularly limited, but specific examples 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. And propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate; methyl methoxypropionate, ethyl methoxypropionate and methyl ethoxypropionate And propionates such as ethyl ethoxypropionate; methyl lactate, ethyl lactate, butyl lactate, etc. Lactate esters; diethylene glycols such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; acetate esters such as methyl acetate, ethyl acetate and butyl acetate; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane; acetone, methyl ethyl ketone and methyl butyl Ketones such as ketone and cyclohexanone; and alcohols such as methanol, ethanol, butanol, isopropyl alcohol and benzyl alcohol.

  These may be used alone or in combination of two or more. The amount of the organic solvent to be used is preferably 40 to 10,000 parts by mass, more preferably 100 to 1,000 parts by mass, based on 100 parts by mass of the total solid content of the colored resin composition.

The coloring composition of the present invention contains a curing agent.
Examples of the curing agent used in the present invention 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 of these include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol. (Meth) acrylate, tetraethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, glycerol (meth) acrylate, bisphenol-A type epoxy di (meth) acrylate, bisphenol-F type epoxy Sidi (meth) acrylate, bisphenol-fluorene type epoxy di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanurate Acid tri (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, Kayarad RP-1040 ( Nippon Kayaku), Kayarad DPCA-30 (Nippon Kayaku), UA-33H (Shin-Nakamura Chemical), UA-53H (Shin-Nakamura Chemical), M-8060 (Toagosei); As monomers, TEMPIC (manufactured by Sakai Chemical), TMMP (manufactured by Sakai Chemical), PEMP (manufactured by Sakai Chemical), DPMP (manufactured by Sakai Chemical); Epoxy resins include NC-6000, NC-3000, EOCN manufactured by Nippon Kayaku -1020, XD-1000, EPPN-501H, BREN-S, NC-7300L, Daicel products Celoxite 2021P, EHPE3150, Cyclomer M100, Epolide PB3600, Japan Epoxy Resin product Epicoat 828, Epicoat YX8000, Epicoat YX4000, Silaace S510 (Manufactured by JNC), TEPIC (manufactured by Nissan Chemical) and the like; Examples of the melamine curing agent include methylolated melamine and Mw-30 (manufactured by Sanwa Chemical). These can be used alone or in combination of two or more. The content of these is 1 to 80 parts by mass, preferably 5 to 30 parts by mass based on 100 parts by mass of the total solid content of the colored resin composition.

In the colored resin composition of the present invention, a dye other than the triarylmethane dye represented by the formula (1) and the xanthene dye having a betaine structure may be used in combination.
Dyes that can be used in combination in the colored resin composition of the present invention preferably have spectral characteristics compatible with the color filter, and can be appropriately selected from dyes, organic pigments, and inorganic pigments. Two or more kinds can be used in combination. The content of these is 0 to 60 parts by mass, preferably 5 to 30 parts by mass based on 100 parts by mass of the total solid content of the colored resin composition. These various pigments and dyes are shown below.

  Organic pigments that can be used in combination other than the essential components in the colored resin composition of the present invention are not particularly limited.For example, anthraquinone, phthalocyanine, triphenylmethane, benzimidazolone, quinacridone, azochelate, and azo System, isoindoline system, isoindolinone system, pyranthrone system, indathrone system, anthrapyrimidine system, dibromoanzanthrone system, flavanthrone system, perylene system, perinone system, quinophthalone system, thioindigo system, dioxazine system, quinacridone system, xanthene system Lake pigments and dyed lake pigments in which acid dyes, basic dyes, direct dyes and the like are insolubilized with their respective precipitants. More specifically, in the color index, for example, Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19 , 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76 , 78, 79, Pigment Violet 1, 1: 1, 2: 2, 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29 , 31, 32, 37, 39, 42, 44, 47, 49, 50, Pigment Violet 3, 4, 27, 39, Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48. : 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 8 : 5, 122, 146, 168, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, 279, Pigment Orange 43, 71, 73, Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 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, 15 , 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. Among them, metal phthalocyanine pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 75, 76, 79 having excellent hue and resistance; Violet 23, Pigment Red 177, 254, and Pigment Yellow 83, 138, 139, 150 are preferred, and Pigment Blue 15: 6 of a copper phthalocyanine pigment is particularly preferred.

  Inorganic pigments that can be used in addition to the essential components in the colored resin composition of the present invention are not particularly limited. For example, composite metal oxide pigments, carbon black, black lower titanium oxide, titanium oxide, barium sulfate, zinc white , Lead sulfate, yellow lead, red iron oxide, ultramarine, navy blue, chromium oxide, antimony white, iron black, lead red, zinc sulfide, cadmium yellow, cadmium red, zinc, manganese purple, cobalt purple, barium sulfate, magnesium carbonate, etc. Oxides, metal sulfides, sulfates, metal hydroxides, metal carbonates and the like can be mentioned.

  Dyes that can be used in addition to the essential components in the colored resin composition of the present invention are not particularly limited, and include acid dyes, basic dyes, direct dyes, sulfur dyes, vat dyes, naphthol dyes, reactive dyes, disperse dyes, and the like. Can be Above all, any dye that is soluble in an organic solvent may be used, but a dye that is insoluble in an organic solvent can be used as appropriate by forming a dispersion. A dye insoluble in an organic solvent is a well-known formulation. For example, in the case of an acid dye, an organic amine compound (e.g., n-propylamine, ethylhexylpropionate, etc.) is reacted to modify the dye 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 dyes include, for example, Basic Blue 7, Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, and 51 having CI numbers in the color index. , 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 Iolet 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 Green 9, 16, etc. Is mentioned.

  Among these pigments that can be used in combination, it is a preferred embodiment to use a metal phthalocyanine pigment in combination. The phthalocyanine-based pigment mentioned here is not particularly limited as long as it has a phthalocyanine (including naphthalocyanine) skeleton.

  As the photopolymerization initiator that can be used in combination when the colored resin composition of the present invention is used in a photography method, those having sufficient sensitivity to ultraviolet light emitted from an ultrahigh pressure mercury lamp generally used as an exposure light source are preferable. Examples thereof include a radically polymerizable photoradical initiator, an ion-curable photoacid generator, and a photobase generator. In photopolymerization, a component of a polymerization accelerator called a sensitizer that cures with less exposure energy can be used in combination. The photopolymerization initiator that can be used is not particularly limited, but specific examples include benzyl, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, benzoyl benzoic acid, and benzoyl benzoate. Acid ester, 4-benzoyl-4′-methyldiphenyl sulfide, benzyldimethyl ketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, isopropylthioxanthone, dimethylthioxanthone, diethylthioxanthone, diisopropyl Thioxanthone, dimethylaminomethylbenzoate, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one 1-hydroxycyclohexylphenylketone, 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) 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'-biimi Dazol, diazonaphthoquinone-based initiator, commercially available Kayacure DMBI, Kayacure BDKM, Kayacure BP-100, Kayacure BMBI, Kayacure DETX-S, Kayacure EPA (all manufactured by Nippon Kayaku), Darocure 1173, Darocure 1116 (Iremo Merck Japan), Irgacure 907, Irgacure 369 (made by Ciba Specialty Chemicals), Irgacure 379EG (made by Ciba Specialty Chemicals), Irgacure OXE-01 (made by Ciba Specialty Chemicals), Irgacure OXE- 02 (manufactured by Ciba Specialty Chemicals), Irgacure PAG103 (manufactured by Ciba Specialty Chemicals), TME-triazine (manufactured by Sanwa Chemical), Biimi Tetrazole (Kurogane Kasei), STR-110, STR-1 (manufactured by less Bae Chemicals any), and the like.

  When the colored resin composition of the present invention is used as a thermosetting resin composition by an ink-jet method or the like, a thermal polymerization initiator is generally used in combination. However, if necessary, a photopolymerization initiator may be used in combination. Examples of the thermal polymerization initiator include an azo compound and an organic peroxide-based one. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), di-t-butyl peroxide, dibenzoyl peroxide, cumyl peroxy neodecanoate, and the like.

  These initiators can be used alone or in combination of two or more as needed. These contents are 0.5 to 50 parts by mass, preferably 1 to 25 parts by mass, when the solid content of the colored resinous composition is 100 parts by mass.

  The colored resin composition of the present invention is produced by mixing and stirring the above-mentioned binder resin, curing agent, specific coloring material compound, organic solvent and the like with a dissolver, a homomixer or the like. Further, if necessary, other pigments and dyes can be added, but in the case of a pigment or a dye having low solubility, a dispersion is obtained by a disperser such as a paint shaker using an appropriate dispersant, It is mixed with the colored resin composition.

  The colored resin composition of the present invention, if necessary, further various additives, for example, a filler, a surfactant, a photopolymerization initiator, a thermal polymerization initiator, a polymerization inhibitor, an adhesion promoter, an antioxidant, An ultraviolet absorber, an anti-agglomeration agent and the like can be added. Further, the colored resin composition of the present invention can be subjected to microfiltration with a filter or the like in order to remove foreign substances and the like after preparation.

  Next, a method for preparing a cured product from the colored resin composition of the present invention will be described. First, the colored resin composition of the present invention is applied to a glass substrate, a silicon substrate or the like on a substrate such as a spin coat method, a roll coat method, a slit and spin method, a die coat method, a bar coat method or the like to a thickness of about 0. 1 to 20 μm, more preferably 0.5 to 5 μm, and if necessary, in a vacuum chamber at drying conditions at a temperature of 23 to 150 ° C. for a time of 1 to 60 minutes, more preferably a temperature of 23 to 150 ° C. The film is dried under reduced pressure at 60 to 120 ° C. for 1 to 10 minutes, and is further subjected to a pre-baking treatment using a hot plate or a clean oven to form a film. Next, radiation (for example, electron beam or ultraviolet ray is preferable, ultraviolet ray is preferable) is irradiated through a predetermined mask pattern by a general photolithography method, and a surfactant aqueous solution, an alkali aqueous solution, or a surfactant and an alkali agent are applied. Develop with a mixed aqueous solution of The developing method includes a dipping method, a spray method, a shower method, a paddle method, an ultrasonic developing method, and the like, and any of these methods may be combined. After removing the unirradiated 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 a temperature of 150 to 250 ° C. for 1 to 30 minutes. The process is carried out under the conditions to obtain a pixel composed of the colored cured film of the present invention.

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

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

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

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

Synthesis Example 1
Basic Blue 7 (2 parts) was dissolved in water (150 parts), and a solution obtained by dissolving potassium salt of bistrifluoromethanesulfonium imide (1.2 parts) in water (10 parts) was added with stirring. After stirring for 3 hours, the precipitated crystals were collected by filtration, washed with water, and dried to obtain a triarylmethane dye (0.7 parts) represented by the following formula (100) as blue crystals.

Synthesis Example 2
A xanthene compound having a betaine structure represented by the following formula (2-2) was obtained in the same manner as in Experimental Example 1 of Published Patent Publication;

Synthesis Example 3
A xanthene compound having a betaine structure represented by the following formula (2-3) was obtained in the same manner as in Experimental Example 1 of Published Patent Publication;

Synthesis Example 4 (Preparation of binder resin (copolymer (A)))
A 500 ml four-necked flask is charged with methyl ethyl ketone (160 parts), methacrylic acid (10 parts), benzyl methacrylate (33 parts), and α, α′-azobis (isobutyronitrile) (1 part), and stirred with 30 parts. Nitrogen gas was flowed into the flask for minutes. Thereafter, the temperature was raised to 80 ° C., and the mixture was stirred at 80 to 85 ° C. for 4 hours. After completion of the reaction, the 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 weight average molecular weight in terms of polystyrene of the obtained copolymer (A) was 18,000, and the acid value was 152.

Example 1
Copolymer (A) (5.7 parts) as a binder resin, Kayarad DPHA (Nippon Kayaku) (6 parts) as a curing agent (photopolymerizable monomer), and Irgacure 907 (Ciba Specialty) as a photopolymerization initiator Chemicals) (2.4 parts), a compound represented by formula (100) obtained in Synthesis Example 1 as a dye (0.3 part), and a compound represented by Formula (2-2) obtained in Synthesis Example 2 The compound (0.3 part) represented, cyclopentanone (17 parts) and propylene glycol monomethyl ether acetate (13.3 parts) as a solvent were mixed to obtain a blue colored resin composition 1 of the present invention. The colored resin composition 1 obtained above was spin-coated on a glass substrate, dried at 80 ° C. for 10 minutes, and further subjected to a heat treatment at 200 ° C. for 5 minutes to produce a colored dye 1.

Example 2
The dye-colored product 2 of the present invention was prepared according to Example 1, except that the compound represented by the formula (2-2) was changed to the compound represented by the formula (2-3) obtained in Synthesis Example 3. Obtained.

Comparative Example 1
A dye colorant 3 for comparison was obtained in the same manner as in Example 1 except that the compound represented by the formula (2-2) was changed to rhodamine B.

Comparative Example 2
A dye colorant 4 for comparison was obtained according to Example 1, except that the compound represented by the formula (2-2) was changed to a compound represented by the following formula (300).

(Light fastness test of colored dyes)
The dye-colored bodies obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were placed in a xenon weatherometer XL75 (manufactured by Suga Test Instruments Co., Ltd.) using a holder, and the temperature was 24 ° C. Light was irradiated for 6 hours under the conditions of humidity of 60% RH and illuminance of 100 klux. The absorbance at the maximum absorption wavelength before and after the irradiation test was measured for each colored dye, and the residual dye ratio was calculated by the following formula, and evaluated according to the following evaluation criteria. Those having a large value of the dye residual ratio are more excellent in light resistance (fastness). The evaluation results are shown in Table 2 below.

(Calculation formula for residual dye ratio)
Dye residual rate = (absorbance at maximum absorption wavelength after test / absorbance at maximum absorption wavelength before test) × 100 (%)
(Light resistance evaluation criteria)
Dye residual ratio is 70% or more: A
Dye residual ratio is 65% or more and less than 70%: B
Dye residual ratio is less than 65%: C

From the results shown in Table 2, the dye-colored products of the examples showed better results in the light resistance test than the dye-colored products of the comparative examples.

As described above, the colored resin composition of the present invention using the specific coloring material compound has clear and excellent color filter characteristics (heat resistance, light resistance, contrast, etc.), high quality and high reliability. A high color filter pixel can be obtained. In addition, it can be used in a good mixture with pigments and other dyes depending on the application, and shows wide applicability, so it can be said that it has high industrial value.

Claims (9)

The following equation (1)

(In the formula (1), R _{1 to} R ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group. R _{7 to} R ₂₀ each independently represent a hydrogen atom, It represents an alkyl group or a halogen atom having 1 to 6 carbon atoms .X ^- represents bistrifluoromethanesulfonylimide anion or tris trifluoromethanesulfonyl methide anion).
A color resin composition for a color filter, comprising a triarylmethane dye represented by the formula (1), a xanthene dye having a betaine structure, a binder resin, a solvent and a curing agent. The triarylmethane dye is represented by the formula (1-1)

(In the formula (1-1), X ⁻ represents a bistrifluoromethanesulfonylimide anion or a tristrifluoromethanesulfonylmethide anion.)
The colored resin composition according to claim 1, which is a compound represented by the formula: The xanthene dye having a betaine structure is represented by the following formula (2)

(In the formula (2), R _{21 to} R ₂₆ each independently represent a hydrogen atom, a deuterium, a halogen atom, a nitro group, a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms. A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted monocyclic group having 2 to 30 carbon atoms or One of R _{27 to} R ₃₁ , R ₃₅ and R ₃₆ represents an anionic group, and the remaining six independently represent a hydrogen atom, deuterium, hydroxy, A substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted carbon group Represents a monocyclic or polycyclic heteroaryl group having a number of 2 to 30. R ₃₅ and R ₃₆ are bonded to each other to be substituted or unsubstituted, a monocyclic or polycyclic aromatic hydrocarbon having 6 to 30 carbon atoms. A ring or a substituted or unsubstituted monocyclic or polycyclic heterocyclic ring having 2 to 30 carbon atoms may be formed, R _{32 to} R ₃₄ each independently represent a hydrogen atom, deuterium, substituted or unsubstituted L1 represents a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms, or a dianhydride group containing a nitrogen atom. And L2 each independently represent a direct bond or a divalent linking group.)
The colored resin composition according to claim 1, comprising a compound represented by the formula: The xanthene dye having a betaine structure is represented by the following formula (2-1)

(In the formula (2-1), R ₃₃ and R ₃₄ each independently represent a hydrogen atom, deuterium, a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, substituted or unsubstituted Represents a monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms, or a dianhydride group containing a nitrogen atom, and L1 and L2 each independently represent a direct bond or a divalent linking group. )
The colored resin composition according to any one of claims 1 to 3, further comprising a compound represented by the following formula: The colored resin composition according to any one of claims 1 to 4, further comprising a metal phthalocyanine pigment. Colored resin composition according to any one of claims 1 to 5 is bistrifluoromethanesulfonylimide anion ^- X of the formula (1). 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, an organic EL display, or a solid-state imaging device provided with the color filter according to claim 8.