TW201308009A - Colored resin composition - Google Patents

Abstract

The invention provides a highly reliable color filter having high quality feature with high contrast and excellent resistance while comparing with prior products. A colored resin composition contains at least one xanthane acid dye represented by the following formula (1) as a pigment, a triaryl methane acid dye classified as C. I. acid blue, a binder resin, an organic solvent, a curing agent, and a photo radical polymerizing initiator. (wherein, X1 and X2 represent respectively independently a hydrogen atom or a C1 to 30 alkyl group. R1 to R21 represent respectively independently a hydrogen atom, a C1 to C30 alkyl group, a C1 to C30 alkoxyl group, a C6 to C30 aromatic hydrocarbon group, a C3 to C30 aromatic heterocyclic group, a halogen atom, a nitro group, a phenoxyl group, a carboxyl group, a carboxylic acid ester group, a carboxylic acid salt group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid salt group, -SO2NHR22-group or -SO2NR23R24-group, at least one of R1 to R21 represents a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid salt group, -SO2NHR22-group or -SO2NR23R24-group. R22 to R24 represent respectively independently a C1 to C30 alkyl group. The sulfonic acid salt and the carboxylic acid salt are salts formed with a monovalent cation, the monovalent cation is one of Na+, K+ or quaternary ammonium cation).

Description

Colored resin composition

The present invention relates to a colored resin composition used for forming a blue pixel of a color filter, a color filter formed using the colored resin composition, and a liquid crystal display device and an image formed using the color filter. Electronic display devices such as components (CCD, CMOS) and organic EL displays.

Liquid crystal display devices such as liquid crystal displays (LCDs) and organic EL displays, such as notebook computers, LCD TVs, and mobile phones, and color imaging devices (CCD, CMOS) used as input devices such as digital cameras and color photocopiers Use color filters. As a method of producing the color filter used in the liquid crystal display device or the solid-state image sensor, there are a dyeing method, a plating method, a printing method, a pigment dispersion method, and the like. In recent years, a pigment dispersion method using a patterning method has become mainstream. As a method of patterning, a photolithography method is typically used, and a color filter is formed using a mixture of a photosensitive resin composition and a pigment dispersion. Further, recently, a method of directly applying a colored ink to a substrate without interposing a mask by using an ink jet printer to form a color filter has been carried out.

It is particularly important to increase the color purity, chroma, brightness, and contrast characteristics required as color filters. By increasing the brightness, the amount of light of the backlight can be suppressed, and as a result, the power consumed can be reduced, so that it is also an essential technology from the environmental point of view. In order to increase 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 shape. On the other hand, in order to increase the brightness, it is necessary to reduce the pigment concentration or reduce the film thickness. Increase penetration. In order to achieve these opposite characteristics, a method of atomizing the pigment is also performed. However, in the case of the pigment dispersion method, there is a limit in terms of the dispersion stability of the photosensitive resin composition containing the pigment and the improvement of the resistance to light, heat or solvent of the color filter, and the contrast. Increased brightness also does not have the same resistance.

As another attempt to solve the above problems, studies have been conducted on color filters using dyes. When a dye is used, there is an advantage that both color purity and brightness which cannot be achieved when a pigment is used can be achieved, and light scattering can be suppressed because it is not a particle, so that contrast can be improved and a certain degree of resistance can be achieved. However, in display applications requiring long-term reliability such as television, excellent color characteristics and more excellent light resistance and heat resistance are required, and a color filter using a blue dye cannot meet this requirement. The resistance of the dye is generally inferior to that of the pigment, and in particular the resistance of the blue dye is mostly significantly inferior to the pigment. For example, in the patent documents 1 and 2, there is a report on a color filter using a triphenylmethane-based compound, which is excellent in blue color characteristics, but is inferior in light resistance and heat resistance, and does not reach a practical level. In addition, most of the color filters with good tolerance have higher x values in the chromaticity coordinates, in other words, red, and the color characteristics as blue are insufficient. Patent Document 3 describes a xanthene compound having excellent brightness. However, there is no record of tolerance. Patent Document 4 describes a phthalocyanine dye which is excellent in resistance, but its color characteristics are not blue, but are generally reddish cyan. Therefore, a vivid blue pixel cannot be formed. In other words, in the field of a liquid crystal display device and a solid-state image sensor, a color filter having high blue pixel quality and high reliability and high resistance is required. However, the current state of the art is hardly practical.

Patent Document 1: Japanese Patent Publication No. 8-94826

Patent Document 2: Japanese Patent Laid-Open Publication No. 2002-14222

Patent Document 3: Japanese Laid-Open Patent Publication No. 2002-212469

Patent Document 4: Japanese Laid-Open Patent Publication No. 60-249102

Patent Document 5: Japanese Laid-Open Patent Publication No. 63-172772

An object of the present invention is to provide a colored resin composition capable of producing a high-quality and highly reliable color filter excellent in heat resistance, solvent resistance, contrast, and the like, and a color filter produced using the colored resin composition.

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that an acid dye containing at least a xanthene skeleton containing at least the following formula (1) is used in a color filter pixel (hereinafter, an acid dye containing a xanthene skeleton) An acid dye containing a triarylmethane skeleton classified as CI acid blue (hereinafter, an acid dye containing a triarylmethane skeleton is referred to as a triarylmethane acid dye) as a coloring resin of a pigment The composition can solve the above problems, thereby completing the present invention.

That is, the present invention relates to the invention described below.

(1) A colored resin composition for a color filter comprising a xanthene-based acid dye represented by the following formula (1), a triarylmethane-based acid dye classified into CI acid blue, a binder resin, an organic solvent, Hardener and free radical polymerization photoinitiator,

(wherein, X ₁ and X ₂ each independently represent a hydrogen atom or an alkyl group of C1 to C30. R ₁ to R ₂₁ each independently represent a hydrogen atom, an alkyl group of C1 to C30, an alkoxy group of C1 to C30, C6 to C30 aromatic hydrocarbon group, C3 to C30 aromatic heterocyclic group, halogen atom, nitro group, phenoxy group, carboxyl group, carboxylate group, carboxylate, alkoxycarbonyl group, hydroxyl group, sulfonic acid group, sulfonate An acid ester group, a sulfonate group, a -SO ₂ NHR ₂₂ group or a -SO ₂ NR ₂₃ R ₂₄ group. At least one of R ₁ to R ₂₁ represents a sulfonic acid group, a sulfonate group, a sulfonate group, - Any of SO ₂ NHR ₂₂ or -SO ₂ NR ₂₃ R ₂₄ groups. R ₂₂ to R ₂₄ each independently represent a C1 to C30 alkyl group. The sulfonate and carboxylate are formed with a monovalent cation. The salt, the monovalent cation is any one of Na ⁺ , K ⁺ or a 4-grade ammonium cation).

(2) The colored resin composition according to the above (1), wherein both of X ₁ and X _{2 of the} formula (1) are a methyl group, an isopropyl group, a butyl group, an isobutyl group or an isopentyl group.

(3) The colored resin composition according to (1) or (2) above, wherein the triarylmethane acid dye classified as CI acid blue is CI Acid Blue 7, CI Acid Blue 90 or CI Acid Blue 104 .

(4) The colored resin composition for a color filter according to any one of the above-mentioned (1), further comprising a metal phthalocyanine pigment.

(5) A colored cured film for a color filter, which is patterned by using the colored resin composition according to any one of the above (1) to (3) Former.

(6) A coloring cured film for a color filter formed by patterning using the colored resin composition according to (4) above.

(7) A color filter comprising the colored cured film for a color filter according to (5) or (6) above.

(8) A liquid crystal display device in which the color filter according to (7) above is mounted.

(9) An organic EL display in which the color filter described in (7) above is mounted.

(10) A solid-state image sensor comprising the color filter according to (7) above.

By using the colored resin composition for a color filter of the present invention, it is possible to provide a blue pixel of a color filter having excellent quality and high reliability such as heat resistance and contrast.

The colored resin composition for a color filter of the present invention (hereinafter also referred to simply as "colored resin composition") contains at least a xanthene-based acid dye represented by the above formula (1) and the above-mentioned triarylmethane-based acid dye as a pigment. .

In the formula (1), X ₁ and X ₂ each independently represent a hydrogen atom or an alkyl group of C1 to C30, and the alkyl group is not limited to a linear or branched chain as long as it is an alkyl group having 1 to 30 carbon atoms. Any of a shape or a ring shape. Further, the alkyl group may have a substituent, and specific examples of the substituent include hydroxyethyl, hydroxypropyl, hydroxybutyl, 2-sulfoethyl, carboxyethyl, cyanoethyl, and An oxyethyl group, an ethoxyethyl group, a butoxyethyl group, a trifluoromethyl group, a pentafluoroethyl group, an amine carbenyl group, a carboxyl group or the like.

Specific examples of the C1 to C30 alkyl group in X ₁ and X ₂ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a t-butyl group, and an isobutyl group. Base, pentyl, 1-ethylpropyl, 1-methylbutyl, cyclopentyl, hexyl, 1-methylpentyl, 1-ethylbutyl, cyclohexyl, hydroxypropyl, 2-sulfo Ethyl, carboxyethyl, cyanoethyl, methoxyethyl, ethoxyethyl, butoxyethyl, trifluoromethyl, pentafluoroethyl, 2-heptyl, heptyl, octyl , mercapto, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecane Base, arachyl, eicosyl, icosyl, behenyl, docosyl, tetracosyl, hexadecyl, twenty-six Alkyl, heptadecyl, octadecyl, octadecyl, tridecyl, isohexyl, isoheptyl, isooctyl, isodecyl, isodecyl, isececyl , isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl Iso-octadecyl, iso-heptadecyl, iso-epiyl, iso-eicosyl, iso-eicoyl, iso-docosyl, iso-tris-trialkyl, iso-tetracosyl , iso-tetradecyl, iso-hexadecyl, iso-heptadecyl, iso-octadecyl, iso-dodecyl, iso-t-octadecyl, 1-methylhexyl, 1- Ethyl heptyl, 1-methylheptyl, 1-cyclohexylethyl, 1-heptyloctyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,6 - dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3 , 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, 2-ethylhexyl, 1-adamantyl, 2-adamantyl, and the like. In general, it is preferred that both of X ₁ and X ₂ are the same group, and it is more preferred that both of them are hydrogen atoms or both are the same alkyl group.

Preferred examples of X ₁ and X ₂ may each independently be a hydrogen atom or a C1 to C6 alkyl group, more preferably a C1 to C4 alkyl group, still more preferably a C1 to C3 alkyl group. More preferably, it is preferred that both of X ₁ and X ₂ are the same group. More preferably, when both of them are a methyl group, an isopropyl group, a butyl group, an isobutyl group or an isopentyl group, it is preferred that both of them are methyl groups.

In the formula (1), R ₁ to R ₂₁ each independently represent a hydrogen atom, a C1 to C30 alkyl group, a C1 to C30 alkoxy group, a C6 to C30 aromatic hydrocarbon group, and a C3 to C30 aromatic heterocyclic group. , halogen atom, nitro group, phenoxy group, carboxyl group, carboxylate group, carboxylate group, alkoxycarbonyl group, hydroxyl group, sulfonic acid group, sulfonate group, sulfonate group, -SO ₂ NHR ₂₂ group or -SO ₂ NR ₂₃ R ₂₄ group, at least one of R ₁ to R ₂₁ represents a sulfonic acid group, a sulfonate group, a sulfonate group, a -SO ₂ NHR ₂₂ group or a -SO ₂ NR ₂₃ R ₂₄ group Any one. R ₂₂ to R ₂₄ each independently represent an alkyl group of C1 to C30. The sulfonate group and the carboxylate group are salts formed with a monovalent cation, and the monovalent cation is preferably any of Na ⁺ , K ⁺ or a 4-grade ammonium cation.

R ₁ to R ₂₁ is C1 to C30 alkyl group is a long alkyl group having a carbon number of 1 to 30, in a linear, branched or cyclic, and is not limited and may have a substituent group. Specific examples of the substituent which the alkyl group may have and the alkyl group include the same groups as those described for the alkyl group of C1 to C30 in X ₁ and X ₂ , and preferably C1 to C4. alkyl.

The alkoxy group of C1 to C30 in R ₁ to R ₂₁ may have a substituent. Specific examples of the substituent include the same substituents as the substituent which the C1 to C30 alkyl group in X ₁ and X ₂ may have. Specific examples of the C1 to C30 alkyl group in the C1 to C30 alkoxy group include the same groups as those described in the description of the C1 to C30 alkyl group in X ₁ and X ₂ . Specific examples of the alkoxy group include alkoxy groups of the alkyl group described in the specific examples of the alkyl group having from C1 to C30.

The C6 to C30 aromatic hydrocarbon group in R ₁ to R ₂₁ means a group obtained by removing one hydrogen atom from an aromatic hydrocarbon having 6 to 30 carbon atoms. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group, and a benzindenyl group. Further, the aromatic hydrocarbon group of C6 to C30 may have a substituent, and specific examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a sulfo group, a carboxyl group, an alkoxycarbonyl group, an amine formazan group, and a cyanogen group. Base.

The C3 to C30 aromatic heterocyclic group in R ₁ to R ₂₁ means a group obtained by removing one hydrogen atom from an aromatic hetero ring having 3 to 30 carbon atoms. Specific examples of the aromatic heterocyclic ring include pyridyl group and pyridyl group. A group, a pyrimidinyl group, a quinolyl group, an isoquinolyl group, a pyrrolyl group, a fluorenyl group, an imidazolyl group, a carbazolyl group, a thienyl group, a furyl group or the like. Further, the aromatic heterocyclic group of C3 to C30 may have a substituent, and specific examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a sulfo group, a carboxyl group, an alkoxycarbonyl group, and an amine methyl group. , cyano and the like.

Specific examples of the halogen atom in R ₁ to R ₂₁ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Specific examples of the carboxylate group in R ₁ to R ₂₁ include methyl carboxylate, ethyl carboxylate, isopropyl carboxylate, and benzyl carboxylate.

Specific examples of the quaternary ammonium cation constituting the carboxylate group and the sulfonate group in R ₁ to R ₂₁ include a tetramethylammonium cation, an ethyltrimethylammonium cation, and a tetrapropylammonium cation. Alkyl ammonium cations and the like.

The alkoxycarbonyl group in R ₁ to R ₂₁ may, for example, be an alkoxycarbonyl group of C1 to C30. Specific examples of the C1 to C30 alkyl group in the alkoxycarbonyl group include the same groups as those described in the description of the C1 to C30 alkyl group in X ₁ and X ₂ . Specific examples of the alkoxycarbonyl group include an alkoxycarbonyl group having an alkyl group described in Specific Examples of the C1 to C30 alkyl group in X ₁ and X ₂ .

Specific examples of the sulfonate group in R ₁ to R ₂₁ include a C1 to C4 alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group or a hexylsulfonyl group.

In the formula (1), R ₂₂ to R ₂₄ each independently represent an alkyl group of C1 to C30, and the alkyl group is not limited to a linear chain, a branched chain or a ring as long as it is an alkyl group having 1 to 30 carbon atoms. Any of the shapes. Further, the alkyl group may have a substituent. Specific examples of the alkyl group and specific examples of the substituent include the same groups as those described in the description of the alkyl group of C1 to C30 in X ₁ and X ₂ and the description of the substituent.

Specific examples of the -SO ₂ NHR ₂₂ group in R ₁ to R ₂₁ include an aminesulfonyl group, a methanesulfonyl group, an ethanesulfonyl group, a propaneamine sulfonyl group, and an isopropanamine sulfonium sulfonate. Base, butaneamine sulfonyl, isobutaneamine sulfonyl, pentamamine sulfonyl, isoamylamine sulfonyl, cyclopentylamine sulfonyl, hexane sulfonyl, cyclohexane Aminesulfonyl, heptylamine sulfonyl, 2-ethylhexylamine sulfonyl, 1,5-dimethylhexylsulfonyl, tricyclodecylamine sulfonyl, methoxypropane Aminesulfonyl, ethoxypropanylsulfonyl, isopropoxypropanylsulfonyl and the like. Preferred examples of the -SO ₂ NHR ₂₂ group include a (C2 to C12) alkylamine sulfonyl group, more preferably a (C2 to C8) alkylamine sulfonyl group, and still more preferably a (C4 to C8) alkane. The sulfamidino group is preferably 2-ethylhexylamine sulfonyl.

Specific examples of the -SO ₂ NR ₂₃ R ₂₄ group in R ₁ to R ₂₁ include a dimethylamine sulfonyl group, a methyl ethylamine sulfonyl group, a diethylamine sulfonyl group, and a dipropyl group. Amidoxime, diisopropylamine sulfonyl, methylpropylamine sulfonyl, methyl isopropyl sulfonyl, ethyl propyl sulfonyl, ethyl isopropyl sulfonate Mercapto, dibutylamine sulfonyl, methylbutylamine sulfonyl, diisobutylamine sulfonyl, ethylbutylamine sulfonyl, dipentylamine sulfonyl and the like. Preferred examples of the -SO ₂ NR ₂₃ R ₂₄ group include a di(C1 to C4) aminsulfonyl group, more preferably a diethylaminesulfonyl group.

As the -SO ₂ NHR ₂₂ group and -SO ₂ NR ₂₃ R ₂₄ group in R ₁ to R ₂₁ , preferably ethane sulfonyl sulfonyl group, butane sulfonyl sulfonyl group, isoamylamine sulfonyl group, 2 -ethylhexylamine sulfonyl, dimethylamine sulfonyl, diethylamine sulfonyl and dibutylamine sulfonyl, more preferably 2-ethylhexylamine sulfonyl or diethyl Amidoxime.

R ₁ to R ₂₁ in the formula (1) are preferably each independently a hydrogen atom, a C1 to C4 alkyl group, a sulfonic acid group, a sodium sulfonate group, a 2-ethylhexylamine sulfonyl group or two. Ethylamine sulfonyl, and at least one of R ₁ to R ₂₁ is a sulfonic acid group, a sodium sulfonate group, a 2-ethylhexylsulfonyl group or a diethylaminesulfonyl group. More preferably, each of R ₁ to R _{21 is} independently a group selected from the group consisting of a hydrogen atom, a C1 to C4 alkyl group, a sulfonic acid group, and a sodium sulfonate group, and at least one of R ₁ to R ₂₁ is Sulfonic acid group or sodium sulfonate group.

Preferred examples of the xanthene-based acid dye represented by the formula (1) include the following.

(i) a xanthene-based acid dye (hereinafter referred to as a dye in the xanthene-based acid dye), wherein X ₁ and X ₂ in the formula (1) are each independently a methyl group, an ethyl group, a propyl group, Isopropyl, butyl, isobutyl or isopentyl, R ₁ to R ₂₁ are each independently a hydrogen atom, a C1 to C4 alkyl group, a sulfonic acid group, a sulfonate group, a (C2 to C8) alkylamine A sulfonyl group or a di(C1 to C4)alkylamine sulfonate group, and at least one of R ₁ to R ₂₁ is a sulfonic acid group or a sulfonate group.

(ii) The dye according to the above (i), wherein one of R ₁ to R ₂₁ is a sulfonic acid group or a sulfonic acid salt group, and (a) the remaining groups are all hydrogen atoms, or (b) the rest Of the groups, four are C1 to C4 alkyl groups, and the remaining one is a sulfonic acid group, a sulfonate group, a (C2 to C8) alkylamine sulfonyl group or a di(C1 to C4) alkylamine sulfonyl group. The rest are hydrogen atoms.

(iii) The dye according to the above (i) or (ii), wherein the four C1 to C4 alkyl groups of (b) are a C1 to C3 alkyl group, and the balance is a sulfonic acid group, a sulfonic acid salt or (C4 to C8). An alkylamine sulfonyl group.

(iv) The dye according to the above (i) or (ii), wherein one of R ₁₇ to R ₂₁ is a sulfonic acid group or a sodium sulfonate group, the balance being a hydrogen atom, and (a) R ₁ to R ₁₆ All of them are hydrogen atoms, or, (b) two of R ₁ to R ₅ are C1 to C4 alkyl groups, the remaining groups are hydrogen atoms, and two of R ₁₂ to R ₁₆ are C1 to C 4 alkyl groups, One is a sulfonic acid group, a sodium sulfonate group, a 2-ethylhexylamine sulfonyl group or a diethylamine sulfonyl group, and the balance is a hydrogen atom.

(v) The dye according to any one of the above (i) to (iii), wherein one of R ₁₇ to R ₂₁ is a sulfonic acid group or a sodium sulfonate group, the balance being a hydrogen atom, and (a) R ₁ to R ₁₆ are each a hydrogen atom, or, in (b) R ₁ to R ₁₆ , R ₁ , R ₅ , R ₁₂ and R ₁₆ are a C1 to C3 alkyl group, and R ₁₄ is a hydrogen atom, a sulfonic acid group or a sulfonate. An acid group or a (C4 to C8) alkylamine sulfonyl group, the remainder being a hydrogen atom.

(vi) The dye according to the above (i), wherein, in R ₁ to R ₂₁ , R ₁ , R ₅ , R ₁₂ and R ₁₆ are a methyl group, R ₁₄ is a sulfonic acid group, and R ₁₇ is a sodium sulfonate group. The salt is a hydrogen atom other than this.

(vii) The dye according to any one of the above (i) to (vi), wherein X ₁ and X ₂ are a methyl group.

(viii) The dye according to the above (i), wherein X ₁ and X ₂ in the formula (1) are a methyl group, and R ₁ , R ₅ , R ₁₂ and R _{16 in the} R ₁ to R ₂₁ are a methyl group, R ₁₄ is a sodium salt of a sulfonic acid group or a sulfonic acid group, and R ₁₇ is a sodium salt of a sulfonic acid group or a sulfonic acid group, and is a hydrogen atom other than this.

(ix) The dye according to the above (i), wherein X ₁ and X ₂ in the formula (1) are a methyl group, and R ₁ , R ₅ , R ₁₂ and R _{16 in} R ₁ to R ₂₁ are a methyl group, R ₁₇ is a sodium sulfonate group, and is a hydrogen atom other than this.

X (x) of the above dyes (I), wherein Formula (1) ₁ and X ₂ is methyl, R ₁ to R ₂₁ in R ₁₇ is a sulfonic acid group, except a hydrogen atom.

Among the above, the dyes of the above (vii) and (ix) are particularly preferred.

The xanthene-based acid dye represented by the formula (1) may be used singly in the coloring resin composition of the present invention, or two or more kinds thereof may be used in combination.

The xanthene-based acid dye represented by the formula (1) of the present invention (hereinafter also referred to simply as the dye of the formula (1)) is known in part, and even if it is not a known compound, it can be opened by the Japanese Patent Laid-Open No. 2010-32999 The compound described in paragraph 0078 is methylated, or N-methyl which may have a substituent represented by R ₁ to R ₅ or R ₁₂ to R ₁₆ in the corresponding formula (1) The anilide compound has a cyclobutyl fluorene compound represented by the following formula (100) or a butyl ring compound having a substituent such as an alkyl group in the dye of the formula (1) on the benzene ring of the condensed cyclobutane ring of the cyclobutyl fluorene compound. Obtained by reaction.

Hereinafter, the colored resin composition for a color filter of the present invention will be specifically described.

The colored resin composition for a color filter of the present invention (hereinafter also referred to simply as "colored resin composition") is a curable colored resin containing at least both the dye of the above formula (1) and the above-mentioned triarylmethane-based acid dye. Composition. The colored resin composition contains a binder resin, a solvent, a curing agent, and a radical polymerization photoinitiator as components other than the above two acid dyes.

Also, "C.I." means "color index".

The dye of the above formula (1) may be used singly or in combination of two or more. Further, the triarylmethane acid dyes used in combination with the dye of the formula (1) may be used singly or in combination of two or more. The dye of the formula (1) has been described above, and therefore, the above triarylmethane-based acid dye will be described below.

As the triarylmethane acid dye classified as CI acid blue, CI Acid Blue 1, CI Acid Blue 3, CI Acid Blue 5, CI Acid Blue 7, CI Acid Blue 9, CI Acid Blue 11, CI Acid Blue 13, CI Acid Blue 15, CI Acid Blue 17, CI Acid Blue 22, CI Acid Blue 24, CI Acid Blue 26, CI Acid Blue 34, CI Acid Blue 38, CI Acid Blue 48, CI Acid Blue 75, CI Acid Blue 83, CI Acid Blue 84, CI Acid Blue 86, CI Acid Blue 88, CI Acid Blue 90, CI Acid Blue 90:1, CI Acid Blue 91, CI Acid Blue 93, CI Acid Blue 93:1, CI Acid Blue 99, CI Acid Blue 100, CI Acid Blue 103, CI Acid Blue 104, CI Acid Blue 108, CI Acid Blue 109, CI Acid Blue 110, CI Acid Blue 119, CI Acid Blue 123, CI Acid Blue 147, CI Acid Blue 213, and CI Acid Blue 269, and the like.

Among them, a dye having a maximum absorption wavelength of 550 to 650 nm and an absorbance of 550 to 650 nm of 0.3 or more is preferred. More preferably, it is a triarylmethane-based acid dye having a maximum absorption wavelength of 550 to 650 nm and an absorbance of 550 to 650 nm of 0.6 or more.

Therefore, as a preferred triarylmethane acid dye, it is preferred to have a triarylmethane structure, have at least one sulfonic acid group or sulfonic acid salt in its structure, and have a maximum absorption wavelength in the wavelength range of 550 to 650 nm, and The dye having an absorbance at 550 to 650 nm of 0.3 or more and preferably 0.6 or more.

Specific examples of the acid dye satisfying the above conditions include C.I. Acid Blue 7, C.I. Acid Blue 90, and C.I. Acid Blue 104.

The content of two acid dyes (the dye of the above formula (1) and the above-mentioned triarylmethane acid dye) used in the present invention in the colored resin composition, based on the total of the two acid dyes, in the coloring resin of the present invention The total solid content of the composition (refer to the total amount of components other than the solvent composed of a dye, a binder resin, a curing agent, or the like; the same meaning is used hereinafter), preferably 0.01 to 70 parts by mass, preferably 0.01 to 70 parts by mass. It is contained in a proportion of 0.5 to 30 parts by mass, more preferably 1 to 30 parts by mass.

In addition, in the following, "parts" and "%" are not specifically stated. In the case of mass parts and mass%.

Further, depending on the case, the preferred total content of the two acid dyes may be in the range of 1 to 20%, more preferably in the range of 2 to 10%, based on the total solid content.

Further, the preferred content of each of the two acid dyes is from about 0.2% to about 20%, more preferably from about 0.5% to about 10%, still more preferably from about 1% to about 10%, and most preferably from about 1% to about 10%, based on the total solid content. 1 to 5%. Further, the content ratio of the two acid dyes varies depending on the combination of the dyes, and cannot be generalized, and is usually about 30% by mass to 70% by mass, and the other is about 70% by mass to 30% by mass, preferably 40% by weight. 60% by mass, and the other is 60 to 40% by mass.

Further, the above triarylmethane-based acid dye may be used in combination with respect to the dye of the formula (1) in an amount of 0.2 to 5 parts, preferably 0.5 to 2 parts, as the case may be.

When the content of the two acid dyes is too large, there is a problem of precipitation or aggregation, or the adhesion to the substrate is lowered due to insufficient curing. On the other hand, when the content is too small, sufficient color purity is not obtained as a color characteristic.

The binder resin contained in the colored resin composition for a color filter of the present invention has dispersion stability when dispersed in a dye or a pigment, and thus functions as a dispersing agent or/and a dispersing aid. In the case where the colored resin composition is used in the photolithography method, it is desirable that the binder resin is also soluble in the alkaline developer used in the development treatment step in the production of the color filter. In order to form a good fine pattern, it is desirable that the binder resin has a radical polymerization photoinitiator and light. A property in which a polymerizable monomer or the like is sufficiently cured. In addition, the binder resin and the color filter pigment, the polymerization initiator, the photopolymerizable monomer, and the pigment dispersion liquid have good compatibility, and must be stabilized so that the colored resin composition does not precipitate or aggregate. When the colored resin composition is used by an inkjet method, alkali solubility is not particularly required, and therefore, an adhesive resin having good compatibility with other constituent materials may be selected.

As the binder resin, a known resin can be used, and a polymer of an ethylenically unsaturated monomer is preferable. Examples of the raw material monomer of the preferred binder resin include an ethylenically unsaturated monomer having one or more carboxyl groups or a hydroxyl group, or an ethylenically unsaturated monomer having an aromatic hydrocarbon group or an aliphatic hydrocarbon group. As the binder resin, a homopolymer of the above raw material monomers can be used, but a copolymer of the above raw material monomers is usually used.

Further, the term "ethylenically unsaturated monomer" means the meaning of a monomer having a polymerizable vinyl group.

The weight average molecular weight of the binder resin is usually from 2,000 to 400,000, preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 6,000 to 40,000. In the case of the colored resin composition for development, a copolymer of an ethylenically unsaturated monomer having at least one carboxyl group or a hydroxyl group and an ethylenically unsaturated monomer having no such functional group is used. In the case of a colored resin composition for producing a filter in inkjet, a copolymer containing no ethylenically unsaturated monomer having a carboxyl group or a hydroxyl group can be used.

The binder resin is preferably a copolymer of at least two ethylenically unsaturated monomers which usually contain at least a (meth)acrylic monomer.

In the present specification, the terms "(meth)acrylic acid" or "(meth)acrylate" mean "methacrylic acid and/or acrylic acid" or "methacrylic acid ester and/or acrylate".

Further, the (meth)acrylic monomer means a meaning of a monomer having a (meth)acryl group, and specifically includes either or both of (meth)acrylic acid and (meth)acrylic acid ester.

The copolymer is usually in a proportion of from 30 to 100 mol%, preferably from 40 to 100 mol%, more preferably from 50 to 100 mol%, based on the total amount of the structural units contained in the copolymer. A copolymer containing structural units derived from a (meth)acrylic monomer. In the present invention, the copolymer having the constituent component derived from the (meth)acrylic monomer as a main component is referred to as a (meth)acrylic copolymer. Further, the main component means the meaning of the constituent component having the largest content in the structural unit of the copolymer. In the present invention, as the binder resin, a (meth)acrylic copolymer is preferred.

Further, an epoxy compound having an epoxy group such as an aromatic hydrocarbon group or a side chain or a terminal of an aliphatic hydrocarbon group can also be used. The epoxy (meth) acrylate resin obtained by further adding a (meth) acrylate to the epoxy compound is an ethylenically unsaturated monomer having a hydroxyl group, and can be used as a kind of (meth) acrylate monomer. use. The above monomers or the like may be used singly or in combination of two or more. A polymer or copolymer of the above monomers can usually be used as the binder resin. In the case of developing with an aqueous alkaline solution, a copolymer of a carboxyl group or a hydroxyl group-containing (meth) acrylate and another copolymerizable monomer is preferred.

The above-mentioned carboxyl group-containing unsaturated which can be used as a raw material of the binder resin Examples of the monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, and the like. Unsaturated dicarboxylic acids (anhydrides) such as itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; unsaturated polycarboxylic acids (anhydrides) of three or more kinds; hexahydrophthalic acid 2-( Methyl) propylene methoxyethyl ester, 2-(methyl) propylene methoxyethyl 2-hydroxypropyl phthalate and 2-(methyl) propylene oxychloride 2-hydroxyethyl phthalate Mono-2-(meth)acryloxyethyl ester of a dicarboxylic acid such as ethyl ester. The above ethylenically unsaturated monomer having a carboxyl group may be used singly or in combination of two or more.

The hydroxyl group-containing unsaturated monomer which can be used as a raw material of the binder resin may, for example, be a hydroxyl group-containing mono(meth)acrylate. For example, a (meth) acrylate compound of a polyhydric alcohol, preferably a (meth) acrylate compound of a diol or a triol may be mentioned. Specific examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. , 3-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 4-hydroxypentyl (meth)acrylate, 3-hydroxypentyl (meth)acrylate, (meth)acrylic acid 6-hydroxyhexyl ester, 5-hydroxyhexyl (meth)acrylate, 4-hydroxyhexyl (meth)acrylate, 5-hydroxy-3-methylpentyl (meth)acrylate, cyclohexane-1, a mono(meth) acrylate compound of a C2-C10 diol such as 4-dimethanol-mono (meth) acrylate and glyceryl monomethacrylate; 2-(2-hydroxyethyl oxy) (meth) acrylate Hydroxy-terminated polyalkylene glycols such as ethyl ester, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and poly(ethylene glycol-propylene glycol) monomethacrylate Mono (meth) propylene Acid esters, etc. These hydroxyl group-containing ethylenically unsaturated monomers may be used singly or in combination of two or more.

In addition, as the unsaturated monomer which can be used as a raw material of the binder resin, an unsaturated monomer having no hydroxyl group or a carboxyl group is preferable, and a vinyl compound having no hydroxyl group or carboxyl group is preferable. For example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-methoxystyrene An aromatic vinyl compound; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, Phenoxyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, o-phenyl phenol glycidyl ether (meth) acrylate, o-phenyl phenol ( Unsaturated carboxylic acid esters such as methyl acrylate hydroxyethylate and phenoxyethyl (meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (methyl) Trimethylcyclohexyl acrylate, norbornyl (meth)acrylate, norbornyl methyl (meth)acrylate, phenyl norbornene (meth)acrylate, (meth)acrylic acid Radicyl ester, isobornyl (meth)acrylate, borneol (meth)acrylate, menthyl (meth)acrylate, decyl (meth)acrylate, adamantyl (meth)acrylate, (methyl) Dimethyl methacrylate, trimethyl [meth) acrylate [5.2.1.0 ^2,6 ] 癸-8-yl ester, trimethyl (meth) acrylate [5.2.1.0 ^2,6 ] 癸-4- An alicyclic skeleton such as methyl ester, cyclodecyl (meth) acrylate, 2-(meth) propylene methoxyethyl hexahydrophthalate, and t-butylcyclohexyl (meth) acrylate ( Methyl) acrylate compound; methoxy polyethylene glycol monomethacrylate, dodecyloxy polyethylene glycol mono (meth) acrylate, octadecyloxy polyethylene glycol polypropylene glycol single ( Methyl)acrylate, nonylphenoxy polyethylene glycol monoacrylate, nonylphenoxy polypropylene glycol monoacrylate, and alkyl groups such as aryloxy polyethylene glycol-polypropylene glycol mono(meth)acrylate Blocked polyalkylene glycol mono(meth)acrylates; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, acrylic acid 3-amino Aminoalkyl esters of unsaturated carboxylic acids such as esters and 3-aminopropyl methacrylate; glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth)acrylate, (methyl) ) an unsaturated carboxylic acid glycidyl ester such as (3,4-epoxycyclohexyl)methyl acrylate and 4-hydroxybutyl methacrylate (glycidyl ether); vinyl acetate, vinyl propionate, ethylene butyrate Vinyl esters such as esters and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and methallyl glycidyl ether; acrylonitrile, methacrylonitrile , cyanoethylene compounds such as α-chloroacrylonitrile and vinylidene cyanide; acrylamide, methacrylamide, α-chloropropenylamine, N-phenylmaleimide, N- Cyclohexylmaleimide, N-(methyl)propenyl phthalimide, N-(2-hydroxyethyl) decylamine, N-(2-hydroxyethyl)methacryl Unsaturated guanamine or unsaturated quinone imines such as guanamine and maleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; and polyphenylene Ethylene Polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polyoxyalkylene, etc. have a monopropenyl fluorenyl group or a monomethacryl fluorenyl group at the end of the polymer molecular chain. Macromonomers and the like. The above unsaturated monomers may be used singly or in combination of two or more.

The vinyl compound having no hydroxyl group or carboxyl group as described above is preferably a (meth) acrylate monomer.

a ratio of the copolymer of an ethylenically unsaturated monomer having at least one carboxyl group or a hydroxyl group in the binder resin to an ethylenically unsaturated monomer having no carboxyl group or a hydroxyl group, as long as the binder resin is soluble in the alkali developable The liquid is not particularly limited. Usually, the ratio of the two is a ratio of 1 molar with respect to an ethylenically unsaturated monomer having a carboxyl group or a hydroxyl group (preferably (meth)acrylic acid or a hydroxyl group-containing (meth)acrylate), and has no carboxyl group. Or a hydroxyl group of an ethylenically unsaturated monomer (preferably a (meth) acrylate monomer) of from about 0.2 moles to about 10 moles, preferably from about 0.5 moles to about 5 moles, more preferably 1 mole. The ear is about 4 mu.

As the binder resin, a homopolymer may be used depending on the case, and a copolymer in which at least two of the above monomers are used is usually used. When the copolymer is produced, a polymerization initiator is used. Here, specific examples of the polymerization initiator used in the synthesis of the copolymer include, for example, α,α'-azobis(isobutyronitrile), and 2,2'-azobis(2-methylbutyronitrile). ), tert-butyl peroxy (2-ethylhexanoic acid), dibutyl butyl peroxide, benzamidine peroxide, methyl ethyl ketone peroxide, and the like. The use ratio of the polymerization initiator is 0.01 to 25 parts by mass based on 100 parts by mass of the total amount of the monomers used in the synthesis of the copolymer. Further, in the case of synthesizing a copolymer, an organic solvent is preferably used, and an organic solvent having sufficient solubility for a monofunctional monomer or a polymerization initiator to be used can be used. Examples of the organic solvent that can be used to produce the binder resin include those described later. The same organic solvent as the organic solvent contained in the colored resin composition of the present invention.

The reaction temperature at the time of synthesizing the copolymer is preferably from 50 to 120 ° C, particularly preferably from 80 to 100 ° C. Further, the reaction time is preferably from 1 to 60 hours, more preferably from 3 to 20 hours.

The copolymer preferably has a acid value of 10 to 300 (mgKOH/g), preferably a hydroxyl value of 10 to 200 (mgKOH/g). The acid value is a value measured according to JIS K-2501, and the weight average molecular weight is a result of measurement based on GPC (Gel Permeation Chromatography), and is converted into a value of polystyrene. When the acid value or the hydroxyl value is 10 or less, the developability is lowered. 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 lowered.

Further, when development is not used in the production of the color filter, the acid value or the hydroxyl value of the binder resin does not cause a particular problem. Therefore, it does not matter if the acid value or the hydroxyl value is even zero.

Further, a polymer further having an unsaturated double bond introduced into the side chain of the copolymer can also be used as the binder resin. For example, (i) a maleic anhydride moiety of a copolymer of maleic anhydride and styrene, vinyl phenol, acrylic acid, acrylate, acrylamide or the like copolymerizable therewith may have an alcohol such as hydroxyethyl acrylate or the like. a compound in which an epoxy group-containing (meth) acrylate such as a hydroxyl group (meth) acrylate or a glycidyl methacrylate is reacted to be half-esterified, and (ii) in acrylic acid or acrylate and hydroxyethyl acrylate. Hydroxy group of a copolymer of a (meth) acrylate having an alcoholic hydroxyl group to make propylene A compound obtained by acid reaction. In addition, polyurethane resin, polyamide, polyimide resin, polyester resin, commercially available ACA-200M (manufactured by Daicel), ORGA-3060 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), AX3-BNX02 (share Ltd. Japan Catalyst Manufacturing), UXE-3024, UXE-3000, ZGA-287H, TCR-1338H, ZXR-1722H, ZFR-1401H, ZCR-1642H (all manufactured by Nippon Kayaku Co., Ltd.) can also be used as bonding Resin is used.

The binder resin may be used singly or in combination of two or more kinds in the coloring resin composition of the present invention. The content ratio of the binder resin in the coloring resin composition of 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. It is preferably 10 to 50 parts by mass, more preferably 15 to 45 parts by mass. When the content of the binder resin is less than 0.5 part by mass, the alkali developability is lowered, and problems such as contamination or film residue may occur in a region other than the portion where the pixel is formed.

The organic solvent contained in the colored resin composition for a color filter of the present invention can have sufficient dissolving power for a binder resin or a radical polymerization photoinitiator which is a constituent component of the colored resin composition, and is used for a synthetic adhesive resin. The monofunctional monomer, the polymerization initiator, and the like also have an organic solvent having sufficient solubility. Further, an organic solvent capable of maintaining dispersion stability even when a pigment dispersion is produced can be used.

Specific examples of the organic solvent contained in the colored resin composition include aromatic solvents such as benzene, toluene, and xylene; and ceramide solvent such as methyl ceramide, ethyl ceramide, and butyl. Celluloids such as cypress, such as cyanobacteria, and cyanoic acid esters such as methyl sulphate, ethyl cyanoacetate, and butyl cyanoacetate; (i) propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate, (ii) methyl methoxypropionate, methoxy propyl Propionate such as ethyl acetate, methyl ethoxypropionate or ethyl ethoxypropionate, (iii) lactate such as methyl lactate, ethyl lactate and butyl lactate, (iv) methyl acetate Acetate such as ethyl acetate and butyl acetate; diethylene glycol monoalkyl ether such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether or dimethyl ether, diethyl ether, tetrahydrofuran and An ether solvent such as an alkoxide; a ketone solvent such as acetone, methyl ethyl ketone, methyl butyl ketone or cyclohexanone; and an alcohol solvent such as methanol, ethanol, butanol, isopropanol or benzyl alcohol, etc., but is not limited to the above Organic solvents.

Usually, it is a ceramide solvent, an organic acid ester solvent (preferably a C2-C4 organic acid ester solvent), an ether solvent, a ketone solvent, etc., and an organic acid ester solvent and a ketone solvent are preferable.

The organic solvent may be used singly or in combination of two or more kinds in the coloring resin composition of the present invention. The amount of the organic solvent to be used is usually 40 to 10,000 parts by mass, preferably 70 to 2000 parts by mass, more preferably 100 to 1000 parts by mass, still more preferably 200, based on 100 parts by mass of the total solid content of the colored resin composition. Up to 900 parts by mass.

The curing agent contained in the colored resin composition for a color filter of the present invention is preferably a photopolymerizable monomer. Examples of the photopolymerizable monomer include a (meth) acrylate monomer and/or a thiol polymerizable monomer. Specific examples of the curing agent include 2-hydroxyethyl (meth)acrylate and (A) 2-hydroxypropyl acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di(meth) acrylate, diethylene glycol di(meth) acrylate, triethylene glycol (A) Acrylate, tetraethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl alcohol di (meth) acrylate, neopentyl alcohol tri (methyl) Acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA, etc.), glyceryl (meth)acrylate, double Phenol A epoxy di(meth)acrylate, bisphenol F epoxy di(meth)acrylate, bisphenol-oxime epoxy di(meth)acrylate, ethoxylated trimethylol Propane tri(meth) acrylate, propoxylated trimethylolpropane tri(meth) acrylate, ethoxylated glycerol tri(meth) acrylate, ethoxylated isocyanuric acid tris (A) Acrylate, bis(trimethylolpropane)tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, 9,9-bis[4-(2-propene oxime) Oxyethoxy)phenyl]anthracene and the like.

As a commercially available product, KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.), UA-33H (manufactured by Shin-Nakamura Chemical Co., Ltd.), (meth) acrylate monomer such as UA-53H (manufactured by Shin-Nakamura Chemical Co., Ltd.) and M-8060 (manufactured by Toagosei Co., Ltd.); TEMPIC, TMMP, PEMP and DPMP (all are limited by the chemical industry) The thiol-polymerizable monomer is produced by the company, but is not limited to the above.

In the present invention, as the curing agent, a (meth) acrylate monomer is preferably contained. The (meth) acrylate monomer may be used alone as a hardener, and in addition, other hardeners may be combined with the (meth) acrylate monomer. use. Usually, it is preferred to use a (meth) acrylate monomer as a hardener.

Further, the (meth) acrylate monomer as the curing agent may be monofunctional or may be polyfunctional having two or more (meth) acrylonitrile groups. As the curing agent in the present invention, it is generally preferred to contain a polyfunctional (meth) acrylate monomer having two or more (meth) acrylonitrile groups. As the polyfunctional (meth) acrylate monomer, a 2 to 6-functional polyfunctional (meth) acrylate monomer is preferred, and a 3 to 6-functional (meth) acrylate monomer is more preferred. The content ratio of the polyfunctional (meth) acrylate monomer in the total amount of the hardener is usually from about 20% by mass to about 100% by mass, preferably from about 30% by mass to about 100% by mass, more preferably from 40% by mass to more preferably About 100% by mass. The best is 100%.

The curing agent may be used singly or in combination of two or more kinds in the colored resin composition of the present invention. The content of the hardener is usually from 1 to 80 parts by mass, preferably from 5 to 50 parts by mass, more preferably from 10 to 50 parts by mass, still more preferably from 15 to 10 parts by mass, based on 100 parts by mass of the total solid content of the colored resin composition. 45 parts by mass.

In the present invention, the ratio of use of the curing agent to the binder resin is not particularly limited as long as it is within the range of the respective content ratios. When the binder resin is usually used in an amount of 1 part by mass, the use ratio of the curing agent is 0.2 parts by mass to 5 parts by mass. The right and left is preferably from about 0.5 part by mass to about 2 parts by mass, more preferably from about 0.7 part by mass to about 1.5 part by mass.

When the amount of the curing agent is too small, the effect such as solvent resistance is reduced, and when the amount is too large, the developability is lowered and development is sometimes impossible, which is not preferable.

The colored resin composition for a color filter of the present invention usually contains a radical polymerization photoinitiator.

The radically polymerized photoinitiator contained in the colored resin composition is preferably a radically polymerized photoinitiator having sufficient sensitivity to ultraviolet rays emitted from an ultrahigh pressure mercury lamp which is generally used as an exposure light source. Further, in order to perform hardening with less exposure energy, a polymerization accelerator called a sensitizer may be used in combination.

Specific examples of the radical polymerization photoinitiator include benzil, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, and 3,3'-di. Methyl-4-methoxybenzophenone, benzamidine benzoic acid, esterification of benzamidine benzoic acid, 4-benzylidene-4'-methyldiphenyl sulfide, benzoin Ketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, isopropylthioxanthone, dimethyl Thioxanthone, diethylthioxanthone, diisopropylthioxanthone, dimethylaminomethylbenzoate, 1-(4-dodecylphenyl)-2-hydroxy-2- Methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2 -hydroxy-2-methylpropan-1-one, methyl benzhydrazinecarboxylate, 2-methyl-1-(4-methylthiophenyl)-2-N-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-N-morpholinylphenyl)-butanone-1,2,4-bis(trichloromethyl)-6-(4-methoxy Phenyl)-1,3,5-s-three , 2,4,6-gin (trichloromethyl)-1,3,5-s-three 2,4-bis(tribromomethyl)-6-(4'-methoxyphenyl)-1,3,5-s-three , 2,4,6-gin (tribromomethyl)-1,3,5-s-three , 2,4-bis(trichloromethyl)-6-(1,3-benzodioxolan-5-yl)-1,3,5-s-three , benzophenone, benzamidine benzoic acid, 1-(4-phenylthiophenyl)butane-1,2-dione-2-indole-O-benzoate, 1-(4-methyl Thiophenyl)butane-1,2-dione-2-indole-O-acetate, 1-(4-methylthiophenyl)butan-1-one oxime-O-acetate, 4,4'-bis(diethylamino)benzophenone, p-amyldimethylammonium benzoate, ethyl p-dimethylaminobenzoate, 2,2'-bis(O- Chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, diazonaphthoquinone (diazonaphthoquinone)-based initiator, and the like.

In addition, commercially available KAYARAD ^RTM DMBI, KAYARAD ^RTM BDMK, KAYARAD ^RTM BP-100, KAYARAD ^RTM BMBI, KAYARAD ^RTM DETX-S, KAYARAD ^RTM EPA (all manufactured by Nippon Kayaku Co., Ltd.); DAROCUR ^RTM 1173 Or DAROCUR ^RTM 1116 (both manufactured by Merck Japan Co., Ltd.); IRGACURE ^RTM 907, IRGACURE ^RTM 369, IRGACURE ^RTM 379EG, IRGACURE ^RTM OXE-01, IRGACURE ^RTM OXE-02, IRGACURE ^RTM PAG103 (both BASF Japan, Inc.) Manufacturing); TME-three (manufactured by Sanhe Chemical Co., Ltd.); biimidazole (manufactured by Heijin Chemical Co., Ltd.); STR-110, STR-1 (all manufactured by RESPE-CHEMICAL Co., Ltd.), etc., but is not limited to the above.

The sensitizer is not particularly limited as long as it is a sensitizer capable of imparting a sensitizing effect to a radical polymerization photoinitiator.

The radically polymerizable photoinitiator may be used singly or in combination of two or more kinds in the coloring resin composition of the present invention. The content of the radical polymerization photoinitiator is usually 0.5 to 50 parts by mass, preferably 1 to 25 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the total solid content of the colored resin composition. It is preferably 5 to 20 parts by mass.

The colored resin composition for a color filter of the present invention may be used in combination with a dye other than the dye of the above formula (1) and the above-mentioned triarylmethane dye. For any ingredient.

The dye which can be used in combination as an optional component may be appropriately selected from the group consisting of a dye, an organic pigment, and an inorganic pigment, and may be used singly or in combination of two or more kinds as needed. Since the colored resin composition of the present invention relates to blue pixels, it is generally preferred to use a known blue dye, a violet dye, a blue pigment, or a violet pigment.

When a coloring matter (hereinafter referred to as an arbitrary component coloring matter) as an optional component is used in combination, the content of the coloring matter of the arbitrary component is adjusted so that all the coloring matter (100 parts by mass of the total solid content of the colored resin composition of the present invention) The total content of the dye of the formula (1), the above triarylmethane dye, and the optional component pigment is usually from 0.01 to 70 parts by mass, preferably from 0.5 to 50 parts by mass, more preferably from 5 to 50 parts by mass, and further More preferably, it is in the range of 10 to 40 parts by mass.

In general, the color of the component of the component is from 0 to 100 parts by mass, preferably from 0.5 to 100 parts by mass, more preferably from 1 to 50 parts by mass, even more preferably 2, based on 1 part by mass of the pigment represented by the formula (1). It is used in a ratio of 30 parts by mass, preferably 3 to 10 parts by mass.

The dye which can be used as the above-mentioned optional component dye is not particularly limited, and examples thereof include an acid dye, a basic dye, a direct dye, a sulfur dye, a vat dye, a naphthol dye, a reactive dye, a disperse dye, and the like. The dye is not limited to those which are soluble in an organic solvent, and even if it is insoluble in an organic solvent, it can be used as a dispersion.

The organic pigment which can be used as the above-mentioned optional component dye is not particularly limited, and examples thereof include anthraquinones, phthalocyanines, triphenylmethanes, benzimidazolones, quinacridones, and azo chelates. , azo, isoporphyrins, isoindolinones, dermatones, indanthrones, pyridazines, dibromo anthanthrones, flavannes ( Flavanthrone), terpenoids, perinone, quinophthalone, sulphur blue, A pigment such as a xanthene; a lake pigment obtained by insolubilizing an acid dye, a basic dye, a direct dye or the like with various precipitating agents, a dyed lake pigment, and the like. Specific examples of the pigment include, for example, Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, in the color index. 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79; Pigment Violet 1, 1:1, 2, 2: 2, 3, 3: 1, 3: 3, 4, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc.

Among the above organic pigments, a pigment containing a phthalocyanine skeleton (also referred to as a phthalocyanine pigment) is more preferably used as the above-mentioned optional component dye. From the viewpoint of good hue and resistance, etc., pigment blue 15:6 or pigment violet 23 is preferred.

One of preferable aspects of the colored resin composition of the present invention is a method in which a known blue pigment (particularly a phthalocyanine-based pigment) is used in combination as an optional component dye. The above C.I. Pigment Blue 15:6 or Pigment Violet 23 is a preferred pigment. The ratio of use of the blue pigment can be freely used within the range of the content ratio of the above-mentioned optional component dye. In general, the ratio of the dye of the formula (1) is from 1 to 20 parts by mass, preferably from 2 to 15 parts by mass, based on 1 part by mass.

The inorganic pigments which can be used in combination in the coloring composition of the present invention are not Particularly, specific examples thereof include a composite metal oxide pigment, carbon black, black titanium oxide, titanium oxide, barium sulfate, zinc oxide, lead sulfate, lead yellow, ferric oxide, ultramarine blue, and iron blue. , metal oxides such as chromium oxide, antimony white, iron black, lead dan, zinc sulphide, cadmium yellow, cadmium red, zinc, manganese violet, cobalt violet, barium sulfate, magnesium carbonate, metal sulfides, sulfates, metal hydroxides Materials, metal carbonates, etc.

When the dye used in the present invention (the dye of the above formula (1), the triarylmethane dye, and the dye which is optionally used in combination) has low solubility in the colored resin composition, it may be used in advance or in the case of producing a colored resin composition. Further, it is used in the form of being dispersed in a solvent using a dispersing agent, a dispersing aid or the like. As the dispersant or the like, a dye-based dispersant having a good adsorption property to a dye, a resin-based dispersant, a surfactant, or the like can be used. As a dye-based dispersing agent, a known technique is known, a method of mixing a sulfonated product of a dye according to Patent Document 4 or a metal salt thereof with a dye, a method of mixing a substituted aminomethyl derivative, and the like. The resin-based dispersant is a non-polar resin-based dispersant, and is usually a polymer resin having an acid value, an amine value, or the like which can impart good pigment adsorption properties, and examples thereof include an acrylic resin, a polyurethane resin, and a polycarboxylate. Acid, polyamide resin, polyester resin, and the like. As a commercial product of the resin dispersing agent, for example, ED211 (manufactured by Nanmoto Chemical Co., Ltd.), AJISPER PB821 (manufactured by Ajinomoto Fine-Techno), Solsperse 5000 and Solsperse 71000 (manufactured by Avecia), Disperbyk-2001 (manufactured by BYK‧Japan), and the like are exemplified. . The content of the dispersant is from 0% by mass to 30% by mass, preferably from 0% by mass to 20% by mass, based on the total solid content of the resin composition of the present invention.

Further, an organic solvent-insoluble pigment is known to be soluble in an organic solvent by, for example, an acid amine or a basic dye, such as n-propylamine or ethylhexylpropionic acid. The amine or the like is modified to be an amine salt dye, or the organic amine compound is reacted with a sulfonic acid group of the dye to be modified into a dye having a sulfonamide group. The above amine-modified dye can also be used in the colored resin composition of the present invention. Examples of the dye capable of performing amine modification include solvent blue 2, 3, 4, 5, 6, 23, 35, 36, 37, 38, 43, 48, 58, 59, 67, 70 in the color index. , 78, 98, 102, 104; basic blue 7; acid blue 80, 83, 90; solvent violet 8, 9 as purple dye; purple 4, 5, 14; alkaline purple 10 and the like.

The coloring resin composition of the present invention is obtained by mixing a dye, a binder resin, a solvent, a radical polymerization photoinitiator, a curing agent, a curing accelerator, and the like represented by the formula (1) with a dissolver, a homomixer, or the like. Manufacturing. Further, other pigments and dyes may be added as needed, and in the case of a pigment or a dye having low solubility, a dispersion is obtained by using a dispersing agent such as a paint shaker using a suitable dispersing agent, and added to the colored resin composition. Mix and mix.

Further, various additives such as a filler, a surfactant, a thermal polymerization inhibitor, an adhesion promoter, an antioxidant, an ultraviolet absorber, a coacervation inhibitor, and the like may be further added to the colored resin composition of the present invention as needed. Further, in order to remove foreign matter or the like after preparing the colored resin composition of the present invention, it is also possible to perform precision filtration using a filter or the like.

As a color filter using the coloring resin composition of the present invention The method for producing a colored cured film (hereinafter also simply referred to as "colored cured film") mainly includes a photolithography method and an inkjet method.

When used in the photolithography method, first, the coloring resin composition of the present invention is formed into a film thickness by a spin coating method, a roll coating method, a slit spin coating method, a die coating method, a bar coating method, or the like. It is applied to a substrate such as a glass substrate or a tantalum substrate in a manner of 0.1 to 20 μm (preferably 0.5 to 5 μm). Then, if necessary, it is dried under reduced pressure in a decompression chamber at 23 to 150 ° C for 1 to 60 minutes, preferably 60 to 120 ° C for 1 to 10 minutes, and further, using a hot plate or a clean oven. A prebaking treatment is performed to form a film. Next, the radiation is irradiated by a predetermined mask pattern by a general photolithography method (for example, an electron beam or an ultraviolet ray, preferably ultraviolet ray), and an aqueous surfactant solution, an alkaline aqueous solution or a surfactant and an alkaline solution are used. The mixed aqueous solution of the agent is developed. Examples of the development method include a dipping method, a spraying method, a shower method, a paddle method, and an ultrasonic developing method. Any of the above methods can be combined. The unirradiated portion is removed by development, rinsed with water, and post-baked at a temperature of usually 130 to 300 ° C for 1 to 120 minutes, preferably 150 to 250 ° C for 1 to 30 minutes, to obtain the present invention. Coloring the cured film.

In the above method, a polyoxyethylene alkyl ether, a polyoxyalkylene alkyl ether or the like can be used as a surfactant. Further, as the alkaline agent, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide or the like can be used. In the present invention, an aqueous solution containing both an alkaline agent and a surfactant is preferably used. Development is usually carried out at a treatment condition of 10 to 50 ° C for 30 to 600 seconds, preferably at 20 to 40 ° C for 30 to 120 seconds. Conditions are carried out.

Further, for example, when the colored resin composition of the present invention is used in an inkjet method or the like, a thermal polymerization initiator may be used in combination with a radical polymerization photoinitiator. Examples of the thermal polymerization initiator include a thermal polymerization initiator of an azo compound or an organic peroxide, and examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-azobis (2, 4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), ditributyl peroxide, dibenzoyl peroxide, cumene peroxy neodecanoate Wait.

Further, in the case where a thermal polymerization initiator is used in combination, the total amount of the radical polymerization photoinitiator and the thermal polymerization initiator may be within the range of the content of the radical polymerization photoinitiator.

An example of a preferred coloring resin composition for a color filter of the present invention is as follows. Parts or %, etc., unless otherwise specified, are parts by mass.

(I) A coloring resin composition in which, in 100 parts of the total solid content of the colored resin composition, the dye of the formula (1) and the above-mentioned triarylmethane acid dye, 5 in total, are contained in an amount of 0.5 to 30 parts by weight. To 50 parts of the binder resin, 5 to 50 parts of the hardener, and 1 to 25 parts of the radically polymerized photoinitiator, and 50 to 10,000 parts of the solvent based on 100 parts of the total solid content.

(II) The colored resin composition according to the above (I), wherein both of X ₁ and X ₂ of the dye of the formula (1) are a hydrogen atom or a C1 to C5 alkyl group.

(III) The colored resin composition according to the above (I), wherein both of X ₁ and X ₂ of the dye of the formula (1) are a methyl group, an isopropyl group, a butyl group, an isobutyl group or an isopentyl group. .

(IV) The colored resin composition according to the above (I), wherein both of X ₁ and X ₂ of the dye of the formula (1) are a methyl group.

R (V) as to (IV) according to a dye-colored resin composition, wherein the formula (1) of any of the above (I) in ₁ to R _21, R ₁₇ is a sulfonic acid group or sulfonate And (a) R ₁ to R ₁₆ , R ₁₈ to R ₂₁ are each a hydrogen atom, or (b) R ₁ , R ₅ , R ₁₂ and R ₁₆ are each a hydrogen atom or a methyl group, R ₂ to R ₄ and R ₆ to R ₁₁ are a hydrogen atom, and one of R ₁₃ to R ₁₅ is a sulfonic acid group or a sodium sulfonate group, and the balance is a hydrogen atom.

(VI) The colored resin composition according to the above (I), wherein the dye of the formula (1) is a No. 1-1 compound described in Synthesis Example 1 to be described later or No. 1 described in Synthetic Example 2 to be described later. 2 compounds.

The colored resin composition according to any one of the above-mentioned (1), wherein the phthalocyanine-containing skeleton is further contained in a ratio of from 1 to 20 parts by weight based on 1 part of the dye of the formula (1). The pigment acts as a blue pigment.

(VIII) The colored resin composition according to the above (VII), wherein the blue pigment is C.I. Pigment Blue 15:6.

(IX) The colored resin composition according to the above (I) to (VIII), wherein the binder resin is a (meth)acrylic copolymer having a weight average molecular weight of 3,000 to 100,000.

(X) The colored resin composition according to any one of the above (II) to (IX), wherein the curing agent is a (meth)acrylic monomer.

(XI) The colored resin composition according to (X) above, which contains a polyfunctional (meth)acrylic monomer as a curing agent.

The colored cured film of the present invention can be used as a liquid crystal display device, A color filter such as a solid-state image sensor used in an EL display or a digital camera, which is a blue pixel formed of the colored cured film of the present invention prepared as described above.

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

(Example)

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by the examples. Further, in the following examples, unless otherwise specified, parts represent parts by mass, and % means mass%. In addition, the maximum absorption wavelength was measured using an ultraviolet spectrophotometer UV-2450 (manufactured by Shimadzu Corporation).

Synthesis Example 1 (Synthesis of a dye containing Compound No. 1-1 as a main component: a dye of the formula (1))

Into a 300 ml four-necked flask, 5.8 parts of Acid Red 289 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 82.5 parts of dry dimethyl hydrazine were placed, and the mixture was stirred at normal temperature. 1.7 parts of oily sodium hydride (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and stirred at room temperature for 1.5 hours. Then, the reaction solution was cooled in an ice bath while 75 parts of methyl iodide was added dropwise (Tokyo Chemical Industry Co., Ltd.) Made by the company), stirred at room temperature for 20 hours. Will get the opposite After the solution was poured into a mixed aqueous solution of 750 parts of water and 50 parts of 35% hydrochloric acid, 35% hydrochloric acid was added to bring the pH to 0.3. The volume after the addition of hydrochloric acid was 1000 ml. 200 parts of sodium chloride was added thereto, and the precipitated crystals were filtered off, and the crystals were suspended in 200 parts of 6% hydrochloric acid, and the mixture was stirred at room temperature for 2 hours, and then the crystallized wet cake was filtered. Next, the wet cake was suspended in 100 parts of 6% hydrochloric acid, and after stirring at room temperature for 1 hour, the crystals were filtered off and dried. The obtained crystals were washed with diethyl ether and hexane, and then filtered and dried to obtain 4.1 parts of a color filter pigment of the present invention containing the following compound No. 1-1 as a main component. The maximum absorption wavelength of the pigment was 543 nm (cyclohexanone).

Compound No.1-1

Synthesis Example 2 (Synthesis of Pigment Containing Compound No. 1-2 as a Main Component: Dye of Formula (1))

Into a 500 ml four-necked flask, 4.1 parts of sulfofluoran of the following formula (100), 312 parts of methanol and 10.7 parts of N-methylaniline were charged and refluxed for 30 hours. The reaction solution was filtered at 60 ° C to remove insoluble components, and then the solvent was removed under reduced pressure until the reaction mixture reached about 70 ml, and poured into 200 parts of 6% hydrochloric acid. Then, 600 parts of water was added, and after stirring at room temperature for 30 minutes, the wet cake was filtered off. The wet cake was suspended in 100 parts of water, After stirring at 60 ° C for 2 hours, the mixture was filtered again, washed with water at 60 ° C, and then dried to obtain 2.5 parts of the color filter of the present invention containing the following compound No. 1-2 as a main component. Use pigments. The maximum absorption wavelength of the pigment was 546 nm (cyclohexanone).

Compound No. 1-2

Synthesis Example 3 (Bonding Resin: Synthesis of Copolymer (A))

In a 500 ml four-necked flask, 160 g of methyl ethyl ketone, 10 g of methacrylic acid, 33 g of benzyl methacrylate and 1 g of α,α'-azobis(isobutyronitrile) were placed in a flask while stirring. Allow 30 minutes of nitrogen. Then, the temperature was raised to 80 ° C, and the mixture was stirred for 4 hours while maintaining the temperature at 80 to 85 °C. 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, and the solid component was taken out by filtration and dried to obtain a copolymer (A). The obtained copolymer (A) has a weight average molecular weight of 18,000 and an acid value of 152 in terms of polystyrene. (mgKOH/g).

Example 1 (Preparation of Colored Resin Composition 1 : Pigment: No. 1-1 + Acid Blue 90+C.I. Pigment Blue 15:6)

CI Pigment Blue 15:6, Disperbyk-2001 (manufactured by BYK‧Japan), Solsperse 5000, PGMEA (propylene glycol monomethyl ether acetate) were mixed at a composition ratio of 12.0:8.0:1.0:79.0 (mass ratio). Next, 400 g of 0.3 mm zirconia beads were added thereto, and the mixture was treated with a paint shaker for 60 minutes, and filtered to obtain a blue pigment dispersion liquid 1. In the above-mentioned blue pigment dispersion liquid 1, 5.5 g of the copolymer (A) obtained in Synthesis Example 3 and 5.5 g of KAYARAD ^RTM DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a photopolymerizable monomer were mixed as a binder resin. 1.0 g of IRGACURE ^RTM 907 (manufactured by BASF Japan), 0.1 g of IRGACURE ^RTM OXE-02 (manufactured by BASF Japan), and 0.5 g of KAYARAD ^RTM DETX-S (manufactured by Nippon Kayaku Co., Ltd.) as a radical polymerization photoinitiator, 0.5 g of a synthesis example The coloring resin composition 1 of the present invention was obtained by the pigment No. 1-1 obtained in the first step, 0.5 g of acid blue 90 (manufactured by Tokyo Chemical Industry Co., Ltd.), and 30 g of ethyl lactate as a solvent.

Example 2 (Preparation of Colored Resin Composition 2: Pigment No. 1-1 + Acid Blue 104+C.I. Pigment Blue 15:6)

The colored resin composition 2 of the present invention was obtained in accordance with Example 1 except that the acid blue 90 was changed to Acid Blue 104 (manufactured by Wako Pure Chemical Industries, Ltd.).

Example 3 (Preparation of Colored Resin Composition 3: Pigment No. 1-2 + Acid Blue 90+C.I. Pigment Blue 15:6)

The colored resin composition 3 of the present invention was obtained in the same manner as in Example 1 except that the dye No. 1-1 was changed to the dye No. 1-2 obtained in Synthesis Example 2.

Example 4 (Preparation of Colored Resin Composition 4: Pigment No. 1-2 + Acid Blue 104+C.I. Pigment Blue 15:6)

The colored resin composition 4 of the present invention was obtained in accordance with Example 3, except that the acid blue 90 was changed to Acid Blue 104 (manufactured by Wako Pure Chemical Industries, Ltd.).

Example 5 (Preparation of Colored Resin Composition 5: Pigment No. 1-1 + Acid Blue 90)

5.5 g of the copolymer (A) obtained in Synthesis Example 3 as a binder resin, 5.5 g of KAYARAD ^RTM DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a photopolymerizable monomer, and 1.0 g as a radical polymerization photoinitiator IRGACURE ^RTM 907 (manufactured by BASF Japan), 0.1 g of IRGACURE ^RTM OXE-02 (manufactured by BASF Japan), and 0.5 g of KAYARAD ^RTM DETX-S (manufactured by Nippon Kayaku Co., Ltd.), 0.25 g of Pigment No. 1-1 of Synthesis Example 1, 0.25 g of Acid Blue 90 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 g of ethyl lactate as a solvent were mixed to obtain the colored resin composition 5 of the present invention.

Example 6 (Preparation of Colored Resin Composition 6: Pigment No. 1-1 + Acid Blue 104)

The colored resin composition 6 of the present invention was obtained in accordance with Example 5 except that the acid blue 90 was changed to Acid Blue 104 (manufactured by Wako Pure Chemical Industries, Ltd.).

Comparative Example 1 (Preparation of Comparative Resin Composition 1)

5.5 g of the copolymer (A) obtained in Synthesis Example 3 as a binder resin, 5.5 g of KAYARAD ^RTM DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a photopolymerizable monomer, and 1.0 g of IRGACURE as a radical polymerization photoinitiator ^RTM 907 (manufactured by BASF Japan), 0.1 g of IRGACURE ^RTM OXE-02 (manufactured by BASF Japan), and 0.5 g of KAYARAD ^RTM DETX-S (manufactured by Nippon Kayaku Co., Ltd.), 0.5 g of Basic Blue 7 (manufactured by Tokyo Chemical Industry Co., Ltd.) And 30 g of ethyl lactate as a solvent were mixed, and the comparative resin composition 1 was obtained.

Comparative Example 2 (Preparation of Comparative Resin Composition 2)

The comparative resin composition 2 was obtained in accordance with Comparative Example 1, except that the basic blue 7 was changed to Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.).

Comparative Example 3 (Preparation of Comparative Resin Composition 3)

The comparative resin composition 3 was obtained in accordance with Comparative Example 1, except that the basic blue 7 was changed to the dye No. 1-1 obtained in Synthesis Example 1.

Comparative Example 4 (Preparation of Comparative Resin Composition 4)

A comparative resin composition 4 was obtained in accordance with Comparative Example 1, except that 0.5 g of Basic Blue 7 was changed to 25 g of the blue pigment dispersion 1 prepared in the same manner as in Example 1.

1. Preparation of evaluation substrate, evaluation of developability, resolution, and adhesion to a substrate

The colored resin compositions 1 to 6 of the present invention obtained above were applied to respective glass substrates, and prebaked under the conditions of 80 ° C × 100 seconds. Next, the obtained coating film is exposed through a mask having a pattern to cure the exposed portion. Then, development was carried out using an alkaline aqueous solution containing a surfactant, rinsed with water, and then heat-hardened at 200 ° C for 5 minutes. As a result, a substrate for evaluation having a colored pattern was obtained.

When the evaluation substrate was used, the developability, the resolution, and the adhesion to the substrate were evaluated. As a result, the obtained pattern had a resolution of a line pitch of 5 μm square, and no residue or peeling of the pixels was observed. Therefore, it is also applicable to a high-resolution color filter for solid-state imaging devices.

2. Evaluation of heat resistance and contrast

The evaluation substrate was produced in the same manner as in the above-described production of the evaluation substrate except that the mask exposure was changed to the entire surface exposure and the development and the rinsing treatment were not performed in the production of the evaluation substrate. In the case of using the colored resin compositions 1 to 6 of the present invention and the comparative resin compositions 1 to 4, a color filter substrate having vivid color characteristics was obtained. Each evaluation was performed by the method described below using the above-mentioned evaluation substrate.

For the heat resistance, the spectral transmittance of the substrate for evaluation before and after the heat treatment was measured, and the color difference (ΔEab) before and after the heat treatment was calculated and evaluated. The heat treatment was carried out by exposing the obtained evaluation substrate at 200 ° C for 120 minutes. In addition, the spectral transmittance of the substrate for evaluation was measured by a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation).

For the contrast, the evaluation substrate was used, and the luminance value (cd/cm ² ) when the two polarizing plates were parallel and the luminance value when orthogonal were used by the contrast meter (CT-1 manufactured by Hiroshi Electric Co., Ltd.). The ratio of (cd/cm ² ) (luminance value in parallel/luminance value in orthogonal) is calculated.

The evaluation results of the heat resistance are shown in Table 1, and the evaluation results of the contrast are shown in Table 2.

As is clear from the results of Table 1, the spectral color difference of the colored resin compositions 1 to 3 of the present invention was 4 or less, and showed good results. The colored resin composition of the present invention is suitable for use in color filter applications requiring high reliability. On the other hand, the comparative color difference of the resin compositions 1 and 2 using the known dyes as the dyes is 22 or more, which is remarkably poor, and thus is not suitable for use in color filters requiring high reliability.

As is clear from the results of Table 2, the contrast of the colored resin compositions 1 to 6 of the present invention is superior to the use of the dye of the formula (1) as the comparative resin composition 3 of the dye, and is also superior to the use of the pigment as a pigment. Resin composition 4 was used. The present invention is a colored resin composition suitable for a next generation color filter.

As described above, the color filter obtained by using the colored resin composition of the present invention has higher contrast than the conventional pigment, and therefore, can obtain a vivid pixel and has color filter capable of withstanding heat resistance. Highly reliable color filter performance for the wafer manufacturing process. As described above, the colored resin composition of the present invention has various characteristics required for the next generation color filter.

(industrial availability)

By using the colored resin composition for a color filter of the present invention, it is possible to provide a blue pixel of a color filter having excellent quality and high reliability such as heat resistance and contrast.

Claims (10)

A colored resin composition for a color filter comprising a xanthene-based acid dye represented by the following formula (1), a triarylmethane-based acid dye classified as CI acid blue, an adhesive resin, an organic solvent, a hardener, and a free Base polymerization photoinitiator, (In the formula (1), X ₁ and X ₂ each independently represent a hydrogen atom or an alkyl group of C1 to C30; and R ₁ to R ₂₁ each independently represent a hydrogen atom, an alkyl group of C1 to C30, and an alkyl group of C1 to C30. Oxyl group, C6 to C30 aromatic hydrocarbon group, C3 to C30 aromatic heterocyclic group, halogen atom, nitro group, phenoxy group, carboxyl group, carboxylate group, carboxylate group, alkoxycarbonyl group, hydroxyl group, sulfonate An acid group, a sulfonate group, a sulfonate group, a -SO ₂ NHR ₂₂ group or a -SO ₂ NR ₂₃ R ₂₄ group; at least one of R ₁ to R ₂₁ represents a sulfonic acid group, a sulfonate group, a sulfonate Any one of a group of -SO ₂ NHR ₂₂ or -SO ₂ NR ₂₃ R ₂₄ ; R ₂₂ to R ₂₄ each independently represent a C1 to C30 alkyl group; the sulfonate and carboxylate are monovalent A salt formed by a cation, the monovalent cation being any one of Na ⁺ , K ⁺ or a 4-grade ammonium cation). The colored resin composition according to claim 1, wherein both of X ₁ and X _{2 of the} formula (1) are a methyl group, an isopropyl group, a butyl group, an isobutyl group or an isopentyl group. The colored resin composition according to claim 1, wherein the triarylmethane acid dye classified as C.I. Acid Blue is C.I. Acid Blue 7, C.I. Acid Blue 90 or C.I. Acid Blue 104. The colored resin composition according to any one of claims 1 to 3, further comprising a metal phthalocyanine pigment. A colored cured film for color filters is formed by patterning using the colored resin composition according to any one of claims 1 to 3. A coloring cured film for a color filter is formed by patterning using the colored resin composition described in claim 4 of the patent application. A color filter comprising the colored cured film for a color filter according to claim 5 of the patent application. A liquid crystal display device in which the color filter described in claim 7 is mounted. An organic EL display mounted with the color filter described in claim 7 of the patent application. A solid-state imaging device mounted with the color filter described in claim 7 of the patent application.