JP2019045591A - Coloring composition for color filter and color filter - Google Patents

Abstract

To provide a photosensitive coloring composition for color filter having good chemical resistance, and to provide a color filter having a filter segment excellent in chemical resistance using the coloring composition.SOLUTION: A coloring composition for color filter contains a pigment (A), a binder resin (B), a solvent (C), a photopolymerization initiator (D), a photopolymerizable monomer (E) and a thermosetting agent (F), where the thermosetting agent (F) contains an oxazoline group.SELECTED DRAWING: None

Description

  The present invention relates to a color liquid crystal display device, a color composition for color filter used in the production of a color filter used in a color imaging device, and the like, and a color filter including a filter segment formed using the same. is there.

  In recent years, color filters are required to have high color reproducibility in order to display darker and more vivid colors. In order to achieve high color reproduction, it is necessary to increase the amount of pigment contained in each color fill pixel of red, green, and blue. As a method of increasing the pigment content, there is a method of increasing the film thickness of each pixel. However, with the demand for high color reproducibility, it is also required to reduce the thickness of each color fill pixel in order to produce a thinner color filter. Therefore, by increasing the pigment concentration of each color fill pixel of red, green, and blue, it is possible to achieve both a reduction in the thickness of the color filter and high color reproducibility. Further, in order to increase the pigment concentration of the color filter pixel, it is necessary to increase the pigment concentration in the photosensitive coloring composition.

  However, when the pigment concentration in the photosensitive coloring composition is increased, the content of binder resin, photopolymerizable compound and the like is decreased. Therefore, chemical resistance necessary for producing a color filter, particularly N-methyl which is a solvent for an alignment film There is a problem that resistance to -2-pyrrolidone (NMP) deteriorates.

Japanese Patent Laid-Open No. 2004-070342 JP 2009-251481 A

  The subject of this invention is providing the photosensitive coloring composition for color filters with favorable chemical resistance. Moreover, it is providing the color filter which comprises the filter segment which is excellent in chemical resistance using this coloring composition.

  As a result of intensive studies to solve the above problems, the present inventors have used a specific thermosetting agent as a photosensitive coloring composition for a color filter, so that the color filter has good chemical resistance. The present inventors have found that a photosensitive color composition can be obtained, and that the color filter having good chemical resistance can be produced by the photosensitive color composition.

  That is, the present invention is a color containing pigment (A), binder resin (B), solvent (C), photopolymerization initiator (D), photopolymerizable monomer (E) and thermosetting agent (F). It is a coloring composition for filters, Comprising: It is related with the coloring composition for color filters in which a thermosetting agent (F) contains an oxazoline group.

  Moreover, this invention relates to the said photosensitive coloring composition for color filters whose content of a thermosetting agent (F) is 0.5-30 mass% with respect to the total amount of solids.

  Moreover, this invention relates to the said coloring composition for color filters whose thermosetting agent (F) is a copolymer resin of a styrene and an oxazoline group containing monomer.

  The present invention also relates to the above color filter coloring composition, wherein the binder resin (B) is an active energy ray-curable resin having an ethylenically unsaturated double bond.

  In the present invention, the active energy ray-curable resin having an ethylenically unsaturated double bond is a copolymer of an ethylenically unsaturated monomer having an epoxy group and one or more other monomers. The side chain epoxy group of the copolymer thus obtained is subjected to an addition reaction with a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and a polybasic acid anhydride is added to the generated hydroxyl group. It is related with the said coloring composition for color filters which is the resin made to react.

  In the present invention, the pigment (A) is C.I. I. It is related with the said coloring composition for color filters containing the pigment green 58. FIG.

  Moreover, this invention relates to the said coloring composition for color filters whose content of a pigment (A) is 30-45 mass% with respect to the total solid content in the coloring composition for color filters.

  Furthermore, this invention relates to the color filter which comprises the filter segment formed from the said coloring composition for color filters on a board | substrate.

  With the coloring composition for color filter of the present invention, a coloring composition for color filter having good chemical resistance can be obtained. In addition, a high-quality color filter using the color filter coloring composition can be obtained.

Hereinafter, the present invention will be described in detail.
In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is particularly described, Unless otherwise indicated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. It shall represent. Further, “CI” in this specification means a color index (CI). Further, the total solid content of the color filter coloring composition means the total mass of nonvolatile components excluding the solvent and the like from the color filter coloring composition.

  The present invention relates to a coloring composition for a color filter comprising a pigment (A), a binder resin (B), a solvent (C), a photopolymerization initiator (D), a photopolymerizable compound (E) and a thermosetting agent (F). The thermosetting agent (F) contains an oxazoline group.

<Coloring composition for color filter>
<Pigment (A)>
The pigment that can be used in the coloring composition of the present invention can be arbitrarily selected from conventionally known various pigments. These pigments can be used alone or in admixture of two or more at any ratio as required. Either an organic pigment or an inorganic pigment can be used as the pigment, but it is preferable to use an organic pigment from the viewpoint of brightness.

The content of the pigment is preferably 10% by mass or more, more preferably 15% by mass or more, and most preferably from the viewpoint of obtaining sufficient color reproducibility based on the total nonvolatile components of the colored composition (100% by mass). Is 20% by mass or more. Further, from the viewpoint of the stability of the coloring composition, the preferable pigment content is 90% by mass or less, more preferably 80% by mass or less, and most preferably 70% by mass or less. Pigment (A) is C.I. I. When the pigment green 58 is included, the content of the pigment (A) is preferably 30% by mass or more and 45% by mass or less based on the total nonvolatile components of the coloring composition (100% by mass).
Moreover, the coloring composition of this invention may contain dye other than a pigment. When it contains dye, it is preferable that content of dye is 1-800 mass parts with respect to 100 mass parts of pigments. More preferably, it is 5-400 mass parts. When the addition amount of the dye is within this range, the lightness and contrast ratio can be excellent.

<Organic pigment>
Specific examples of pigments that can be used when forming color filter pixels as pigments are shown below.
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276, and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254, more preferably C.I. I. Pigment Red 177, 209, 224, 242, or 254.

  Examples of blue pigments include C.I. I. 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 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment Blue 15: 6. Moreover, it is also preferable to use an aluminum phthalocyanine pigment, and the aluminum phthalocyanine pigment described in JP-A No. 2004-333817, Japanese Patent No. 4893859 and the like can also be used.

  Examples of the green pigment include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36 or 58.

  Examples of yellow pigments include C.I. I. Pigment yellow, C.I. I. 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, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 182,187,188,192,193,194,196,198,199,213,214, may be used yellow pigment quinophthalone pigments described in Japanese Patent No. 4,993,026 discloses. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 or a quinophthalone pigment described in Japanese Patent No. 4993026, particularly from the viewpoint of heat resistance, light resistance, and brightness of the filter segment As yellow pigments, C.I. I. Pigment Yellow 138, 139, 150 and at least one selected from quinophthalone pigments described in Japanese Patent No. 4993026 are preferable. More preferably, C.I. I. Pigment Yellow 83, 138, 139, 150, 185 or a quinophthalone pigment described in Japanese Patent No. 4993026.

  Examples of purple pigments include C.I. I. 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 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

The coloring composition for a color filter of the present invention is optimal for a composition that needs to increase the pigment concentration in the photosensitive coloring composition in order to increase the pigment concentration of the color filter pixel. From the above viewpoint, the colored composition for a color filter of the present invention is preferably a green composition or a red composition, and more preferably a green composition.
In the case of a green composition, C.I. I. It is preferable to include an aluminum phthalocyanine pigment described in CI Pigment Green 7, 36, 58, or Japanese Patent Application Laid-Open No. 2004-333817 or Japanese Patent No. 4893859.
In the case of a red composition, C.I. I. Pigment Red 177, 209, 224, 242, or 254 is preferably included.

[Miniaturization of pigment]
When the pigment is used in the present invention, it is preferably used after being refined, but the refinement method is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation can be used, and examples are given in the present invention. Thus, a salt milling process by a kneader method, which is a kind of wet grinding, can be performed. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the pigment carrier. Further, it is preferably 100 nm or less because a color filter having a high contrast ratio can be formed. A particularly preferable range is a range of 25 to 85 nm. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is obtained by approximating it to a cube of the obtained particle size, and the volume average particle size is defined as the average primary particle size.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by mass, and most preferably 300 to 1000 parts by mass with respect to 100 parts by mass of the pigment in terms of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, and most preferably 50 to 500 parts by mass with respect to 100 parts by mass of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. It is preferable that the usage-amount of resin is the range of 5-200 mass parts with respect to 100 mass parts of pigments.

<Binder resin (B)>
The binder resin (B) contained in the colored composition for a color filter of the present invention disperses or penetrates a pigment, and examples thereof include a thermoplastic resin. The binder resin (B) is preferably a transparent resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type photosensitive coloring composition, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic substituent containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic substituent-containing ethylenically unsaturated monomer include resins having an acidic substituent such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic substituent, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, Or an isobutylene / (anhydrous) maleic acid copolymer etc. are mentioned. Among them, at least one resin selected from an acrylic resin having an acidic substituent and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic substituent, is preferably used because of its high heat resistance and transparency. It is done.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins into which an ethylenically unsaturated double bond has been introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers is used. Addition reaction of a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and further reacting a polybasic acid anhydride with the generated hydroxyl group to convert an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of a carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and a monomer of an unsaturated monobasic acid having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

  Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl methacrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. In addition, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate added with poly-12-hydroxystearic acid or the like can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl methacrylate or glycerol methacrylate is preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis [methacryloyloxy] ethyl isocyanate, but are not limited thereto. Two or more types can be used in combination.

  In order to disperse the pigment preferably, the weight average molecular weight (Mw) of the binder resin (B) is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  In addition, from the viewpoints of dispersibility, stability, developability, and heat resistance of the pigment, a carboxyl group that functions as a pigment adsorption group and an alkali-soluble group during development, an aliphatic group that functions as an affinity group for the pigment carrier and solvent, and an aromatic group. The balance of the group is important for the dispersibility of the pigment, the permeability of the developer in the coating film, the solubility of the developer in the uncured part, and the durability, and a resin having an acid value of 20 to 300 mgKOH / g should be used. preferable. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, a fine pattern may not remain.

  The binder resin (B) is preferably used in an amount of 30 parts by mass or more with respect to 100 parts by mass of the total weight of the pigment (A) because the film formability and various resistances are good, and the pigment concentration is high. Since good color characteristics can be expressed, it is preferably used in an amount of 500 parts by mass or less. More preferably, it is 100-400 mass parts. More preferably, it is 160-320 mass parts. The chromaticity region can be expanded by such a composition ratio of the pigment.

<Solvent (C)>
A solvent is used in order to make it easy to apply | coat the coloring composition of this invention on substrates, such as a glass substrate, so that a dry film thickness may be 0.2-5 micrometers, and to form a filter segment.
Since the solvent needs to be dried, it is necessary to use a solvent having a boiling point of less than 200 ° C. Examples of the solvent include 1,2,3-trichloropropane, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, P-chlorotoluene, P-diethylbenzene, sec-butylbenzene, te rt-butylbenzene, isobutyl alcohol, ethylene glycol diethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene Glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohex Non, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, propylene glycol diacetate, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, methyl isobutyl ketone, Le cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used singly or in combination of two or more at any ratio as required.

<Photopolymerization initiator (D)>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. Used in the form of

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Is a benzoin compound such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Enyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound or the like is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The photopolymerization initiator content is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 5 to 400 parts by mass from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.
Sensitizers include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler's ketone derivatives and the like.
These sensitizers can be used singly or in combination of two or more at any ratio as required.

Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.
Among the sensitizers, particularly preferred sensitizers include thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

  The content of the sensitizer is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by mass from the viewpoint of photocurability and developability. It is more preferable that

<Photopolymerizable monomer (E)>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.
Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate and other acrylic acid esters and methacrylic acid esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, ru (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The content of the photopolymerizable monomer is preferably 5 to 500 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 10 to 400 parts by mass from the viewpoint of photocurability and developability. .

<Thermosetting agent (F)>
The coloring composition for a color filter of the present invention contains an oxazoline group-containing thermosetting agent. By including a thermosetting agent containing an oxazoline group, it is possible to obtain a coating film with high hardness by reacting during the heating process and forming a network-like coating film structure. Etc., it can also be excellent in fastness. Moreover, you may contain other thermosetting agents suitably other than the oxazoline group containing thermosetting agent as needed.

[Oxazoline group-containing thermosetting agent]
The thermosetting agent containing an oxazoline group may be a low molecular compound or a high molecular compound. Examples of the low molecular compound include 2,2′-bis (2-oxazoline) and 2,2′-bis (4-methyl-2- Oxazoline), 2,2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (5-methyl-2-oxazoline), 2,2'-bis (4,4-dimethyl-2- Oxazoline), 2,2′-bis (5,5-diethyl-2-oxazoline), 2,2′-bis (4-propyl-2-oxazoline), 2,2′-bis (4-phenyl-2-) Oxazoline), 1,2-bis (2-oxazolin-2-yl) ethane, 1,2-bis (4-methyl-2-oxazolin-2-yl) ethane, 1,4-bis (2-oxazoline-2) -Yl) cyclohexane, 1,4-bis (4,4-dimethyl) Ru-2-oxazolin-2-yl) cyclohexane, 1,3-bis (2-oxazolin-2-yl) benzene, 1,2-bis (5-methyl-2-oxazolin-2-yl) benzene, 1, 3-bis (4-methyl-2-oxazolin-2-yl) benzene, 1,3-bis (5-methyl-2-oxazolin-2-yl) benzene, 1,3-bis (4,4-dimethyl- 2-oxazolin-2-yl) benzene, 1,4-bis (4,4-dimethyl-2-oxazolin-2-yl) naphthalene, 2,2′-bis (2-oxazolin-2-yl) biphenyl, 2 , 6-bis (4,4-dimethyl-2-oxazolin-2-yl) pyridine, 2,2′-9,9′-diphenoxyethanebis (2-oxazoline), and the like.

Examples of the polymer compound include an acrylic resin copolymerized with isopropynyl oxazoline, or a copolymer resin of styrene and an oxazoline group-containing monomer. As commercially available products, Epocross (R) K-2010E, Epocross (R) K-2020E, Epocross (R) E-2030E, Epocross (R) RPS-1005, Epocross (R) WS-300, Epocross (R) WS-500 Epocross (R) WS-700 (Nippon Catalyst Co., Ltd.) and the like can be mentioned, but are not limited thereto.
Among these, from the viewpoint of contrast, it is preferably a polymer compound, more preferably a copolymer resin of styrene and an oxazoline group-containing monomer, and Epocros (R) RPS-1005 is a commercially available product.

[Other thermosetting agents]
Examples of other thermosetting agents include epoxy compounds and melamine compounds.
The epoxy compound may be a low molecular compound or a high molecular compound, and representative examples include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, and novolac epoxy. Resins, cycloaliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, epoxy resins such as epoxidized oil; brominated derivatives of the above epoxy resins, tris (glycidylphenyl) methane, Triglycidyl isocyanurate etc. are mentioned. Among them, bisphenyl A type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolac type epoxy resin, cycloaliphatic type epoxy resin, glycidyl ester type resin, glycidylamine type resin, tris (glycidylphenyl) methane This is preferable in that the cured density is high and the adverse effect on the developability of the colored composition is small.

  As a commercial item, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (above are trade names; manufactured by Mitsubishi Chemical Corporation), Epicoat 1004, Epicoat 1256 (above are commodities) Name: manufactured by Mitsubishi Chemical Corporation), TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name; Mitsubishi Chemical) Co., Ltd.), JER 157S65, 157S70 (trade name; manufactured by Mitsubishi Chemical Corporation), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (above are trade names; Mitsubishi Chemical Corporation) Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EO N-1020 (above are trade names; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (above trade names: manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-810, EX-830, EX-851 , EX-611, EX-512, EX-421, EX-313, EX-201, EX-111 (the above are trade names; manufactured by Nagase ChemteX Corporation), etc., but are not limited thereto. is not.

  As a melamine compound, for example, Nicarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW- are commercially available products. 24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410 (manufactured by Sanwa Chemical Co., Ltd.), Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370, 506 (manufactured by Nippon Cytec Industries, Inc.), etc. It is not something.

  The oxazoline group-containing thermosetting agent is preferably used in an amount of 0.1 to 50.0% by mass, more preferably 0, based on the solid content weight of the color filter coloring composition (100% by mass). 0.5 to 30.0% by mass. When it is 0.1% by mass or more, yellowing or the like is prevented and sufficient color characteristics are obtained, and when it is 50.0% by mass or less, a sufficient hardness improving effect is obtained.

<Multifunctional thiol>
The coloring composition for a color filter of the present invention can contain a polyfunctional thiol. A polyfunctional thiol is a compound having two or more thiol (SH) groups. By using polyfunctional thiol together with the above-mentioned photopolymerization initiator, in the radical polymerization process after light irradiation, it acts as a chain transfer agent and generates a thiyl radical that is less susceptible to polymerization inhibition by oxygen. The composition becomes highly sensitive. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.

Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3- Mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate) ), Dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s- Examples include triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine.
These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  0.05-100 mass parts is preferable with respect to 100 mass parts of coloring agents, and, as for content of a polyfunctional thiol, 1.0-50.0 mass parts is more preferable. By using 0.05 part by mass or more of polyfunctional thiol, better development resistance can be obtained. When a monofunctional thiol having one thiol (SH) group is used, such an improvement in development resistance cannot be obtained.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 1.0 parts by mass with respect to 100 parts by mass of the total weight of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Ultraviolet absorber, polymerization inhibitor>
The coloring composition for a color filter of the present invention can contain an ultraviolet absorber or a polymerization inhibitor. By containing an ultraviolet absorber or a polymerization inhibitor, the shape and resolution of the pattern can be controlled.

Examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, etc. Hydroxyphenyltriazine, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, Benzotriazoles such as 2- (3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4-di Benzophenone series such as droxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, salicylate series such as phenyl salicylate, p-tert-butylphenyl salicylate Cyanoacrylates such as ethyl-2-cyano-3,3′-diphenylacrylate, 2,2,6,6, -tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis (2 , 2,6,6-tetramethyl-4-piperidyl) -sebacate, poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3,5-triazine-2,4-diyl ] Hindered amines such as [(2,2,6,6-tetramethyl-4-piperidinyl) imino].
These ultraviolet absorbers can be used singly or in combination of two or more at any ratio as required.

Examples of the polymerization inhibitor include hydroquinone such as methyl hydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol. Derivatives and phenol compounds, amine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. And manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine, etc. Toroso compounds and their ammonium salts or aluminum salts and the like.
These polymerization inhibitors can be used singly or as a mixture of two or more at any ratio as required.

  The ultraviolet absorber and the polymerization inhibitor can be used in an amount of 0.01 to 20 parts by mass, preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the colorant in the coloring composition. By using 0.01 part by mass or more of the ultraviolet absorber or the polymerization inhibitor, better resolution can be obtained.

<Antioxidant>
The colored composition for a color filter of the present invention can contain an antioxidant in order to increase the transmittance of the coating film. Antioxidants prevent the photopolymerization initiator contained in the color filter coloring composition from being oxidized and yellowed by the thermal process during thermal curing and ITO annealing, and thus increase the transmittance of the coating film. it can. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and high coating film transmittance can be obtained.

Preferable examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfide-based antioxidants. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.
These antioxidants can be used singly or as a mixture of two or more at any ratio as required.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) and 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5- And di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

  In the hindered amine antioxidant, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N , N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4- Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3,4 -Butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6- Tetramethyl-4-piperidyl) Mino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2,2 , 6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl) -4 Polycondensate with -hydroxy-2,2,6,6-tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2, 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine and the like.

  As the phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine- 6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2- Yl) oxy] ethyl] amine and ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl).

  As sulfide-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like.

  The content of the antioxidant is preferably 0.1 to 5% by mass in a total of 100% by mass of the solid content of the color filter coloring composition. When the amount of the antioxidant is less than 0.1% by mass, the effect of increasing the transmittance is small.

<Other ingredients>
The coloring composition for a color filter of the present invention contains an adhesion improver such as a silane coupling agent or an amine compound that has a function of reducing dissolved oxygen in order to improve adhesion to a transparent substrate. Can be made.

  Examples of the silane coupling agent include vinyl silanes such as vinyl tris (β-methoxyethoxy) silane, vinyl ethoxy silane, and vinyl trimethoxy silane, (meth) acryl silanes such as γ-methacryloxypropyl trimethoxy silane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxy (Cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-amino Propyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, Examples include aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  The silane coupling agent can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant in the coloring composition.

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 -2-ethylhexyl dimethylaminobenzoate, N, N-dimethyl paratoluidine, etc. are mentioned.

<Method for producing colored composition for color filter>
The coloring composition for a color filter of the present invention includes a kneader, a two-roll mill, a three-roll mill, and a ball mill in a colorant carrier such as a binder resin and / or a solvent, if necessary, using a dispersing agent as a coloring agent. Further, it can be produced by finely dispersing using various dispersing means such as a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of colorants or the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed.
The active energy ray-curable resin having an ethylenically unsaturated double bond may be added at the stage of preparing the colorant dispersion, or the same effect can be obtained by adding to the prepared colorant dispersion later. From the viewpoint of the stability of the coloring composition, it is preferable to add it at the stage of adjusting the photosensitive coloring composition.
When the solubility of the colorant such as a dye is high, specifically, it is highly soluble in the solvent to be used, and if it is dissolved and no foreign matter is confirmed by stirring, it is finely dispersed as described above. There is no need. In this case, the dispersion aid can be used by simply adding and mixing it with a colorant solution in which a dye or the like is dissolved.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

<Dispersing aid>
When dispersing the colorant in the colorant carrier, a dispersion aid such as a resin-type dispersant, a pigment derivative, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good.

[Resin dispersant]
The resin-type dispersant has a colorant-affinity part that has the property of adsorbing to the additive colorant and a part that is compatible with the colorant carrier, and is adsorbed to the additive colorant and dispersed in the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-based dispersants such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resin, water-soluble polymer compound, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

  The dispersant used in the present invention is preferably a polymer dispersant having a basic functional group, such as a nitrogen atom-containing graft copolymer, a tertiary amino group in the side chain, a quaternary ammonium base, or a nitrogen-containing heterocyclic ring. A nitrogen atom-containing acrylic block copolymer and a urethane polymer dispersant having a functional group containing are preferable. The resin-type dispersant is preferably used in an amount of about 5 to 200% by weight based on the total amount of the colorant, and more preferably about 10 to 100% by weight from the viewpoint of film formability.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, manufactured by Big Chemi Japan. 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or LACTIMON, LACTIMON-WS or BYKUMEN, etc., SOLPERSE-3000, 9000, manufactured by Nippon Lubrizol, Inc. 3000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4 00,5010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of Ajisupa -PA111, PB711, PB821, PB822, PB824, and the like are preferable.

Moreover, as a resin type dispersing agent used by this invention, it is also preferable to contain the following (S1) or (S2) as a resin type dispersing agent which has a carboxyl group.
(S1) A resin-type dispersant that is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic dianhydride.
(S2) A polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic dianhydride. A resinous dispersant that is a coalescence.

≪Resin type dispersant (S1) ≫
The resin-type dispersant (S1) can be produced by a known method such as WO2008 / 007776, JP2008-029901A, or JP2009-155406A. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal. For example, the ethylenically unsaturated monomer (r) is polymerized in the presence of the compound (q) having a hydroxyl group. It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since it is preferable that there are a plurality of terminal hydroxyl groups, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

  That is, a polymer having two hydroxyl groups at one end, which is a more preferable example, includes the monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. It can obtain as a polymer (p1) which polymerized the ethylenically unsaturated monomer (r) containing. The hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride to form an ester bond, while the anhydride ring is opened, and the carboxylic acid Produce.

≪Resin type dispersant (S2) ≫
The resin-type dispersant (S2) can be produced by a known method such as JP2009-155406A, JP2010-185934A, JP2011-157416A, for example, a compound having a hydroxyl group By polymerizing the ethylenically unsaturated monomer (r) in the presence of a reaction product of the hydroxyl group of (q) and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride. can get. In particular, in the presence of a reaction product of the hydroxyl group of the compound (q1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride. And a polymer obtained by polymerizing the ethylenically unsaturated monomer (r) containing the monomer (r1).

The difference between (S1) and (S2) is whether the polymer site obtained by polymerizing the ethylenically unsaturated monomer (r) is introduced first or later. The molecular weight and the like may be slightly different depending on various conditions, but theoretically the same can be obtained if the raw materials and reaction conditions are the same.

[Dye derivative]
Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazettes, Japanese Patent No. 4585781 etc. can be used. Al may be used either individually or in combination of two or more.

  The content of the pigment derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more with respect to 100 parts by mass of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by mass or less, more preferably 35 parts by mass or less.

[Surfactant]
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate. Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these may be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When adding a surfactant, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant. When the content of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the added effect. When the content is more than 55 parts by mass, the dispersion may be affected by an excessive dispersant. .

<Removal of coarse particles>
The colored composition of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment on a base material, and further includes a magenta filter segment, a cyan filter segment, or a yellow filter segment. Alternatively, the at least one filter segment is formed from the coloring composition of the present invention.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.
The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a substrate such as a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

  If the black matrix is formed in advance before forming the filter segment on the transparent substrate, the contrast of the liquid crystal display panel can be further increased. As the black matrix, chromium, a chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used. However, the present invention is not limited thereto, and the coloring composition for color filters of the present invention A black matrix formed from is preferable. A thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment and / or the black matrix on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

  The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

  Formation of each color filter segment and black matrix by photolithography is performed by the following method. That is, the color composition for color filter prepared as a color composition for solvent development type or alkali development type color filter is dried on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It is applied so that the film thickness is 0.2 to 10 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film.

  Thereafter, the filter segment and the black matrix can be formed by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove the uncured portion and forming a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment and the black matrix formed by development, heating can be performed as necessary. According to the photolithography method, it is possible to form a filter segment and a black matrix with higher accuracy than the printing method.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase UV exposure sensitivity, after applying and drying the above color filter coloring composition, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. Ultraviolet exposure can also be performed after forming a film.

  An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed on the color filter as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by mass” and “mass%”, respectively. “PGMAC” means propylene glycol monomethyl ether acetate. The weight average molecular weight (Mw) and number average molecular weight (Mn) measuring methods of the resin and the dispersant are as follows.

(Weight average molecular weight (Mw) and number average molecular weight (Mn) of resin and dispersant)
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin and the dispersant are GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using a TSKgel column (manufactured by Tosoh Corporation), and a developing solvent. The weight average molecular weight (Mw) in terms of polystyrene measured using THF.

(Acid value of resin and dispersant (mgKOH / g))
The acid value of the resin and the dispersant is a value obtained by converting the measured acid value (mgKOH / g) into a solid content according to the potentiometric titration method of JIS K0070.

  Then, the manufacturing method of the pigment, pigment | dye derivative, pigment dispersion, binder resin, thermosetting agent (F), and resist material which were used for the Example and the comparative example is demonstrated.

<Manufacture of finer pigments>
(Miniaturized PB15: 6 pigment (PB-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyocolor Co., Ltd. “LIONOL BLUE ES”, specific surface area 60 m ² / g) 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho). It knead | mixed at 80 degreeC for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine blue pigment (PB-1) was obtained.

(Miniaturized PV23 pigment (PV-1))
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for one day. As a result, a dioxazine-based purple refined purple pigment (PV-1) was obtained.

(Refined PY138 pigment (PY-1))
Yellow pigment C.I. I. 200 parts of Pigment Yellow 138 ("Pariotol Yellow K0961HD" manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 6 hours. Next, this kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY-1) was obtained.

(Miniaturized PR177 pigment (PR-1))
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“chromophthaled red A2B” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. Anthraquinone-based fine red pigment (PR-1) was obtained.

(Miniaturized PR254 pigment (PR-2))
Diketopyrrolopyrrole pigment C.I. I. 200 parts of Pigment Red 254 ("B-CF" manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a refined diketopyrrolopyrrole pigment (PR-2) was obtained.

(Miniaturized PG58 pigment (PG-1))
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine green pigment (PG-1) was obtained.

<Production of pigment derivative>
(Dye derivative 1)
After 50 parts of copper phthalocyanine as a dye component was chlorosulfonated, it was reacted with 14 parts of N, N-dimethylaminopropylamine as an amine component to obtain a dye derivative 1 having a basic group.

Dye derivative 1

[CuPc represents a copper phthalocyanine residue. ]

(Dye derivative 2)
By using diphenyl diketopyrrolopyrrole as a dye component and N-aminopropylmorpholine as an amine component, a dye derivative 2 having a basic group was obtained in the same manner as in the preparation of dye derivative 1.

Dye derivative 2

(Dye derivative 3)
Synthesis was performed as described in JP-A-2007-79094 to obtain Dye Derivative 3.

Dye derivative 3

(Dye derivative 4)
The dye derivative 4 was obtained by synthesis as described in JP-A-2007-156395.

Dye derivative 4

<Preparation of resin-type dispersant solution>
(Resin Dispersant Solution 1)
A commercially available resin type dispersant, EFKA4300 manufactured by BASF, and propylene glycol monoethyl ether acetate were used to prepare a 20% by mass solution of non-volatile content, and used as the resin type dispersant solution 1.

(Resin Dispersant Solution 2)
A commercially available resin type dispersant, BYK-LPN6919 manufactured by Big Chemie Japan Co., Ltd. and propylene glycol monoethyl ether acetate were used to prepare a 20% by mass non-volatile solution and used as the resin type dispersant solution 2.

<Manufacture of binder resin>
(Acrylic resin solution (B-1))
Into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction tube, 100 parts of cyclohexanone was heated to 80 ° C. while injecting nitrogen gas into the vessel, and 68 parts of glycidyl methacrylate at the same temperature, A mixture of 17 parts of methyl methacrylate, 7.5 parts of n-butyl methacrylate, 7.5 parts of benzyl methacrylate and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and then the mixture was stirred at the same temperature for 3 hours. Obtained. Subsequently, dry air was introduced into the reaction vessel, and 55 parts of acrylic acid, 83 parts of cyclohexanone, 1 part of dimethylbenzylamine and 0.1 part of methoquinone were charged, and stirring was continued for 10 hours at the same temperature. Further, 117 parts of tetrahydrophthalic anhydride was charged and stirring was continued for 10 hours at the same temperature. After cooling to room temperature, it was diluted with cyclohexanone to obtain an acrylic resin solution (B-1) containing a photopolymerizable functional group having a solid content of 20% and a carboxyl group. The weight average molecular weight was 44,000.

(Acrylic resin solution (B-2))
Put 100 parts of cyclohexanone into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction tube, heat to 80 ° C. while injecting nitrogen gas into the vessel, and 40 parts of methacrylic acid at the same temperature, A mixture of 25 parts of methyl methacrylate, 12.5 parts of styrene, 17.5 parts of n-butyl methacrylate, 5 parts of 2-methoxyethyl acrylate, and 4 parts of 2,2′-azobisisobutyronitrile is added dropwise over 1 hour. The polymerization reaction was carried out. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and then the mixture was stirred at the same temperature for 3 hours. Obtained. Subsequently, dry air was introduced into the reaction vessel, and 25 parts of glycidyl methacrylate, 37 parts of cyclohexanone, 1 part of dimethylbenzylamine, and 0.1 part of methoquinone were charged, and stirring was continued at the same temperature for 10 hours. After cooling to room temperature, it was diluted with cyclohexanone to obtain an acrylic resin solution (B-2) containing a photopolymerizable functional group having a solid content of 20% and a carboxyl group. The weight average molecular weight was 41,000.

(Acrylic resin solution (B-3))
Put 100 parts of cyclohexanone into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction tube, heat to 80 ° C. while injecting nitrogen gas into the vessel, and 25 parts of methacrylic acid at the same temperature, A mixture of 20 parts of 2-hydroxyethyl methacrylate, 30 parts of methyl methacrylate, 25 parts of styrene and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and then the mixture was stirred at the same temperature for 3 hours. Obtained. Subsequently, the temperature of the reaction vessel was cooled to 70 ° C., and dry air was further introduced into the reaction vessel, and 24 parts of 2-methacryloyloxyethyl isocyanate, 36 parts of cyclohexanone, 0.1 part of dibutyltin dilaurate, 0.1 part of methoquinone 0.1 Then, stirring was continued at the same temperature for 10 hours. After cooling to room temperature, dilution with cyclohexanone gave an acrylic resin solution (B-3) containing a photopolymerizable functional group having a solid content of 20% and a carboxyl group. The weight average molecular weight was 42,000.

(Acrylic resin solution (B-4))
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 70.0 parts of propylene glycol monoethyl ether acetate, heated to 80 ° C., and the reaction vessel was filled with nitrogen. After the substitution, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) )) A mixture of 7.4 parts and 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a solid content of 30% by mass and a weight average molecular weight of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Ether acetate was added to obtain an acrylic resin solution (B-4) which is an alkali-soluble resin containing a carboxyl group.

<Manufacture of pigment dispersion>
(Pigment dispersion (DP-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a blue pigment dispersion (DP-1) was obtained. The pigment dispersion was adjusted with propylene glycol monoethyl ether acetate to a solid content of 20% by mass. Hereinafter, solid content weight is shown.
Finer pigment (PB-1): 11.0 parts Dye derivative 1: 1.0 part Resin-type dispersant 1: 40.0 parts PGMAc: 48.0 parts

(Pigment dispersion (DP-2 to 6))
Except having changed into the composition shown in Table 1, it carried out similarly to the pigment dispersion (DP-1), and obtained the pigment dispersion (DP-2-6).

<Manufacture of coloring composition>
(Blue coloring composition (DPB-1))
The pigment dispersion (DP-1) and the pigment dispersion (DP-2) were dried at a coating film having a chromaticity of x = 0. 0 in a microspectrophotometer ("OSP-SP100" C light source manufactured by Olympus Optical Co., Ltd.). 141, y = 0.084, and the mixture was stirred and mixed with a disper for 1 hour to obtain a blue colored composition (DPB-1).

(Red coloring composition (DPR-1))
In the pigment dispersion (DP-4) and the pigment dispersion (DP-5), the chromaticity of the dried coating film is x = 0 in the microspectrophotometer (“OSP-SP100” C light source manufactured by Olympus Optical Co., Ltd.) measurement. .655 and y = 0.325, and the mixture was stirred and mixed with a disper for 1 hour to obtain a red colored composition (DPR-1).

(Green coloring composition (DPG-1))
In the pigment dispersion (DP-3) and the pigment dispersion (DP-6), the chromaticity of the dried coating film is y = 0 in the microspectrophotometer (“OSP-SP100” C light source manufactured by Olympus Optical Co., Ltd.) measurement. The blending ratio was adjusted to 600.x and 0.291, and the mixture was stirred and mixed with a disper for 1 hour to obtain a green colored composition (DPG-1).

<Production of photosensitive coloring composition for color filter>
[Example 1]
(Photosensitive coloring composition (DR-1))
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare a photosensitive coloring composition (DR-1).
Green coloring composition (DPG-1): 71.7 parts Binder resin (B-1): 1.7 parts Photopolymerizable monomer: 3.0 parts ("Aronix M402" manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator: 0.3 part ("Irgacure OXE02" manufactured by BASF)
Thermosetting agent containing an oxazoline group: 2.0 parts (Epocross (R) RPS-1005 manufactured by Nippon Shokubai Co., Ltd.)
PGMAC: 21.3 parts

[Examples 2 to 7, Comparative Example 1]
(Photosensitive coloring composition (DR-2 to 9))
Except having changed into the material and preparation amount shown in Table 2, the photosensitive coloring composition (DR-2-9) was produced similarly to the photosensitive coloring composition (DR-1).

Abbreviations in Table 2 are shown.
M402: Dipentaerythritol hexaacrylate (“Aronix M402” manufactured by Toagosei Co., Ltd.)
OXE02: ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime)
(BASF "Irgacure OXE02")
IRG907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (“IRGACURE 907” manufactured by BASF)
RPS1005: high molecular weight thermosetting agent containing an oxazoline group. Copolymer resin of styrene and oxazoline group-containing monomer (Epocross (R) RPS-1005 manufactured by Nippon Shokubai Co., Ltd.)

<Preparation and evaluation of coating film of photosensitive coloring composition>
About the obtained photosensitive coloring composition, chemical-resistant evaluation was performed by the following method. Table 3 shows the evaluation results.

[chemical resistance]
The obtained photosensitive coloring composition was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, and using an ultrahigh pressure mercury lamp, Ultraviolet exposure was performed with an integrated light amount of 150 mJ / cm 2 and development was performed with an alkaline developer at 23 ° C. Subsequently, it heated at 220 degreeC for 30 minute (s), and after standing to cool, the coating-film board | substrate was obtained. The prepared coated substrate was heat-treated at 220 ° C., then C = 0. The blue colored composition was y = 0.060, the red colored composition was x = 0.640, and the green colored composition was y = 0.600. To match the chromaticity of.
The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Furthermore, after that, the coating film obtained as a chemical resistance test was immersed in 1-methyl-2-pyrrolidone for 30 minutes, and after washing 1-methyl-2-pyrrolidone with pure water, the chromaticity ( [L * (2), a * (2), b * (2)]) were measured, and the color difference ΔE * ab was determined by the following calculation formula and evaluated in the following four stages. X is a difficult level to use.
ΔE * ab = [[L * (2) −L * (1)] 2+ [a * (2) −a * (1)] 2+ [b * (2) −b * (1)] 2] 1/2
◎: ΔE * ab is less than 1.5 ○: ΔE * ab is 1.5 or more and less than 3.0 Δ: ΔE * ab is 3.0 or more and less than 5.0 ×: ΔE * ab is 5.0 or more

As shown in Table 3, the coloring composition for a color filter containing a thermosetting agent containing an oxazoline group is more resistant to chemicals than Comparative Example 1 which does not contain a thermosetting agent containing an oxazoline group. Excellent results were obtained.
In addition, the comparison between Example 1 to Example 4 and Comparative Example 1 shows that the content of the oxazoline group-containing thermosetting agent is particularly excellent in heat resistance when it is 0.5 to 30.0% by mass. It was.
Further, the comparison between Example 1 and Example 5 shows that the use of a copolymer resin of styrene and an oxazoline group-containing monomer, which is an oxazoline group-containing high molecular weight thermosetting agent, is particularly excellent in heat resistance. It was done.
Furthermore, the comparison between Example 1 and Example 6 shows that when an active energy ray-curable resin having an ethylenically unsaturated double bond is used, the heat resistance is particularly excellent.

<Production of color filter>
A black matrix is patterned on a glass substrate, and a red photosensitive coloring composition (DR-8) is spin-coated on the substrate with a C light source (hereinafter also used for green and blue) x = 0.655, A colored film was formed by coating so that y = 0.325. The film was irradiated with ultraviolet rays of 150 mJ / cm ² using a super high pressure mercury lamp through a photomask.
Next, spray development was performed with an alkali developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 220 ° C. for 20 minutes to obtain a red filter segment. Formed. In the same manner, the blue photosensitive coloring composition (DR-7) of the present invention was adjusted so that x = 0.291 and y = 0.600. A green filter segment and a blue filter segment were formed using x = 0.141 and y = 0.084 to obtain a color filter.

  By using the photosensitive coloring composition of the present invention, a high quality color filter excellent in chemical resistance could be produced.

Claims (8)

A coloring composition for a color filter containing a pigment (A), a binder resin (B), a solvent (C), a photopolymerization initiator (D), a photopolymerizable monomer (E), and a thermosetting agent (F). A coloring composition for a color filter, wherein the thermosetting agent (F) contains an oxazoline group. The photosensitive coloring composition for a color filter according to claim 1, wherein the content of the thermosetting agent (F) is 0.5 to 30% by mass with respect to the total solid content. The coloring composition for a color filter according to claim 1 or 2, wherein the thermosetting agent (F) is a copolymer resin of styrene and an oxazoline group-containing monomer. The coloring composition for a color filter according to any one of claims 1 to 3, wherein the binder resin (B) is an active energy ray-curable resin having an ethylenically unsaturated double bond. A copolymer obtained by copolymerizing an active energy ray-curable resin having an ethylenically unsaturated double bond with an ethylenically unsaturated monomer having an epoxy group and one or more other monomers. A resin in which a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is added to the side chain epoxy group of the polymer, and a polybasic acid anhydride is reacted with the generated hydroxyl group. The coloring composition for color filters according to claim 4. The pigment (A) is C.I. I. The coloring composition for a color filter according to any one of claims 1 to 5, comprising Pigment Green 58. The coloring composition for a color filter according to claim 6, wherein the content of the pigment (A) is 30 to 45 mass% with respect to the total solid content in the coloring composition for the color filter. The color filter which comprises the filter segment formed from the coloring composition for color filters of any one of Claims 1-7 on a board | substrate.