JP2018097128A - Color filter coloring composition and color filters - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter coloring composition which minimizes wrinkling, through-hole residues, and film thickness change even for thick films such as COA films, and to provide a high-resolution color filter fabricated using the same.SOLUTION: The above problem is cleared by a color filter coloring composition comprising a colorant (A), resin dispersant (B), binder resin (C), photopolymerizable monomer (D), photopolymerization initiator (E), and antioxidant (F). The photopolymerizable monomer (D) contains an urethane-based photopolymerizable monomer (D1), a photopolymerizable monomer (D2) with an acid radical, and a (meth)acrylic monomer (D3) having 1 to 3 unsaturated bond groups per molecule. The resin dispersant (B) contains a resin dispersant having a glass transition temperature (Tg) of 30-100°C, and an amine number of 50-150 mgKOH/g.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive coloring composition, and in particular, a photosensitive coloring composition used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, etc., particularly a thin film transistor (TFT) type color. A photosensitive coloring composition for use in a color filter of a color filter on array system (hereinafter sometimes abbreviated as COA system), comprising a filter segment having a colored layer formed on a driving substrate of a liquid crystal display device, and The present invention relates to a color filter formed using a photosensitive coloring composition.

In the liquid crystal display device, a liquid crystal material and a pixel are interposed between two polarizing plates, a voltage is applied to each pixel to change the alignment state of the liquid crystal material, and the degree of polarization of light passing through the first polarizing plate is changed. It is a display device that changes and controls the transmitted light passing through the second polarizing plate to display the screen.
By providing a color filter between the two polarizing plates, color display is possible, and it has come to be used for televisions, personal computer monitors and the like. In recent years, color liquid crystal display devices are required to have high image quality and low power consumption, and color filters are also required to be designed to achieve high image quality and low power consumption.

  The color filter is provided with a grid-like light-shielding film black matrix (hereinafter referred to as BM) for the purpose of preventing color mixture of transmitted light and increasing display contrast on a transparent substrate such as a glass plate, and then a plurality of colors (usually red, Green and blue) filter segments are provided. The filter segments are as fine as several microns to several hundreds of microns, and the filter segments are arranged in the form of fine bands (stripes) of two or more different hues (stripe arrangement), or are arranged vertically and horizontally. (Delta arrangement). The filter segment and the BM are formed by drying at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. by applying a coloring composition. Further, in the color liquid crystal display device, a transparent electrode for driving the liquid crystal is formed on the color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher.

  In general, when improving the image quality of a color liquid crystal display device, the resolution of the color filter is increased, that is, the number of pixels is increased. However, as the number of pixels increases, the number of light-shielding parts such as BMs formed so as to surround the pixels and thin-film transistors (TFTs) for driving the liquid crystal also increases, and the ratio of light transmission parts per unit area of the color filter, that is, The aperture ratio is lowered. As a result, the brightness of the color filter decreases and the screen display section becomes dark. In order to compensate for this, the illuminance of the backlight must be increased, leading to an increase in power consumption. For this reason, in order to reduce the image quality and power consumption of color liquid crystal display devices, it is necessary to have a conflicting work of increasing the resolution of the color filter and increasing the aperture ratio, and various methods and structures have been considered. .

  In particular, a colored layer is formed directly or via a passivation film such as a silicon nitride film on a driving substrate on which TFTs are arranged in a high aperture ratio structure which has been attracting attention recently, and this substrate and liquid crystal are driven. For example, there is a COA method in which a transparent electrode for bonding is attached to a substrate formed by vapor deposition or sputtering (see Patent Document 1). A normal color filter cannot reduce the width of the light-shielding portion beyond a certain level in order to prevent crosstalk between the gate electrode and the transparent electrode, whereas the COA method has a thickness on the driving substrate on which the TFT is disposed. By forming a colored layer on the film, insulation can be ensured and the width of the light shielding portion can be reduced. As a result, the COA method can greatly increase the aperture ratio and achieve high image quality and low power consumption of a color liquid crystal display device.

  The COA method requires a thicker film than the conventional color filter pixel from the viewpoint of insulation, but the photocuring and thermosetting shrinkage difference between the color filter surface layer and the substrate is small. There arises a problem that the image quality deteriorates due to the occurrence of wrinkles. In order to reduce curing shrinkage, there is a method of using a photopolymerizable monomer having a low functional group number of 2 or less (see Patent Document 2). However, the filter segment, BM, and alignment film are reduced due to a decrease in sensitivity of the colored composition. There is a problem that the colored composition itself is decomposed in a high-temperature baking process such as formation, and the film thickness change (film shrinkage ratio) becomes large. In addition, there is a problem that a through-hole residue is generated due to a development speed delay due to a thick film design and a decrease in solubility.

JP 2004-94263 A JP, 2006-030764, A

  The present invention relates to a photosensitive coloring composition having high resolution capable of responding to high image quality and low power consumption of a color liquid crystal display device in recent years, particularly wrinkles and through holes even in a thick film such as a COA system. It is an object of the present invention to provide a color filter coloring composition that suppresses changes in the residue and film thickness, and a high-resolution color filter that is formed using the color filter coloring composition.

As a result of intensive studies to solve the above problems, the present inventor has developed a wrinkle, a through hole in a color filter coloring composition containing a urethane-based photopolymerizable compound and a photopolymerizable compound having an acid group. It was found that residue and film thickness changes were significantly suppressed, and a high-resolution color filter was obtained.

That is, the present invention provides a color for a color filter containing a colorant (A), a resin-type dispersant (B), a binder resin (C), a photopolymerizable monomer (D), and a photopolymerization initiator (E). It is a composition, Comprising: Content of a coloring agent (A) is 20 to 30 weight% in the total solid of a coloring composition, Photopolymerizable monomer (D) is urethane type photopolymerizable monomer ( And a photopolymerizable monomer (D2) having an acid group (except for a photopolymerizable monomer having an acid group) (D1).

In the color filter, the urethane photopolymerizable compound (D1) may contain a photopolymerizable monomer having 3 or more urethane bonds in one molecule. The present invention relates to a coloring composition.

In the color filter, the photopolymerizable monomer (D2) having an acid group contains a photopolymerizable monomer having a carboxyl group and a urethane bond. The present invention relates to a coloring composition.

Furthermore, the photopolymerizable monomer (D) is a (meth) acrylic monomer (urethane photopolymerizable monomer or photopolymerizable acid group having 1 to 3 ethylenically unsaturated bonds). And (D3) except for the monomer).

The present invention also relates to the coloring composition for a color filter comprising an antioxidant (F).

  The present invention also relates to the coloring composition for a color filter, wherein the antioxidant (F) contains a hindered phenol-based antioxidant.

  Further, the present invention is characterized in that the resin type dispersant (B) contains a resin type dispersant having a glass transition temperature (Tg) of 30 to 100 ° C. and an amine value of 50 to 150 mgKOH / g. The present invention relates to a coloring composition for a color filter.

  The present invention also relates to a color filter comprising a filter segment formed on the substrate using the colored composition for a color filter.

A high-resolution filter that does not change wrinkles or through-hole residues and does not change film shrinkage even when exposed to color filters or heat-treated at 200 ° C. or higher with the color filter coloring composition of the present invention. A segment can be formed. Therefore, a color liquid crystal display device with low power consumption and high quality can be manufactured using this color filter.

Hereinafter, embodiments of the present invention will be described in detail.
In the present application, when expressed as “(meth) acrylate”, “(meth) acrylic acid”, or “(meth) acrylamide”, unless otherwise specified, “acrylate and / or methacrylate”, It shall represent “acrylic acid and / or methacrylic acid” or “acrylamide and / or methacrylamide”.
Further, “CI” in this specification means a color index (CI).

The coloring composition for a color filter of the present invention comprises a colorant (A), a resin-type dispersant (B), a binder resin (C), a photopolymerizable monomer (D), a photopolymerization initiator ( E), an antioxidant (F), and an organic solvent are contained.
First, various components of the coloring composition for a color filter of the present invention will be described.

<Colorant (A)>
The colorant that can be used in the coloring composition of the present invention can be arbitrarily selected from conventionally known various pigments and dyes. These pigments / dyes can be used alone or in admixture of two or more at any ratio as required.

  The content of the colorant is preferably 20% by weight or more, more preferably 22% by weight or more from the viewpoint of obtaining sufficient color reproducibility by the COA method based on the total nonvolatile components of the coloring composition (100% by weight). is there. Further, from the viewpoint of thick film design and developability in the COA system, the preferred colorant content is 30% by weight or less, more preferably 28% by weight or less.

  In addition, when a coloring agent contains dye, it is preferable that content of dye is 1 to 50 weight% with respect to 100 weight% of pigments. More preferably, it is 20 to 30% by weight. When the addition amount of the dye is within this range, the lightness and contrast ratio can be excellent. In the color filter coloring composition of the present invention, it is preferable that the colorant contains both a pigment and a dye from the above viewpoint.

(Organic pigment)
Organic pigments include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, or polyazo, anthraquinones such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantrons, anthanthrone, indanthrone, pyranthrone, or violanthrone. Pigments, quinacridone pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments or metal complex pigments.

Specifically, as these organic pigments,
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 9, 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. it can.
Examples of orange pigments that work in the same way as red pigments include C.I. I. Orange pigments such as CI Pigment Orange 36, 38, 43, 51, 55, 59, 61 can be used.
Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment red 254, C.I. I. It is particularly preferable to use Pigment Red 177.

  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.

  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.

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, 5558, 62 or 63. . Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36, 58, 62, or 63.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, 231 or the like. 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 231 and more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180, or 231.

<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 colorant 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.
The colored composition of the present invention is excellent in resistance even when such a finely-treated pigment is used by containing an epoxy compound together with a specific pigment dispersant containing a heat-crosslinkable functional group. In addition, a coloring composition for a color filter having a high luminance and contrast ratio can be obtained.

  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% by weight and most preferably 300 to 1000% by weight based on 100% by weight of the pigment from the viewpoint 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% by weight, most preferably 50 to 500% by weight, based on 100% by weight 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. The amount of the resin used is preferably in the range of 5 to 200% by weight with respect to 100% by weight of the pigment.

<Resin type dispersant (B)>
The resin-type dispersant (B) has a colorant affinity part having a property of adsorbing to the added colorant and a compatible part in the colorant carrier, and adsorbs to the added colorant to cause the colorant It serves to stabilize dispersion in the carrier. The colorant carrier refers to a component excluding a colorant such as a binder resin and a photopolymerizable monomer. Specific examples of the resin type dispersant (B) include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, and polycarboxylic acid. Alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters and their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups And oil-based dispersants such as salts thereof, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resins, water-soluble polymer compounds, polyesters, Polyacrylate, 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.

  A polymer dispersant having a basic functional group is preferred because the viscosity of the dispersion is lowered and a high contrast is exhibited with a small addition amount of the resin type dispersant (B), and a nitrogen atom-containing graft copolymer is preferred. In addition, a nitrogen atom-containing acrylic block copolymer and a urethane polymer dispersant having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, or the like in the side chain are preferable.

  Commercially available resin-type dispersants include Dsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF Japan 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, 4800, 5010, 5065, 5066, 5070, 7500, 7 54,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB411, PB821, PB822, PB824, and the like.

  Among these, the coloring composition for color filters in the present invention is a resin mold in which the resin-type dispersant (B) has a glass transition temperature (Tg) of 30 to 100 ° C. and an amine value of 50 to 150 mgKOH / g. It is preferable to contain a dispersing agent. The amine value is preferably 50 mgKOH / g or more, more preferably 70 mgKOH / g or more and 110 mgKOH / g or less from the viewpoint of viscosity stability and residue. Tg is preferably 30 ° C. or higher from the viewpoint of pattern linearity, preferably 100 ° C. or lower, and most preferably 50 ° C. or higher and 70 ° C. or lower from the viewpoint of residue.

  The blending amount of the resin-type dispersant having a glass transition temperature (Tg) of 30 to 100 ° C. and an amine value of 50 to 150 mgKOH / g is preferably 0.1 to 55 with respect to 100% by weight of the colorant (A). % By weight, more preferably 0.1 to 45 parts by mass. When the blending amount of the resin type dispersant having a glass transition temperature (Tg) of 30 to 100 ° C. and an amine value of 50 to 150 mgKOH / g is less than 0.1 parts by mass, the added effect is hardly obtained. If it is more than 55% by weight, excessive dispersion may adversely affect the dispersion. Other dispersants may be used in combination.

In addition, the glass transition temperature in this invention has shown the value computed by the following Fox formula from Tg of each homopolymer to copolymerize.
Fox formula 1 / Tg = W1 / Tg1 + W2 / Tg2 +... + Wn / Tgn
W1 to Wn represent the weight fraction of the monomer used, and Tg1 to Tgn represent the glass transition temperature of the monomer homopolymer (unit is absolute temperature “K”).

<Other dispersants>
When dispersing the colorant in the colorant carrier, other dispersants other than the resin-type dispersant (B) such as a pigment derivative and a surfactant may be appropriately contained. Since these dispersants have a great effect of preventing re-aggregation of the colorant after dispersion, a color composition obtained by dispersing the colorant in the colorant carrier has good spectral characteristics and viscosity stability.

(Dye derivative)
Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent 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, etc. can be used. These can be used alone or in combination of two or more.

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

(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 can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  The compounding amount of the surfactant 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 (A). When the blending amount of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the added effect, and when it is more than 55 parts by mass, the dispersion may be adversely affected by an excessive dispersant.

<Binder resin (C)>
The binder resin (C) is preferably a 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.

  The weight average molecular weight (Mw) of the binder resin (C) is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. . 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.

  When the binder resin (C) is used as a photosensitive coloring composition for a color filter, a carboxyl group that functions as a colorant adsorption group and an alkali-soluble group during development, a fat that functions as an affinity group for the colorant carrier and the solvent The balance between the group and the aromatic group is important for the dispersibility, penetrability, developability, and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. 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. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin (C) is preferably used in an amount of 20% by weight or more with respect to the total weight of 100% by weight of the colorant (A) because the film formability and various resistances are good. It is preferably used in an amount of 1000% by weight or less because the density is high and good color characteristics can be expressed.

(Thermoplastic resin)
Examples of the thermoplastic resin used for the binder resin (C) include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, Polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin, etc. Is mentioned. Among them, it is preferable to use an acrylic resin.

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

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

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

  Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxy cyclohexyl (meth) acrylates, and these 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 also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

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

[Method (ii)]
As the method (ii), an unsaturated ethylenic 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 unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

  Examples of unsaturated ethylenic monomers 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 (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

(Thermosetting compound)
In the present invention, a thermosetting compound may be further contained in combination with the thermoplastic resin which is a binder resin.

  Examples of the thermosetting compound include epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins, Examples include urea compounds and / or resins, phenol compounds and / or resins, but the present invention is not limited thereto.

<Photopolymerizable monomer (D)>
The photopolymerizable monomer of the present invention contains a urethane-based photopolymerizable monomer (excluding a photopolymerizable monomer having an acid group) (D1), so that it is a thick film used in the COA system. The problem of wrinkle generation at the time of design can be improved.

(Urethane photopolymerizable monomer (D1))
The urethane photopolymerizable compound (D1) of the present invention is a photopolymerizable compound containing at least one ethylenically unsaturated bond and one urethane bond. For example, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional urethane obtained by reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth) acrylate having a hydroxyl group. Examples thereof include urethane acrylate.

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide modified penta (meth) acrylate, dipentaerythritol propylene oxide modified penta (meth) acrylate, dipentaerythritol caprolactone modified penta (meth) acrylate, glycerol acrylate Methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, containing epoxy groups The reaction product of compound and the carboxy (meth) acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

  Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

Moreover, although there is no restriction | limiting in the structure of alcohol, when a polyhydric alcohol is used, since the crosslinking degree of a cured coating film becomes high and coating-film resistance goes up, it is preferable. Examples of the polyhydric alcohol include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, and pentaerythritol.

  These urethane type photopolymerizable monomers (D1) can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

Further, the number of urethane bonds in the urethane photopolymerizable monomer (D1) is preferably 3 or more. Since the number of urethane bonds is 3 or more, it is possible to form hydrogen bonds at multiple points, so that the shrinkage in curing due to light and heat is reduced by improving the crosslink density and Tg of the coating film. Wrinkle generation can be suppressed.

  The content of the urethane-based polymerizable monomer (D1) is 30 to 70% by weight in 100% by weight of the total amount of the photopolymerizable monomer (D). Weight percent is more preferred.

(Photopolymerizable monomer having an acid group (D2))
The present invention is characterized by containing a photopolymerizable monomer (D2) having an acid group as a photopolymerizable monomer. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Among the photopolymerizable monomers having an acid group, a carboxyl group is more preferable from the viewpoint of solubility, stability, and pattern adhesion, and a polyfunctional monomer having two or more functional groups is preferable.

Examples of the photopolymerizable monomer having an acid group include esterified products of free hydroxyl group-containing poly (meth) acrylates of polyhydric alcohol and (meth) acrylic acid and dicarboxylic acids; Examples include esterified products with monohydroxyalkyl (meth) acrylates. Specific examples include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate and the like monohydroxy oligoacrylates or monohydroxy oligomethacrylates And a monoesterified product of free carboxyl group with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids, such as benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And a free carboxyl group-containing oligoester product of monohydroxy monoacrylate or monohydroxy monomethacrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. be able to.

As these commercially available products, Biscoat # 2500P manufactured by Osaka Organic Chemical Co., Ltd., M-5300, M-5400, M-510, M-520 manufactured by Toa Gosei Co., Ltd., and the like can be suitably used.

  These photopolymerizable monomers having an acid group can be used singly or in combination of two or more at any ratio as required.

  Further, the content of the photopolymerizable monomer (D2) having an acid group is 20 to 40% by weight in 100% by weight of the total amount of the photopolymerizable monomer (D). 35% by weight is more preferred.

  Moreover, 10-90 KOH-mg / g is preferable and, as for the acid value of the photopolymerizable monomer (D2) which has an acid group, 20-50 KOH-mg / g is more preferable. In the case of 10 KOH-mg / g or more, the alkali developability becomes better, and the residue other than the pixel formation portion can be reduced. When it is 90 KOH-mg / g or less, it is preferable because defective formation of pixels occurring in the alkali development step can be prevented.

  In the present invention, as the photopolymerizable monomer (D2) having an acid group, from the viewpoint of wrinkle suppression in the COA method, a monomer having a urethane bond by further reacting isocyanates may be used. preferable.

((Meth) acrylic monomer (D3) having 1 to 3 ethylenically unsaturated bonds)
The photopolymerizable monomer (D) of the present invention preferably contains a (meth) acrylic monomer (D3) having 1 to 3 ethylenically unsaturated bonds. The (meth) acrylic monomer (D3) is a (meth) acrylic compound having 1 to 3 unsaturated bonding groups in one molecule, and has 1 to 3 unsaturated bonding groups in one molecule. (Meth) acrylic acid esters of polyfunctional acrylates and / or polyfunctional methacrylates.

  Specifically, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, EO-modified phthalic acid (meth) acrylate, PO-modified phthalic acid (meth) acrylate, acrylated isocyanurate, bis (acrylate) Roxyneopentyl glycol) adipate, polyethylene glycol 200 di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, tetraethylene glycol di (meth) acrylate, EO modified trimethylolpropane triacrylate, PO modified trimethylolpropane tri (meta) ) Acrylate, tripropylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone modified tris (acrylo) Siethyl) isocyanurate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di Examples include (meth) acrylate.

As these commercially available products, KAYARAD R526, KAYARAD PEG400DA, KAYARAD MAND, KAYARD NPGDA, KAYARAD R-167, KAYARAD HX-220, KAYARAD R-551, KAYARAD R712, KAYARAD R-60, KAYARAD R-60, manufactured by Nippon Kayaku Co., Ltd. -684, KAYARAD GPO-303, KAYARAD TMPTA, and M305, M306, M309, M310, M321, M325, M350, M101A manufactured by Toa Gosei Co., Ltd., and Biscoat # 310HP, Biscote # 335HP, Biscote # 700, Biscote manufactured by Osaka Organic Chemical Co., Ltd. # 295, biscoat # 330, biscoat # 360, biscoat #GPT, and the like can be suitably used.

  These (meth) acrylic monomers (D3) having 1 to 3 ethylenically unsaturated bonds can be used alone or in admixture of two or more at any ratio as required. .

  Moreover, it is preferable that the molecular weights of the (meth) acrylic monomer (D3) which has 1-3 ethylenically unsaturated bond groups in 1 molecule are the range of 250-1000. A more preferable range is that the molecular weight of the (meth) acrylic compound is 300 to 600, and the pattern linearity and the residue are good.

The content of the (meth) acrylic monomer (D3) having 1 to 3 ethylenically unsaturated bonding groups in one molecule is 10% by mass to 100% by mass of the total amount of the photopolymerizable monomer (D). 30% by mass is preferable because pattern linearity and residue are improved. More preferably, it is 15-25 mass%.

(Other photopolymerizable monomers)
Moreover, the coloring composition of this invention is a range which does not impair the effect of this invention, the urethane type photopolymerizable monomer (D1), the photopolymerizable monomer (D2) which has an acid group, and ethylenic unsaturated. In addition to the (meth) acrylic monomer (D3) having 1 to 3 bonds, other photopolymerizable monomers may be used in combination. Specifically, various acrylic esters and methacrylic esters deviating from the photopolymerizable monomers (D1) to (D3), (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, penta Examples include erythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

Examples of these commercially available products include KAYARAD R-128H, KAYARAD NPGDA, KAYARAD T-1420 (T), KAYARAD RP-1040, KAYARAD DPHA-12, KAYARAD DPCA-12, and KAYARAD DPCA20 manufactured by Nippon Kayaku Co., Ltd. , KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, Toagosei M-402, M-408, M-7100, M-8030, M-8060, and the like.
<Photopolymerization initiator (E)>
The photopolymerization initiator used in the present invention is a compound that generates active species capable of initiating polymerization of the photopolymerizable monomer by exposure to radiation such as ultraviolet rays, visible rays, far ultraviolet rays, electron beams, and X-rays. is there.

Examples of such a photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 -One, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) Acetophenone series such as methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Compound: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin iso Benzoin compounds such as propyl ether or benzyl dimethyl 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- Thioxanthone compounds such as diethyl thioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, -(P-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4, 6-bis (trichloromethyl) -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, Triazine compounds such as 4-trichloromethyl- (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-ben) Oxime)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound 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 content of the photopolymerization initiator is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the colorant (A), and more preferably 10 to 150 parts by mass from the viewpoint of photocurability and developability. preferable.

(Sensitizer)
Furthermore, the coloring composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as 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, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (E) contained in the colored composition, and 5 to 5 from the viewpoint of photocurability and developability. More preferably, it is 50 mass parts.

<Antioxidant (F)>
The coloring composition for a color filter of the present invention can contain an antioxidant (F). Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. In addition, the antioxidant used in the present invention preferably does not contain a halogen atom.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  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), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2′-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4′-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2′-thio -Bis- (6-tert-butyl-4-methylphenol), 2,5-di-tert-amyl-hydroquinone, 2,2'thiodiethylbis- (3,5-di-tert-butyl-4-hydroxy Phenyl) -propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1- Methyl-cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-) Hydrocinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Examples of hindered amine-based antioxidants include 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-piperidi ) Imino} 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)- Polycondensate with 4-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, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di ( , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy)- Benzene, phosphorous acid ethyl bis (2,4-di-tert- butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As sulfur-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. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2- Hydroxy-4-octadecyloxybenzophenone, 2,2′dihydroxy-4-methoxybenzophenone, 2,2′dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2- Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone and the like can be mentioned. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Examples of the salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

(Amine compounds)
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by mass in 100% by mass of the solid content of the coloring composition because the spectral characteristics and sensitivity are good.

<Organic solvent>
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and permeated in the coloring agent carrier, and is applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to make it easy to form, it is preferable to contain an organic solvent. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl- 1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, N, N-dimethyl Acetamide, N, N-dimethylformamide, n-butyl alcohol, n-butyl Benzene, n-propyl acetate, o-xylene, o-diethylbenzene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol Monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl Ether, ethylene glycol Dimonomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene Glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl Chill ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol Monopropyl ether, propylene glycol monomethyl ether, methoxypropyl acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate , Dibasic acid Le, and the like.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the colorant, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, methoxypropyl acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate It is preferable to use glycol acetates such as alcohol, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  Moreover, since an organic solvent can adjust a coloring composition to appropriate viscosity and can form the colored film of the target uniform film thickness, it is 500-4000 parts mass part with respect to 100 mass parts of colorants (A). It is preferable to use in.

(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 coloring composition for a color filter 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 content of the leveling agent is preferably 0.003 to 0.5% by mass in 100% by mass of the total mass 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.

(Curing agent, curing accelerator)
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Of these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivatives bicyclic amidine compounds and salts thereof (eg imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl) -4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example tri Phenylphosphine ), Guanamine compounds (for example, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino) -S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) Can do. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 mass parts is preferable with respect to 100 mass parts of thermosetting resins.

(Other additive components)
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

(Storage stabilizer)
Examples of the storage stabilizer include organic acids such as lactic acid and oxalic acid and methyl ether thereof, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant (A).

(Adhesion improver)
Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver 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 (A) in the coloring composition.

(Multifunctional thiol)
The coloring composition of the present invention may contain a compound having two or more thiol (SH) groups as the polyfunctional thiol.
By using a polyfunctional thiol together with a photopolymerization initiator, a thiyl radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation, so the resulting colored composition is highly sensitive. It becomes. 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, and ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibu Arylamino) -4,6-dimercapto--s- triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tris thiopropionate, pentaerythritol tetrakis thiopropionate.

These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types.
The content of the polyfunctional thiol is preferably 0.05 to 100 parts by mass, and more preferably 1.0 to 50.0 parts by mass with respect to 100 parts by mass of the colorant (A). When the polyfunctional thiol content is less than 0.05 parts by mass, the effect of the chain transfer agent is small, and even when the content is more than 100 parts by mass, the polymerization initiation function is not improved, and developability, adhesion, and the like become insufficient. .

(Method for producing colored composition)
The coloring composition of the present invention comprises a colorant (A) in a colorant carrier such as a binder resin (C) and / or a solvent, preferably together with a dispersion aid, a kneader, a two-roll mill, a three-roll mill. And finely dispersed using various dispersing means such as a ball mill, 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.
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.

  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 includes 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.

(Removal of coarse particles)
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. Coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 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)
The color filter of the present invention is a color filter comprising at least one filter segment formed from the coloring composition for a color filter of the present invention.
The color filter comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the at least one filter segment comprises the coloring composition for a color filter of the present invention. It is preferable to form by using.

(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 filter segments by printing methods allows patterning by simply printing and drying the colored composition prepared as a printing ink, making it a low cost and excellent mass productivity as a color filter manufacturing method. Yes. 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. Further, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted with a dispersant or extender pigment.

  The coloring composition of the present invention is applied on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating so that the dry film thickness is 0.2 to 5 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. Then, after dipping in a potassium hydroxide 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.

  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 material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, etc. 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.

If the black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast of the display panel can be further increased. 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 a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the panel can be increased and the luminance can be improved.
On the color filter of the present invention, an overcoat film or a transparent conductive film is formed 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.

  Moreover, the measuring method of the average primary particle diameter of a pigment, the weight average molecular weight (Mw) of resin, and the measuring method of the acid value of resin are as follows.

(Average primary particle diameter of pigment)
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission electron microscope (TEM). 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 primary pigment particles. Next, with respect to 100 or more pigment particles, the volume (weight) of each particle is obtained by approximating the obtained particle size cube, and the volume average particle size is taken as the average primary particle size and shown in Table 1.

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

(Amine number of resin-type dispersant (mgKOH / g))
The amine value is a value obtained by converting the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 into a solid content.

<Manufacture of refined pigments>
(Red refined pigment (PR-1))
Red pigment C.I. I. Pigment Red 254 (PR254) ("Irga Fore Red B-CF" manufactured by BASF) 152 parts, 8 parts of a pigment derivative of the chemical formula (1), 1600 parts of sodium chloride, and 190 parts of diethylene glycol 1 gallon kneader (Inoue Seisakusho) And kneaded at 60 ° C. for 10 hours. Next, the mixture is poured into 3 liters of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and solvent, and then 80 It was dried for 1 day at 0 ° C. to obtain a red refined pigment (PR-1). The average primary particle diameter of the obtained pigment was 35 nm.

Chemical formula (1)

(Red refined pigment (PR-2))
Red pigment C.I. I. 500 parts of Pigment Red 177 (PR177) (“chromophthaled red A2B” manufactured by BASF), 3500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. . Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a red-refined pigment (PR-2) was obtained. The average primary particle diameter of the obtained pigment was 30 nm.

(Blue refined pigment (PB-1))
Blue pigment C.I. I. Pigment Blue 15: 6 (PB15: 6) (“Lionol Blue ES” manufactured by Toyocolor Co., Ltd.) 500 parts, 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), 120 The mixture was kneaded for 12 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a blue refined pigment (PB-1) was obtained. The average primary particle diameter of the obtained pigment was 25 nm.

(Purple refinement treatment pigment (PV-1))
Dioxazine-based purple pigment C.I. I. 500 parts of Pigment Violet 23 (PV23) (“Fast Violet RL” manufactured by Clariant), 2500 parts of sodium chloride, and 250 parts of polyethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho). The mixture was kneaded at 120 ° C. for 12 hours. Next, this mixture is poured into about 5 liters of warm water, heated to about 70 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, then filtered and washed to remove sodium chloride and diethylene glycol, Drying at 80 ° C. for a whole day and night gave a purple finely treated pigment (PV-1). The average primary particle diameter of the obtained pigment was 30 nm.
(Green refined 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 with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine green pigment (PG-1) was obtained. The average primary particle diameter of the obtained pigment was 30 nm.

(Green refined pigment (PG-2))
To a three-necked flask, add 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following formula (2), 500 parts of N-methylpyrrolidone, and 13.9 parts of diphenyl phosphate, and heat to 90 ° C. The reaction was allowed for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and then dried to obtain PG-2 as a phthalocyanine pigment. The average primary particle diameter of the obtained pigment was 30 nm.

(Green refined pigment (PG-3))
In a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following formula (2), and 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred. The reaction was carried out at 20 ° C. for 6 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added and stirred at 80 ° C. for 1 hour. Thereafter, the mixture was collected by filtration, washed with water, and dried to obtain a pigment having an average of 10.1 bromine atoms substituted on the phthalocyanine ring.
Next, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having an average of 10.1 bromine atoms substituted on the resulting phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added to a three-necked flask. The mixture was heated to 0 ° C. and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and then dried to obtain PG63-1, which is a phthalocyanine pigment. The average primary particle diameter of the obtained pigment was 30 nm.

Formula (2)

(Yellow refined pigment (PY-1))
Yellow pigment C.I. I. 200 parts of Pigment Yellow 138 (BASF “PAliotol Yellow L 0962 HD”), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the 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. , PY-1 was obtained. The average primary particle diameter of the obtained pigment was 30 nm.

(Yellow refined pigment (PY-2))
To 200 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 150 parts of 2,3-naphthalenedicarboxylic anhydride and 154 parts of benzoic acid were added, heated to 180 ° C., and stirred for 4 hours. Further, after cooling to room temperature, the reaction mixture was added to 5440 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 116 parts of a quinophthalone compound (a) represented by the following formula (3). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (a).

Formula (3) Quinophthalone Compound (a)

  Subsequently, using quinophthalone compound (a) as a raw material, compound (4) was obtained according to the synthesis method described in JP-A-2008-81666.

Formula (4)

To 300 parts of methyl benzoate, 100 parts of compound (4), 108 parts of tetrachlorophthalic anhydride and 143 parts of benzoic acid were added, heated to 180 ° C. and reacted for 4 hours. The formation of the quinophthalone compound (b) and the disappearance of the starting compound (4) were confirmed by TOF-MS. Furthermore, after cooling to room temperature, the reaction mixture was added to 3510 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 120 parts of a quinophthalone compound (b) represented by the following formula (5). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (b).

Formula (5) Quinophthalone Compound (b)

  Subsequently, 100 parts of the obtained quinophthalone compound (b), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of refined pigment (PY-2) were obtained. The average primary particle size was 40 nm.

<Production of resin-type dispersant solution>
(Production of resin-type dispersant solution (B-1))
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of methoxypropyl acetate and heated to 110 ° C. while purging with nitrogen. The reaction vessel was charged with 38 parts of dimethylaminoethyl methacrylate, 162 parts of methyl methacrylate, and 6 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and stirred until uniform. Thereafter, the reaction was carried out at the same temperature for 3 hours. In this way, a resin type dispersant solution having an amine value per solid content of 67.8 mg KOH / g and a weight average molecular weight of 9000 (Mw) was obtained.
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 non-volatile content. Then, methoxypropyl acetate was added so that the non-volatile content was 20% by mass, and the resin-type dispersant was added. A solution (B-1) was obtained.

(Production of resin-type dispersant (B-2 to 7))
Resin-type dispersant solutions (B-2 to 7) were synthesized in the same manner as the resin-type dispersant solution (B-1) except that the composition and the amount (parts by mass) shown in Table 1 were changed.

<Method for producing binder resin solution>
(Production of binder resin solution (C-1))
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Was added to prepare a binder resin solution (C-1). The weight average molecular weight (Mw) was 26000.

<Method for producing pigment dispersion>
(Red pigment dispersion (P-R1))
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 red pigment dispersion (P-R1) was produced.

Red refined pigment (PR-1): 20.0 parts Resin type dispersant (B-1): 5.0 parts Binder resin (C-1): 25.0 parts Solvent
PGMAC (methoxypropyl acetate): 50.0 parts

(Red pigment dispersion (P-R2), blue pigment dispersion (P-B1), purple pigment dispersion (P-V1), green pigment dispersion (P-G1-9), yellow pigment dispersion (P- Y1-2))
A red pigment was prepared in the same manner as the red pigment dispersion (P-R1) except that the colorant, resin-type dispersant, acrylic resin solution, and solvent were changed to the compositions and blending amounts (parts by mass) shown in Table 3. Dispersion (P-R2), blue pigment dispersion (P-B1), purple pigment dispersion (P-V1), green pigment dispersion (P-G1-9), yellow pigment dispersion (P-Y1-2) ) Was produced.

<Method for producing photopolymerizable monomer (D)>
(Production of urethane photopolymerizable monomer 1 (D-1))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 5.0 g trimethylolpropane, 18.8 g hexamethylene diisocyanate, 51.3 g pentaerythritol triacrylate, propylene glycol monomethyl ether acetate 75. 1 g, 0.02 g of methylhydroquinone, and then 0.12 g of dioctyltin were charged as a catalyst, and the temperature was raised to 100 ° C. After reacting at 100 ° C. for 3 hours and confirming disappearance of the isocyanate peak by IR, the reaction was terminated by cooling to room temperature. Thereafter, the solvent was removed from the reaction solution under reduced pressure using an evaporator to obtain a colorless and transparent urethane-based photopolymerizable monomer 1 (D-1) having a weight average molecular weight MW of 7,600.

(Production of urethane photopolymerizable monomer 2 (D-2))
In a 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 5.0 g of 2-ethyl-2-methyl-1,3-propanediol, 18.8 g of hexyl isocyanate, pentaerythritol triacrylate 51 .3 g, 75.1 g of propylene glycol monomethyl ether acetate, 0.02 g of methylhydroquinone, and then 0.12 g of dioctyltin as a catalyst were added and the temperature was raised to 100.degree. After reacting at 100 ° C. for 3 hours and confirming disappearance of the isocyanate peak by IR, the reaction was terminated by cooling to room temperature. Then, the solvent was removed from this reaction solution under reduced pressure by using an evaporator to obtain a colorless and transparent urethane-based photopolymerizable monomer 2 (D-2) having a weight average molecular weight MW 4,800.

(Production of urethane photopolymerizable monomer 3 (D-3))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 5.0 g of trimethylolpropane, 18.8 g of hexyl isocyanate, 51.3 g of pentaerythritol triacrylate, 75.1 g of propylene glycol monomethyl ether acetate Then, 0.02 g of methylhydroquinone and then 0.12 g of dioctyltin were charged as a catalyst, and the temperature was raised to 100 ° C. After reacting at 100 ° C. for 3 hours and confirming disappearance of the isocyanate peak by IR, the reaction was terminated by cooling to room temperature. Thereafter, the solvent was removed from the reaction solution under reduced pressure using an evaporator to obtain a colorless and transparent urethane-based photopolymerizable monomer 3 (D-3) having a weight average molecular weight MW of 7,000.

(Production of photopolymerizable monomer 4 having an acid group (D-4))
A 4-neck flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 10.0 g of trimethylolpropane, 11.3 g of tetrahydrophthalic anhydride, 0.1 g of dimethylbenzylamine (Wako Pure Chemical Industries, Ltd.) Then, 21.3 g of propylene glycol monomethyl ether acetate was charged and the temperature was raised to 120 ° C. The mixture was stirred at 120 ° C. for 2 hours and cooled to 80 ° C. Next, 0.05 g of methylhydroquinone, 21.3 g of hexamethylene isocyanate, 68.4 g of pentaerythritol triacrylate, and 93.5 g of propylene glycol monomethyl ether acetate were charged, and then 0.23 g of dioctyltin was charged as a catalyst, and the temperature was raised to 100 ° C. did. After reacting at 100 ° C. for 3 hours and confirming disappearance of the isocyanate peak by IR, the reaction was terminated by cooling to room temperature. Thereafter, the solvent was removed from the reaction solution under reduced pressure using an evaporator to obtain a photopolymerizable monomer 4 (D-4) having a colorless and transparent acid group having a weight average molecular weight MW of 7,200.

<Number of urethane bonds of photopolymerizable monomer (D), presence / absence of acid group, and number of unsaturated functional groups>
Table 4 shows the number of urethane bonds, the presence or absence of acid groups, and the number of unsaturated functional groups in the photopolymerizable monomer (D) used.

<Photopolymerizable initiator (E)>
"Irgacure 907" manufactured by BASF

<Antioxidant (F)>
Antioxidant (F-1): Hindered phenol antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate Antioxidant (F-2): Phosphorus antioxidant tris [2,4-di- (tert) -butylphenyl] phosphine

[Example 1]
(Coloring composition (R-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a colored composition (R-1).

Pigment dispersion (P-R1): 30.0 parts Pigment dispersion (P-R2): 10.0 parts Binder resin solution (C-1): 5.0 parts Urethane photopolymerizable compound (D1): 6 0.0 part of photopolymerizable monomer 1 (D-1)
Photopolymerizable compound having acid group (D2): 4.0 parts Photopolymerizable monomer 4 (D-4)
(Meth) acrylic compound (D3): 2.0 parts "Aronix M-309" (D-3) manufactured by Toa Gosei Co., Ltd.
Photopolymerizable initiator (E): 2.0 parts “Irgacure 907” manufactured by BASF
Antioxidant (F): 1.0 part Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (F-1)
Solvent: 40.0 parts Methoxypropyl acetate (PGMAC)

[Examples 2 to 19, Comparative Examples 1 to 5]
(Coloring composition (B-1, G-1-22)
After stirring and mixing the mixture shown in Table 5 and the blending amount (parts by weight) uniformly, the mixture was filtered through a 1 μm filter and the same as the colored composition (R-1) of Example 1, The coloring composition (B-1, G-1-22) of Examples 2-19 and Comparative Examples 1-5 was obtained.

<Evaluation of coloring composition>
The test of the coating film of the obtained coloring composition (R-1, B-1, G-1-22) was done by the following method. The results of the test are shown in Table 6.

(Wrinkle evaluation)
About the obtained coloring composition (R-1, B-1, G-1-22), a coloring composition was apply | coated so that it might become a film thickness of 3.4 micrometers on a 100 mm x 100 mm and 0.7 mm glass substrate. Then, UV exposure was performed under a condition of 40 mJ / cm ² through a mask having a predetermined pattern. Thereafter, an alkali developer was sprayed by spraying to remove the uncured portion and form a desired pattern. About the obtained coating film, the heat processing (post-baking) were performed for 20 minutes in 230 degreeC oven, and the presence or absence of wrinkles was confirmed with the microscope (OLYMPUS Optical Co., Ltd. "BX-51"). In the evaluation, a square pixel of 400 μm × 400 μm was observed with a microscope and evaluated as follows. The film thickness of the coating film was measured using Dektak 8 (manufactured by Nippon Vacuum Technology Co., Ltd.).

○: No wrinkle △: Generated on the pattern end face ×: Generated on the entire pattern surface

(Through hole (TH) residue evaluation)
About the obtained coloring composition (R-1, B-1, G-1-22), a coloring composition was apply | coated so that it might become a film thickness of 3.4 micrometers on a 100 mm x 100 mm and 0.7 mm glass substrate. Then, UV exposure was performed under a condition of 40 mJ / cm ² through a mask having a predetermined pattern. Thereafter, an alkali developer was sprayed by spraying to remove the uncured portion and form a desired pattern. About the obtained coating film, the heat processing (post-baking) were performed for 20 minutes in 230 degreeC oven, and the presence or absence of the residue was confirmed with the microscope (OLYMPUS Optical Co., Ltd. "BX-51"). In the evaluation, the remaining area of the residue in the TH pattern having a radius of 15 μm was calculated and evaluated as follows. The film thickness of the coating film was measured using Dektak 8 (manufactured by Nippon Vacuum Technology Co., Ltd.).

◎: No residue ○: Less than 50 μm ² Δ: 50 μm ² or more and less than 150 μm ²
×: 150 μm ² or more

(Evaluation of membrane shrinkage)
In the 400 μm photomask portion of the formed filter segment, after heat treatment (post-bake) for 20 minutes in a 230 ° C. oven, the pattern film thickness after additional post-bake for 180 minutes in a 240 ° C. oven is measured and heated. The degree of film thickness change was calculated and evaluated. The evaluation method and rank are as follows.

Film thickness change in heat treatment = film thickness after heat treatment for 180 minutes in 240 ° C oven / film thickness after heat treatment for 20 minutes in 230 ° C oven (%)

◯: The rate of change in film thickness is 95% or more and good Δ: The rate of change in film thickness is 90% or more and less than 95% ×: The rate of change in film thickness is less than 90%

(Pattern linearity evaluation)
About the obtained coloring composition (R-1, B-1, G-1-22), a coloring composition was apply | coated so that it might become a film thickness of 3.4 micrometers on a 100 mm x 100 mm and 0.7 mm glass substrate. Then, UV exposure was performed under a condition of 40 mJ / cm ² through a mask having a predetermined pattern. Thereafter, an alkali developer was sprayed by spraying to remove the uncured portion and form a desired pattern. About the obtained coating film, heat processing (post-baking) were performed for 20 minutes in 230 degreeC oven, and the presence or absence of the omission of the pattern of a pixel was confirmed with the microscope (OLYMPUS Optical Co., Ltd. "BX-51"). In the evaluation, the number of missing rectangular pixel patterns of 1000 μm × 100 μm was calculated and evaluated as follows. The film thickness of the coating film was measured using Dektak 8 (manufactured by Nippon Vacuum Technology Co., Ltd.).

○: No missing pattern Δ: 1 to 10 pieces / 10 ⁵ μm ²
×: 11 or more / 10 ⁵ μm ²

(Resist stability evaluation)
About the obtained photosensitive coloring composition, the viscosity after the initial stage and 40 degreeC seven days was measured, and the viscosity increase degree with respect to an initial stage viscosity was calculated and evaluated. The rank of evaluation is as follows.

◯: Viscosity increase rate is 5% or less and good Δ: Viscosity increase rate is greater than 5% and 10% or less

  As shown in Table 6, the colorant (A) of the present invention, the resin-type dispersant (B), the binder resin (C), the urethane photopolymerizable monomer (D1), and the photopolymerization having an acid group. By using the coloring composition containing the polymerizable monomer (D2), the generation of wrinkles, the through-hole residue, and the film thickness change were suppressed even in the thick film as in the COA system.

  Among them, the number of urethane bond sites of the urethane photopolymerizable monomer (D1) is 3 or more, and the photopolymerizable monomer (D2) having an acid group has a urethane bond site and is a carboxyl group. Is a polyfunctional acrylate compound having a group, the hindered phenol type is contained in the antioxidant (F), the Tg of the resin-type dispersant (B) is 50 to 70 ° C., and the amine value is 50 to 150 mgKOH / The coloring composition characterized by g was particularly free from wrinkles and TH residues, and was excellent in film shrinkage, pattern linearity, and resist stability.

Therefore, according to the present invention, it was possible to produce a high-quality color filter with good linearity, which is free from wrinkles and through-hole residues in the COA method, has a small change in film thickness in the panel process.
Thereby, it was confirmed that a color filter excellent in resolution and a liquid crystal display device were obtained.

Claims (8)

  A color composition for a color filter comprising a colorant (A), a resin-type dispersant (B), a binder resin (C), a photopolymerizable monomer (D), and a photopolymerization initiator (E). The content of the colorant (A) is 20 to 30% by weight in the total solid content of the colored composition, and the photopolymerizable monomer (D) is a urethane-based photopolymerizable monomer (light having an acid group). A coloring composition for a color filter comprising (D1) excluding a polymerizable monomer) and a photopolymerizable monomer (D2) having an acid group.   2. The color filter according to claim 1, wherein the urethane photopolymerizable monomer (D1) contains a photopolymerizable monomer having 3 or more urethane bonds in one molecule. Coloring composition.   3. The photopolymerizable monomer (D2) having an acid group contains a photopolymerizable monomer having a carboxyl group and having a urethane bond. Coloring compositions for color filters.   Furthermore, the photopolymerizable monomer (D) is a (meth) acrylic monomer (urethane photopolymerizable monomer or photopolymerizable acid group having 1 to 3 ethylenically unsaturated bonds). The coloring composition for a color filter according to any one of claims 1 to 3, further comprising (D3) excluding a monomer.   Furthermore, antioxidant (F) is contained, The coloring composition for color filters of any one of Claims 1-4 characterized by the above-mentioned.   The coloring composition for a color filter according to claim 5, wherein the antioxidant (F) contains a hindered phenol-based antioxidant.   The resin type dispersant (B) contains a resin type dispersant having a glass transition temperature (Tg) of 30 to 100 ° C and an amine value of 50 to 150 mgKOH / g. The coloring composition for color filters of any one of Claims 1. A color filter comprising a filter segment formed using the colored composition for a color filter according to claim 1 on a substrate.