JP2018163283A - Photosensitive coloring composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive coloring composition for a color filter having excellent developability and pattern adhesion even when a dye is used as a colorant, and having high brightness and high contrast ratio. The subject is a photosensitive coloring composition containing a blue dye (A), a binder resin (B), a photopolymerization initiator (C), and a photopolymerizable monomer (D). The solution is solved by a photosensitive coloring composition characterized in that the photopolymerizable monomer (D) contains a polyfunctional urethane acrylate (D1). [Selection diagram] None

Description

  The present invention relates to a photosensitive color composition for a color filter used in the production of a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color comprising a filter segment formed using the same. It relates to filters.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. Other typical liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and electrolysis is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) method for vertically aligning nematic liquid crystal with optical properties, and Optical Convencence Bend (OCB) method in which the optical axes of uniaxial retardation films are orthogonal to each other to perform optical compensation Etc., and each has been put to practical use.

  A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. Increasing demands are being made.

  A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

As a method of forming a color filter, a color resist is formed by mixing and preparing a photosensitive agent or an additive in a resin in which pigment particles as a colorant are dispersed in a resin, and this color resist is formed on a substrate by a spin coater or the like. A method of forming a coating film with a coating apparatus is generally used. Then, a method of obtaining pixels of each color by performing selective exposure through a photomask with an aligner, a stepper, etc., developing with an alkali developer to dissolve and remove the unexposed portions, and performing thermosetting (for example, (See Patent Documents 1 and 2). This is a method for producing a color filter by repeating this operation.

  In general, in a color liquid crystal display device, a transparent electrode for driving liquid crystal is formed on a color filter by vapor deposition or sputtering. In order to sufficiently obtain the performance of these transparent electrodes, it is necessary to form them at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, as a method for producing a color filter, a method called a pigment dispersion method in which a pigment having excellent heat resistance is used as a colorant has become the mainstream.

  Quality items required for the color filter include brightness and contrast ratio. When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light must leak or be transmitted (ON) In other words, the transmitted light is attenuated in the state), resulting in a blurred screen. Therefore, in order to realize a high-quality liquid crystal display device, high contrast is indispensable.

  If a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights as light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend. Furthermore, as described above, since the color liquid crystal device has been used for televisions, personal computer monitors, and the like, the demand for high reliability and high lightness and contrast for color filters has also increased.

  In recent years, in order to realize a high contrast ratio and high brightness that cannot be achieved with a pigment, a technique using a dye as a colorant has been proposed, as in Patent Document 1. However, the dye is generally soluble in a solvent or a polymer, and in a colored composition using the dye, an exposed portion remaining as a pattern is also peeled off in a step of developing with an alkaline developer when forming a color filter. There is a problem.

JP-A-2-144502 JP-A-3-53201

An object of the present invention is to provide a coloring composition for a color filter which is excellent in developability and pattern adhesion even when a dye is used as a colorant, and has high brightness and high contrast ratio.

  As a result of intensive studies to solve the above problems, the inventors of the present invention include a blue dye (A) and a polyfunctional urethane acrylate (D1), thereby achieving high brightness, a high contrast ratio, and a high level. It has been found that the developability and pattern adhesion are achieved, and the present invention has been made.

That is, the present invention is a photosensitive coloring composition comprising a blue dye (A), a binder resin (B), a photopolymerization initiator (C), and a photopolymerizable monomer (D), wherein the photopolymerization The photosensitive monomer (D) contains a polyfunctional urethane acrylate (D1).

The present invention also relates to the above photosensitive coloring composition, wherein the blue dye (A) is a triarylmethane dye (A1).

Moreover, this invention relates to the said photosensitive coloring composition characterized by including the compound that polyfunctional urethane acrylate (D1) has three or more photopolymerizable functional groups in 1 molecule.

The present invention also provides the photosensitive coloring, wherein the number of urethane groups of the polyfunctional urethane acrylate (D1) is 1.5 mmol / g or more and the number of double bond groups is 4.0 mmol / g or more. Relates to the composition.

The present invention also provides the photosensitive coloring composition, wherein the content of the photopolymerizable monomer (D) is 7 to 50% by weight based on the solid content weight of the coloring composition. About.

Moreover, this invention relates to the said photosensitive coloring composition characterized by the polyfunctional urethane acrylate (D1) having an acid group.

The present invention also relates to a color filter comprising a filter segment formed from the photosensitive coloring composition on a substrate.

Hereinafter, 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”.

<Blue dye>
Examples of the dye used in the photosensitive coloring composition of the present invention include triarylmethane dyes, flavin dyes, auramine dyes, safranine dyes, phloxine dyes, and methylene blue dyes.
Of these, a triarylmethane dye or a methylene blue dye is preferably used, more preferably a triarylmethane dye, in terms of good color developability.

  Among these, those exhibiting blue, purple, magenta, and cyan are preferable. I. Dyes classified as basic blue are preferred.

  Specifically, examples of the triarylmethane dye include C.I. I. Basic Violet 1 (Methyl Violet), 3 (Crystal Violet), 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 26 (Victoria Blue B conc.), C.I. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green) and the like. Among them, C.I. I. Basic blue 7 is preferably used.

  Examples of methylene blue dyes include C.I. I. Basic Blue 9 (Methylene Blue FZ, Methylene Blue B), 25 (Basic Blue GO), 24 (New Methylene Blue NX) and the like.

The triarylmethane dye will be described in detail below.
<Triarylmethane dye>
Triarylmethane dyes are colored by the formation of a quinone structure by oxidation of NH ₂ or OH groups located in a para position relative to the central carbon.
Depending on the number of NH ₂ and OH groups, it can be divided into the following three types. Among them, the form of a triaminoarylmethane-based dye is preferable in terms of good blue, red, and green coloring.
a) Diaminotriarylmethane dyes b) Triaminotriarylmethane dyes c) Rosolic acid dyes having an OH group Triaminotriarylmethane dyes and diaminotriarylmethane dyes have clear colors, It is preferable because it has better sunlight fastness than those. Further, diphenylnaphthylmethane dyes and / or triarylmethane dyes are preferable.

  The blue triarylmethane dye has spectral characteristics with high transmittance at 400 to 440 nm.

  That is, triarylmethane basic dyes and methylene blue basic dyes are preferable. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 9 (Methylene Blue FZ, Methylene Blue B), 24 (New Methylene Blue NX), 25 (Basic) Blue GO), 26 (Victoria Blue B conc.) And the like.

  Further, as a complementary color of the blue pixel, a safranin-based basic dye or a phloxine-based basic dye exhibiting red or magenta color can also be used.

<Other colorants>
The coloring composition for a color filter of the present invention can further contain other colorant in addition to the blue dye (A). Other colorants are preferably blue pigments, purple pigments or dyes, and red dyes.

  When other colorants are contained, the content of the other colorants is preferably 1 to 300 parts by weight based on 100 parts by weight of the blue dye (A). More preferably, it is 25-200 weight part, More preferably, it is 50-100 weight part. When the amount of the other colorant added is 1 part by weight or more and 300 parts by weight or less, the reproducible chromaticity region is widened, which is preferable.

  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.

  In particular, when a colored composition is used for a blue filter segment, the spectral spectrum has a high transmittance in the vicinity of 425 to 500 nm having a characteristic peak of many backlights by using a blue pigment in combination. This is preferable because a high brightness can be obtained as a blue filter segment rather than a colorant combining a conventional blue pigment and other pigments.

  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 purple dyes include C.I. I. Acid Violet 1, 2, 3, 4, 5, 5: 1, 6, 7, 7: 1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, etc. Is mentioned.
In addition, C.I. I. Direct violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97, etc. can also be used.

Examples of red dyes include C.I. I. Acid Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25: 1, 26, 26: 1, 26: 2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76: 1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131, 132, 133, 134, 135, 37, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 249, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388 and the like.
In addition, C.I. I. Direct Red 1, 2, 2: 1, 4, 5, 6, 7, 8, 10, 10: 1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26: 1, 28, 29, 31, 33, 33: 1, 34, 35, 36, 37, 39, 42, 43, 43: 1, 44, 46, 49, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67: 1, 68, 72, 72: 1, 73, 74, 75, 77, 78, 79, 81, 81: 1, 85, 86, 88, 89, 90, 97, 100, 101, 101: 1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 122: 1, 124, 125, 127, 127: 1, 127: 2, 128, 129, 130, 132, 134, 135, 136, 137, 1 8, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238, etc. can also be used.

Examples of combinations of colorants include C.I. I. Pigment Blue 15: 6 / C.I. I. Pigment violet 23, C.I. I. Pigment Blue 15: 3 / C.I. I. Pigment violet 23, C.I. I. Pigment Blue 15: 6 / C.I. I. Pigment violet 23 / C.I. I. Acid Red 289, C.I. I. Pigment Blue 15: 6 / C.I. I. Pigment violet 23 / C.I. I. Acid Red 52, C.I. I. Pigment Blue 15: 6 / C.I. I. Acid Red 289, C.I. I. Pigment Blue 15: 6 / C.I. I. Acid Red 52 and the like can be mentioned, but the effect of the present invention is not limited to these.
In order to achieve both solvent resistance and sensitivity, from the viewpoint of obtaining an appropriate ultraviolet transmittance of the coating film, the ratio of the purple colorant or the red colorant to the blue colorant is based on 100 parts by weight of the blue colorant. 120 parts by weight or less is preferable, and 100 parts by weight or less is more preferable.

<Miniaturization of pigment>
When the colorant used in combination with the coloring composition of the present invention is a pigment, it can be refined by a salt milling treatment or the like. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. If the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult. If the thickness is larger than 90 nm, sufficient spectral characteristics may not be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

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

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts 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 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts 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 parts by weight with respect to 100 parts by weight of the pigment.

  The content of the colorant is preferably in the range of 10 to 45% by weight, more preferably in the range of 15 to 40% by weight, based on the solid content of the color filter coloring composition. If it is this range, since the color reproducibility at the time of using a color filter in a general film thickness range (about 1.0-3.0 micrometers) is favorable, it is preferable.

<Binder resin>
The colored composition for a color filter of the present invention further contains a binder resin. The binder resin can be used as a binder resin that disperses, dyes, or penetrates a colorant.
By including a resin, the dispersion stability of the colored composition of the present invention becomes better, and when a colored pixel layer of a color filter is formed using the colored composition for a color filter, there is little pigment aggregate and developability. Further, a colored pixel layer having a good pattern shape can be obtained.

The binder resin 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.
Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.
In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. This is more preferable because the photocuring density is increased, and as a result, resistance is improved.

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

Examples of the alkali-soluble resin obtained by copolymerizing 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 into which an ethylenically unsaturated double bond has been introduced by the following methods (i) and (ii).

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

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 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. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

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

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

  Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Polyether mono (meth) acrylates 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 ethylenically unsaturated 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.

  The weight average molecular weight (Mw) of the resin is preferably in the range of 5,000 to 100,000, more preferably in the range of 6,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the resin is used as a photosensitive coloring composition for a color filter, it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g from the viewpoints of dispersibility, penetrability, developability, and resistance of the pigment. 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.

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  The resin is preferably used in an amount of 20 parts by weight or more with respect to 100 parts by weight of the colorant because the film formability and various resistances are good, and since the colorant concentration is high and good color characteristics can be expressed. It is preferably used in an amount of 1000 parts by weight or less.

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

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Or benzoin compounds such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ' Benzophenone compounds such as 1,4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethyl Thioxanthone compounds such as thioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-me Xylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxy) )], 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 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<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 Nobu Okawara et al., “Dye Handbook” (1986, Kodansha), Nobu Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Chusaburo 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 weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Photopolymerizable monomer>
The photopolymerizable monomer includes a monomer or oligomer that is cured by ultraviolet rays or heat to generate a transparent resin. The photopolymerizable monomer of the present invention is characterized by containing a polyfunctional urethane acrylate (D1). By containing polyfunctional urethane acrylate, it can be set as the photosensitive coloring composition excellent in pattern adhesiveness.
The polyfunctional urethane acrylate (D1) can be obtained, for example, by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate or reacting a polyfunctional alcohol with a (meth) acrylate having an isocyanate group.

The polyfunctional urethane acrylate (D1) preferably has three or more photopolymerizable functional groups in one molecule from the viewpoint of high sensitivity.
The polyfunctional urethane acrylate having three or more photopolymerizable functional groups in one molecule is, for example, a compound having two or more photopolymerizable functional groups and one hydroxyl group in one molecule, and two or more. It can be obtained by reacting a compound having one isocyanate group or reacting a compound having one photopolymerizable group and one hydroxyl group in one molecule with a compound having three or more isocyanate groups. it can.

Moreover, it is preferable from a developable viewpoint that polyfunctional urethane acrylate (D1) uses what has an acid group. The urethane acrylate having an acid group is, for example, a reaction of a compound having a mercapto group and a carboxyl group with the (meth) acryloyl group of the polyfunctional urethane acrylate (D1), or a (meth) acrylate having a hydroxyl group in the polyfunctional isocyanate. It can be obtained by reacting a hydroxy acid.

<(Meth) acrylate having a hydroxyl group>
As the (meth) acrylate having a hydroxyl group, a compound having one photopolymerizable group and one hydroxyl group in one molecule such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate;
Compounds having two photopolymerizable groups and one hydroxyl group in one molecule, such as trimethylolpropane di (meth) acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, and the like;
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, Compounds having three or more photopolymerizable groups and one hydroxyl group in one molecule such as dipentaerythritol caprolactone-modified penta (meth) acrylate;
A compound having one photopolymerizable group and two hydroxyl groups in one molecule such as glycerin mono (meth) acrylate;
Examples thereof include compounds having two or more photopolymerizable groups and two hydroxyl groups in one molecule such as a reaction product of an epoxy group-containing compound and (meth) acrylic acid.

<Polyfunctional isocyanate>
Examples of the polyfunctional isocyanate include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and bifunctional or higher functional isocyanate compounds such as burettes, nurate bodies, and adducts.

Examples of the aromatic diisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6- Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-Triphenylmethane triisocyanate, ω, ω'-diisocyanate-1,3-dimethylbenzene (also known as XDI, m-xylylene diisocyanate), ω, ω'-diisocyanate-1,4-dimethylbenzene (other : P-xylylene diisocyanate), omega, omega .'- diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethyl xylylene diisocyanate.

Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene diisocyanate. , Dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like.

Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI, isophorone diisocyanate), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1, Examples include 4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane and the like.

Examples of burettes include hexamethylene diisocyanate burettes (product name “Sumijour N-75”, manufactured by Sumika Bayer Urethane Co., Ltd .; product names “Duranate 24A-90CX”, manufactured by Asahi Kasei Chemicals).

Examples of nurate bodies include hexamethylene diisocyanate nurate (product name “Sumijour N-3300”, manufactured by Sumika Bayer Urethane Co., Ltd.), isophorone diisocyanate nurate (product name “Desmodur Z-4370”, Sumika). Bayer Urethane Co., Ltd., tolylene diisocyanate nurate (product name “Coronate 2030”, manufactured by Nippon Polyurethane Co., Ltd.), and the like.

Examples of adducts include bifunctional or higher isocyanate compounds obtained by reacting the above aromatic isocyanates, aliphatic isocyanates, and / or alicyclic isocyanates with polyfunctional alcohols, such as trimethylolpropane. Hexamethylene diisocyanate adduct (product name "Takenate D-160N", manufactured by Mitsui Chemicals), trimethylolpropane tolylene diisocyanate adduct (product name "Coronate L", manufactured by Nippon Polyurethanes; product name "Takenate D- 102 ", manufactured by Mitsui Chemicals), xylylene diisocyanate adduct of trimethylolpropane (product name" Takenate D-110N ", manufactured by Mitsui Chemicals), isophorone diisocyanate adduct of trimethylolpropane (product name" Takenate D-1 ") 0N ", and the like is manufactured by Mitsui Chemicals, Inc.), and the like.

<Polyfunctional alcohol>
The polyfunctional alcohol is a reaction with the (meth) acrylate having an isocyanate group for obtaining the polyfunctional urethane acrylate (D1), the aromatic isocyanate, the aliphatic isocyanate for obtaining the adduct, and It can be used in the reaction with alicyclic isocyanate.
Examples of the polyfunctional alcohol include ethylene glycol, propylene glycol diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3′-dimethylol heptane, and 2-methyl-1. , 8-octanediol, 3,3′-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, 1,5 -Pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedi Methanol, Tricyclodecane, cyclopentadiene engine methanol, aliphatic or alicyclic diols and dimer diol;
1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4′-methylenediphenol, 4, 4 ′-(2-norbornylidene) diphenol, 4,4′-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4′-isopropylidenephenol, or bisphenols such as bisphenol A and bisphenol F Aromatic diols such as bisphenols obtained by adding alkylene oxide such as ethylene oxide and propylene oxide to
1,1,1-trimethylolpropane, 1,1,1-trimethylolbutane, 1,1,1-trimethylolpentane, 1,1,1-trimethylolhexane, 1,1,1-trimethylolheptane, 1,1,1-trimethyloloctane, 1,1,1-trimethylol nonane, 1,1,1-trimethyloldecane, 1,1,1-trimethylolundecane, 1,1,1-trimethyloldodecane, 1,1,1-trimethylol tridecane, 1,1,1-trimethylol tetradecane, 1,1,1-trimethylol pentadecane, 1,1,1-trimethylol hexadecane, 1,1,1-trimethylol hepta Decane, 1,1,1-trimethylol octadecane, 1,1,1-trimethylol nanodecane, 1,1,1-trimethylol-sec Butane, 1,1,1-trimethylol-tert-pentane, 1,1,1-trimethylol-tert-nonane, 1,1,1-trimethylol-tert-tridecane, 1,1,1-trimethylol- tert-heptadecane, 1,1,1-trimethylol-2-methyl-hexane, 1,1,1-trimethylol-3-methyl-hexane, 1,1,1-trimethylol-2-ethyl-hexane, Trimethylol branched alkanes such as 1,1,1-trimethylol-3-ethyl-hexane, 1,1,1-trimethylolisoheptadecane;
Trimethylol butene, trimethylol heptene, trimethylol pentene, trimethylol hexene, trimethylol heptene, trimethylol octene, trimethylol decene, trimethylol dodecene, trimethylol tridecene, trimethylol pentadecene, trimethylol hexadecene, tri Trifunctional polyols such as metrolheptadecene, trimethyloloctadecene, 1,2,6-butanetriol, 1,2,4-butanetriol, glycerin;
Tetrafunctional or higher functional polyols such as pentaerythritol, dipentaerythritol, sorbitol, xylitol;
Examples thereof include polymer polyols such as polyester polyol, polycarbonate polyol, polyether polyol, and polyurethane polyol. These polyfunctional alcohols may be used individually by 1 type, and may be used in combination of 2 or more type.

<(Meth) acrylate having an isocyanate group>
As the (meth) acrylate having an isocyanate group, 2-methacryloyloxyethyl isocyanate (product name “Karenz MOI”, manufactured by Showa Denko KK), 2-acryloyloxyethyl isocyanate (product name “Karenz AOI”, manufactured by Showa Denko KK) A compound having one photopolymerizable group and one isocyanate group in one molecule, such as
1,1- (Bisacryloyloxymethyl) ethyl isocyanate (product name “Karenz B
Compounds having two or more photopolymerizable groups and one isocyanate group in one molecule such as “EI” (manufactured by Showa Denko).

<Compound having a mercapto group and a carboxyl group>
Examples of the compound having a mercapto group and a carboxyl group include thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid and the like.

<Hydroxy acid>
Hydroxy acids include glycolic acid, lactic acid, tartronic acid, glyceric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, malic acid, citric acid, isocitric acid, citramalic acid, leucine acid, ricinoleic acid, ricinaleic acid, cerebric acid, Hydroxy acids having one hydroxyl group such as salicylic acid, creosote acid, vanillic acid, syringic acid, mandelic acid, benzylic acid, atrolactic acid, merirotic acid, coumaric acid, ferulic acid, sinapinic acid;
Examples thereof include hydroxy acids having two or more hydroxyl groups, such as tartaric acid, mevalonic acid, pantoic acid, shikimic acid, pyrocatechuic acid, resorcylic acid, protocatechuic acid, gentisic acid, orceric acid, caffeic acid, and umbelic acid.

A hydroxy acid can be obtained by reacting a partial hydroxyl group of a polyfunctional alcohol with a polybasic acid anhydride. Examples of the polyfunctional alcohol include those described above.
The polybasic acid anhydride is not particularly limited as long as it is a compound containing at least one acid anhydride group in the molecule. For example, succinic anhydride, maleic anhydride, glutaric anhydride, butyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecyl succinic anhydride, butyl maleic anhydride, pentyl maleic anhydride, hexyl Maleic anhydride, octyl maleic anhydride, decyl maleic anhydride, dodecyl maleic anhydride, butyl glutamic anhydride, hexyl glutamic anhydride, heptyl glutamic anhydride, octyl glutamic anhydride, decyl glutamic anhydride, dodecyl glutamic acid Aliphatic dibasic acid anhydrides such as anhydrides;
Methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl nadic acid anhydride, nadic anhydride, hydrogenated methyl nadic anhydride, stilendostyrene styrene tetrahydrophthalic anhydride, trialkyltetrahydro Alicyclic dibasic acid anhydrides such as phthalic anhydride;
Alicyclic polybasic acid anhydrides of tribasic acid or higher such as hydrogenated trimellitic acid anhydride;
Aromatic dibasic acid anhydrides such as phthalic anhydride and tetrabromophthalic anhydride;
An aromatic polybasic acid anhydride having a tribasic acid or higher such as trimellitic anhydride can be used.

The photopolymerizable monomer that can be used in the coloring composition of the present invention includes (meth) acryloyl when the polyfunctional isocyanate is reacted with a (meth) acrylate having a hydroxyl group in addition to the polyfunctional urethane acrylate described above. A component having a double bond group that was not obtained as a polyfunctional urethane acrylate having a group may be contained as another monomer.

The number of urethane groups in the polyfunctional urethane acrylate (D1) is preferably 1.5 × 10 ⁻³ mol / g or more. More preferably in the range of ^{1.5 × 10 -3 mol / g~4.0 ×} 10 -3 mol / g.
This range is preferable from the viewpoint of substrate adhesion. In the range exceeding 4.0 × 10 ⁻³ mol / g, the colorability deteriorates in the heating step.

The number of double bond groups is preferably 4.0 mmol / g or more from the viewpoint of high exposure sensitivity and excellent shape in the development process. More preferably, it is 6.0 mmol / g-10.0 mmol / g. Within this range, the curing shrinkage is low, which is preferable from the viewpoint of the remaining film ratio.

The content of the photopolymerizable monomer (D) is preferably 7 to 50% by weight, more preferably 10 to 40% by weight, based on the solid content weight of the colored composition. Within this range, both photosensitivity and cure shrinkage can be achieved, which is preferable from the viewpoint of adhesion.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

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.

<Antioxidant>
The coloring composition for a color filter of the present invention can contain an antioxidant. 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 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.

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 And Polymer type compounds 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, 2-hydroxy-4-chlorobenzophenone 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 salicylic acid ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-t-butylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

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 weight based on the solid content weight of the color filter coloring composition because the brightness and sensitivity are good.

<Amine compound>
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.

<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. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. 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.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative 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- Til-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 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 be used. These may be used alone or in combination of two or more.
As content of a hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part 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.

Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

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 weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation. 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, 1,2,3-trichloropropane, 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, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, 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 monomethyl 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 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, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

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

In addition, the organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the colored composition can be adjusted to an appropriate viscosity to form a filter segment having a desired uniform film thickness. Is preferred.

<Method for producing colored composition>
In the coloring composition for a color filter of the present invention, a coloring agent containing the pigment monomer (A) and the salt-forming compound (B) of the present invention is contained in a coloring agent carrier comprising the resin and a solvent as necessary. In addition, it can be produced by finely dispersing together with a dispersing aid such as a pigment derivative using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor.

  In addition, the coloring composition for a color filter of the present invention is obtained by mixing the pigment monomer (A), the salt-forming compound (B) of the present invention, and other colorants separately dispersed in a colorant carrier. It can also be manufactured. Further, when the solubility of the dye monomer (A) and the salt-forming compound (B) of the present invention is high, specifically, the solubility in a solvent to be used is high, so that no dissolution or foreign matter is confirmed by stirring. If it exists, it is not necessary to manufacture by finely dispersing as described above.

<Dispersing aid>
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing reaggregation of the colorant after dispersion. Therefore, a dispersion composition is used to disperse the colorant in the colorant carrier using the dispersion aid. When used, a color filter having a high spectral transmittance can be obtained.

  In the present invention, the dye monomer (A) of the present invention can also serve as a dispersion aid for the pigment used in combination.

  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% by weight or more, more preferably 1% by weight or more, and most preferably 3% by weight or more with respect to 100% by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40% by weight or less, and most preferably 35% by weight or less with respect to 100% by weight of the colorant.

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

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167 manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti -Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116 or LACTIMON, LACTIMON-WS or BYKUMEN, etc., SOLPERSE-3000 manufactured by Lubrizol Japan, 000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, manufactured by BASF Japan 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 45 0, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Fine Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824, etc. Can be mentioned.

  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.

  When a resin-type dispersant and a surfactant are added, the amount is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight with respect to 100% by weight of the colorant. When the blending amount of the resin type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the added effect. When the blending amount is more than 55% by weight, the dispersion is affected by an excessive dispersant. May affect.

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

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment.
The color filter may further comprise a magenta filter segment, a cyan filter segment, and a yellow filter segment, and the yellow filter segment is formed from the colored composition of the present invention. There may be.

  Preferably, at least one blue filter segment is formed using the coloring composition for a color filter of the present invention.

  As a base material such as a transparent substrate constituting the color filter, a glass plate such as soda-lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. Used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

<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.

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

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the UV exposure sensitivity, after coating and drying the colored resist 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, an ink jet method or the like in addition to the above method, but the color filter coloring composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

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

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

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

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 weight” and “% by weight”, respectively. “PGMAC” means propylene glycol monomethyl ether acetate.

First, a method for measuring the weight average molecular weight (Mw) of the resin and the acid value of the resin, the number of urethane groups of the photopolymerizable monomer, and the method of calculating the number of double bond groups of the photopolymerizable monomer will be described. .

<Weight average molecular weight (Mw) of resin>
The weight average molecular weight (Mw) of the resin was converted to polystyrene using HLC-8220GPC (manufactured by Tosoh Corporation) as a device, TSK-GELSUPERHZM-N connected in series as a column, and THF as a solvent. Molecular weight.

<Resin acid value (mgKOH / g)>
The acid value of the resin is a value obtained by converting the measured acid value (mgKOH / g) into a solid content in accordance with the potentiometric titration method of JISK0070.

<Number of urethane groups in photopolymerizable monomer>
The number of urethane groups (mmol / g) of the photopolymerizable monomer is a measure of the number of urethane bonds contained in the molecule, and was calculated as follows.
(Number of urethane groups of photopolymerizable monomer in one molecule) / (Molecular weight of photopolymerizable monomer)
In the case of a mixture, the product sum of the weight ratio of each component and the number of urethane groups is the number of urethane groups in the photopolymerizable monomer in one molecule, and the number average molecular weight is the molecular weight of the photopolymerizable monomer.

<Number of double bond groups of photopolymerizable monomer>
The number of double bond groups of the photopolymerizable monomer is a measure of the number of double bonds contained in the molecule,
It was calculated by the following formula.
(Number of carbon-carbon double bonds in one molecule) / (Molecular weight of photopolymerizable monomer)
In the case of a mixture, the product sum of the weight ratio of each component and the number of carbon-carbon double bonds is the number of carbon-carbon double bonds in one molecule, and the number average molecular weight is the molecular weight of the photopolymerizable monomer.

Then, the photopolymerizable monomer used for the Example and the comparative example, resin, a coloring agent, a pigment dispersion, and the manufacturing method of the photosensitive green coloring composition are demonstrated.

<Method for producing photopolymerizable monomer>
(Photopolymerizable monomer (D1-1))
In a 2 L four-necked flask, 801 g of dipentaerythritol pentaacrylate, 128 g of hexamethylene diisocyanate, 1.0 g of N, N-dimethylbenzylamine, and 1.0 g of 4-methoxyphenol are charged and heated at a temperature of 70 ° C. for 8 hours. It was made to react and the disappearance of isocyanate absorption was confirmed by IR analysis.
After cooling to room temperature, 70.3 g of mercaptopropionic acid was added and reacted at a temperature of 50 to 60 ° C. for 6 hours to obtain a photopolymerizable monomer (D1-1).
The acid value of this photopolymerizable monomer (D1-1) was 43, the number of urethane groups was 1.53 mmol / g, and the number of double bond groups was 6.88 mmol / g.

(Photopolymerizable monomer (D1-2))
Into a 2 L four-necked flask, 416 g of a trimethylolpropane adduct of hexamethylene diisocyanate, 584 g of pentaerythritol triacrylate, 1.0 g of N, N-dimethylbenzylamine, and 1.0 g of 4-methoxyphenol were charged at 70 ° C. For 8 hours to obtain a photopolymerizable monomer (D1-2).
In addition, it was confirmed by IR analysis that no isocyanate group was present in the reaction product.
This photopolymerizable monomer (D1-2) had a urethane group number of 3.92 mmol / g and a double bond group number of 5.87 mmol / g.

(Photopolymerizable monomer (D1-3))
In a 2 L four-necked flask, 862 g of dipentaerythritol pentaacrylate, 138 g of hexamethylene diisocyanate, 1.0 g of N, N-dimethylbenzylamine, and 1.0 g of 4-methoxyphenol are charged at a temperature of 70 ° C. for 8 hours. The photopolymerization monomer (D1-3) was obtained by reaction.
In addition, it was confirmed by IR analysis that no isocyanate group was present in the reaction product.
This photopolymerizable monomer (D1-3) had a urethane group number of 1.64 mmol / g and a double bond group number of 8.22 mmol / g.

(Photopolymerizable monomer (D1-4))
Into a 2 L four-necked flask, 632 g of 4-hydroxybutyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.) and 368 g of hexamethylene diisocyanate were charged and reacted at 60 ° C. for 8 hours to give a photopolymerizable monomer (D1-4 )
In addition, it was confirmed by IR analysis that no isocyanate group was present in the reaction product.
This photopolymerizable monomer (D1-4) had a urethane group number of 4.39 mmol / g and a double bond group number of 4.39 mmol / g.

(Photopolymerizable monomer (D1-5))
In a 2 L four-necked flask, 591 g of Kuraray polyol P2010 (manufactured by Kuraray Co., Ltd.), 99.3 g of hexamethylene diisocyanate, and 1.0 g of N, N-dimethylbenzylamine are charged and reacted at a temperature of 70 ° C. for 8 hours. It was.
After cooling to room temperature, 310 g of dipentaerythritol pentaacrylate and 1.0 g of 4-methoxyphenol were added and reacted at a temperature of 70 ° C. for 6 hours to obtain a photopolymerizable monomer (D1-5).
In addition, it was confirmed by IR analysis that no isocyanate group was present in the reaction product.
This photopolymerizable monomer (D1-5) had a urethane group number of 1.18 mmol / g and a double bond group number of 2.96 mmol / g.

(Photopolymerizable monomer (D1-6))
In a 2 L four-necked flask, 36.7 g of 1,6 hexanediol, 622 g of Kuraray polyol P2010 (manufactured by Kuraray Co., Ltd.), 157 g of hexamethylene diisocyanate, and 1.0 g of N, N-dimethylbenzylamine are charged at 70 ° C. The reaction was carried out at a temperature of 8 hours.
After cooling to room temperature, 185 g of pentaerythritol triacrylate and 1.0 g of 4-methoxyphenol were added and reacted at a temperature of 70 ° C. for 6 hours to obtain a photopolymerizable monomer (D1-6).
In addition, it was confirmed by IR analysis that no isocyanate group was present in the reaction product.
This photopolymerizable monomer (D1-6) had a urethane group number of 1.86 mmol / g and a double bond group number of 1.86 mmol / g.

(Photopolymerizable monomer (D1-7))
In a 2 L four-necked flask, 477 g of hexamethylene diisocyanate trimethylolpropane adduct, 445 g of pentaerythritol triacrylate, 77.7 g of γ-hydroxybutyric acid, 1.0 g of N, N-dimethylbenzylamine, 4-methoxyphenol 1.0 g was charged and reacted at 70 ° C. for 8 hours to obtain a photopolymerizable monomer (D1-7).
In addition, it was confirmed by IR analysis that no isocyanate group was present in the reaction product.
This photopolymerizable monomer (D1-7) had an acid value of 42, a urethane group number of 4.48 mmol / g, and a double bond group number of 4.48 mmol / g.

(Photopolymerizable monomer (D1-8))
In a 2 L four-necked flask, 241 g of trimethylolpropane and 759 g of acryloyloxyethyl isocyanate were charged and reacted at 60 ° C. for 8 hours to obtain a photopolymerizable monomer (D1-8).
In addition, it was confirmed by IR analysis that no isocyanate group was present in the reaction product.
This photopolymerizable monomer (D1-8) had a urethane group number of 5.39 mmol / g and a double bond group number of 5.39 mmol / g.

Table 1 shows a list of the photopolymerizable monomers (D1-1 to 8).

Abbreviations in Table 1 are shown below.
HD: 1,6-hexanediol P2010: Kuraray polyol P2010 (manufactured by Kuraray Co., Ltd.)
TMP: trimethylolpropane TMP-3HDI: trimethylolpropane adduct of hexamethylene diisocyanate (“Takenate D-160N” manufactured by Mitsui Chemicals)
PTA: pentaerythritol triacrylate DPPA: dipentaerythritol pentaacrylate 4HBA: 4-hydroxybutyl acrylate TGA: thioglycolic acid γHBA: γ-hydroxybutyric acid AOI: acryloyloxyethyl isocyanate HDI: hexamethylene diisocyanate DMBA: N, N-dimethylbenzyl Amine MQ: 4-methoxyphenol

<Method for producing resin solution>
(Resin solution (B1))
70.0 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen Thereafter, 15 parts of styrene, 13.5 parts of methacrylic acid, 30 parts of methyl methacrylate, 17.5 parts of n-butyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, paracumylphenol ethylene oxide modified acrylate (manufactured by Toagosei Co., Ltd.) A mixture of 14 parts of Aronix M110) and 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours to carry out a polymerization reaction. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a solid content of 50% by weight.
After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Ether acetate was added to obtain a resin solution (B1).

<Method for producing dispersant>
(Dispersant (DI-1))
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 50 parts of methyl methacrylate, 50 parts of n-butyl methacrylate, and 45.4 parts of PGMAc and replaced with nitrogen gas. The inside of the reaction vessel was heated to 70 ° C., 6 parts of 3-mercapto-1,2-propanediol was added, 0.12 part of AIBN (azobisisobutyronitrile) was further added, and the reaction was carried out for 12 hours. It was confirmed that 95% had reacted by solid content measurement. Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 part of DBU (1,8-diazabicyclo- [5.4.0] -7-undecene) as a catalyst were added at 120 ° C. For 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. PGMAc was added to adjust the non-volatile content to 50% to obtain a dispersant (DI-1) having an acid value of 43 and a weight average molecular weight of 9000.

<Production method of fine pigment>
(Fine refined pigment (PB-1))
C. I. 100 parts of Pigment Blue 15: 6 (PB15: 6) (“Rionol Blue ES” manufactured by Toyocolor Co., Ltd.), 800 parts of crushed salt, and 100 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho), 70 The mixture was kneaded for 12 hours. The mixture was added to 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 98 parts fine Pigmented pigment (PB-1) was obtained. The average primary particle size was 28.3 nm.

<Method for producing pigment derivative>
(Dye derivative (PD-1))
After 50 parts of copper phthalocyanine as a pigment component was chlorosulfonated, it was reacted with 14 parts of N, N-dimethylaminopropylamine as an amine component to obtain a pigment derivative (PD-1) having a basic group.
CuPc represents a copper phthalocyanine residue.

<Dye production method>
(Dye (DY-1)) (Triphenylethane salt forming compound)
C. I. 12 parts of Basic Blue 7 (Tokyo Chemicals), 7.4 parts of sodium dodecyl sulfate (Tokyo Chemicals), 130 parts of dichloromethane and 200 parts of water were mixed and stirred at room temperature for 2 hours. Thereafter, the organic layer was extracted, washed with water, and the organic layer was concentrated under reduced pressure. And it dried with the 60 degreeC vacuum dryer, and obtained 14.7 parts DY1. The yield was 84.8%.

<Method for producing pigment dispersion>
(Pigment dispersion (DP-1))
After the following mixture was stirred and mixed so as to be uniform, it was dispersed for 5 hours with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm Filtration through a filter gave a blue pigment dispersion (DP-1).
The pigment dispersion was adjusted to have a solid content of 20% by weight with PGMAc.
Hereinafter, solid content weight is shown.
Finer pigment (PB-1): 13.0 parts Dye derivative (PD-1): 1.0 part Dispersant (DI-1): 6.0 parts

<Method for producing dye solution>
(Dye solution (DD-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a dye solution (DD-1).
DY-1: 20.0 parts PGMAC: 80.0 parts

[Example 1]
(Photosensitive coloring composition (RB-1))
The following mixture (500 parts in total) was stirred and mixed so as to be uniform and then filtered through a 1.0 μm filter to obtain a photosensitive green coloring composition (RB-1).
Dye solution (DD-1): 214.3 parts Resin solution (B-1): 205.7 parts Photopolymerizable monomer (D1-1): 15.0 parts Photopolymerization initiator (C-1): 1.0 part ("Irgacure OXE02" manufactured by BASF)
Organic solvent: 64.0 parts (PGMAC)

[Examples 2 to 15, Comparative Example 1]
(Photosensitive green coloring composition (RB-2 to 16))
Photosensitive coloring compositions (RB-2 to 16) were produced in the same manner as the photosensitive coloring composition (RB-1) except that the types and amounts (parts by weight) shown in Table 1 were changed.

Abbreviations in Table 2 are shown below.
Photopolymerization initiator (C-1): ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime)
(BASF "Irgacure OXE02")
Photopolymerization initiator (C-2): “Irgacure OXE04” manufactured by BASF
Photopolymerizable monomer (DHPA): Dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.)

<Evaluation of photosensitive coloring composition>
The developability evaluation and adhesion evaluation of the photosensitive coloring compositions obtained in Examples and Comparative Examples were performed by the following methods.

<Formation of filter segment>
A black matrix is patterned on a 100 mm × 100 mm, 1.1 mm thick glass substrate, and the resulting photosensitive coloring composition is applied onto the substrate with a spin coater and dried at 70 ° C. for 20 minutes to remove the solvent. And the coating film whose film thickness is 3.0 micrometers was obtained. Next, the film was irradiated with 100 mJ / cm ² of ultraviolet rays using a super high pressure mercury lamp through a photomask having a stripe pattern of 10 μm and 20 μm in width to form a filter segment. The film thickness of the coating film was performed using Dektak 3030 (made by Nippon Vacuum Technology Co., Ltd.).

<Developability evaluation>
Alkaline developer comprising 0.15% by weight of sodium carbonate 0.15% by weight sodium bicarbonate 0.05% by weight of anionic surfactant (“Pelex NBL” manufactured by Kao Corporation) and 99.7% by weight of water. After spray development in 30 seconds and 50 seconds, the substrate was washed with ion-exchanged water, and the development state of the unexposed area was visually observed.
Evaluation was performed in the following three stages.
A: The uncured portion is developed with a development time of 30 seconds.
○: The uncured portion is developed with a development time of 50 seconds.
X: The uncured part is not developed even with a development time of 50 seconds.

<Adhesion evaluation>
Alkaline developer comprising 0.15% by weight of sodium carbonate 0.15% by weight sodium bicarbonate 0.05% by weight of anionic surfactant (“Pelex NBL” manufactured by Kao Corporation) and 99.7% by weight of water. After spray development for 50 seconds, the substrate was washed with ion-exchanged water, and 10 μm and 20 μm wide stripe pattern portions were observed using a metal microscope “BX60” (manufactured by Olympus System).
Evaluation was performed in the following three stages.
A: No peeling up to 10 um fine wire.
○: No peeling up to 20um thin wire.
X: 20um thin line peels.

Table 3 shows the evaluation results.

A photosensitive coloring composition comprising the blue dye (A), binder resin (B), photopolymerization initiator (C), and photopolymerizable monomer (D) of the present invention, wherein the photopolymerizable monomer A photosensitive coloring composition comprising a polyfunctional urethane acrylate (D1) having a (meth) acryloyl group obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group (D). The developability was good and the adhesion was good.
In particular, when the polyfunctional urethane acrylate (D1) has an acid group, excellent developability was exhibited while maintaining good adhesion.

Moreover, from the above result, it has confirmed that the color filter which was compatible with the outstanding developability and adhesiveness can be provided with the coloring composition for color filters of this invention.

Claims (7)

A photosensitive coloring composition comprising a blue dye (A), a binder resin (B), a photopolymerization initiator (C), and a photopolymerizable monomer (D), wherein the photopolymerizable monomer (D ) Contains a polyfunctional urethane acrylate (D1). The photosensitive coloring composition according to claim 1, wherein the blue dye (A) is a triarylmethane dye (A1). The photosensitive coloring composition according to claim 1 or 2, wherein the polyfunctional urethane acrylate (D1) has three or more photopolymerizable functional groups in one molecule. The number of urethane groups of polyfunctional urethane acrylate (D1) is 1.5 mmol / g or more, and the double bond group number is 4.0 mmol / g or more, The photosensitive property in any one of 1-3 characterized by the above-mentioned. Coloring composition. 5. The photosensitive coloring according to claim 1, wherein the content of the photopolymerizable monomer (D) is 7 to 50% by weight based on the solid content weight of the coloring composition. Composition. The photosensitive coloring composition according to claim 1, wherein the polyfunctional urethane acrylate (D1) has an acid group. A color filter comprising a filter segment formed from the photosensitive coloring composition according to claim 1 on a substrate.