JP5708028B2 - Color filter coloring composition and color filter - Google Patents

Description

  The present invention relates to a colored composition for a color filter used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. is there.

  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. This liquid crystal display device can display color by providing a color filter between two polarizing plates. Therefore, liquid crystal display devices are being developed for use in televisions and personal computer monitors.

  A color filter has two or more kinds of fine band (striped) filter segments (pixels) arranged in parallel or intersecting on the surface of a transparent substrate such as glass, or the fine filter segments are vertically and horizontally. It consists of things arranged in a fixed arrangement. 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.

  On the color filter used in the color liquid crystal display device, a transparent electrode for driving the liquid crystal is generally formed by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. Has been. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to perform the formation process at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher.

  Quality items required for the color filter include contrast ratio and brightness. 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.

  When 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 that are 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.

  In addition, a color imaging tube element typified by a C-MOS (Complementary Metal Oxide Semiconductor: Complementary Metal Oxide Semiconductor), CCD (Charge Coupled Device), etc. has a blue (B) on the light receiving element, In general, color separation is performed by disposing color filters each having an additive mixed primary color filter segment of G (green) and R (red). In recent years, there is an increasing demand for color characteristics of color filters, such as transmittance, brightness, and a wide color reproduction region, in color filters used in color image pickup tube elements.

  The color filter production method includes a dyeing method using a dye or a salt-forming dye as a colorant, a dye dispersion method, a pigment dispersion method using a pigment as a colorant, a printing method, and an electrodeposition method. Among these, the dyeing method or the dyeing and dispersing method has a drawback that the heat resistance and light resistance are slightly inferior because the colorant is a dye. Therefore, a pigment having excellent heat resistance and light resistance is used as a colorant for the color filter, and a pigment dispersion method is often used as a manufacturing method because of the accuracy and stability of the forming method.

  In the pigment dispersion method, a color resist is formed by mixing and preparing a photosensitizer and additives in a pigment in which pigment particles as a colorant are dispersed in a transparent resin, and this color resist is applied on a substrate such as a spin coater. It is a method for forming a color filter by forming a coating film with an apparatus, selectively exposing through a mask with an aligner, a stepper, etc., patterning by alkali development and thermosetting, and repeating this operation. .

  In general, pigment particles are subjected to a micronization process, and a colored composition in which the micronized pigment is brought close to primary particles to the limit is produced, whereby light scattering by the pigment is suppressed and high contrast can be achieved. In addition, since the transparency of the dispersion is improved, the spectral spectrum of the dispersion has high transmittance, and high brightness is realized. By using this dispersion as a color resist, a color filter having high contrast and high brightness can be obtained.

  However, highly refined pigments have a significant increase in surface area and therefore agglomeration between particles becomes strong, and it is difficult to disperse to the size of primary particles by dispersion. Aggregation can be solved to some extent by dispersion with media, but it requires a great deal of energy, and in many cases, the aggregation is not solved and the contrast is lowered despite being fine.

  In addition, a method for preventing dry aggregation by solvent substitution and a method for making a pigment dispersion without flashing by flushing have been reported, but the former requires a large amount of solvent and is inefficient, and the latter is flashing. In addition, it is difficult to find the conditions to be used, and there is a concern that water remains in the dispersion.

JP 2003-89756 A JP 2007-2077 A JP 2007-191699 A

  An object of the present invention is to provide a coloring composition for a color filter having a high contrast ratio by easily crushing highly refined pigments into primary particles and a color filter using the same.

As a result of intensive studies to solve the above problems, the present inventors have obtained a hydroxyl group having a vapor pressure at 20 ° C. of 0.01 mmHg or less and a melting point of 40 ° C. or less in an organic pigment (E) water paste. The present inventors have found that the problem can be solved by adding a compound which is an alcohol or a glycol having a salt.

That is, the present invention relates to a color filter coloring composition containing at least a colorant (A), a dispersant (B) and a transparent resin (C), wherein the colorant (A) is an aqueous paste of an organic pigment (E). a colored color filter, wherein a vapor pressure at 20 ° C. is an organic Pigments that less and melting point 0.01mmHg is treated with a polyhydric alcohol having a 40 ° C. or less of hydroxyl groups (D) Relates to the composition.

  The present invention also relates to the colored composition for a color filter, wherein the polyhydric alcohol (D) is glycerin.

  The present invention also relates to the color composition for a color filter, wherein the polyhydric alcohol (D) is polyethylene glycol having a weight average molecular weight of 1500 or less.

  In the present invention, the ratio of the polyhydric alcohols (D) contained in the colorant (A) is 0.01% to 7% by weight with respect to the organic pigment (E) in the colorant (A). It is related with the said coloring composition for color filters characterized by the above-mentioned.

  The present invention also relates to a method for producing a colored composition for a color filter, wherein the organic pigment (E) is wet-treated with a polyhydric alcohol (D).

  The present invention also provides a color filter comprising at least one red filter segment, at least one blue filter segment, and at least one green filter segment, wherein the at least one filter segment is the color filter coloring composition. The present invention relates to a color filter formed from

  The color filter of the present invention has an easy-dispersion treatment that easily aggregates primary particles easily by adding to the highly refined pigment a substance having high affinity for pigment and low volatility before drying. High contrast can be achieved by fully drawing out the pigment performance.

Hereinafter, the present invention will be described in detail. The color filter coloring composition of the present invention is a color filter coloring composition having at least a colorant (A), a dispersant (B) and a transparent resin (C), wherein the colorant (A) is an organic pigment ( the aqueous paste E), an organic Pigments vapor pressure is less and the melting point 0.01mmHg formed by treatment with a polyhydric alcohol having a 40 ° C. or less of hydroxyl groups (D) at 20 ° C., and coloring A coloring component containing a compound in which the ratio of the polyhydric alcohols (D) contained in the agent (A) is 0.01% to 7% by weight with respect to the organic pigment (E) in the coloring agent (A) is used. It is a coloring composition for color filters.

<Colorant (A)>
The colorant (A) in the color filter coloring composition of the present invention comprises an organic pigment (E) and a polyhydric alcohol (D). Examples of the organic pigment (E) used in the present invention include azo, ansanthrone, anthrapyrimidine, anthraquinone, isoindolinone, isoindoline, indanthrone, xanthene, quinacridone, quinophthalone, Organic pigments and dyes such as subphthalocyanine, dioxazine, diketopyrrolopyrrole, thiazine, thioindigo, triphenylmethane, pyranthrone, phthalocyanine, flavanthrone, perinone, perylene, benzimidazolone Is mentioned.

  Preferably, the yellow pigment is C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 17 , It can be mentioned 177,179,180,181,182,185,187,188,191,193,194,198,199,213,214 like.

  Examples of red pigments include C.I. I. Pigment Red 4, 5, 7, 9, 14, 23, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 52, 53, 57, 81: 1, 81: 2, 81: 3, 97, 112, 122, 144, 146, 147, 149, 150, 166, 168, 169, 170, 176, 177, 178, 179, 184, 185, 187, 200, 202, 206, 207, 208, 209, 210, 214, 220, 221,226,238,242,246,254,255,262,264,270,272,273,274,276,277,278,279,280,281,282,283, 284, 285, 286, 287 and the like.

  As the blue pigment, 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, 80, etc. it can.

  Examples of green pigments include C.I. I. Pigment Green 7, 10, 36, 37, 58 and the like.

  As an orange pigment, C.I. I. Pigment orange 13, 36, 37, 38, 43, 51, 55, 59, 61, 64, 71, 74, and the like.

  As a purple pigment, C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 55: 1, 14, 15, 16, 19, 23, 25, 27, 29, 30, 31, 32, 37, 39, 40, 42, 44, 47, 49, 50 and the like.

  As the polyhydric alcohols (D), substances having extremely low volatility are suitable because they have a high affinity for pigments and maintain the effect of preventing aggregation, and those having a vapor pressure at 20 ° C. of 0.01 mmHg or less Is used. Moreover, in order to mix uniformly with an organic pigment (E), a melting | fusing point is 40 degrees C or less. Since a substance having a melting point exceeding 40 ° C. is a solid, it is not suitable from the viewpoint of poor uniformity and preventing aggregation.

  Examples of the polyhydric alcohols (D) include 1,5-pentanediol, 1,7-heptanediol, 2-methyl-1,3-hexanediol, 2-ethyl-1,3-hexanediol, glycerin, dipropylene Examples include glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 1000, and polypropylene glycol.

  As a method for measuring the vapor pressure, there are a static method, a gas flow method, a boiling point measurement method, etc., but the gas flow method is particularly suitable for measuring a substance having a low vapor pressure.

  The method of adding the polyhydric alcohol (D) to the organic pigment (E) is preferably mixed in a state where the organic pigment (E) is not dried, and particularly preferably in the state of a water paste. Specifically, after pigment synthesis, it is washed with a solvent or water to remove impurities, or the acid paste method or acid slurry method is used to dissolve or disperse the pigment in acid and add it into water for reprecipitation. The most effective result is a pigment water paste from which acid has been removed by washing with water, or a pigment water paste from which water-soluble inorganic salts and water-soluble organic solvents have been removed by washing with water after fine milling by solvent milling.

  The water paste after the treatment can obtain the colorant (A) by removing moisture by drying. The higher the drying temperature, the faster the moisture can be removed. However, since the polyhydric alcohols (D) may volatilize and dry agglomeration may occur, the drying temperature is preferably 20 ° C. or higher and 100 ° C. or lower.

The content of the polyhydric alcohol (D) is preferably between 0.01% by weight and 7% by weight, more preferably between 0.01% by weight and 5% by weight, based on the organic pigment (E). Particularly preferred is between 05% and 3% by weight. When the content is less than 0.01% by weight, the effect of preventing the aggregation of the pigment cannot be exhibited, resulting in difficult dispersion. When the content is more than 7% by weight, the drying property and solvent resistance of the resist are adversely affected.

  The content of the polyhydric alcohols (D) may be measured by chromatographic analysis of an extract extracted with water in the case of a water-soluble additive and extracted with a solvent in the case of a water-insoluble additive. At this time, ethylene glycol, diethylene glycol or the like can be quantified by gas chromatography, and a low-volatile solvent such as polyethylene glycol can be quantified by liquid chromatography. In the case of measurement by liquid chromatography, quantification is performed by a suggestion refraction detector or the like, but when the detection is difficult due to low sensitivity, the extract can be concentrated and measured using an evaporator or the like.

<Miniaturization of pigment>
The pigment used in the colored composition of the present invention can be refined by performing a salt milling treatment. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is obtained by approximating it to a cube of the obtained particle size, and the volume average particle size is defined as the average primary particle size.

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

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

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

  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 resin used is preferably in the range of 5 to 200% by weight based on the total weight of the pigment (100% by weight). For example, rosin resins such as rosin, disproportionated rosin, polymerized rosin, hydrogenated rosin, rosin ester, rosinamine, maleated rosin, fumarated rosin, rosin metal salt, rosin modified phenolic resin and rosin modified maleic resin, epoxy resin , Synthetic resins such as acrylic resin, maleic resin, butyral resin, polyester resin, melamine resin, phenol resin, polyurethane resin and polyamide resin, modified resins derived from fiber and rubber, etc. From the viewpoint of price, a rosin resin is preferable.

  The content of the colorant (A) is 7 to 20% by weight, preferably 8 to 18% by weight, based on the total weight of the coloring composition (100% by weight), and between 10 to 15% by weight. Is more preferable.

<Dispersant (B)>
As the dispersant that can be used in the color composition for a color filter of the present invention, a pigment derivative, a resin-type dispersant, a surfactant, and the like can be used.

<Dye derivative>
In the present invention, a pigment derivative can be used for improving dispersibility. The structure of the dye derivative is a compound represented by the following general formula (1).

P-Lm General formula (1)

(However,
P: organic pigment residue, anthraquinone residue, acridone residue or triazine residue L: basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group m: an integer of 1 to 4 is there)

  Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; copper phthalocyanine, halogenated copper phthalocyanine, zinc phthalocyanine, halogenated zinc phthalocyanine, Phthalocyanine pigments such as metal-free phthalocyanine; Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigment; dioxazine pigment; perinone pigment; Thioindigo pigments; isoindoline pigments; isoindolinone pigments; selenium pigments; quinophthalone pigments; dioxazine pigments; metal complex pigments.

  Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. You can use what you have.

  The blending amount of the pigment derivative is 0.5% by weight or more, preferably 1% by weight or more, more preferably 3% by weight based on the total amount of the colorant (A) (100% by weight) from the viewpoint of improving dispersibility. That's it. If it is this range, even if it passes through the process accompanied by the high heat at the time of color filter manufacture, since the fall of contrast ratio does not arise, it is preferable. From the viewpoint of heat resistance and light resistance, the total amount of the colorant (A) is 40% by weight or less, preferably 35% by weight or less, based on the total amount (100% by weight). If it exceeds this range, a hue change occurs undesirably through a process involving high heat during the production of the color filter.

<Resin type dispersant>
The resin-type dispersant has a colorant-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-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 addition compound, phosphate ester-based and the like are used, it can be used alone or in admixture of two or more.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171 manufactured by Big Chemie. 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, Anti-Terra-U, 203, 204, BYK-P104, P104S , 220S, 6919, Lactimon, Lactimon-WS, Bykumen, etc., SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 28000, manufactured by Nippon Lubrizol Corporation 000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA manufactured by EFKA Chemicals -46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 15 , 1501, 1502, and 1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

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

  When adding a resin-type dispersant and a surfactant, the total amount of the colorant (A) is based on 100% by weight, preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight. %. 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.

<Transparent resin (C)>
The transparent resin (C) used in the green coloring composition of the present invention is 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. preferable. The transparent resin (C) may be any of a thermoplastic resin, a thermosetting resin, and a photocurable resin, and is used in an amount of 30 to 500% by weight based on the total weight of the colorant (A). . If it is less than 30% by weight, the film formability and various resistances are insufficient, and if it exceeds 500% by weight, the pigment concentration is low and color characteristics cannot be expressed.

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

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

  As the photocurable resin, a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group has a reactive substituent such as an isocyanate group, an aldehyde group, an epoxy group, or a carboxyl group (meta ) A resin obtained by reacting an acrylic compound or cinnamic acid to introduce a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  When the coloring composition is used in the form of an alkali development type colored resist material, it is preferable to use an alkali-soluble resin having an acidic group such as a (meth) acrylic acid copolymer resin (alkali-soluble acrylic resin). In order to disperse the pigment preferably, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 30,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  In the present invention, the weight average molecular weight (Mw) of the transparent resin (C) is TPCgel column (manufactured by Tosoh Corporation), GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, and THF as a developing solvent. It is the weight average molecular weight (Mw) in terms of polystyrene measured using.

<Monomer>
The coloring composition for a color filter of the present invention can contain a monomer. Monomers include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin, and these can be used alone or in admixture of two or more. The amount of the monomer is preferably 5 to 400% by weight based on the total weight of the colorant (A) (100% by weight), and 10 to 300% by weight from the viewpoint of photocurability and developability. It is more preferable.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

<Photopolymerization initiator>
When the colored composition for a color filter of the present invention is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method, a photopolymerization initiator or the like is added.

  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 ben Benzoin compounds such as rudimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, 4 Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphene) ) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], or Oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) phenyl Phosphine compounds such as phosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; imidazole A titanocene compound or the like.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 5 to 200% by weight based on the total amount of the colorant (A) in the color filter coloring composition (100% by weight), and are photocurable and developable. From the viewpoint, it is more preferably 10 to 150% by weight.

<Sensitizer>
Furthermore, the coloring composition for a color filter 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.

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

  Two or more kinds of sensitizers may be used in any ratio as required. The blending amount when using the sensitizer is preferably 3 to 60% by weight based on the total weight of the photopolymerization initiator contained in the colored composition (100% by weight). From the viewpoint of developability, it is more preferably 5 to 50% by weight.

<Solvent>
In the colored composition of the present invention, a colorant is sufficiently dispersed in a colorant carrier, and applied to a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm to form a filter segment. In order to facilitate this, a solvent can be included.

  Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, benzyl alcohol, 1,3-butylene glycol diacetate, 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-butylal 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 Ether 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 Ter, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, 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, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate , Propyl acetate, milk Examples include ethyl acid, butyl lactate, and dibasic acid esters.

  Among them, since the dispersibility and solubility of the colorant of the present invention are good, glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, It is preferable to use ketones such as cyclohexanone and aromatic alcohols such as benzyl alcohol.

  A solvent can be used individually by 1 type or in mixture of 2 or more types. Moreover, since the solvent can adjust the colored composition to an appropriate viscosity to form a filter segment having a desired uniform film thickness, the total weight of the colorant (A) is 400 to 4000 based on the total weight (100% by weight). It is preferably used in an amount of% by weight.

<Amine compound>
Moreover, the coloring composition for color filters 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.

<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.

<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- D Ru-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 the said hardening accelerator, 0.01 to 15 weight% is preferable with respect to the thermosetting resin whole quantity.

<Other additive components>
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over 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 in the coloring composition.

  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.

<The manufacturing method of a coloring composition>
The coloring composition of the present invention comprises a mixture of a coloring agent (A), a dispersing agent (B), and a coloring agent carrier such as a transparent resin (C) and / or an organic solvent. The coloring agent (A) can be finely dispersed in a resin solvent liquid by using various dispersing means such as a roll mill, a sand mill, a kneader, and an attritor (coloring composition). The colored composition of the present invention can also be produced by mixing several types of colorants separately dispersed in a colorant carrier. The coloring composition can be prepared as a green coloring composition (resist material) for a solvent developing type or alkali developing type color filter. The coloring composition for a solvent developing type or alkali developing type color filter is prepared by mixing the coloring composition with a monomer, a photopolymerization initiator, and if necessary, other resins, solvents, dispersants, additives and the like. be able to.

<Removal of coarse particles>
The colored composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove 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 is a color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein at least one green filter segment is colored for the color filter of the present invention. It is formed using a composition.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

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

  When forming a filter segment by a photolithography method, a coating composition such as spray coating, spin coating, slit coating, roll coating, or the like is applied to the transparent composition on the transparent composition prepared as the solvent developing type or alkali developing type coloring resist. To apply a dry film thickness of 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after 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, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

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

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

  If the black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast of the liquid crystal display panel can be further increased. Examples of the black matrix include, but are not limited to, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, and a resin film in which a light-shielding agent is dispersed. A thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

  Examples using the organic dye derivative of the present invention will be shown and described below. In each example, unless otherwise specified, “parts” represents parts by weight, and “%” represents percent by weight.

<Miniaturization of pigment>
Process example 1
Under a nitrogen atmosphere, 450 g of dehydrated tert-amyl alcohol and 30 g of metallic sodium were added to a 1 L stainless steel reaction vessel equipped with a reflux tube and heated to 90 ° C. After 1 hour, the mixture was heated to 100 ° C. or higher and refluxed, and the molten metal sodium was continuously stirred for 10 hours with vigorous stirring to dissolve the metal sodium and prepare an alcoholate solution. On the other hand, 120 g of dehydrated tert-amyl alcohol, 88 g of diisopropyl succinate, and 100 g of p-chlorobenzonitrile are added to a 500 ml glass flask and heated to 90 ° C. with stirring to dissolve the mixture. It was adjusted. The heated solution of this mixture was slowly dropped into the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring. After completion of the dropwise addition, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt solution of a dichlorodiketopyrrolopyrrole pigment.

  600 g of methanol, 600 g of water and 117 g of acetic acid were added to a 3 L glass-jacketed reaction vessel and cooled to 0 ° C. While cooling this cooled mixture vigorously, the above obtained alkali metal salt solution of dichlorodiketopyrrolopyrrole pigment at 90 ° C. was cooled using a refrigerant so as to keep the temperature at 10 ° C. or lower. However, when added in small portions, a deep red suspension was formed. The suspension was vigorously stirred for 10 minutes, and then filtered using a Nutsche, and then washed with 300 g of methanol cooled to 10 ° C. and 1000 ml of water, to obtain Pigment Red254 water paste.

Process example 2
100 parts of Pigment Red 177 was added to 600 parts of 98% sulfuric acid, and the mixture was completely dissolved by stirring at 10 ° C. for 2 hours, and then poured into 1000 parts of water while stirring. After stirring for 30 minutes, the mixture was filtered and washed with water to obtain an aqueous pigment paste.

Process example 3
100 parts of Pigment Green 36, 1000 parts of sodium chloride and 200 parts of diethylene glycol were charged into a 3000-volume part double-arm kneader and kneaded for 10 hours while maintaining a dense lump at 70 ° C. After grinding, the mixture was taken out into 2000 parts of a 1% aqueous sulfuric acid solution at 70 ° C., stirred for 1 hour with heat, filtered and washed with water to obtain an aqueous pigment paste.

  When 1 part of Pigment Green 36 obtained in Process Example 1 dried in 10 parts of purified water was added, dispersed with ultrasound for 1 hour, and the supernatant was analyzed by GC, diethylene glycol was not detected.

Process example 4
Pigment Blue 15: 6 (100 parts), sodium chloride (1000 parts), and diethylene glycol (200 parts) were charged in a 3000-volume part double-arm kneader and kneaded for 10 hours while maintaining a dense lump at 70 ° C. After grinding, the mixture was taken out into 2000 parts of a 1% aqueous sulfuric acid solution at 70 ° C., stirred for 1 hour with heat, filtered and washed with water to obtain an aqueous pigment paste.

  When 1 part of Pigment Blue 15: 6 obtained in Process Example 1 dried in 10 parts of purified water was added, dispersed for 1 hour with ultrasonic waves, and the supernatant was analyzed by GC, diethylene glycol was not detected.

Process example 5
100 parts of Pigment Violet 23 was added to 600 parts of 98% sulfuric acid, and the mixture was stirred at 10 ° C. for 2 hours for complete dissolution, and then poured into 1000 parts of water with stirring. After stirring for 30 minutes, the mixture was filtered and washed with water to obtain an aqueous pigment paste.

<Treatment of pigment>
Process example 6
100 parts of Pigment Red254 water paste (solid content 70%) prepared in Process Example 1 and 200 parts of water were reslurried and stirred in a uniform state. 6 parts of polyethylene glycol 200 was added and stirring was continued for 3 hours. Excess water was filtered, the solid content was reduced to 70%, and dried to obtain Pigment Red254 which was subjected to easy dispersion treatment.

Add 1 part of Pigment Red254 obtained in Step 6 to 10 parts of purified water, disperse with ultrasound for 1 hour, concentrate the supernatant 10 times with an evaporator, and then use HPLC with a suggested refraction detector as a detector. Analysis revealed that 1% polyethylene glycol 200 was present in the pigment.

Process example 7
100 parts of Pigment Red 177 water paste (solid content 20%) prepared in Process Example 2 and 200 parts of water were reslurried and stirred in a uniform state. 0.7 parts of glycerin was added and stirring was continued for 3 hours. Excess water was filtered, the solid content was reduced to 50%, and dried to obtain Pigment Red 177 which was easily dispersed.

One part of Pigment Red 177 obtained in Step 7 was added to 10 parts of purified water, dispersed for 1 hour with ultrasonic waves, and the supernatant was analyzed by GC. As a result, it was found that 1% glycerin was present in the pigment.

Process example 8
100 parts of Pigment Green 36 water paste (solid content 70%) prepared in Process Example 3 and 200 parts of water were reslurried and stirred in a uniform state. 6 parts of glycerin was added and stirring was continued for 3 hours. Excess moisture was filtered, dried to a solid content of 70%, and dried to obtain Pigment Green 36 that had been easily dispersed.

One part of Pigment Green 36 obtained in Step 8 was added to 10 parts of purified water, dispersed for 1 hour with ultrasonic waves, and the supernatant was analyzed by GC. As a result, it was found that 1% glycerin was present in the pigment.

Process example 9
100 parts of Pigment Blue 15: 6 water paste (solid content 70%) prepared in Process Example 4 and 200 parts of water were reslurried and stirred in a uniform state. 6 parts of glycerin was added and stirring was continued for 3 hours. Excess water was filtered, the solid content was lowered to 70%, and dried to obtain Pigment Blue 15: 6 which was subjected to easy dispersion treatment.

1 part of Pigment Blue 15: 6 obtained in Process Example 9 was added to 10 parts of purified water, dispersed for 1 hour with ultrasound, and the supernatant was analyzed by GC. As a result, it was found that 1% glycerin was present in the pigment. .

Process example 10
100 parts of water pigment (20% solid content) of Pigment Violet 23 produced in Process Example 5 and 200 parts of water were reslurried and stirred in a uniform state. 0.7 parts of glycerin was added and stirring was continued for 3 hours. Excess water was filtered, the solid content was lowered to 50%, and dried to obtain Pigment Violet 23 which was easily dispersed.

When 1 part of Pigment Violet 23 obtained in Process Example 10 was added to 10 parts of purified water, dispersed for 1 hour with ultrasonic waves, and the supernatant was analyzed by GC, it was found that 1% glycerin was present in the pigment.

Process example 11
100 parts of pigment red 242 water paste (solid content 70%) and 200 parts of water were reslurried and stirred in a uniform state. 6 parts of polyethylene glycol 600 was added and stirring was continued for 3 hours. Excess moisture was filtered, dried to a solid content of 70%, and dried to obtain Pigment Red 242 that had been easily dispersed.

Add 1 part of Pigment Red242 obtained in Step 11 to 10 parts of purified water, disperse with ultrasound for 1 hour, concentrate the supernatant 10 times with an evaporator, and then use HPLC with a suggested refraction detector as a detector. Analysis revealed that 1% polyethylene glycol 600 was present in the pigment.

Process example 12
100 parts of Pigment Yellow 138 water paste (solid content 70%) and 200 parts of water were reslurried and stirred in a uniform state. 6 parts of polyethylene glycol 600 was added and stirring was continued for 3 hours. Excess water was filtered, the solid content was lowered to 70%, and dried to obtain Pigment Yellow 138 that had been easily dispersed.

Add 1 part of Pigment Yellow 138 obtained in Process Example 12 to 10 parts of purified water, disperse with ultrasound for 1 hour, concentrate the supernatant 10 times with an evaporator, and then use HPLC with a suggested refraction detector as a detector. Analysis revealed that 1% polyethylene glycol 600 was present in the pigment.

Process example 13
100 parts of Pigment Yellow 139 water paste (solid content 70%) and 200 parts of water were reslurried and stirred in a uniform state. 6 parts of polyethylene glycol 200 was added and stirring was continued for 3 hours. Excess water was filtered, dried to a solid content of 70%, and dried to obtain Pigment Yellow 139 that had been easily dispersed.

Add 1 part of Pigment Yellow 139 obtained in Step 13 to 10 parts of purified water, disperse with ultrasound for 1 hour, concentrate the supernatant 10 times with an evaporator, and then use HPLC with a suggested refraction detector as a detector. Analysis revealed that 1% polyethylene glycol 200 was present in the pigment.

Process example 14
100 parts of Pigment Yellow 150 water paste (solid content 70%) and 200 parts of water were reslurried and stirred in a uniform state. 6 parts of polyethylene glycol 1000 was added and stirring was continued for 3 hours. Excess water was filtered, the solid content was lowered to 70%, and dried to obtain Pigment Yellow 150 which was subjected to easy dispersion treatment.

Add 1 part of Pigment Yellow 150 obtained in Example 14 to 10 parts of purified water, disperse with ultrasound for 1 hour, concentrate the supernatant 10 times with an evaporator, and then use HPLC with a suggested refraction detector as a detector. Analysis revealed that 1% polyethylene glycol 1000 was present in the pigment.

Process example 15
100 parts of water paste of Pigment Green 58 (solid content 70%) and 200 parts of water were reslurried and stirred in a uniform state. 6 parts of polyethylene glycol 200 was added and stirring was continued for 3 hours. Excess water was filtered, the solid content was lowered to 70%, and dried to obtain Pigment Green 58 which was subjected to easy dispersion treatment.

Add 1 part of Pigment Green 58 obtained in Process Example 15 to 10 parts of purified water, disperse with ultrasound for 1 hour, concentrate the supernatant 10 times with an evaporator, and then use HPLC with a suggested refraction detector as a detector. Analysis revealed that 1% polyethylene glycol 200 was present in the pigment.

<Preparation of acrylic resin solution>
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Addition to prepare an acrylic resin solution.

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

<Preparation of colored composition 1>
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The colored composition 1 was produced by filtration using a filter.

Polyethylene glycol 200 produced in Process Example 6 1% treated PR254: 12.0 parts acrylic resin solution: 20.0 parts propylene glycol monomethyl ether acetate (PGMAC): 56.0 parts resin-type dispersant (Disperbyk-161 manufactured by BYK) (Solid content 30%): 12.0 parts

Colored composition list (1)

<Preparation of colored compositions 2 to 11 >
It was prepared in the same manner as wearing colored composition 1.

<Preparation of colored composition 12>
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The colored composition 12 was produced by filtration using a filter.

Glycerol 1% treated PR177 produced in Process Example 7: 12.0 parts acrylic resin solution: 20.0 parts propylene glycol monomethyl ether acetate (PGMAC): 56.0 parts resin-type dispersant (Disperbyk-161 manufactured by BYK, solid content) 30%): 12.0 parts

Colored composition list (2)

<Preparation of colored compositions 13 to 16 >
It was prepared in the same manner as wearing colored composition 12.

<Preparation of colored composition 17>
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A colored composition 17 was produced by filtration using a filter.
Polyethylene glycol 600 produced in Process Example 11 1% treated PR242: 12.0 parts acrylic resin solution: 20.0 parts propylene glycol monomethyl ether acetate (PGMAC): 64.0 parts resin type dispersant (PB-821 Ajinomoto Fine Techno) (Made by company): 4.0 parts

Coloring composition list (3)

<Preparation of colored compositions 18 to 21 >
It was prepared in the same manner as wearing colored composition 17.

<Preparation of colored composition 22>
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The colored composition 22 was produced by filtering with a filter.

Glycerol 1% -treated PG36 produced in Process Example 8: 12.0 parts acrylic resin solution: 20.0 parts propylene glycol monomethyl ether acetate (PGMAC): 50.0 parts cyclohexanone: 14.0 parts resin-type dispersant (PB- 821 Ajinomoto Fine Techno Co., Ltd.): 4.0 parts

Coloring composition list (4)

<Preparation of colored compositions 23 to 32 >
It was prepared in the same manner as wearing colored composition 22.

<Preparation of colored composition 33>
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A colored composition 33 was produced by filtration using a filter.

Glycerol 1% -treated PB15: 6 produced in Process Example 9: 12.0 parts acrylic resin solution: 20.0 parts propylene glycol monomethyl ether acetate (PGMAC): 40.0 parts cyclohexanone: 14.0 parts resin-type dispersant ( Disperbyk-161 BYK, solid content 30%): 12.0 parts

Colored composition list (5)

<Preparation of colored compositions 34 to 44 >
It was prepared in the same manner as wearing colored composition 33.

<Preparation of colored composition 45>
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A colored composition 45 was produced by filtration using a filter.

Polyethylene glycol 600 produced in Process Example 12 1% treated PY138: 12.0 parts acrylic resin solution: 20.0 parts propylene glycol monomethyl ether acetate (PGMAC): 64.0 parts resin-type dispersant (PB-821 Ajinomoto Fine Techno) (Made by company): 4.0 parts

Coloring composition list (6)

<Preparation of colored compositions 46 to 49 >
It was prepared in the same manner as wearing colored composition 45.

<Preparation of colored composition 50>
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The colored composition 50 was produced by filtering with a filter.

Polyethylene glycol 200 1% treated PY139 produced in Process Example 13: 12.0 parts acrylic resin solution: 20.0 parts propylene glycol monomethyl ether acetate (PGMAC): 64.0 parts resin type dispersant (PB-821 Ajinomoto Fine Techno) (Made by company): 4.0 parts

Colored composition list (7)

<Preparation of colored compositions 51 to 54 >
It was prepared in the same manner as wearing colored composition 50.

<Preparation of colored composition 55>
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The colored composition 55 was produced by filtering with a filter.

Polyethylene glycol 1000 produced in Process Example 14 1% treated PY150: 12.0 parts acrylic resin solution: 20.0 parts propylene glycol monomethyl ether acetate (PGMAC): 56.0 parts resin type dispersant (Disperbyk-161 manufactured by BYK) (Solid content 30%): 12.0 parts

Colored composition list (8)

<Preparation of colored compositions 55 to 65 >
It was prepared in the same manner as wearing colored composition 55.

<Preparation of colored composition 66>
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The colored composition 66 was produced by filtering with a filter.

Glycerol 1% treated PV23 produced in Process Example 10: 12.0 parts acrylic resin solution: 20.0 parts propylene glycol monomethyl ether acetate (PGMAC): 40.0 parts cyclohexanone: 14.0 parts Resin-type dispersant (Disperbyk- 161 BYK, solid content 30%): 12.0 parts

Colored composition list (9)

<Preparation of colored compositions 67 to 70 >
It was prepared in the same manner as wearing colored composition 66.

<Preparation of colored composition 71>
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A colored composition 71 was produced by filtration using a filter.

Polyethylene glycol 200 1% treated PG58 produced in Process Example 15: 12.0 parts acrylic resin solution: 20.0 parts propylene glycol monomethyl ether acetate (PGMAC): 62.0 parts resin-type dispersant (Disperbyk 6919 BYK, solid content) 60%): 6.0 parts

Coloring composition list (10)

<Preparation of colored compositions 72 to 75 >
It was prepared in the same manner as wearing colored composition 71.

[Example 1]
<Adjustment of resist material 1>
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain an alkali developing resist material 1.

Coloring composition 1: 70.0 parts acrylic resin solution: 11.0 parts trimethylolpropane triacrylate: 4.2 parts (“NK Ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan): 1.2 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts propylene glycol monomethyl ether acetate (PGMAC): 23 .2 parts

[Examples 2 to 60, Comparative Examples 1 to 14]
<Adjustment of resist materials 2 to 74>
Hereinafter, alkali-developable resist materials 2 to 74 were obtained in the same manner as the resist material 1 except that the colored composition 1 was changed to the colored compositions 2 to 74.

<Evaluation of resist material>
The contrast ratio of the resist materials 1 to 74 obtained in the examples and comparative examples was measured by the following method.

[Contrast ratio]
Each color filter coloring composition was coated on a 10 cm × 10 cm glass substrate with a spin coater, left in an oven at 70 ° C. for 15 minutes, and the excess solvent was removed and dried, and the thickness was about 2.0 μm. A glass substrate coated with the color filter coloring composition was prepared, and the contrast ratio was measured by the following method.

  A coloring composition coating substrate for a color filter is sandwiched between two polarizing plates, and light is irradiated from one polarizing plate side using a backlight unit for liquid crystal display. The light emitted from the backlight unit passes through the first polarizing plate and is polarized, and then passes through the color filter coloring composition coating substrate and reaches the second polarizing plate. If the polarization planes of the first polarizing plate and the second polarizing plate are parallel, light passes through the first polarizing plate, but if the polarization plane is perpendicular, the light passes through the second polarizing plate. Are blocked by the polarizing plate. However, when the light polarized by the first polarizing plate passes through the coloring composition coating substrate for the color filter, if scattering or the like by the pigment particles occurs and a part of the polarization plane shifts, the polarizing plate When parallel, the amount of light transmitted through the second polarizing plate is reduced, and when the polarizing plate is perpendicular, a part of the light is transmitted through the second polarizing plate. The luminance of the transmitted light is measured with a luminance meter on the polarizing plate, and the ratio of the luminance when the polarizing plate is parallel to the luminance when the polarizing plate is perpendicular is taken as the contrast ratio.

Contrast ratio = (Luminance when parallel) / (Luminance when direct)

  When scattering occurs due to the pigment in the color composition coating film for the color filter, the brightness when parallel is reduced and the brightness when perpendicular is increased, the contrast ratio is lowered. The luminance meter used was “Color Luminance Meter BM-5A” manufactured by Topcon Corporation, and the polarizing plate used was “Polarized Film LLC2-92-18” manufactured by Sanritsu. In the measurement, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

Pigment Red 254 evaluation result

Pigment Red 177 evaluation result

Pigment Red 242 evaluation result

Pigment Green 36 evaluation results

Pigment Blue 15: 6 evaluation result

Pigment Yellow 138 evaluation result

Pigment Yellow 139 evaluation result

Pigment Yellow 150 evaluation result

Pigment Violet 23 evaluation results

Pigment Green 58 evaluation results

  According to the present invention, by adding a substance having high affinity for pigment and low volatility to highly refined pigment before drying, it is possible to perform an easy dispersion treatment in which aggregation of primary particles is easy to break up. High contrast can be achieved by fully drawing out the performance of the pigment.

Claims (4)

In a coloring composition for a color filter containing at least a coloring agent (A), a dispersing agent (B) and a transparent resin (C), the coloring agent (A) is a water paste of an organic pigment (E) at 20 ° C. polyhydric alcohol vapor pressure contained an organic Pigments less and melting point 0.01mmHg is treated with a polyhydric alcohol having a 40 ° C. or less of hydroxyl groups (D), and the colorant (a) of A coloring composition for a color filter, wherein the ratio of the class (D) is 0.01 to 7% by weight relative to the organic pigment (E) in the coloring agent (A).   The polyhydric alcohol (D) is at least one selected from the group consisting of glycerin, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, and polyethylene glycol 1000. Coloring compositions for color filters. A color filter comprising at least one red filter segment, at least one blue filter segment, and at least one green filter segment,
The color filter in which the said at least 1 filter segment is formed from the coloring composition of Claim 1 or 2 . The colorant (A) containing the organic pigment (E), the dispersant (B) and the transparent resin (C), and the ratio of the polyhydric alcohols (D) contained in the colorant (A) is the colorant. (A) It is a manufacturing method of the coloring composition for color filters which is 0.01 to 7 weight% with respect to the organic pigment in (A), Comprising: Water vapor paste of an organic pigment (E) is 20 degreeC vapor pressure. Having an organic pigment treatment step of stirring in the presence of a polyhydric alcohol (D) having a hydroxyl group of 0.01 mmHg or less and a melting point of 40 ° C. or less. .