JP5266900B2 - Green colorant composition for color filter, and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter which is a thin film and ensures high color purity, high luminance, and a high contrast ratio. <P>SOLUTION: A green colorant composition for a color filter includes at least a resin, a solvent, and a chlorinated copper phthalocyanine pigment, wherein the average number of chlorine atoms introduced into a molecule of the chlorinated copper phthalocyanine of the chlorinated copper phthalocyanine pigment is 15.1-16.0, and the green colorant composition includes a yellow pigment. Furthermore, the green colorant composition includes a pigment derivative which has sulfonic acid groups introduced into the copper phthalocyanine pigment wherein the average number of sulfonic acid groups introduced into a molecule of the pigment derivative is 1.9-2.4. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a green colorant composition for a color filter and a color filter used for a liquid crystal display.

  Liquid crystal displays are used for various applications such as notebook computers, personal digital assistants, digital cameras, desktop monitors, etc., taking advantage of their characteristics such as light weight, thinness, and low power consumption, and color reproduction equivalent to existing cathode ray tube (CRT) TVs. Liquid crystal displays having a range have been developed. The color reproduction range is expressed as an area ratio with respect to the NTSC (National Television System Committee) standard of a triangle formed by connecting the chromaticity coordinates of red (R), green (G), and blue (B) in the XYZ color system chromaticity diagram. Is done. The color reproduction range of the CRT is about 72% compared to the NTSC standard, and the chromaticity coordinates (x, y) in the XYZ color system chromaticity diagram of each RGB color are R (0.640, 0.330) and G (respectively). 0.290, 0.600) and B (0.150, 0.080).

  In recent years, the NTSC standard ratio has been brought close to 100% in order to faithfully reproduce the bright colors of crimson roses and beautiful green colors of tropical seas that could not be expressed on conventional CRT TVs. There has been a strong demand. The NTSC standard ratio 100% indicates that the chromaticity coordinates (x, y) in the XYZ color system chromaticity diagram of each RGB color are R (0.670, 0.330), G (0.210, 0.710), B (0.150, 0.060).

  A thin film transistor (TFT) color liquid crystal display that is currently widely used is referred to as a backlight in which a liquid crystal is sealed between a transparent glass substrate on which a color filter is formed and a transparent glass substrate on which a TFT is formed. Consists of a light source. When light emitted from the backlight passes through the liquid crystal panel, an image is displayed by controlling the transmittance by the voltage applied to the liquid crystal. In order to obtain a high-quality image, that is, a bright image with a wide color reproduction range, the pigment used in each pixel of the color filter is selected so as to match the light transmission characteristics of the backlight, and two or more types of pigments are fixed. It is often used after being toned in proportion. Normally, the G pixel of the color filter is selected from two or more pigments of green, orange, and yellow, and is used after toning. The green pigments are high brominated copper phthalocyanine, high chlorinated copper phthalocyanine, and high bromine. Zinc phthalocyanine is used. Particularly in the case of a color filter G pixel, it is necessary to increase y of the chromaticity coordinates (x, y) in order to bring the chromaticity coordinates close to G (0.210, 0.710) and to achieve high color purity. It is.

  In Patent Document 1, by using a green colorant composition containing Pigment Green (PG) 36 as a highly brominated copper phthalocyanine pigment and PY138 as a quinophthalone pigment, a color filter having a contrast of about 1000 at y = 0.59. Is obtained. However, in Patent Document 1, since PG36 is used as the G pigment, there is a problem that the color filter cannot be highly purified with a thin film.

  Further, in Patent Document 2, by using a green colorant composition containing PG36 as a highly brominated copper phthalocyanine pigment, PG7 as a highly chlorinated copper phthalocyanine pigment, PY185 as an isoindoline pigment, and PY138 as a quinophthalone pigment, The color purity of the filter is improved (at a film thickness of 1.0, y = 0.60). However, in Patent Document 2, since the average number of chlorine atoms introduced per molecule of chlorinated copper phthalocyanine of PG7 is small (estimated to be 15.1 or less), it is said that the color filter cannot be highly purified with a thin film. There are challenges.

  Furthermore, there is a technique for changing the number of introduced chlorine atoms in the chlorinated copper phthalocyanine pigment (Patent Documents 3 to 6). In Patent Document 3, copper phthalocyanine is chlorinated by using titanium tetrachloride and aluminum chloride, and the average number of introduced chlorine atoms per molecule of chlorinated copper phthalocyanine is 8.6 to 15.4. Of chlorinated copper phthalocyanine. However, since the average number of introduced chlorine atoms per molecule is not so large, there is a problem that even if a color filter is formed using this chlorinated copper phthalocyanine, it cannot be highly purified with a thin film. Patent Document 6 describes a method for producing a chlorinated metal phthalocyanine pigment having a low hexachlorobenzene content by washing chlorinated metal phthalocyanine with an aqueous emulsion. In this method, although the number of chlorine atoms introduced per molecule of chlorinated copper phthalocyanine is 16, even if a color filter is formed because it does not contain a yellow pigment, high purity is achieved with a thin film. There is a problem that you can not.

On the other hand, in Patent Document 6, by using a green colorant composition containing brominated zinc phthalocyanine and PY83, both high transmittance and high color purity of the color filter are achieved. In this method, since the F10 light source, which is more advantageous for higher color purity than the C light source, is used for the backlight, the color purity is increased to y = 0.593, but the film thickness is still as thick as 2.5 μm. Even with this method, high color purity cannot be achieved with a thin film.
JP 2003-3073 A JP2007-1112919 JP-A H1-279975 JP H9-68607 JP H2-305862 JP2007-332302A JP 2004-70342 A

  An object of the present invention is to provide a color filter that is a thin film and has ultrahigh color purity and high brightness. It is another object of the present invention to provide a color filter that is a thin film and has ultra-high color purity, high brightness, and high contrast ratio.

1. A green colorant composition for a color filter containing at least a resin, a solvent, a chlorinated copper phthalocyanine pigment , and a yellow pigment , wherein the average introduction number of chlorine atoms per molecule of the chlorinated copper phthalocyanine of the chlorinated copper phthalocyanine pigment is A green colorant composition for a color filter, which is 15.1 to 16.0 and contains PY138 and PY185 as yellow pigments.
2. 2. The copper phthalocyanine pigment further comprising a pigment derivative having a sulfonic acid group introduced therein, wherein the average number of introduced sulfonic acid groups per molecule of the pigment derivative is 1.9 to 2.4. Green colorant composition for color filters.
3. The green colorant composition for color filters according to 1 or 2, wherein the weight mixing ratio of the chlorinated copper phthalocyanine pigment and the yellow pigment is 90:10 to 50:50.
4). A color filter having a pixel composed of a colored film provided in a desired pattern for each color with an arbitrary number of colors, wherein the colored film is a green colorant composition for a color filter according to any one of 1 to 3 A color filter characterized by being formed.

  The green colorant composition for a color filter of the present invention contains a chlorinated copper phthalocyanine pigment having a mean introduction number of chlorine atoms per molecule of copper phthalocyanine of 15.1 to 16.0 and a yellow pigment. Therefore, the color filter of the present invention is a thin film and has ultrahigh color purity and high luminance. Furthermore, the green colorant composition for a color filter of the present invention preferably contains a pigment derivative having an average sulfone introduction number per molecule of 1.9 to 2.4. Therefore, the color filter of the present invention is a thin film and has an ultrahigh color purity, high luminance, and a high contrast ratio. Therefore, the liquid crystal display using the color filter of the present invention has a sufficiently wide color reproduction range and excellent visibility.

  The present invention is a green colorant composition for a color filter containing at least a resin, a solvent, and a chlorinated copper phthalocyanine pigment, wherein the average number of introduced chlorine atoms per molecule of the copper phthalocyanine of the chlorinated copper phthalocyanine pigment is 15. It is necessary to contain 1 to 16.0 and a yellow pigment. The average number of introduced chlorine atoms per molecule of copper phthalocyanine is preferably 15.5 to 16.0, more preferably 15.7 to 16.0.

  Usually, the number of introduced chlorine atoms per molecule of chlorinated copper phthalocyanine is 1 to 16, and the pigment composed of an aggregate of copper phthalocyanine molecules having one introduced chlorine atom has PB15: 1 and the number of introduced chlorine atoms is 4. A pigment composed of an aggregate of ˜8 copper phthalocyanine molecules is PG37, and a pigment composed of an aggregate of copper phthalocyanine molecules having 12 to 16 chlorine atoms introduced is PG7. Conventionally, PG7, which has 12 to 16 chlorine atoms introduced per molecule of copper phthalocyanine, has an average number of introduced chlorine atoms smaller than 15.1. There was a problem that it could not be purified. In contrast, according to the present invention, when the average number of introduced chlorine atoms per molecule of chlorinated copper phthalocyanine is 15.1 to 16.0 and a yellow pigment is contained, the color filter can be highly purified with a thin film. Further, it has been found that the effect of increasing the color purity in the thin film is remarkable when the number is 15.5 to 16.0 or more.

  The chlorinated copper phthalocyanine pigment used in the present invention can be synthesized, for example, by heating and melting a copper phthalocyanine pigment together with sodium chloride and aluminum chloride and introducing chlorine gas into the melt. In addition, by appropriately controlling the synthesis conditions as follows, the average number of introduced chlorine atoms per copper phthalocyanine molecule can be 15.1 to 16.0.

  When synthesizing the chlorinated copper phthalocyanine pigment used in the present invention, the weight mixing ratio of the raw material copper phthalocyanine pigment, sodium chloride, and aluminum chloride is preferably copper phthalocyanine: sodium chloride: aluminum chloride = 1: 1: 1-1. 1:20:20. If the mixing ratio is less than 1: 1: 1, the copper phthalocyanine pigment cannot be melted and the number of introduced chlorine atoms may be less than 15.1, and if the mixing ratio is greater than 1:20:20 Efficiency is reduced.

  Moreover, it is desired that the temperature at which chlorine gas is introduced and the chlorination reaction is performed is preferably 150 to 200 ° C. If the chlorination reaction temperature is too high or too low, it will be difficult to set the number of introduced chlorine atoms per molecule to 15.1-16.0.

  Furthermore, the time for introducing chlorine gas and performing the chlorination reaction is preferably 1 to 50 hours, more preferably 5 to 25 hours. If the chlorination reaction time is shorter than 1 hour, it is difficult to set the number of introduced chlorine atoms per molecule to 15.1-16.0.

  In the chlorinated copper phthalocyanine pigment used in the present invention, the average number of introduced substituents other than chlorine atoms per molecule of chlorinated copper phthalocyanine is 0.9 to 0. Examples of the substituent include bromine atom, hydrogen atom, hydroxyl group, nitro group, amino group, cyano group, alkyl group, cyclic alkyl group, alkoxy group, cyclic alkoxy group, alkoxyalkyl group, alkylthio group, cyclic alkylthio group, alkenyl. Group, cyclic alkenyl group, alkenyloxy group, alkylamino group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group, alkylaminocarbonyl group, fluoroalkyl group, fluoroalkoxy group, fluoroalkylthio group, carboxyl group, formyl group, Sulfonic acid group, alkylsulfonyl group, alkylaminosulfonyl group, alkylaminosulfonic acid group, chlorosulfone group, carbamide group, sulfonamido group, aryl group, aryloxy group, arylthio group, aliphatic compound Such ring group or an aromatic heterocyclic group.

  In order to use the chlorinated copper phthalocyanine pigment having the introduced number of chlorine atoms per molecule of 15.1 to 16.0 obtained as described above for a color filter, the chlorinated copper phthalocyanine pigment is refined. It is desirable to do. That is, for example, the contrast ratio of a color filter using the chlorinated copper phthalocyanine pigment can be increased by reducing the primary particle size of the chlorinated copper phthalocyanine pigment to 50 nm or less, preferably 30 nm or less by salt milling. In salt milling, a chlorinated copper phthalocyanine pigment, a water-soluble inorganic salt, and an organic solvent that does not dissolve the inorganic salt are put into an apparatus such as a kneader or a mix muffler, kneaded, and then the mixture is put into water and the slurry is filtered. , By washing with water to remove inorganic salts.

  The green colorant composition of the present invention is obtained by dispersing a chlorine copper phthalocyanine pigment having an average introduction number of chlorine atoms of 15.1 to 16.0 obtained as described above together with a solvent using a disperser. Is manufactured by adding a resin and various additives to the green pigment dispersion. That is, the chlorinated copper phthalocyanine pigment is in a state of secondary particles in which primary particles are aggregated in a powder state (second particle size is usually 1 to 50 μm). Therefore, after adding a solvent and a resin if necessary Then, it is necessary to apply a shear stress to the secondary particles of the chlorinated copper phthalocyanine pigment using a disperser to refine the particles into primary particles or aggregates of a small number of primary particles.

  A sand mill, a ball mill, a bead mill, a three-roll mill, an attritor or the like is used as a disperser for applying a shear stress to the coarse pigment particles in a solvent. In particular, a bead mill is preferably used because of excellent dispersion efficiency. Examples of the dispersed beads include zirconia beads, alumina beads, glass beads, and the like. In order to reduce the size efficiently, it is particularly preferable to use zirconia beads. As the dispersion conditions, the shear stress can be adjusted to an appropriate size by appropriately controlling the bead diameter of the zirconia beads, the peripheral speed of the disperser, and the coarse particles of the pigment can be efficiently refined. . The bead diameter of zirconia beads used for dispersion is preferably in the range of 0.01 to 0.3 mmφ. If the bead diameter is larger than 0.3 mmφ, the shearing stress applied to the pigment is too large, so that the dispersion stability of the pigment dispersion may be reduced. On the other hand, if the diameter of the zirconia beads is smaller than 0.01 mmφ, In some cases, it may be difficult to remove the zirconia beads from the pigment dispersion.

  In the present invention, by adding a pigment derivative in which a sulfonic acid group is introduced to a copper phthalocyanine pigment, together with a chlorinated copper phthalocyanine pigment having a number of introduced chlorine atoms of 15.1 to 16.0, The introduced pigment derivative is strongly bonded to the pigment by intermolecular force, negatively charges the surface of the pigment fine particles, and can maintain a stable state of particles dispersed by electrostatic repulsion. Thereby, since the pigment particles in the green colorant composition for a color filter of the present invention are stable without being re-aggregated in a dispersed state, a color filter having a high contrast ratio can be obtained. Furthermore, the average number of introduced sulfonic acid groups per molecule of the pigment derivative used in the present invention is preferably 1.9 to 2.4, and more preferably 2.0 to 2.3. If the average number of introduced sulfonic acid groups in the pigment derivative is less than 1.9, the negative charge on the surface of the pigment particles is reduced, the electrostatic repulsion is reduced, the dispersion state of the pigment particles becomes unstable, and the contrast ratio of the color filter Is likely to decline. On the other hand, if the average number of sulfonic acid groups introduced per molecule of pigment derivative is more than 2.4, the solubility of the pigment derivative in the solvent is too high and the pigment derivative is not adsorbed to the pigment and the pigment particles are dispersed. Is unstable and the contrast ratio of the color filter is likely to decrease. The weight mixing ratio of the chlorinated copper phthalocyanine pigment and the pigment derivative when adding the pigment derivative is preferably chlorinated copper phthalocyanine: pigment derivative = 99.5: 0.5 to 80:20, more preferably chlorination Copper phthalocyanine: pigment derivative = 99: 1 to 90:10. If the amount of the pigment derivative is too small, it becomes difficult to stabilize the dispersion state of the pigment, and if it is too large, the hue may change unfavorably.

  A polymer dispersant can also be added to the green pigment dispersion used in the present invention. By adding a polymer dispersant, further improvement in dispersion stability can be expected. The addition of the polymer dispersant is particularly effective when the pigment dispersion and the colorant composition of the present invention are acrylic resins. As the polymer dispersant that can be used, those having a basic group in the structure thereof are preferable. Examples of commercially available products include “Solsperse” (Avicia), “EFKA” (Efka), “Ajisper”. (Ajinomoto Fine Techno Co., Ltd.), “BYK” (Bic Chemie Co., Ltd.) and the like can be preferably used. The use of “Solsparse” 24000, “EFKA” 4300, 4330, 4340, “Ajisper” PB821, PB822, “BYK” 161-163, 2000, 2001 is preferred because the dispersion stabilization effect is enhanced. The addition amount of the polymer dispersant used in the present invention is not particularly limited, but is preferably 2 to 100 parts by weight, more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the pigment. is there. If the addition amount of the polymer dispersant is less than 2 parts by weight, good pigment dispersion stability cannot be obtained, and if it is more than 100 parts by weight, the developability may be poor.

  The present invention has found that an ultrahigh color purity of a color filter can be achieved by toning a chlorinated copper phthalocyanine pigment having an average introduction number of chlorine atoms of 15.1 to 16.0 with a yellow pigment. Is.

  Examples of yellow pigments include PY12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 154, 166. 168, 185 and the like. Among them, in order to obtain a color filter having a thin film with high color purity, high brightness, and high contrast, a chlorinated copper phthalocyanine pigment having an average introduction number of chlorine atoms of 15.1 to 16.0 is added to PY138 and Toning is preferably performed with PY185. By adding PY138 and PY185, the transmittance of 400 to 470 nm of the transmission spectrum of the color filter can be selectively reduced, so that the transmission spectrum becomes sharp and the color purity becomes extremely high. On the other hand, even if PY138 and PY185 are added, the transmittance at 470 to 550 nm does not decrease, so that the luminance increases. Therefore, it is possible to achieve both ultra high color purity and high brightness with a thin film. The weight mixing ratio of the chlorinated copper phthalocyanine pigment and the yellow pigment is preferably chlorinated copper phthalocyanine: yellow pigment = 90: 10-50: 50, more preferably chlorinated copper phthalocyanine: yellow pigment = 80: 20-55: 45. It is. If the content of chlorinated copper phthalocyanine is more than 90% by weight, the chromaticity of the color filter may become too bluish. If the content of chlorinated copper phthalocyanine is less than 50% by weight, the chromaticity of the color filter will be reduced. It may be too yellow. In the present invention, chlorinated copper phthalocyanine: yellow pigment = 80: 20 to 55:45 is preferable because the color filter can be made of a thin film to achieve both ultrahigh color purity and high luminance. If the content of PY138 is more than 30% by weight, the color purity of the color filter is likely to be lowered. If the content of PY185 is more than 15% by weight, the contrast ratio of the color filter is likely to be lowered. Become.

  The resin used in the green colorant composition of the present invention is not particularly limited, and a resin usually used for a color filter, that is, an acrylic, epoxy, or polyamic acid resin can be preferably used. . Depending on the resin used, it can be non-photosensitive or photosensitive, and can be appropriately selected according to the color filter manufacturing process.

  Hereinafter, a case where a polyamic acid is used as a typical example of a resin used for a non-photosensitive green colorant composition and an acrylic resin is used as a typical example of a resin used for a photosensitive green colorant composition will be described. .

  A polyamic acid can be obtained by reacting a tetracarboxylic dianhydride and a diamine. In the synthesis of the polyamic acid in the present invention, for example, an aliphatic or alicyclic one can be used as the tetracarboxylic dianhydride, and specific examples thereof include 1,2,3,4. -Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5 -Bicyclohexene tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo -3-furanyl) -naphtho [1,2-C] furan-1,3-dione and the like. Further, when an aromatic material is used, a polyamic acid that can be converted into a film having good heat resistance can be obtained. As a specific example, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid Dianhydride, pyromellitic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 4,4 ′ -Oxydiphthalic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ", 4,4"- Examples include paraterphenyl tetracarboxylic dianhydride and 3,3 ″, 4,4 ″ -metaterphenyl tetracarboxylic dianhydride. Further, when a fluorine-based tetracarboxylic dianhydride is used, a polyamic acid that can be converted into a film having good transparency in the short wavelength region can be obtained. As a specific example, 4,4′- (Hexafluoroisopropylidene) diphthalic anhydride and the like. In the present invention, tetracarboxylic dianhydrides can be used alone or in combination of two or more without being limited thereto.

  In the synthesis of the polyamic acid in the present invention, for example, an aliphatic or alicyclic diamine can be used as the diamine, and specific examples thereof include ethylenediamine, 1,3-diaminocyclohexane, 1 4,4-diaminocyclohexane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexyl, and the like. In addition, when an aromatic diamine is used, a polyamic acid that can be converted into a film having good heat resistance can be obtained. Specific examples thereof include 4,4′-diaminodiphenyl ether and 3,4′-diamino. Diphenyl ether, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfide, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, benzidine, 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, o-tolidine, 4, 4 "-diaminoterphenyl, 1,5-diaminonaphthalene, 3,3 ' Dimethyl-4,4′-diaminodiphenylmethane, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-amino Phenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, etc. When a fluorinated diamine is used, A polyamic acid that can be converted into a film having good transparency in the short wavelength region can be obtained. Specific examples thereof include 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane and the like. Is mentioned.

  Moreover, when siloxane diamine is used as a part of diamine, the adhesiveness with an inorganic substrate can be made favorable. Siloxane diamine is usually used in an amount of 1 to 20 mol% in the total diamine. If the amount of siloxane diamine is too small, the effect of improving adhesiveness is not exhibited, and if it is too large, the heat resistance tends to decrease. Specific examples of the siloxane diamine include bis-3- (aminopropyl) tetramethylsiloxane. The present invention is not limited to this, and one or more diamines are used.

  In general, the polyamic acid is synthesized by mixing and reacting a tetracarboxylic dianhydride and a diamine in a polar organic solvent. At this time, the polymerization degree of the polyamic acid obtained can be adjusted by the mixing ratio of diamine and tetracarboxylic dianhydride.

Next, an acrylic resin will be described as an example of the resin used for the photosensitive colorant composition. The acrylic resin generally contains at least an acrylic polymer, a polyfunctional monomer or oligomer, and a photopolymerization initiator in order to provide photosensitivity.
The acrylic polymer that can be used is not particularly limited, but a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound can be preferably used. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides.

  These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. Specific examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, and methacrylic acid. Isopropyl, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, N-pentyl acrylate, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, and other unsaturated carboxylic acid alkyl esters, styrene, p-methyls Rene, aromatic vinyl compounds such as o-methylstyrene, m-methylstyrene and α-methylstyrene, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, aliphatic conjugated dienes such as 1,3-butadiene and isoprene, acryloyl groups at the terminals, Alternatively, macromonomers such as polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and polysilicone having a methacryloyl group And the like, but is not limited to these.

  In addition, it is preferable to use an acrylic polymer having an ethylenically unsaturated group added to the side chain, since the sensitivity during processing is improved. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group. As a method of adding such a side chain to an acrylic copolymer, when the acrylic copolymer has a carboxyl group or a hydroxyl group, an ethylenically unsaturated compound having a glycidyl group, acrylic acid or methacrylic acid is used. A method of addition reaction of chloride is common. In addition, a compound having an ethylenically unsaturated group can be added using isocyanate. Examples of the ethylenically unsaturated compound having glycidyl group and acrylic acid or methacrylic acid chloride include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonic acid, and glycidyl isocrotonate. Examples include ether, acrylic acid chloride, and methacrylic acid chloride.

  Examples of polyfunctional monomers that can be used include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (meth) acrylic acid ester , Phthalic anhydride propylene oxide (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin modified epoxy di (meth) acrylate, alkyd modified (meth) acrylate, tripropylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaeryth Torutori (meth) acrylate, triacrylformal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate. These can be used alone or in combination. Also, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, n-butyl methacrylate, glycidyl methacrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, etc. A monofunctional monomer can also be used in combination, and a mixture of two or more of these or a mixture with other compounds is used. By selecting and combining these polyfunctional and monofunctional monomers and oligomers composed of these monomers, it is possible to control the sensitivity and processability characteristics of the paste. In particular, in order to increase the hardness, it is preferable to use a methacrylate compound rather than an acrylate compound, and in order to increase sensitivity, it is preferable to use a compound having three or more functional groups. Melamines, guanamines and the like can also be preferably used.

  The mixing ratio of the acrylic polymer and the polyfunctional monomer in the photosensitive green colorant composition of the present invention is a weight ratio, preferably in the range of 70:30 to 30:70. If the content of the acrylic polymer is less than 30% by mass, the dissolution in the developer may be lowered, which may cause a problem in patterning performance. In some cases, the required exposure amount becomes too large due to the lowering, resulting in tact over.

  There are no particular limitations on the photopolymerization initiator, and known ones can be used, such as benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2 , 2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholino-1-propane, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1, 4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, etc. Can be given. Further, inorganic photopolymerization initiators such as other acetophenone compounds, imidazole compounds, benzophenone compounds, thioxanthone compounds, phosphorus compounds, triazine compounds, and titanates can also be preferably used. Further, it is preferable to add a sensitizing aid such as p-dimethylaminobenzoic acid ester because the sensitivity can be further improved. Moreover, these photoinitiators can also be used in combination of 2 or more types.

  In the present invention, when a non-photosensitive polyamic acid is used as the resin, the polyamic acid is used as the resin amount, and when a photosensitive acrylic resin is used, the total amount of the acrylic polymer, the acrylic monomer, and the polymer dispersing agent is set. The amount of resin.

  In the green colorant composition of the present invention, the solid content concentration of the pigment and the resin is preferably in the range of 5 to 20% by mass from the viewpoints of coating property and drying property.

  As the solvent used in the green colorant composition of the present invention, a solvent that dissolves the resin to be used can be preferably used. Examples of the solvent for dissolving polyamic acid include amide polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, β-propiolactone, γ-butyrolactone, γ- Examples include lactones such as valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone. In the case of acrylic resins, in addition to these, ethylene glycol or propylene glycol derivatives such as methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, propylene glycol monoethyl ether, or propylene glycol monoethyl ether acetate , Aliphatic esters such as ethyl acetoacetate, methyl-3-methoxypropionate, 3-methyl-3-methoxybutylacetate, or aliphatic alcohols such as ethanol, 3-methyl-3-methoxybutanol, cyclo Examples include ketones such as pentanone and cyclohexanone.

  Moreover, as a solvent used for the green colorant composition of this invention, it may be individual or may use the mixed solvent which combined 2 or more types of solvents suitably. In the case of a mixed solvent, it is possible to use a poor solvent for the resin to be used as a secondary solvent.

  A surfactant may be added to the green colorant composition of the present invention for the purpose of improving the coating property and the drying property of the colored film. The addition amount of the surfactant is usually in the range of 0.001 to 10% by mass, preferably 0.01 to 1% by mass of the pigment. If the addition amount is too small, the effect of improving the coatability and the drying property of the colored coating film is small, and if too much, the reliability of the coating film may be poor. Specific examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, lauryldimethylamine oxide, Amphoteric surfactants such as lauryl carboxymethyl hydroxyethyl imidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate, and silicones based on polydimethylsiloxane Surfactant etc. are mentioned. In the present invention, the surfactant is not limited to these, and one or more surfactants can be used. In addition to the surfactant, an adhesion improver, a curing accelerator, and the like can be added.

The flow characteristics and pigment dispersion stability of the green colorant composition of the present invention can be evaluated using the viscosity and Casson yield value of the green colorant composition. The viscosity of the green colorant composition is preferably 1 to 300 mPa · s, more preferably 5 to 100 mPa · s. If the viscosity of the green colorant composition is too high or too low, it is difficult to uniformly apply the green colorant composition. On the other hand, the Casson yield value of the green colorant composition is preferably 1 × 10 ⁻³ Pa or less, more preferably 1 × 10 ⁻⁴ Pa or less. A smaller Casson yield value is preferable because the pigment in the green colorant composition is more stably dispersed and the contrast ratio of the color filter obtained from the green colorant composition is increased.

Hereinafter, a method for producing a color filter using the green colorant composition of the present invention will be described.
The color filter usually has a structure in which pixels of three colors of red, green, and blue are formed on a transparent substrate on which a black matrix is formed.

  In the color filter of the present invention, a green pixel is formed using a green colorant composition containing a chlorinated copper phthalocyanine pigment and a yellow pigment having an average number of introduced chlorine atoms per molecule of 15.1 to 16.0. It is necessary to form. The red colorant composition for forming red pixels and blue pixels, and the blue colorant composition are not particularly limited. For example, as with the green colorant composition of the present invention described above, a resin, It is prepared by toning with a pigment system comprising a main pigment and a sub-pigment in a solvent.

  As the black matrix, a resin black matrix in which a light shielding material such as carbon black or titanium black is dispersed in the resin can be preferably used.

  As a method of applying the colorant composition on the substrate, a method of applying to the substrate by a spin coater, a bar coater, a blade coater, a roll coater, a die coater, an ink jet printing method, a screen printing method, or the like, and immersing the substrate in a solution Various methods such as spraying a solution onto a substrate can be used. As the substrate, a transparent substrate such as soda glass, non-alkali glass, borosilicate glass, or quartz glass, or a semiconductor substrate such as silicon or gallium arsenide is usually used, but is not particularly limited thereto. In addition, when a pigment green colorant composition is applied on a substrate, if the substrate surface is treated with an adhesion aid such as a silane coupling agent, an aluminum chelating agent, or a titanium chelating agent, the adhesion between the colored coating and the substrate is achieved. Power can be improved and done as needed.

  After coating the green colorant composition on the transparent substrate by the method as described above, a coating film of the green colorant composition is formed by air drying, heat drying, vacuum drying or the like. In the case of heat-drying, it is preferable to use an oven, a hot plate, etc., and carry out at 50-180 degreeC for 1 minute-3 hours. Next, when the green colorant composition is non-photosensitive, a photoresist is applied on the coating film to form a photoresist film. In the case of photosensitivity, a photoresist is not necessary, but an oxygen blocking film may be formed if necessary. Subsequently, a mask is placed on the coating and irradiated with ultraviolet rays using an exposure apparatus. Next, the color paste coating film is etched with an alkali developer. When there is a photoresist film or an oxygen barrier film, the development or etching of these is performed at the same time, and then these are removed with a stripping solution.

  The alkaline substance used in the alkaline developer is not particularly limited. For example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, ethylamine, n -Primary amines such as propylamine, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, tetraalkylammonium hydroxy such as tetramethylammonium hydroxide (TMAH) Quaternary ammonium salts such as choline, triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol, pyrrole, piperidine, 1,8-dia Bicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, organic alkalis such as cyclic amines such as morpholine. Depending on development conditions and coating film conditions, the inorganic alkali is preferably potassium hydroxide or sodium carbonate, and the organic alkali is a hydroxyl-containing organic amine such as a tetraalkylammonium hydroxide or an alcoholamine. More specifically, diethylaminoethanol, dimethylaminoethanol, and TMAH are particularly preferable because of excellent permeability to the etching film. Further, a water-soluble organic solvent such as ethanol, γ-butyrolactone, dimethylformamide, N-methyl-2-pyrrolidone may be appropriately added to the above alkaline developer.

  Thereafter, the obtained coating film pattern is heated to be a color filter in which green pixels are patterned. The heat treatment is usually performed in air, in a nitrogen atmosphere, or in a vacuum at a temperature of 150 to 350 ° C., preferably 180 to 300 ° C., for 0.5 to 5 hours continuously or stepwise. Done. By this heating step, the polyimide precursor is converted into polyimide, and the photosensitive acrylic resin is cured.

  When the patterning process as described above is sequentially performed for each color such as red, green, and blue, a color filter for a liquid crystal display device can be manufactured. Here, the patterning order of each color is not limited. In the present invention, the green pixel of the color filter is green-colored containing a chlorinated copper phthalocyanine pigment, a yellow pigment, a resin and a solvent having an average number of introduced chlorine atoms per molecule of 15.1 to 16.0. By forming using the agent composition, a color filter with high color purity, high contrast ratio, and high brightness can be obtained with a thin film.

  The film thickness of the green pixel of the color filter of the present invention is usually 0.5 to 2.5 μm, preferably 0.8 to 2.3 μm. When the film thickness is thinner than 0.8 μm, the light absorption is small and the color purity of the color filter is likely to be low. On the other hand, if the film thickness is greater than 2.3 μm, various problems such as a decrease in flatness of the color filter, a decrease in pattern workability, and a decrease in reliability are likely to occur.

  The color purity of the green pixel of the color filter of the present invention can be evaluated from the relationship between y and the film thickness of chromaticity coordinates (x, y) in the C light source XYZ display system. The green pixel of the color filter usually has higher color purity as the pixel film thickness increases, but the upper limit of the practical film thickness is 2.5 μm as described above. It is required to be purified. In the case of a green pixel, the color purity can be evaluated from the film thickness at a constant y or the film thickness y at a constant film thickness. The smaller the film thickness at a constant y, the more the y at a constant film thickness. The larger the value is, the thinner the film is and the higher the color purity.

  In the color filter of the present invention, the film thickness at chromaticity coordinates (x, y) at y = 0.650 is preferably 1.9 μm or less, more preferably 1.7 μm or less. By setting the film thickness at y = 0.650 to 1.7 or less, it is possible to obtain a color filter having a very high color purity with a thin film. The average number of introduced chlorine atoms per molecule of chlorinated copper phthalocyanine is 15.1-16.0, preferably chlorinated copper phthalocyanine: yellow pigment = 90: 10-50: 50 (weight ratio). As a result, the film thickness of the green pixel at y = 0.650 can be reduced to 1.9 μm or less, and the green pixel of the color filter can be highly purified with a thin film.

  Since the color filter of the present invention is obtained by toning a chlorinated copper phthalocyanine pigment having an average number of introduced chlorine atoms of 15.1 to 16.0 per molecule of chlorinated copper phthalocyanine with a yellow pigment, With a film thickness of 2.5 μm or less, a wide range of colors with chromaticity coordinates (x, y) of y = 0.50 to 0.710 and x = 0.160 to 0.260 can be reproduced. The display can greatly widen the color reproduction range.

  The luminance of the color filter of the present invention can be evaluated using, for example, the luminance (Y) in the C light source XYZ display system. In the color filter of the present invention, Y at y = 0.650 of the chromaticity coordinates (x, y) is preferably 40, more preferably 41 or more. By setting Y at y = 0.650 to 40 or more, it is possible to obtain a color filter that is a thin film and has ultrahigh color purity and high luminance.

  In the color filter of the present invention, the contrast ratio at y = 0.650 of chromaticity coordinates (x, y) is usually 1000 or more, preferably 2000 or more. The larger the contrast ratio of the color filter, the better the visibility of the liquid crystal display. The average number of introduced chlorine atoms per molecule of chlorinated copper phthalocyanine is 15.1-16.0, a yellow pigment is added, and the average number of introduced sulfonic acid groups per molecule of the copper phthalocyanine pigment derivative is 1. The contrast ratio of the color filter can be set to 1000 or more by setting the number of .9 to 2.4.

  Hereinafter, although this invention is demonstrated in more detail using a preferable embodiment, the efficacy of this invention is not restrict | limited at all by the embodiment used.

  Evaluation of the chlorinated copper phthalocyanine pigment, the copper phthalocyanine pigment derivative, the green colorant composition, and the color filter in the examples was performed by the following methods.

<Measurement method>
(Average number of introduced chlorine atoms in chlorinated copper phthalocyanine pigment)
Using a laser time-of-flight mass spectrometer (AXIMA-TOF ² manufactured by Shimadzu Corporation), negative ions of chlorinated copper phthalocyanine pigments were measured by a laser desorption ionization method. For the measurement, a nitrogen laser having a wavelength of 337 nm was used, and no matrix was used. The number of introduced chlorine in the chlorinated copper phthalocyanine pigment is determined in the range of 10 to 2000 in terms of the ratio (m / z) of the mass (m) and the charge (z) of ions generated by ionization. Asked.

(Average number of introduced sulfonic acid groups in pigment derivatives)
Using m-nitrobenzyl alcohol as a matrix, negative ion measurement of the pigment derivative was performed using a fast atom bombardment ionization mass spectrometer (JMS-SX102A, manufactured by JEOL Ltd.). The measurement is carried out in the range of 10 to 2000 by the ratio (m / z) of the mass (m) and charge (z) of ions generated by ionization, and the sulfonic acid group introduction of the pigment derivative is introduced from the obtained intensity ratio of m / z. I asked for a number.

(Viscosity of pigment dispersion)
The viscosity of the pigment dispersion at 25 ° C. was measured using a conical plate viscometer (RE100L manufactured by Toki Sangyo Co., Ltd.).

(Yield value of pigment dispersion)
Using a conical plate viscometer (RE100L manufactured by Toki Sangyo Co., Ltd.), the viscosity at different shear rates was measured at three points, and the yield value was determined by using the Casson equation. The dispersion stability of the pigment dispersion was evaluated from the obtained yield value.

(Contrast ratio of color filter formed from green colorant composition)
A colored film formed by coating a green colorant composition on a glass substrate is prepared, placed between the polarizer and the analyzer so that the film surface falls within the entire measurement area, and the polarizer and the analyzer are parallel to each other. The contrast ratio was calculated by measuring the light transmittance (I1) at the time and the ratio (I1 / I2) of the light transmittance (I2) when the polarizer and the analyzer were orthogonal. A polarizing film “NPF-G1220DUN” manufactured by Nitto Denko Corporation was used for the polarizer and the analyzer. “FL8A-EX / 70” manufactured by Meidaku System, which is a backlight unit using a hot cathode tube as a light source, was used, and “BM-5A” manufactured by Topcon Corporation was used as a color luminance meter.

(Chromaticity of the color filter formed from the colorant composition)
The chromaticity coordinates (x, y) and luminance (Y) in the C light source XYZ color system of the colored film were measured using a microspectrophotometer “MCPD-2000” manufactured by Otsuka Electronics Co., Ltd.

(The film thickness of the color filter formed from the colorant composition)
The film thickness of the colored film was measured using a surface step meter “Surfcom 1400D” manufactured by Tokyo Seimitsu Co., Ltd.

Reference example 1
Into a glass reaction vessel having a gas introduction tube, 50 g of copper phthalocyanine pigment (Clariant's “Hosta Palm Blue” (trade name) A2-R), 350 g of sodium chloride, and 350 g of aluminum chloride are charged. did. Thereafter, the slurry was heated to 180 ° C. to melt the slurry. Chlorine gas was injected into the molten slurry, and a chlorination reaction was performed at 180 ° C. for 24 hours. After completion of the reaction, the melt was poured into 2000 g of ice water, and the resulting precipitate was filtered. The obtained wet crystals were washed with pure water and then dried at 80 ° C. The operations obtained by drying, washing with pure water, filtering, and drying were repeated 10 times to obtain chlorinated copper phthalocyanine pigment 1. When the number of introduced chlorine in the chlorinated copper phthalocyanine pigment 1 was measured by the above method, a peak at m / z = 1126 indicating that 16 chlorine atoms were introduced, indicating that 15 chlorine atoms were introduced. A peak at m / z = 1093 and a peak at m / z = 1059 indicating that 14 chlorine atoms were introduced were confirmed. When the number of introduced chlorine was calculated from these peak intensity ratios, it was 87% for 16 introduced chlorine, 11% for 15 introduced chlorine, 2% for 14 introduced chlorine, chlorine The average number of introduced chlorine per molecule of copper phthalocyanine was 15.85.

Reference example 2
A chlorination reaction was carried out in the same manner as in Synthesis Example 1 except that the chlorination reaction time was 8 hours to obtain a chlorinated copper phthalocyanine pigment 2. When the number of chlorine introductions of this chlorinated copper phthalocyanine pigment 2 was measured by the above method, a peak of m / z = 1126 indicating that 16 chlorine atoms were introduced, indicating that 15 chlorine atoms were introduced. A peak at m / z = 1093 and a peak at m / z = 1059 indicating that 14 chlorine atoms were introduced were confirmed. When the number of chlorine introductions was calculated from these peak intensity ratios, it was 66% for 16 chlorine introductions, 28% for 15 chlorine introductions, and 6% for 14 chlorine introductions by weight. Yes, the average number of introduced chlorine per molecule of chlorinated copper phthalocyanine was 15.60.

Reference example 3
A chlorination reaction was carried out in the same manner as in Synthesis Example 1 except that the chlorination reaction time was 4 hours to obtain a chlorinated copper phthalocyanine pigment 3. When the number of introduced chlorine in the chlorinated copper phthalocyanine pigment 3 was measured by the above method, a peak at m / z = 1126 indicating that 16 chlorine atoms were introduced, indicating that 15 chlorine atoms were introduced. A peak at m / z = 1093 and a peak at m / z = 1059 indicating that 14 chlorine atoms were introduced were confirmed. When the number of chlorine introductions was calculated from these peak intensity ratios, the number of chlorine introductions of 16 was 46%, the number of chlorine introductions of 15 was 43%, and the number of chlorine introductions of 14 was 11%. The average number of chlorine introduced per molecule of copper phthalocyanine was 15.35.

Reference example 4
60 g of PB15: 3 (Clariant “Hosta Palm Blue” B2G) was added to 780 g of fuming sulfuric acid (28% SO ₃ ) heated to 70 ° C. with stirring. After stirring for 3 hours, the mixture was added on 1500 g of ice. After standing for 30 minutes, the resulting suspension was filtered, and the resulting product was washed with 300 ml of pure water. The product was put into 2000 ml of pure water, neutralized with an aqueous ammonia solution (added with an aqueous ammonia solution until the pH reached 7 or more), and filtered. The obtained wet crystals were washed with pure water and then dried at 80 ° C. The operations obtained by drying, washing with pure water, filtering, and drying were repeated 10 times to obtain 69 g of a derivative in which a sulfonic acid group was introduced into a copper phthalocyanine pigment. Next, after mixing this copper phthalocyanine pigment-containing derivative and ion-exchanged water, the slurry was dialyzed using a PMMA dialysis module ("Filtizer" (trade name) B3-20A manufactured by Toray Industries, Inc.) A phthalocyanine pigment derivative dialyzate 1 was obtained. When the number of introduced sulfonic acid groups in the dialyzed copper phthalocyanine pigment derivative 1 after dialysis was measured by the above method, two peaks of m / z = 654 indicating that one sulfonic acid group was introduced were introduced. A peak at m / z = 734 indicating that 3 peaks were observed, and a peak at m / z = 814 indicating that 3 were introduced. When the number of introduced sulfonic acid groups was calculated from these peak intensity ratios, the number of introduced sulfonic acid groups was 1%, that of 2 introduced sulfonic acid groups was 71%, and the number of introduced sulfonic acid groups was 3 And the average number of introduced sulfonic acid groups per molecule of the copper phthalocyanine pigment derivative was 2.1.

Reference Example 5
4,4′-diaminobenzanilide 161.3 g, 3,3′-diaminodiphenylsulfone 176.7 g, and bis (3-aminopropyl) tetramethyldisiloxane 18.6 g were replaced with γ-butyrolactone 2667 g, N-methyl-2 -Charged with 527 g of pyrrolidone, added 439.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, reacted at 70 ° C. for 3 hours, then added 2.2 g of phthalic anhydride, Furthermore, it was made to react at 70 degreeC for 2 hours, and the 20 weight% polyamic acid solution 1 was obtained.

Reference Example 6
4,5′-Diaminodiphenyl ether 95.1 g and bis (3-aminopropyl) tetramethyldisiloxane 6.2 g were charged together with 525 g of γ-butyrolactone and 220 g of N-methyl-2-pyrrolidone. After adding 144.1 g of '-biphenyltetracarboxylic dianhydride and reacting at 70 ° C for 3 hours, adding 3.0 g of phthalic anhydride and further reacting at 70 ° C for 2 hours, 25% by weight of polyamic acid was added. An acid solution 2 was obtained.

Example 1
(Preparation of green colorant composition)
34.5 g of the chlorinated copper phthalocyanine pigment 1 obtained in Reference Example 1, 1.0 g of the copper phthalocyanine pigment derivative dialyzed product 1 obtained in Reference Example 4, 19.5 g of PY138 (“Pariotol Yellow, manufactured by BASF Corporation) "D0960), 8 g of PY185 (" Pariotol Yellow "D1155 manufactured by BASF), 35 g of the polyamic acid solution 1 obtained in Reference Example 5, and 902 g of γ-butyrolactone were mixed and stirred with a homodisper. A slurry was prepared. The beaker containing the slurry was connected with a circulation type bead mill disperser ("Dynomill" KDL-A manufactured by Willy et Bacofen) and a tube, and zirconia beads having a diameter of 0.3 mm were used as a medium at 3200 rpm for 3 hours. Dispersion treatment was performed to obtain a green pigment dispersion.

13.5 g of polyamic acid solution 2, 13.3 g of γ-butyrolactone, and 13.1 g of 3-methoxy-3-methyl-1-butanol were added to 59.5 g of this green pigment dispersion, and bic chemie was further added. Surfactant “BYK361” manufactured by the company was added to a total solid content of 1000 ppm to obtain a green colorant composition.
The mixing ratio of the pigment and the resin in the green colorant composition was 50:50 by weight, and chlorinated copper phthalocyanine pigment: PY138: PY185 = 56: 31: 13.
(Production of color filter)
The said green colorant composition was apply | coated using the spinner on the transparent glass substrate, and the green coloring film was obtained by heat-processing in 120 degreeC after that for 10 minutes in a hot air oven after that. Subsequently, a positive photoresist (“OFPR-800” manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied on the green colored film and dried at 90 ° C. for 10 minutes. Using a UV exposure machine “PLA-501F” manufactured by Canon Inc., exposure was performed at 60 mJ / cm 2 (ultraviolet intensity of 365 nm) through a chrome photomask. After the exposure, the film was immersed in a developer composed of a 2.25% aqueous solution of tetramethylammonium hydroxide, and development of the photoresist and etching of the colored coating film of the polyimide precursor were simultaneously performed. The photoresist layer that became unnecessary after etching was stripped with methyl cellosolve acetate. Furthermore, the colored coating film of the polyimide precursor was heat-treated at 270 ° C. for 30 minutes to convert to polyimide. Thus, a color filter having green pixels was formed. The spinner rotation speed of the green colorant composition was adjusted so that the chromaticity of the green pixel after curing the color filter was y = 0.650 with a C light source.

Example 2
(Production of color filter)
Except that the green colorant composition obtained in Example 1 was used and the spinner rotation speed was adjusted so that the chromaticity of the green pixel after curing the color filter was y = 0.600 with a C light source. A color filter was formed in the same manner as in Example 1.

Example 3
(Production of color filter)
Except that the green colorant composition obtained in Example 1 was used and the spinner rotation speed was adjusted so that the chromaticity of the green pixel after curing the color filter was y = 0.695 with a C light source. A color filter was formed in the same manner as in Example 1.

Comparative Example 1
(Production of green colorant composition and color filter)
34.5 g of PG7 (“Hosta Palm Green” (trade name) GNX manufactured by Clariant), 1.0 g of the copper phthalocyanine pigment derivative dialyzate 1 obtained in Reference Example 4, 19.5 g of PY138 (manufactured by BASF) A green colorant composition and a color filter were prepared in the same manner as in Example 1 using “Pariol Yellow” D0960) and 8 g of PY185 (“Pariotol Yellow” D1155 manufactured by BASF). When the number of chlorine introductions of Hosta Palm Green GNX was measured by the above method, m / z = 1126 peak indicating that 16 chlorine atoms were introduced, m indicating that 15 chlorine atoms were introduced. A peak at / z = 1093, a peak at m / z = 1059 indicating that 14 chlorine atoms were introduced, and a peak at m / z = 1027 indicating that 13 chlorine atoms were introduced were confirmed. When the number of chlorine introductions was calculated from these peak intensity ratios, the number of chlorine introductions of 16 was 25%, the number of chlorine introductions of 15 was 55%, the number of chlorine introductions of 14 was 18%, the number of chlorine introductions Thirteen were 2% and the average number of introduced chlorine per molecule of chlorinated copper phthalocyanine pigment was 15.03. The mixing ratio of the pigment and the resin in the green colorant composition was 50:50 by weight, and chlorinated copper phthalocyanine pigment: PY138: PY185 = 56: 31: 13.

Comparative Example 2
(Production of green colorant composition and color filter)
Using 61.1 g of the chlorinated copper phthalocyanine pigment 1 obtained in Reference Example 1 and 1.9 g of the copper phthalocyanine pigment derivative dialyzate 1 obtained in Reference Example 4, the same procedure as in Example 1 was carried out to give a green color. An agent composition and a color filter were prepared. The mixing ratio of the pigment and the resin in the green colorant composition was 50:50 by weight, and chlorinated copper phthalocyanine pigment: yellow pigment = 100: 0. Except that this green colorant composition was used and the spinner rotation speed was adjusted so that the chromaticity of the green pixel after curing the color filter was y = 0.455 with a C light source, the same as in Example 1. A color filter was formed.

Comparative Example 3
(Production of green colorant composition and color filter)
34.5 g of the chlorinated copper phthalocyanine pigment 2 obtained in Reference Example 2, 1.0 g of the copper phthalocyanine pigment derivative dialyzed product 1 obtained in Reference Example 4, 19.5 g of PY138 (“Pariol, manufactured by BASF Corporation) A green colorant composition and a color filter were produced in the same manner as in Example 1 using yellow “D0960) and 8 g of PY185 (“ Pariol Yellow ”D1155 manufactured by BASF). The mixing ratio of the pigment and the resin in the green colorant composition was 50:50 by weight, and chlorinated copper phthalocyanine pigment: PY138: PY185 = 56: 31: 13.

Comparative Example 4
(Production of green colorant composition and color filter)
34.5 g of the chlorinated copper phthalocyanine pigment 3 obtained in Reference Example 3, 1.0 g of the copper phthalocyanine pigment derivative dialyzed product 1 obtained in Reference Example 4, 19.5 g of PY138 (“Pariol, manufactured by BASF Corporation) A green colorant composition and a color filter were produced in the same manner as in Example 1 using yellow “D0960) and 8 g of PY185 (“ Pariol Yellow ”D1155 manufactured by BASF). The mixing ratio of the pigment and the resin in the green colorant composition was 50:50 by weight, and chlorinated copper phthalocyanine pigment: PY138: PY185 = 56: 31: 13.

Example 6
(Production of green colorant composition and color filter)
18. 34.5 g of chlorinated copper phthalocyanine pigment 1 obtained in Reference Example 1, a commercially available pigment derivative in which a sulfonic acid group is introduced into 1.0 g of copper phthalocyanine pigment (“Solsperse” 12000, manufactured by Avicia), A green colorant composition was used in the same manner as in Example 1, except that 5 g of PY138 (BSS, “Pariol Yellow” D0960) and 8 g of PY185 (BSS, “Pariol Yellow” D1155) were used. A color filter was prepared. The mixing ratio of the pigment and the resin in the green colorant composition was 50:50 by weight, and chlorinated copper phthalocyanine pigment: PY138: PY185 = 56: 31: 13.

  When the number of sulfonic acid groups introduced into Solsperse 12000 was measured by the above method, m / z = 654 peak indicating that one sulfonic acid group was introduced, and m / z indicating that two sulfonic acid groups were introduced. = 734 peak, m / z = 814 peak indicating that 3 were introduced was observed. When the number of sulfonic acid groups introduced was calculated from these peak intensity ratios, the number of introduced sulfonic acid groups was 26%, the number of introduced sulfonic acid groups was 2%, the number of introduced sulfonic acid groups was 3%. The average number of introduced sulfonic acid groups per molecule of the copper phthalocyanine pigment derivative was 1.8%.

Example 7
(Preparation of photosensitive green colorant composition using acrylic polymer)
56.4 g of the chlorinated copper phthalocyanine pigment 1 obtained in Reference Example 1, 1.6 g of the copper phthalocyanine pigment derivative dialyzed product 1 obtained in Reference Example 4, 31 g of PY138 (“Pariol Yellow” manufactured by BASF) D0960), 13 g of PY185 (“Pariotol Yellow” D1155, manufactured by BASF), 90 g of Ajinomoto Finetechno “Asper” PB821 in propylene glycol monomethyl ether acetate solution (30 wt%), 16 g of “Dycel Chemical” cyclomer A green pigment dispersion was obtained in the same manner as in Example 6 using ACA250 (45 wt% solution) and 794 g of propylene glycol monomethyl ether acetate.
7.9 g of cyclomer ACA250 (45 wt% solution), 4.2 g of Nippon Kayaku multifunctional monomer “Kayarad” DPHA, 2.5 g of Ciba・ After adding Photochemical Initiator "Irgacure" 907, Nippon Kayaku Sensitizer "Kayacure" DETX-S, and 14.9 g Propylene Glycol Monomethyl Ether Acetate, Bic Chemie Interface An activator “BYK333” was added to a total solid content of 2000 ppm to obtain a photosensitive green colorant composition.
The mixing ratio of the pigment and the resin in the photosensitive green colorant composition was 40:60 by weight, and the chlorinated copper phthalocyanine pigment: PY138: PY185 = 56: 31: 13.

(Production of color filter)
The photosensitive green colorant composition obtained on the transparent glass substrate was applied with a spinner, and then heat-treated in a hot air oven at 90 ° C. for 10 minutes to obtain a green colored film. Next, a predetermined area is exposed through a negative mask, and “Emulgen” A-60 (HLB12.8, polyoxyethylene derivative) as a nonionic surfactant is added to a 0.04% aqueous potassium hydroxide solution (manufactured by Kao Corporation). ) Was developed by immersing with an alkali developer added at 0.1% by mass with respect to the total amount of the developer for 90 seconds, followed by washing with pure water to obtain a patterned substrate. The obtained patterned substrate was held in a hot air oven at 220 ° C. for 30 minutes to cure the acrylic resin. Thus, a color filter having green pixels was produced.
The spinner rotation number of the green colorant composition was adjusted so that the chromaticity of the green pixel after curing the color filter was y = 0.650 with a C light source.

  Table 1 shows various evaluation results of the green colorant composition and the color filter obtained in Examples 1 to 7 and Comparative Examples 1 and 2.

Claims (3)

A green colorant composition for a color filter containing at least a resin, a solvent, a chlorinated copper phthalocyanine pigment, and a yellow pigment, wherein the average introduction number of chlorine atoms per molecule of the chlorinated copper phthalocyanine of the chlorinated copper phthalocyanine pigment is 15.7 to 16.0, and further contains a pigment derivative having a sulfonic acid group introduced into a copper phthalocyanine pigment, and the average number of introduced sulfonic acid groups per molecule of the pigment derivative is 1.9 to 2.4. A green colorant composition for a color filter , which is individual and contains PY138 and PY185 as yellow pigments. Mixing ratio by weight of the chlorinated copper phthalocyanine pigment and a yellow pigment, 90: 10-50: claim 1 Symbol mounting color filters for green colorant composition characterized in that it is a 50. The color filter composition for color filters according to claim 1 or 2 , wherein the color film has a pixel comprising a colored film provided in a desired pattern for each color with an arbitrary number of colors. A color filter formed by the method described above.