JP2010152054A - Color filter substrate for liquid crystal display device and liquid crystal display device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter which has a wide color reproduction range, excels in white balance, and has a high contrast ratio, and to provide a liquid crystal display device which excels in visibility. <P>SOLUTION: In a color filter substrate for a liquid crystal display device where a red pixel, a green pixel and a blue pixel are formed on a transparent substrate, a pigment red 177 and a pigment red 254 are contained as pigments of the red pixel, a pigment green 7 and a pigment yellow 150 are contained as pigments of the green pixel, and a pigment blue 15:6 and a pigment violet 23 are contained as pigments of the blue pixel, and at least one color pixel contains a complementary color pigment of the pixel and/or a black pigment. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a color filter substrate for a liquid crystal display device and a liquid crystal display device using the same.

  Liquid crystal displays are used for various applications such as notebook PCs, mobile phones, digital cameras, desktop monitors, etc., taking advantage of their characteristics such as light weight, thinness, and low power consumption, and the color reproduction range equivalent to that of existing cathode ray tube (CRT) TVs. A liquid crystal display having the above has been developed. The color reproduction range is expressed by an area ratio with respect to the NTSC (National Television System Committee) standard of a triangle formed by connecting the chromaticity coordinates of red, green, and blue in the XYZ color system chromaticity diagram.

  In recent years, the NTSC ratio has been brought closer to 100% to faithfully reproduce the vivid colors of crimson roses and beautiful green colors of tropical seas that could not be expressed on conventional CRT TVs. Has been strongly demanded. The chromaticity coordinates (x, y) in the XYZ color system chromaticity diagram of each color of red, green and blue having an NTSC ratio of 100% are red pixel (0.670, 0.330) and green pixel (0.210, 0.710), respectively. ), Blue pixels (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.

  In Patent Document 1, pigment red 254, pigment red 177 and the like are used as pigments for red pixels, pigment green 7 and pigment yellow 150 are used as pigments for green pixels, and pigment blue 15: 6 and pigment are used as pigments for blue pixels. By using Violet 23 or the like, a color filter having a color reproduction range NTSC ratio of 72 to 88% and excellent white balance is provided. However, when trying to expand the color reproduction range to 100% of the NTSC ratio with this pigment system, there is a problem that the white balance rapidly deteriorates.

  Further, in Patent Document 2, by using Pigment Red 254 and Pigment Violet 23 as red pixel pigments, a color filter having a color reproduction range NTSC ratio of 72% and excellent white balance is provided. However, even with this pigment system, there is a problem that white balance is rapidly deteriorated when the color reproduction range is expanded to 100% of the NTSC ratio.

On the other hand, there is a method of adjusting white balance by including an achromatic colorant in a pixel (Patent Document 3). In Patent Document 3, white balance is adjusted by adding carbon black or the like to the green pixel and the red pixel of the color filter for organic EL display. However, this method has a problem that the color reproduction range of the color filter is low at 40% of NTSC. Furthermore, since it is difficult to stabilize carbon black with nano-dispersion, when this color filter is used for a liquid crystal display, the contrast ratio may be lowered.
JP 2008-96471 A JP 2002-350627 A JP 2005-331796 A

  An object of the present invention is to provide a color filter having a wide color reproduction range and excellent white balance. It is another object of the present invention to provide a color filter having a high contrast ratio. Furthermore, it aims at providing the liquid crystal display device which is excellent in visibility.

1. In a color filter substrate for a liquid crystal display device in which red pixels, green pixels, and blue pixels are formed on a transparent substrate, pigment red 177 and pigment red 254 are pigments for red pixels, and pigment green 7 and pigment yellow 150 are pigments for green pixels. A color filter for a liquid crystal display device comprising: Pigment Blue 15: 6 and Pigment Violet 23 as a pigment for a blue pixel, and at least one color pixel containing a complementary color pigment and / or a black pigment for the pixel substrate.
2. 2. The color filter substrate for a liquid crystal display device according to item 1, wherein the complementary color pigment of the red pixel is at least one pigment selected from a green pigment, a blue-green pigment, and a blue pigment.
3. 3. The color filter substrate for a liquid crystal display device according to item 2, wherein the complementary color pigment of the red pixel is Pigment Blue 15: 6.
4). 4. The color filter substrate for a liquid crystal display device according to any one of 1 to 3, wherein the complementary color pigment of the blue pixel is at least one pigment selected from a red pigment and a yellow pigment.
5). 5. The color filter substrate for a liquid crystal display device according to item 4, wherein the complementary color pigment of the blue pixel is Pigment Yellow 150.
6). 6. The color filter substrate for a liquid crystal display device according to any one of 1 to 5, wherein the black pigment is carbon black.
7. A liquid crystal display device using the color filter substrate for a liquid crystal display device according to any one of items 1 to 6.

  The color filter of the present invention contains pigment red 177 and pigment red 254 as pigments for red pixels, pigment green 7 and pigment yellow 150 as pigments for green pixels, and pigment blue 15: 6 and pigment violet 23 as pigments for blue pixels. For this reason, the color reproduction range can be expanded to 100% of the NTSC ratio, and at least one color pixel contains a complementary color pigment and / or a black pigment of the pigment, and thus has an excellent white balance.

Furthermore, the color filter of the present invention can preferably have a high contrast ratio by setting the complementary color pigment contained in the red pixel to Pigment Blue 15: 6 and the complementary color pigment contained in the blue pixel to Pigment Yellow 150. .
Therefore, the liquid crystal display using the color filter of the present invention is excellent in visibility.

  The color filter of the present invention has a red pixel, a green pixel, and a blue pixel, pigment red 177 (PR177) and pigment red 254 (PR254) as pigments for red pixels, and pigment green 7 (PG7) as a pigment for green pixels and Pigment Yellow 150 (PY150), Pigment Blue 15: 6 (PB15: 6) and Pigment Violet 23 (PV23) as pigments of blue pixels, and at least one color pixel of the above-mentioned complementary pigment and / or black pigment It is necessary to contain.

  In the color filter of the present invention, the weight mixing ratio of PR177 and PR254 contained in the red pixel is usually PR177: PR254 = 10: 90 to 90:10, preferably PR177: PR254 = 30: 70 to 60:40. If the weight mixing ratio is less than 10:90, the transmission spectrum in the red region becomes broad and the color reproduction range of the color filter becomes narrow. On the other hand, when the weight mixing ratio is larger than 90:10, it is difficult to cut the transmittance other than the red region, and thus the color reproduction range of the color filter is narrowed. If the weight mixing ratio is less than 30:70, the contrast ratio of the color filter may be low, and if it is less than 60:40, the brightness of the color filter may be low.

  The weight mixing ratio of PG7 and PY150 contained in the green pixel is usually PG7: PY150 = 30: 70 to 90:10, preferably PG7: PY150 = 50: 50 to 70:30. When the weight mixing ratio is less than 30:70, it is difficult to cut the transmittance other than the green region, and the color reproduction range of the color filter is narrowed. On the other hand, if it is larger than 90:10, the transmission spectrum in the green region becomes broad, and the color reproduction range of the color filter becomes narrow. Further, when the weight mixing ratio is smaller than 50:50, the contrast ratio of the color filter may be lowered, and when larger than 70:30, the luminance of the color filter may be lowered.

  The weight mixing ratio of PB15: 6 and PV23 contained in the blue pixel is usually PB15: 6: PV23 = 60: 40 to 95: 5, preferably PB15: 6: PV23 = 70: 30 to 90:10. When the weight mixing ratio is less than 60:40, it is difficult to cut the transmittance other than the blue region, and the color reproduction range of the color filter is narrowed. On the other hand, if the weight mixture ratio is larger than 95: 5, the transmission spectrum in the blue region becomes broad, and the color reproduction range of the color filter becomes narrow. Further, when the weight mixing ratio is less than 70:30, the contrast ratio of the color filter may be lowered, and when larger than 90:10, the luminance of the color filter may be lowered.

  Usually, when the color reproduction range of the color filter is expanded to 100% with the above pigment system, the white chromaticity is greatly shifted to red. Therefore, a color filter with a preferable white balance is required for adjusting the pigment density and film thickness of each pixel. Can't get. On the other hand, in the present invention, a color filter that can expand the color reproduction range up to 100% of NTSC ratio and has excellent white balance by including at least one color pixel of the color filter with a complementary color pigment and / or a black pigment. Can be provided.

  Usually, the complementary color represents a color having a relationship opposite to that in the color correlation diagram. For example, a red complementary color is blue-green, a yellow-green complementary color is purple, and a blue-purple complementary color is yellow.

  The red pixel of the color filter of the present invention is red in a broad sense, but strictly speaking, depending on the combination of pigments such as PR177 and PR254, the color correlation diagram shows reddish yellow, yellowish orange, orange, reddish orange, yellow It is appropriately adjusted to red, red, purple red, red purple, and reddish purple. For this reason, pigments which are complementary colors of these colors are used as complementary color pigments. In the present invention, when a complementary color pigment is added to a red pixel, a green pigment, a blue-green pigment, or a blue pigment is preferably used as the complementary color pigment. Examples of green pigments include PG7, PG36, PG58, etc., blue-green pigments include PB15: 3, PB15: 4, etc., and blue pigments include PB15: 6, PB60, etc., PB15: 3 PB15: 4 and PB15: 6 are more preferable, and PB15: 6 is more preferable. By containing PB15: 3, PB15: 4, and PB15: 6, the white balance of the color filter becomes good. Particularly, by containing PB15: 6, the white balance of the color filter becomes good and the contrast ratio becomes high. .

  When PB15: 6 is contained in the red pixel as a complementary color pigment, the weight mixing ratio of the total amount of PR177 and PR254 and PB15: 6 is preferably (PR177 + PR254): PB15: 6 = 95: 5 to 99.9: 0.1, more preferably 98: 2 to 99.5: 0.5. If the weight mixture ratio is less than 98: 2, the luminance of the color filter may be undesirably lowered. If the weight mixture ratio is greater than 99.9: 0.1, the white balance may be poor.

  The blue pixel of the color filter of the present invention is blue in a broad sense, but strictly speaking, depending on the combination of pigments such as PB15: 6 and PV23, the color correlation diagram is strictly greenish blue, blue, purple blue, blue purple. The color is adjusted appropriately to bluish purple and purple. For this reason, pigments which are complementary colors of these colors are used as complementary color pigments. When a complementary color pigment is added to a blue pixel in the present invention, a red pigment or a yellow pigment is preferably used as the complementary color pigment. Examples of red pigments include PR177 and PR254, and examples of yellow pigments include PY138, PY139, PY150, and PY185. PY138, PY139, PY150, and PY185 are more preferable, and PY150 is more preferable. By using PY138, PY139, PY150, and PY185, the white balance of the color filter is improved. In particular, by using PY150, the white balance of the color filter is improved and the contrast ratio is high.

  When PY150 is used as a complementary color pigment for a blue pixel, the weight mixing ratio of the combined amount of PB15: 6 and PV23 and PY150 is preferably (PB15: 6 + PV23): PY150 = 95: 5 to 99.9: 0. .1, more preferably 98: 2 to 99.7: 0.3. If the weight mixing ratio is less than 98: 2, the luminance of the color filter may be undesirably lowered. If the weight mixing ratio is more than 99.7: 0.3, the white balance may be poor.

  The green pixel of the color filter of the present invention is green in a broad sense, but strictly speaking, depending on the combination of pigments such as PG7 and PY150, yellow, greenish yellow, yellowish green, yellowish green, green in the color correlation diagram , Adjusted appropriately to bluish green and blue-green. For this reason, pigments which are complementary colors of these colors are used as complementary color pigments. In the present invention, when a complementary color pigment is added to a green pixel, a red pigment or a purple pigment is preferably used as the complementary color pigment. Examples of red pigments include PR122 and PR209, and examples of purple pigments include PV19, PV23, and PV37.

  When a complementary color pigment is added to the pixel of the color filter, the luminance may be lowered. In particular, in the case of a green pixel, the luminance is greatly affected. Therefore, the color filter of the present invention needs to contain the complementary color pigment and / or black pigment of at least one color pixel for white balance adjustment, but the complementary color pigment is added to the red pixel and / or blue pixel. It is desirable that the green pixel contains no complementary color pigment.

  When adjusting the white balance with the black pigment in the present invention, examples of the black pigment used include carbon black, titanium black, iron oxide, and the like, and in particular, it is easy to mix with other pigments and a uniform pixel is easily obtained. Therefore, carbon black is preferable.

  When carbon black is contained in the red pixel, the amount of PR177 and PR254 combined and the weight mixing ratio of carbon black is preferably (PR177 + PR254): carbon black = 95: 5 to 99.9: 0.1. Preferably it is 98: 2-99.5: 0.5. If the weight mixing ratio is less than 98: 2, the luminance of the color filter may be undesirably lowered. If the weight mixing ratio is more than 99.5: 0.5, the white balance may be deteriorated.

  When carbon black is contained in the green pixel, the weight mixing ratio of the total amount of PG7 and PY150 and the carbon black is preferably (PG7 + PY150): carbon black = 98: 2 to 99.9: 0.1. Preferably it is 99: 1-99.7: 0.3. If the weight mixing ratio is less than 99: 1, the luminance of the color filter may be undesirably lowered. If the weight mixing ratio is more than 99.7: 0.3, the white balance may be deteriorated.

  When the blue pixel contains carbon black, the weight mixing ratio of the amount of PB15: 6 and PV23 combined with the carbon black is preferably (PB15: 6 + PV23): carbon black = 99: 5 to 99.9: 0. .1, more preferably 98: 2 to 99.7: 0.3. If the weight mixing ratio is less than 98: 2, the brightness of the color filter may be undesirably lowered. If the weight mixing ratio is more than 99.9: 0.1, the white balance may be deteriorated.

  If a black pigment is added to the color filter pixels, the luminance may be lowered, and particularly in the case of a green pixel, the influence of the luminance reduction is large. Therefore, it is desirable that the color filter of the present invention contains the complementary color pigment in the red pixel and / or the blue pixel and does not contain the complementary color pigment in the green pixel.

  In order to further expand the color reproduction range more than NTSC 100%, the color filter of the present invention can further contain a green pigment and a yellow pigment in addition to PG7 and PY150 contained in the green pixel. The pigment is preferably PG36, PG58, PY129, PY138, PY139, PY185, more preferably PG36, PG58, PY129, and further preferably PY129. By using PY129, the color reproduction range of the color filter can be expanded and the contrast ratio can be improved.

  Generally, PG7 is an aggregate of copper phthalocyanine molecules having 12 to 16 chlorine atoms introduced. The average number of chlorine atoms introduced per phthalocyanine molecule of PG7 used in the present invention is preferably 15.1 to 16.0, more preferably 15.5 to 16.0. By setting the average number of introduced chlorine atoms per molecule of copper phthalocyanine to 15.5 or more, the color reproduction range of the color filter can be improved. PG7 having an average introduction number of chlorine atoms of 15.5 to 16.0 is synthesized by, for example, heating and melting a copper phthalocyanine pigment together with sodium chloride and aluminum chloride and introducing chlorine gas into the melt. Can do.

  The color filter of the present invention requires the use of the pigment as described above for each pixel. The average primary particle size of these pigments is preferably 1 to 50 nm, more preferably 5 to 40 nm. Is desired. By setting the average primary particle size of the pigment to 5 to 40 nm, the contrast ratio of the color filter can be increased. For example, the average primary particle diameter of the pigment can be set to 1 to 50 nm by refining by salt milling. In salt milling, a 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 and kneaded. Then, the mixture is put into water, and the slurry is filtered and washed with water. This is done by removing inorganic salts. The average primary particle diameter of the pigment can be calculated, for example, by observing it with a transmission electron microscope after dispersing the pigment in a solvent.

  Hereinafter, the manufacturing method of the color filter of this invention is demonstrated. First, a pigment dispersion is prepared by dispersing the pigment as described above together with a solvent and a dispersant by a disperser, and then a colorant composition is produced by adding a resin and various additives to the pigment dispersion. Next, after this colorant composition is applied on a substrate, exposure and development are performed, and pixel patterning is performed. This patterning process is sequentially performed for each color such as red, green, and blue to produce the color filter of the present invention.

  Usually, the pigment is in a powder state, and is in a state of secondary particles in which primary particles are aggregated (second particle size is usually 1 to 50 μm). Therefore, after adding a solvent, a dispersant, a resin, etc. It is desirable to apply a shearing stress to the pigment particles using a machine to obtain a pigment dispersion dispersed in the primary particles or the aggregate particles 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 0.01 to 0.3 mmφ. When the bead diameter is larger than 0.3 mmφ, the shear stress applied to the pigment is too large, so that the dispersion stability of the pigment dispersion is lowered and the contrast ratio of the color filter may be lowered. On the other hand, if the diameter of the zirconia beads is smaller than 0.01 mmφ, it may be difficult to remove the zirconia beads from the pigment dispersion.

  It is preferable to add a polymer dispersant to the pigment dispersion used in the present invention. By adding a polymer dispersant, the dispersion stability of the pigment dispersion is improved, and an improvement in the contrast ratio of the color filter 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.

  A pigment derivative having a sulfonic acid group introduced into the pigment may be added to the pigment dispersion used in the present invention. The pigment derivative having a sulfonic acid group introduced is strongly bonded to the pigment by intermolecular force, thereby increasing the adsorptive power between the pigment and the polymer dispersant, thereby improving the dispersion stability of the pigment dispersion, and thus the color filter. An improvement in contrast ratio can be expected.

  In the color filter of the present invention, it is necessary to contain a complementary color pigment and / or a black pigment in at least one color pixel for white balance adjustment, but the complementary color pigment is easier to disperse and stabilize the pigment dispersion than the black pigment, This is more preferable because the contrast ratio of the color filter is likely to be high.

  The resin used in the 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 polyamic acid is used as a representative example of a resin used for a non-photosensitive colorant composition and an acrylic resin is used as a typical example of a resin used for a photosensitive 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 a 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′-diaminodiphenyl sulfide, 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 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 solubility in the developer may be lowered, and a problem may occur in the patterning performance. On the other hand, if the content of the acrylic polymer is more than 70% by weight, the sensitivity is increased. 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. Is 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 colorant composition used in the present invention, the weight mixing ratio of the pigment and the resin is preferably pigment: resin = 15: 85 to 50:50, more preferably 20:80 to 45:55. It is. If the weight mixing ratio is larger than 50:50, the adhesion between the pixel and the glass substrate is likely to be lowered, and if the weight mixing ratio is larger than 45:55, the pattern processability of the pixel may be poor. On the other hand, when the weight mixing ratio is less than 15% by weight, it is difficult to obtain a color filter having a preferable hue, and when the weight mixing ratio is less than 20% by weight, the color reproduction range of the color filter may be narrowed. In the present invention, when a non-photosensitive polyamic acid is used as the resin, the polyamic acid is the total amount of the resin, and when a photosensitive acrylic resin is used, the acrylic polymer, the acrylic monomer, and the polymer dispersant are combined. The total amount of resin.

  As the solvent used in 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.

  In the present invention, a surfactant may be added for the purpose of improving the coating property of the colorant composition 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.

  In the color filter of the present invention, red pixels, green pixels, and blue pixels may be formed on a transparent substrate on which a black matrix is formed. 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 a colorant composition for forming a pixel on a substrate, a method of applying to a 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, etc. Various methods such as a method of immersing the substrate in the solution and spraying the solution onto the 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.

  After coating the colorant composition on the transparent substrate by the method as described above, a coating film of the 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 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.

  The obtained coating film pattern is then heat-treated to form a color filter in which 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 having red pixels, green pixels, and blue pixels can be manufactured. The patterning order of each color is not limited.

  The pixel film thickness 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 color reproduction range of the color filter is likely to be narrowed. On the other hand, when the film thickness is thicker than 2.3 μm, the flatness of the color filter, the pattern processability, and the reliability may be lowered.

  The color reproduction range of the color filter of the present invention is obtained by measuring the chromaticity coordinates (x, y) of red pixels, green pixels, and blue pixels in the XYZ color system chromaticity diagram, and then calculating the chromaticity coordinates (x, y). It can be evaluated by calculating the area ratio of the connected triangle to the NTSC standard. The color reproduction range of the color filter of the present invention is usually 70% or higher, preferably 80% or higher, more preferably 90% or higher. It contains PR177 and PR254 as pigments for red pixels, PG7 and PY150 as pigments for green pixels, PB15: 6 and PV23 as pigments for blue pixels, and the weight mixing ratio of pigment and resin is 15:85 to 50:50, By setting the pixel film thickness to 0.8 to 2.3 μm, the color reproduction range of the color filter can be 90% or more of the NTSC ratio.

  The white balance of the color filter of the present invention can be evaluated by the chromaticity coordinates (x, y) of white in the XYZ color system chromaticity diagram. The chromaticity coordinates (x, y) of white of the color filter of the present invention are usually x = 0.290 to 0.315, y = 0.290 to 0.315, preferably x = 0.300 to 0.00. It is desirable that 310, y = 0.300 to 0.310. For example, by using PR177, PR254, and PB15: 6 as pigments for red pixels, PG7 and PY150 as pigments for green pixels, and PB15: 6, PV23, and PY150 as pigments for blue pixels, The chromaticity coordinates (x, y) of white can be set to x = 0.300 to 0.310 and y = 0.300 to 0.310.

  The contrast ratio of the color filter of the present invention is preferably 5000 or more, more preferably 7000 or more. For example, PR177, PR254, and PB15: 6 are used as pigments for red pixels, PG7 and PY150 are used as pigments for green pixels, PB15: 6, PV23, PY150 are used as pigments for blue pixels, and these By setting the average primary particle diameter of the pigment to 1 to 50 nm, the contrast ratio of the color filter can be set to 7000 or more.

  Next, a liquid crystal display device of the present invention produced using this color filter will be described. A transparent protective film is formed on the color filter as necessary, and a transparent electrode such as an ITO film is formed thereon. Next, this color filter substrate and a transparent electrode substrate in which a transparent electrode such as an ITO film is formed on the transparent substrate are further subjected to a rubbing treatment for liquid crystal alignment provided on those substrates. A film and a spacer for holding a cell gap are attached to face each other. In addition to the transparent electrode, a thin film transistor (TFT) element, a thin film diode (TFD) element, a scanning line, a signal line, and the like are provided on the transparent electrode substrate to form a TFT liquid crystal display device or a TFD liquid crystal display device. Can do. Next, after injecting liquid crystal from the injection port provided in the seal portion, the injection port is sealed, a polarizing plate is bonded to the outside of the substrate, and then an IC driver, a backlight light source, and the like are mounted. A device can be made.

  Examples of the backlight light source used in the liquid crystal display device of the present invention include a cold cathode fluorescent tube, a hot cathode fluorescent tube, a light emitting diode (LED), a flat fluorescent lamp, and a metal halide lamp.

  The liquid crystal display device of the present invention includes a TN (Twisted Nematic) method, an STN (Super Twisted Nematic) method, an IPS (In-Plane switching) method, a VA (Vertical Alignment) method, an OCB (Optically Compensated Birefringence) method, etc. Applicable to.

  Since the liquid crystal display device of the present invention is formed using a color filter having a wide color reproduction range and excellent white balance, it has excellent visibility.

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.
The color filter of the present invention was evaluated by the following method.

<Measurement method>
(Color filter color reproduction range)
Using a microspectrophotometer “MCPD-2000” manufactured by Otsuka Electronics Co., Ltd., transmission spectra of red, green and blue pixels of the color filter were measured. XYZ of the red pixel, the green pixel, and the blue pixel was obtained from the measured transmittance spectrum of the pixel and the spectrum of the LED backlight light source, and chromaticity coordinates (x, y) of the red pixel, the green pixel, and the blue pixel were calculated. The area of the triangle formed by connecting the chromaticity coordinates was compared with the NTSC standard, and the color reproduction range of the color filter was evaluated.
(White balance of color filter)
In the same manner as described above, XYZ of red, green, and blue pixels was obtained, white chromaticity coordinates (x, y) were calculated, and white balance of the color filter was evaluated.
(Color filter pixel film thickness)
Measurements were made using a surface step meter “Surfcom 1400D” manufactured by Tokyo Seimitsu Co., Ltd.
(Contrast ratio of color filter)
The color filter is placed between the polarizer and the analyzer so as to enter the entire measurement area, the light transmittance (I1) when the polarizer and the analyzer are parallel, and the light transmission when the polarizer and the analyzer are orthogonal. The contrast ratio was calculated by measuring the ratio (I1 / I2) of the rate (I2). A polarizing film “NPF-G1220DUN” manufactured by Nitto Denko Corporation was used for the polarizer and the analyzer. “FL8A-EX / 70” manufactured by Meikaku 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.

Reference example 1
84 g of PR177 (average primary particle size 30 nm), 56 g of PR254 (average primary particle size 40 nm), 140 g of Ajinomoto Fine-Techno “Azisper” PB821 in propylene glycol monomethyl ether acetate solution (30 wt%), 93 g of Daicel Chemical “Cyclomer” ACA250 (45 wt% solution) and 627 g of propylene glycol monomethyl ether acetate were stirred with a homodisper to form a slurry. The beaker containing this slurry was connected with a circulation type bead mill disperser ("Dynomill" KDL-A manufactured by Willie et Bacofen) and a tube, and using zirconia beads having a diameter of 0.3 mm as a medium, 3200 rpm, 3 hours Then, a red pigment dispersion was obtained. To 52.6 g of the obtained red pigment dispersion, 5.7 g of “Cyclomer” ACA250 (45 wt% solution), 3.2 g of Nippon Kayaku multifunctional monomer “Kayarad” DPHA, 0.5 g of Ciba After adding Photochemical Initiator “Irgacure” 907, Nippon Kayaku Sensitizer “Kayacure” DETX-S, and 37.8 g of propylene glycol monomethyl ether acetate, a surface activity of Bic Chemie The agent “BYK333” was added to a total solid content of 2000 ppm to obtain a photosensitive red colorant composition 1. In the photosensitive red colorant composition 1, the weight mixing ratio of each pigment was PR177: PR254 = 60: 40, and the weight mixing ratio of pigment to resin was pigment: resin = 42: 58.

Reference example 2
Reference Example 1 except that 82.7 g PR177 (average primary particle size 30 nm), 55.2 g PR254 (average primary particle size 40 nm), 2.1 g carbon black (average primary particle size 30 nm) were used. In the same manner, photosensitive red colorant composition 2 was produced. In the photosensitive red colorant composition 2, the weight mixing ratio of each pigment is PR177: PR254: carbon black = 59.1: 39.4: 1.5, and the weight mixing ratio of the pigment to the resin is : Resin = 42:58.

Reference example 3
Reference Example 1 except that 82.7 g PR177 (average primary particle size 30 nm), 55.2 g PR254 (average primary particle size 40 nm), 2.1 g PB15: 6 (average primary particle size 30 nm) were used. A photosensitive red colorant composition 3 was prepared in the same manner as described above. In the photosensitive red colorant composition 3, the weight mixing ratio of each pigment is PR177: PR254: PB15: 6 = 59.1: 39.4: 1.5, and the weight mixing ratio of the pigment and the resin is Pigment: resin = 42: 58.

Reference example 4
98 g of PG7 (average primary particle size 30 nm), 42 g of PY150 (average primary particle size 30 nm), 140 g of Ajinomoto Fine-Techno “Azisper” PB821 in propylene glycol monomethyl ether acetate solution (30 wt%), 93 g of Daicel Chemical “Cyclomer” ACA250 (45 wt% solution) and 627 g of propylene glycol monomethyl ether acetate were stirred with a homodisper to form a slurry. The beaker containing this slurry was connected with a circulation type bead mill disperser ("Dynomill" KDL-A manufactured by Willie et Bacofen) and a tube, and using zirconia beads having a diameter of 0.3 mm as a medium, 3200 rpm, 3 hours The green pigment dispersion was obtained.

  To 52.6 g of the obtained green pigment dispersion, 5.7 g of “Cyclomer” ACA250 (45 wt% solution), 3.2 g of Nippon Kayaku polyfunctional monomer “Kayarad” DPHA, 0.5 g of Ciba After adding Photochemical Initiator “Irgacure” 907, Nippon Kayaku Sensitizer “Kayacure” DETX-S, and 37.8 g of propylene glycol monomethyl ether acetate, surface activity from Bic Chemie The agent “BYK333” was added to a total solid content of 2000 ppm to obtain a photosensitive green colorant composition 1. In the photosensitive green colorant composition 1, the weight mixing ratio of each pigment was PG7: PY150 = 70: 30, and the weight mixing ratio of the pigment and the resin was pigment: resin = 42: 58.

Reference Example 5
Same as Reference Example 4 except that 97.4 g PG7 (average primary particle size 30 nm), 41.9 g PY150 (average primary particle size 30 nm), 0.7 g PV23 (average primary particle size 40 nm) were used. Thus, a photosensitive green colorant composition 2 was produced. In the photosensitive green colorant composition 2, the weight mixing ratio of each pigment is PG7: PY150: PV23 = 69.6: 29.9: 0.5, and the weight mixing ratio of the pigment and the resin is pigment: Resin = 42: 58.

Reference Example 6
112 g of PB15: 6 (average primary particle size 30 nm), 28 g of PV23 (average primary particle size of 40 nm), 140 g of Ajinomoto Finetechno “Ajisper” PB821 in propylene glycol monomethyl ether acetate solution (30 wt%), 93 g of Daicel Chemical “cyclomer” ACA250 (45 wt% solution) and 627 g of propylene glycol monomethyl ether acetate were stirred with a homodisper to prepare a slurry. The beaker containing this slurry was connected with a circulation type bead mill disperser ("Dynomill" KDL-A manufactured by Willie et Bacofen) and a tube, and using zirconia beads having a diameter of 0.3 mm as a medium, 3200 rpm, 3 hours A blue pigment dispersion was obtained.
To 52.6 g of the obtained blue pigment dispersion, 5.7 g of cyclomer ACA250 (45 wt% solution), 3.2 g of Nippon Kayaku polyfunctional monomer “Kayarad” DPHA, 0.5 g of Ciba Specialty Chemicals After adding photoinitiator “Irgacure” 907, 0.2 g Nippon Kayaku sensitizer “Kayacure” DETX-S, and 37.8 g propylene glycol monomethyl ether acetate, surfactant “Bic Chemie” BYK333 "was added to a total solid content of 2000 ppm to obtain a photosensitive blue colorant composition 1. In the photosensitive blue colorant composition 1, the weight mixing ratio of each pigment was PB15: 6: PV23 = 80: 20, and the weight mixing ratio of pigment to resin was pigment: resin = 42: 58. .

Reference Example 7
Reference Example, except that 111.4 g PB15: 6 (average primary particle size 30 nm), 27.9 g PV23 (average primary particle size 40 nm), 0.7 g carbon black (average primary particle size 30 nm) were used. In the same manner as in No. 6, photosensitive blue colorant composition 2 was produced. In the photosensitive blue colorant composition 2, the weight mixing ratio of each pigment is PB15: 6: PV23: carbon black = 79.6: 19.9: 0.5, and the weight mixing ratio of the pigment and the resin is Pigment: resin = 42: 58.

Reference Example 8
Reference Example 6 except that 111.4 g PB15: 6 (average primary particle size 30 nm), 27.9 g PV23 (average primary particle size 40 nm), 0.7 g PY150 (average primary particle size 30 nm) were used. A photosensitive blue colorant composition 3 was prepared in the same manner as described above. In the photosensitive blue colorant composition 3, the weight mixing ratio of each pigment is PB15: 6: PV23: PY150 = 79.6: 19.9: 0.5, and the weight mixing ratio of the pigment and the resin is Pigment: resin = 42: 58.

Example 1
After applying the photosensitive red colorant composition 2 obtained in Reference Example 2 on a transparent substrate with a spinner, a red colored film was obtained by heat treatment at 90 ° C. for 10 minutes in a hot air oven. 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 and produce a red pixel. Next, using the photosensitive green colorant composition 1 obtained in Reference Example 4 and the photosensitive blue colorant composition 1 obtained in Reference Example 6, a green pixel and blue color are obtained in the same procedure as that for the red pixel. Pixels were patterned to produce a color filter. In addition, the spinner rotation speed of the colorant composition was adjusted so that the film thickness after curing of the red pixel, the green pixel, and the blue pixel of the color filter was 2.2 μm.

Example 2
A red pixel is produced using the photosensitive red colorant composition 2 obtained in Reference Example 2, a green pixel is produced using the photosensitive green colorant composition 1 obtained in Reference Example 4, and Reference Example A color filter was produced in the same manner as in Example 1 except that a blue pixel was produced using the photosensitive blue colorant composition 2 obtained in 7.

Example 3
A red pixel is produced using the photosensitive red colorant composition 3 obtained in Reference Example 3, a green pixel is produced using the photosensitive green colorant composition 1 obtained in Reference Example 4, and a reference example. A color filter was produced in the same manner as in Example 1 except that a blue pixel was produced using the photosensitive blue colorant composition 1 obtained in Step 6.

Example 4
A red pixel is produced using the photosensitive red colorant composition 3 obtained in Reference Example 3, a green pixel is produced using the photosensitive green colorant composition 1 obtained in Reference Example 4, and a reference example. A color filter was produced in the same manner as in Example 1 except that a blue pixel was produced using the photosensitive blue colorant composition 3 obtained in Step 8.

Example 5
A red pixel was produced using the photosensitive red colorant composition 3 obtained in Reference Example 3, a green pixel was produced using the photosensitive green colorant composition 2 obtained in Reference Example 5, and Reference Example A color filter was produced in the same manner as in Example 1 except that a blue pixel was produced using the photosensitive blue colorant composition 1 obtained in Step 6.

Comparative Example 1
A red pixel was produced using the photosensitive red colorant composition 1 obtained in Reference Example 1, a green pixel was produced using the photosensitive green colorant composition 1 obtained in Reference Example 4, and a reference example. A color filter was produced in the same manner as in Example 1 except that a blue pixel was produced using the photosensitive blue colorant composition 1 obtained in Step 6.

  Table 1 shows the weight mixing ratios of the pigments of the red pixel, the green pixel, and the blue pixel of the color filters obtained in Examples 1 to 5 and Comparative Example 1.

  Table 2 shows the evaluation results of white balance, color reproduction range, and contrast ratio of the color filters obtained in Examples 1 to 5 and Comparative Example 1.

  As shown in Table 2, Example 1 contained carbon black as a black pigment in the red pixel, so the color reproduction range of the color filter was wide and the white balance was good. In Example 2, since carbon black was contained in the red pixels and the blue pixels, the color reproduction range of the color filter was wide, and the white balance was particularly good. In Example 3, since the red pixel contains PB15: 6 as a complementary color pigment, the color filter has a wide color reproduction range, a high contrast ratio, and a good white balance. In Example 4, the red pixel contains PB15: 6 as a complementary color pigment, and the blue pixel contains PY150 as a complementary color pigment, so the color filter has a wide color reproduction range, a high contrast ratio, and a particularly good white balance. It was. In Example 5, the red pixel contains PB15: 6 as a complementary color pigment and the green pixel contains PV23 as a complementary color pigment. However, although the white chromaticity shifted to blue, the white balance was within an allowable range.

  On the other hand, in Comparative Example 1, none of the pixels contained any black pigment or complementary color pigment, so the white chromaticity shifted to red and the white balance was poor.

Example 6
An ITO film having a film thickness of 140 nm was formed as a transparent electrode on the color filter produced in Example 1, and then a polyimide-based alignment film was provided and rubbed. On the other hand, a substrate for a liquid crystal display element comprising a TFT element, a scanning line, a signal line, a transparent electrode, an alignment film and the like was produced. A sealant was applied to the frame portions of the two substrates and bonded together. Next, after injecting liquid crystal from the injection port provided in the seal portion, the injection port was sealed, and an IC driver and an LED backlight were mounted to produce a liquid crystal display device.

Example 7
A liquid crystal display device was produced in the same manner as in Example 6 except that the color filter obtained in Example 2 was used.

Example 8
A liquid crystal display device was produced in the same manner as in Example 6 except that the color filter obtained in Example 3 was used.

Example 9
A liquid crystal display device was produced in the same manner as in Example 6 except that the color filter obtained in Example 4 was used.

Example 10
A liquid crystal display device was produced in the same manner as in Example 6 except that the color filter obtained in Example 5 was used.

Comparative Example 2
A liquid crystal display device was produced in the same manner as in Example 6 except that the color filter obtained in Comparative Example 1 was used.

  When the image quality was compared about the liquid crystal display devices produced in Examples 6 to 10 and Comparative Example 2, the liquid crystal display devices in Examples 6 to 10 had good white display and excellent visibility, but were compared. In the liquid crystal display device of Example 2, the white display shifted to red and was poor, and the visibility was poor. Furthermore, in the liquid crystal display device of Example 9, the white display was natural white, the black display was deep, and the visibility was the best.

Claims (7)

In a color filter substrate for a liquid crystal display device in which red pixels, green pixels, and blue pixels are formed on a transparent substrate, pigment red 177 and pigment red 254 are pigments for red pixels, and pigment green 7 and pigment yellow 150 are pigments for green pixels. A color filter for a liquid crystal display device comprising: Pigment Blue 15: 6 and Pigment Violet 23 as a pigment for a blue pixel, and at least one color pixel containing a complementary color pigment and / or a black pigment for the pixel substrate. The color filter substrate for a liquid crystal display device according to claim 1, wherein the complementary color pigment of the red pixel is at least one pigment selected from a green pigment, a blue-green pigment, and a blue pigment. 3. The color filter substrate for a liquid crystal display device according to claim 2, wherein the complementary color pigment of the red pixel is pigment blue 15: 6. The color filter substrate for a liquid crystal display device according to any one of claims 1 to 3, wherein the complementary color pigment of the blue pixel is at least one pigment selected from a red pigment and a yellow pigment. The color filter substrate for a liquid crystal display device according to claim 4, wherein the complementary color pigment of the blue pixel is Pigment Yellow 150. The color filter substrate for a liquid crystal display device according to any one of claims 1 to 5, wherein the black pigment is carbon black. A liquid crystal display device using the color filter substrate for a liquid crystal display device according to claim 1.