JP2019077861A - Coloring resin composition, color filter substrate, and display device - Google Patents

Abstract

To provide a coloring resin composition capable of forming a pixel with high color purity even when a film is thin.SOLUTION: A coloring resin composition contains an addition product of a specific metal azo compound and/or its tautomer containing C.I. pigment green 59, C.I. pigment blue 16, Ni, Zn, Cu, (Al), Fe, (Fe), Coor (Co)with a specific melamine compound, and a binder resin.SELECTED DRAWING: None

Description

  The present invention relates to a colored resin composition, a color filter substrate and a display device.

  Liquid crystal display devices are used in various applications such as televisions, notebook computers, portable information terminals, smart phones, digital cameras, etc., taking advantage of characteristics such as light weight, thinness and low power consumption.

  As the color gamut of display devices, the sRGB standard has long been common, but in recent years it has become a video format for program production and international program exchange of ultra-high definition television (UHDTV: Ultra-High Definition Television). Specified Rec. ITU-R BT. With the issuance of 2020, high color gamut is being sought. The color system is defined as a wide-area system in which RGB on the spectral locus are three primary colors, and the RGB wavelengths correspond to 630 nm, 532 nm, and 467 nm single wavelength light sources, respectively. However, in a general display, the emission wavelength has a distribution, and it is required that the emission wavelength be close to a single wavelength.

  Under such circumstances, a color material most suitable for a colored resin composition constituting a pixel of a color filter substrate responsible for color performance of a liquid crystal display device is being searched for.

  As a green pixel colorant, C.I. I. Pigment green 36, C.I. I. Pigment green 7, C.I. I. Pigment green 58 and the like, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. It is common to combine yellow pigments such as C.I. Pigment Yellow 150 (see, for example, Patent Document 1). However, in order to increase color purity using such a technique, it has been necessary to form the pixels in a thick film.

  Under such circumstances, as a green pigment which realizes high brightness and high color reproduction, C.I. I. Pigment Green 59 has been proposed (see, for example, Non-Patent Document 1). C. I. Pigment green 59 is described in Rec. ITU-R BT. Although suitable for 2020 colors, in order to increase color purity, it was necessary to form the pixels in a thick film.

  In addition, as yellow pigments used for green pixels, C.I. I. It is also proposed to use pigment yellow 185 (see, for example, Patent Document 2). However, even with such a technique, it has been necessary to form the pixels in a thick film in order to improve the color purity.

  Therefore, even with a thin film and an appropriate colorant concentration, good brightness can be exhibited, and Rec. ITU-R BT. As a technique for forming a color filter having a high coverage of the color gamut of 2020, a colorant, a resin, a polymerizable compound and a polymerization initiator are contained, and the colorant is C.I. I. Pigment blue 16 and C.I. I. A pigmented photosensitive resin composition comprising pigment green 59 has been proposed (see, for example, Patent Document 3). However, even with such techniques, the color purity was still insufficient.

  Meanwhile, C.I. I. As an outstandingly suitable pigment for adjusting the hue of the pigment green 36 green, a metal azo pigment has been proposed (see, for example, Patent Document 4).

JP 2014-41341 A JP, 2014-2314, A JP, 2017-120407, A JP, 2014-012838, A

DIC, "Development of a new green pigment for color filters to realize high color reproduction," [online], September 9, 2014, [Search on September 12, 2016], Internet <URL: http: // www.dic-global.com/ja/release/2014/20140909_01.html>

  However, in Patent Document 4, metal azo pigments and C.I. I. The combination with the pigment green 59 is not disclosed, and even if the technology described in Patent Document 4 is used, it is still necessary to form the pixels in a thick film in order to improve the color purity. When forming a pixel in a thick film, since a pixel chipping easily occurs, a colored resin composition capable of forming a pixel of high color purity in a thin film is required. Then, an object of this invention is to provide the coloring resin composition which can form a green pixel of high color purity even if it is a thin film.

  In order to solve the above problems, the present invention relates to C.I. I. Pigment green 59, C.I. I. Pigment blue 16, an addition product of a metal azo compound represented by the following general formula (i) and / or a tautomer thereof, and a compound represented by the following general formula (ii), and a binder resin It is a colored resin composition.

In the above general formula (i), R ¹ and R ² independently of one another represent OH or NHR ⁵ , and R ³ and R ⁴ independently of one another represent O or NR ⁵ . However, ^{R 5} represents hydrogen or an alkyl group having 1 to 20 carbon atoms. Me represents Ni ²⁺ , Zn ²⁺ , Cu ²⁺ , (Al ³⁺ ) _2/3 , Fe ²⁺ , (Fe ³⁺ ) _2/3 , Co ²⁺ or (Co ³⁺ ) _2/3 . However, the total content of Ni ²⁺ and Zn ²⁺ in Me is 95 to 100 mol%, and Cu ²⁺ , (Al ³⁺ ) _2/3 , Fe ²⁺ , (Fe ³⁺ ) _2/3 , Co ²⁺ and The total content of Co ³⁺ ) _2/3 is 0 to 5 mol%, and the molar ratio of Zn ²⁺ and Ni ²⁺ (Ni ²⁺ : Zn ²⁺ ) is 1: 9 to 9: 1. In General Formula (ii) above, R ^{6 to} R ⁸ each independently represent hydrogen or an alkyl group having 1 to 20 carbon atoms.

  According to the colored resin composition of the present invention, it is possible to form a green pixel of high color purity even with a thin film. For this reason, in the color filter substrate using the colored resin composition of the present invention, it is possible to suppress pixel defects and to display green color with high color purity.

  The inventors of the present invention have intensively studied a colored resin composition for achieving high color purity with a thin film, and by setting the peak wavelength of the transmittance of the green pixel to 500 to 530 nm and setting the half width of the peak wavelength to an appropriate range. It has been found that high color purity can be achieved with thin films.

  That is, the colored resin composition of the present invention has C.I. I. Pigment green 59, C.I. I. Pigment blue 16, an addition product of a metal azo compound having a specific structure, and a binder resin. C. I. Pigment green 59 has a peak of transmittance of 520 nm. I. By selecting pigment green 59, the peak wavelength of the transmittance of the green pixel can be specifically set in the above range. C. I. Pigment green 7 (peak wavelength 495 nm), C.I. I. In the case of a colorant such as pigment green 58 (peak wavelength 550 nm), it is difficult to set the peak wavelength to a desired range. For this reason, in order to improve color purity, it is necessary to form the pixels in a thick film, and pixel defects are likely to occur. Also, C.I. I. Pigment Blue 16 suppresses the transmission of long wavelength light at a wavelength of 550 nm or more, and the addition product of a metal azo compound having a specific structure suppresses the transmission of short wavelength light at a wavelength of less than 500 nm. C. I. By combining with pigment green 59, the half value width of the peak wavelength can be easily adjusted to the preferable range described later.

  The colored resin composition of the present invention comprises, together with a specific pigment, a metal azo compound represented by the following general formula (i) and / or a tautomer thereof and a compound represented by the following general formula (ii) It is characterized in that it contains an addition product (hereinafter sometimes referred to as "addition product"). The metal azo compound represented by the following general formula (i) tends to scatter light because it is difficult to finely disperse it in the colored resin composition while having desired light absorption characteristics. By using an addition product with a compound represented by the following general formula (ii), it can be easily miniaturized in the colored resin composition, and light scattering can be suppressed to transmit light of the above-mentioned short wavelength side Can be suppressed.

In the above general formula (i), R ¹ and R ² independently of one another represent OH or NHR ⁵ , and R ³ and R ⁴ independently of one another represent O or NR ⁵ . However, ^{R 5} represents hydrogen or an alkyl group having 1 to 20 carbon atoms. From the viewpoint of solvent affinity, R ¹ and R ² are preferably OH. From the viewpoint of thermal stability, R ³ and R ⁴ are preferably O.

In the above general formula (i), Me represents Ni ²⁺ , Zn ²⁺ , Cu ²⁺ , (Al ³⁺ ) _2/3 , Fe ²⁺ , (Fe ³⁺ ) _2/3 , Co ²⁺ or (Co ³⁺ ) _2/3 . Show. However, the total content of Ni ²⁺ and Zn ²⁺ in Me is 95 to 100 mol%, and Cu ²⁺ , (Al ³⁺ ) _2/3 , Fe ²⁺ , (Fe ³⁺ ) _2/3 , Co ²⁺ and The total content of Co ³⁺ ) _2/3 is 0 to 5 mol%, and the molar ratio of Ni ²⁺ and Zn ²⁺ (Ni ²⁺ : Zn ²⁺ ) is 1: 9 to 9: 1. Depending on the type of Me, the rising wavelength of the transmission spectrum differs depending on the electronic state. In the present invention, by selecting Ni ²⁺ and Zn ²⁺ as the main components of Me, the peak wavelength of the transmittance of the green pixel can be made in the above range. If the total content of metal ions of Ni ²⁺ and Zn ²⁺ is less than 95 mol%, the effect of suppressing transmission of light on the short wavelength side is low, and the color purity of the thin film is reduced. Needs to be thickened. Further, among these metal ions, Ni ²⁺ rises and shifts the wavelength to a relatively short wavelength side and Zn ²⁺ shifts to a relatively long wavelength side, so the molar ratio (Ni ²⁺ : Zn ²⁺ ) By setting it as 1: 9-9: 1, the color purity in a thin film can be improved more. The molar ratio (Ni ²⁺ : Zn ²⁺ ) is more preferably 6: 4 to 9: 1, and still more preferably 70:30 to 85:15.

In General Formula (ii) above, R ^{6 to} R ⁸ each independently represent hydrogen or an alkyl group having 1 to 20 carbon atoms. Hydrogen is preferred because of the ease of formation of the adduct.

  As a tautomer of the metal azo compound represented by the said General formula (i), the isomer group shown below is mentioned, for example.

The addition product can be obtained, for example, by the method described in JP-A-2014-012838. Further, as the addition product, for example, “LEVAS CREEN” (registered trademark) Yellow TP LXS 51084 (Ni ²⁺ : Zn ²⁺ = 78: 22) manufactured by LANXESS can be used.

  In the colored resin composition of the present invention, from the viewpoint of achieving high purity with a thin film by suppressing transmission of light on the short wavelength side and transmission of light on the long wavelength side in a more balanced manner. I. The addition product is preferably contained in an amount of 150 to 1400 parts by weight with respect to 100 parts by weight of the pigment blue 16 content. By setting the content of the addition product to 150 parts by weight or more, the transmission of light on the short wavelength side can be further suppressed, so that the thin film can be further highly purified, and pixel defects can be further suppressed. In addition, the brightness Y can be improved. The content of the addition product is more preferably 200 parts by weight or more. On the other hand, by setting the content of the addition product to 1400 parts by weight or less, the thin film can be further highly purified, and pixel defects can be further suppressed. Also, BT. 2020 simple area ratio can be improved. The content of the addition product is more preferably 1300 parts by weight or less.

  The colored resin composition of the present invention is preferably C.I. I. Pigment green 59, C.I. I. Pigment blue 16 and a total content of 100 parts by weight of the addition product, C.I. I. Preferably, 20 to 60 parts by weight of pigment green 59 is contained. C. I. By setting the content of pigment green 59 to 20 parts by weight or more, the thin film can be further highly purified, and pixel chipping can be further suppressed. C. I. The content of pigment green 59 is more preferably 30 parts by weight or more. Meanwhile, C.I. I. By setting the content of the pigment green 59 to 60 parts by weight or less, the thin film can be further highly purified, and pixel chipping can be further suppressed. C. I. The content of pigment green 59 is more preferably 45 parts by weight or less.

  In the colored resin composition of the present invention, C.I. I. Pigment green 59, C.I. I. The pigment blue 16 and the addition product may further contain other coloring materials. As another coloring material, for example, C.I. I. Pigment greens 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, C.I. I. Pigment yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 , 174, 175, 176, 180, 181, 182, 183, 185, 188, 189, 190, 191, 191, 191, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 211, 213, 218, 220, 221, 228, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 60, and the like. Among these, from the viewpoint of increasing the contrast, C.I. I. Pigment yellow 129, 138, 139, 150, C.I. I. Pigment blue 15: 3, 60 is preferable.

  In the colored resin composition of the present invention, C.I. I. Pigment green 59, C.I. I. From the viewpoint of the strength of the cured product of the colored resin composition, the total content of the pigment blue 16, the addition product and the colorant including the other colorant is preferably 80% by weight or less in the solid content.

  In addition, the coloring material in a coloring resin composition apply | coats a coloring resin composition on a board | substrate, and using a coloring resin composition film | membrane dried, laser Raman (for example, Raman or T-64000 by HOLIBA Jobin Yvon) analysis or , FT-IR (e.g., SPECTR-TECH's FT-IR MICROSCOPE) analysis can be performed and identified by comparison with a sample. Moreover, it can be identified with high accuracy by combining centrifugation, filtration, GPC fractionation etc., NMR, etc. as needed. Moreover, when it contains a metal, a metal can be detected by an ICP emission spectral analyzer and LDI-MS analysis.

  In the colored resin composition of the present invention, the binder resin functions to retain the form of the colored resin composition and each component. Examples of the binder resin include acrylic resin, epoxy resin, polyimide resin, urethane resin, urea resin, polyvinyl alcohol resin, melamine resin, polyamide resin, polyamide imide resin, polyester resin, polyolefin resin, polymer dispersant, and the like. Be Two or more of these may be included. Among these, acrylic resins are preferable in terms of stability.

  As acrylic resin, the polymer of unsaturated carboxylic acid, the copolymer of unsaturated carboxylic acid and other ethylenically unsaturated compounds, etc. are mentioned, for example. Among these, copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds are preferred.

  Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid and the like. Two or more of these may be used.

  Examples of the ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, isopropyl methacrylate, n-propyl methacrylate, n-acrylate Butyl, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, Unsaturated carboxylic acid alkyl esters such as n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate; styrene, p-methylstyrene, o-methyl methacrylate Aromatic vinyl compounds such as styrene, 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; vinyl acetate, propionic acid Carboxylic acid vinyl esters such as vinyl; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and α-chloroacrylonitrile; aliphatic conjugated dienes such as 1,3-butadiene and isoprene; polystyrene having an acryloyl group or a methacryloyl group at the terminal, Examples include macromonomers such as polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and polysilicone.

  The acrylic resin preferably has an ethylenically unsaturated group in a side chain, and can improve the sensitivity when the colored resin composition has photosensitivity. As an ethylenically unsaturated group, a vinyl group, an allyl group, an acryl group, methacryl group etc. are mentioned, for example. As a method of introducing an ethylenically unsaturated group into the side chain of an acrylic resin, when the acrylic resin has a carboxyl group or a hydroxyl group, etc., an ethylenically unsaturated compound having an epoxy group in these, acrylic acid chloride, methacrylic acid Examples thereof include a method of addition reaction of chloride and the like, and a method of adding a compound having an ethylenically unsaturated group using isocyanate.

  As an acrylic resin which has an ethylenically unsaturated group in a side chain, for example, Daicel Ornex Co., Ltd. product, "Cyclomer" (registered trademark) P (ACA) Z 250 (dipropylene glycol monomethyl ether 45 wt% solution, acid) 110 mg KOH / g, weight average molecular weight 20,000), Adeka Co., Ltd. product, “Adeka Awrcles” WR 301 (45% by weight solution of dipropylene glycol monomethyl ether, acid value 100 mg KOH / g, weight average molecular weight 5, 900), KRX-3802 (a 45 wt% solution of dipropylene glycol monomethyl ether, acid value 80 mg KOH / g, weight average molecular weight 5, 500), alkali soluble cardo resin, etc. may be mentioned.

  The weight average molecular weight Mw of the binder resin is preferably 3,000 or more, more preferably 5,000 or more, from the viewpoint of improving the strength of a cured film formed by curing the colored resin composition. On the other hand, from the viewpoint of improving the stability of the colored resin composition, 200,000 or less is preferable, and 100,000 or less is more preferable. In addition, Mw here refers to the standard polystyrene conversion value measured by gel permeation chromatography.

  As the polymer dispersant, for example, “DISPERBYK” (registered trademark) -102 (acid value of solid content 101 mg KOH / g, amine value 0 mg KOH / g), 103 (solid acid value 0 mg KOH / g, amine value 0 mg KOH / g) 106, 108 (solid content acid value 0 mg KOH / g, amine value 71 mg KOH / g), 109 (solid content acid value 0 mg KOH / g, amine value 140 mg KOH / g) 110 (solid content acid value 53 mg KOH / g, amine value 0 mg KOH / G), 111, 112, 116, 130 (solid content acid value 3 mg KOH / g, amine value 190 mg KOH / g), 140 (solid content acid value 73 mg KOH / g, amine value 76 mg KOH / g) 142 (solid content acid value) 46 mg KOH / g, amine number 43 mg KOH / g, 145 (solid content acid number 76 mg KOH / Amine value 71 mg KOH / g), 161 (solid content acid value 0 mg KOH / g, amine value 11 mg KOH / g), 162 (solid content acid value 0 mg KOH / g, amine value 13 mg KOH / g), 163 (solid content acid value 0 mg KOH / g) g, amine value 10 mg KOH / g, 164 (solid content acid value 0 mg KOH / g, amine value 18 mg KOH / g) 166 (solid content acid value 0 mg KOH / g, amine value 13 mg KOH / g) 167 (solid content acid value 0 mg KOH) / G, amine value 13 mg KOH / g), 168 (solid content acid value 0 mg KOH / g, amine value 11 mg KOH / g), 170 (solid content acid value 11 mg KOH / g, amine value 0 mg KOH / g), 171 (solid content acid value 13 mg KOH / g, amine value 0 mg KOH / g, 174 (solid content acid number 22 mg KOH / g, 180 (solid content acid number 9 mg KOH / g, amine number 94 mg KOH / g) 182 (solid content acid number 0 mg KOH / g, amine number 13 mg KOH / g) 2000 (solid content acid number 0 mg KOH / g) Amine value 4 mg KOH / g), 2001 (solid content acid value 19 mg KOH / g, amine value 29 mg KOH / g), 2050 (solid content acid value 0 mg KOH / g, amine value 30 mg KOH / g), 2070, 2150 (solid content acid value 0 mg KOH) / G, amine value 57 mg KOH / g), 6919 (solid content acid value 4 mg KOH / g, amine value 19 mg KOH / g), 21116 (solid content acid value 10 mg KOH / g, amine value 20 mg KOH / g) (all, trade name, BIC Chemie Etc.). Two or more of these may be used. Among these, those having a solid content acid value of 30 mg KOH / g or less and those having an amine value of 10 mg KOH / g or more are preferable. When the solid content acid value is 30 mg KOH / g or less, pixel chipping can be further suppressed. Dispersibility can be improved as an amine titer is 10 mgKOH / g or more.

  The content of the binder resin in the colored resin composition of the present invention is preferably 1% by weight or more, and more preferably 5% by weight or more in the solid content, from the viewpoint of further suppressing pixel chipping. On the other hand, from the viewpoint of further improving the color purity, the solid content is preferably 99% by weight or less, more preferably 95% by weight or less.

  The colored resin composition of the present invention may further contain an organic solvent, an adhesion improver, a surfactant, a dispersant, a reactive monomer, a photopolymerization initiator, a chain transfer agent, a sensitizer, a polymerization inhibitor and the like. .

  By including the organic solvent in the colored resin composition of the present invention, it is possible to obtain flow characteristics suitable for coating on a substrate. Examples of the organic solvent include acetate solvents, (poly) alkylene glycol ether solvents, aliphatic ester solvents, aliphatic alcohols solvents, ketone solvents, hydrocarbon solvents and the like. As an acetate solvent, for example, diethylene glycol monobutyl ether acetate (boiling point 247 ° C.), benzyl acetate (boiling point 214 ° C.), dipropylene glycol monomethyl ether acetate (boiling point 213 ° C.), ethyl benzoate (boiling point 213 ° C.), methyl benzoate (boiling point 200 ° C), diethyl malonate (boiling point 199 ° C), 2-ethylhexyl acetate (boiling point 199 ° C), 2-butoxyethyl acetate (boiling point 192 ° C), ethylene glycol monobutyl ether acetate (boiling point 188 ° C), diethyl oxalate (boiling point) 185 ° C), ethyl acetoacetate (boiling point 181 ° C), cyclohexyl acetate (boiling point 174 ° C), 3-methoxy-butyl acetate (boiling point 173 ° C), methyl acetoacetate (boiling point 172 ° C), ethyl- -Ethoxypropionate (boiling point 170 ° C), 2-ethylbutyl acetate (boiling point 162 ° C), isopentyl propionate (boiling point 160 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), pentyl acetate (boiling point 150 ° C.), propylene glycol monomethyl ether acetate (boiling point 146 ° C.) and the like. Examples of (poly) alkylene glycol ether solvents include ethylene glycol monomethyl ether (boiling point 124 ° C.), ethylene glycol monoethyl ether (boiling point 135 ° C.), propylene glycol monoethyl ether (boiling point 133 ° C.), diethylene glycol monomethyl ether (boiling point 193 ° C), monoethyl ether (boiling point 135 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C, EDM), diethylene glycol monomethyl ether (boiling point 194 ° C), diethylene glycol monoethyl ether (202 ° C), propylene glycol monomethyl ether (boiling point 120) ° C), propylene glycol monoethyl ether (boiling point 133 ° C.), propylene glycol tertiary butyl ether (boiling point 153 ° C.), Propylene glycol monomethyl ether (boiling point 188 ° C.) and the like. Examples of aliphatic ester solvents include ethyl acetate (boiling point 77 ° C.), butyl acetate (boiling point 126 ° C.), isopentyl acetate (boiling point 142 ° C.) and the like. Examples of aliphatic alcohol solvents include butanol (boiling point 118 ° C.), 3-methyl-2-butanol (boiling point 112 ° C.), 3-methyl-3-methoxybutanol (boiling point 174 ° C.) and the like. Examples of ketone solvents include cyclopentanone and cyclohexanone. Examples of hydrocarbon solvents include xylene (boiling point 144 ° C.), ethylbenzene (boiling point 136 ° C.), solvent naphtha (petroleum fraction: boiling point 165-178 ° C.) and the like. Two or more of these may be included. Among these, C.I. I. Pigment green 59 and C.I. I. From the viewpoint of the stability of pigment blue 16, it is preferable to use an acetate solvent as a main solvent. From the viewpoint of improving the solubility in an alkali developing solution, it is more preferable to contain 10% by weight or more, more preferably 55% by weight or more of an acetate solvent having a boiling point of 200 ° C. or more in the total amount of the organic solvent. On the other hand, it is preferable to contain 90% by weight or less of an acetate solvent having a boiling point of 200 ° C. or more in the total amount of the organic solvent from the viewpoint of improving the coating quality. As an acetate solvent having a boiling point of 200 ° C. or more, diethylene glycol monobutyl ether acetate (boiling point 247 ° C.) and dipropylene glycol monomethyl ether acetate (boiling point 213 ° C.) are preferable.

  From the viewpoint of improving the coatability, the content of the organic solvent in the colored resin composition of the present invention is preferably 40% by weight or more, more preferably 50% by weight or more in the colored resin composition. On the other hand, from the viewpoint of improving the drying characteristics, 95% by weight or less is preferable, and 90% by weight or less is more preferable.

  By including an adhesion improver in the colored resin composition of the present invention, the adhesion of the coating formed of the colored resin composition to the substrate can be improved. As the adhesion improver, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino) Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Silane coupling agents such as trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like can be mentioned. Two or more of these may be included. Among these, 3-methacryloxypropyl trimethoxysilane and 3-acryloxypropyl trimethoxysilane are preferable.

  From the viewpoint of improving the compatibility, the content of the adhesion improver in the colored resin composition of the present invention is preferably 10% by weight or less, and more preferably 5% by weight or less, based on the solid content.

  By including the surfactant in the colored resin composition of the present invention, the coatability of the colored resin composition and the surface smoothness of the coated film made of the colored resin composition can be improved. As the surfactant, for example, anionic surfactants such as ammonium lauryl sulfate, polyoxyethylene alkyl ether triethanolamine and the like, cationic surfactants such as stearyl amine acetate and lauryl trimethyl ammonium chloride, lauryl dimethyl amine oxide, lauryl Amphoteric surfactants such as carboxymethyl hydroxyethyl imidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate, fluorinated surfactants, silicone surfactants, etc. Can be mentioned. Two or more of these may be included.

  The content of the surfactant in the colored resin composition of the present invention is preferably 0.001% by weight or more from the viewpoint of improving the coatability and the surface smoothness of the coated film. On the other hand, from the viewpoint of improving the coatability, 1% by weight or less is preferable.

  Dispersion stability can be improved by including a dispersant in the colored resin composition of the present invention. Examples of the dispersant include an alkylamine modified substance of a pigment skeleton, a pigment derivative such as a carboxylic acid derivative and a sulfonic acid derivative, and the like, and as a synergist, it is effective for wetting a pigment and stabilizing a fine pigment. Two or more of these may be included. Among these, sulfonic acid derivatives of organic pigments are more preferable, and the dispersion stability of the fine pigment can be further improved.

  By including the reactive monomer and the photopolymerization initiator in the colored resin composition of the present invention, photosensitivity can be imparted. Furthermore, the sensitivity can be improved by including a chain transfer agent and / or a sensitizer.

  As a reactive monomer, for example, 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, anhydride Phthalic acid propylene oxide (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin modified epoxy di (meth) acrylate, oligomers such as 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, tetra Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacrylic formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, bisphenoxyethanol full Orange acrylate, dicyclopentadienyl diacrylate or their alkyl modified products, alkyl ether modified products and alkyl ester modified products, etc. may be mentioned. Two or more of these may be included. From the viewpoint of compatibility with the binder resin, the molecular weight of the reactive monomer is preferably 400 or more.

  The content of the reactive monomer in the colored resin composition of the present invention is preferably 10% by weight or more in solid content from the viewpoint of suppressing surface roughness during development, and 80% by weight or less in solid content from the viewpoint of compatibility Is preferred.

  Examples of the photopolymerization initiator include benzophenone compounds, acetophenone compounds, anthraquinone compounds, imidazole compounds, benzothiazole compounds, benzooxazole compounds, oxime ester compounds, triazine compounds, phosphorus compounds, and titanates. An inorganic type photoinitiator is mentioned. Two or more of these may be included. In order to easily adjust the content of the photopolymerization initiator to a preferable range described later, a nitrocarbazole-based oxime ester compound which is sensitive to h-ray is preferable.

  More specifically, benzophenone series compounds include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone. As acetophenone compounds, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutyl phenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4-] (Methylthio) phenyl] -2-morpholino-1-propane, "IRGACURE" (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone), 379 (2- (Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone) and the like. As anthraquinone compounds, t-butyl anthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethyl anthraquinone, 1,4-naphthoquinone, 9,10-phenanthra Quinones, 1,2-benzoanthraquinones, 1,4-dimethylanthraquinones, 2-phenylanthraquinones and the like can be mentioned. Examples of the imidazole compounds include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer and the like. Examples of the benzothiazole compound include 2-mercaptobenzothiazole. Examples of benzoxazole compounds include 2-mercaptobenzoxazole. The triazine compounds include 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl) -s-triazine. As an oxime ester compound, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] ("IRGACURE" (registered trademark) OXE01, manufactured by BASF Corp.), ethanone, 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) ("IRGACURE" OXE03), "IRGACURE" OXE04, "Adeka Acres “® NCI-930,“ Adeca Acres ”NCI-831,“ Adeca Acres ”N-1 919, PBG-345 manufactured by Changzhou High Power Electronic Materials Co., Ltd., and the like. Among these, an oxime ester compound is preferable from the point of high sensitivity, and a nitrocarbazole-based oxime ester compound is more preferable from the viewpoint of suppression of reduction in luminance when oxygen is blocked. As a nitrocarbazole type oxime ester compound, NCI-831, PBG-345 etc. are preferable.

  From the viewpoint of suppressing surface roughness during development, the content of the photopolymerization initiator in the colored resin composition of the present invention is preferably 0.1% by weight or more, and more preferably 0.4% by weight or more in solid content. On the other hand, from the viewpoint of compatibility, the solid content is preferably 10% by weight or less, more preferably 1.5% by weight or less. Furthermore, from the viewpoint of further suppressing pixel defects, 0.5% by weight or less is more preferable.

  In order to adjust the content of the photopolymerization initiator within the above-described preferable range, it is preferable to use a chain transfer agent in combination with the photopolymerization initiator. As a chain transfer agent, for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid , 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto -2-Butanol, Melka Tophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), manufactured by Showa Denko KK Karenz® (registered trademark) MT PE-1 (pentaerythritol tetrakis (3-mercaptopropionate)), Showa Denko KK “Karens” MT NR-1 (1,3,5 tris (3-mercaptobutyloxy) Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione)) Showa Denko KK "Kalens" MT BD-1 (1,4 bis (3 mercaptobuty) Mercapto compounds such as ryloxy) butane), and disulfides obtained by oxidizing the mercapto compounds Compound, iodoacetic acid, iodopropionic acid, 2-iodo ethanol, 2-iodo-ethanesulfonic acid, such as iodinated alkyl compounds such as 3-iodo propane sulfonic acid. Two or more of these may be included. Among these, “Curlens” MT PE-1 is more preferable because of its high sensitivity improvement effect.

  From the viewpoint of further improving the sensitivity, the content of the chain transfer agent in the colored resin composition of the present invention is preferably 0.01% by weight or more in the solid content, and from the viewpoint of improving the compatibility with the binder resin, the solid content 10 weight% or less is preferable among them.

  Examples of the sensitizer include thioxanthone sensitizers and aromatic or aliphatic tertiary amines. More specifically, for example, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthene-9-one ("KAYACURE" (registered trademark) DETX-S (Nippon Kayaku Co., Ltd.)) and the like can be mentioned. . Two or more of these may be included.

  10 weight% or less in solid content is preferable, and, as for content of the sensitizer in the colored resin composition of this invention, 3 weight% or less is more preferable.

  By including a polymerization inhibitor in the colored resin composition of the present invention, the stability can be improved. Examples of the polymerization inhibitor include hydroquinone, tert-butylhydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, 2,5-bis (1,1-dimethylbutyl) hydroquinone, Catechol, tert-butyl catechol and the like. Two or more of these may be included.

  From a viewpoint of improving stability, 0.0001 weight% or more in solid content is preferable, and, as for content of the polymerization inhibitor in the coloring resin composition of this invention, 0.005 weight% or more is more preferable. On the other hand, from the viewpoint of improving the sensitivity, 1% by weight or less in solid content is preferable, and 0.5% by weight or less is more preferable.

  The solid content acid value of the colored resin composition of the present invention is preferably 15 to 40 mg KOH / g. When the solid content acid value is 15 mgKOH / g or more, the developer easily penetrates the colored resin composition in the development step of the pixel of the color filter substrate, so the shower pressure during development can be reduced. In addition, it is possible to further suppress pixel defects during development. The solid content acid value of the colored resin composition is more preferably 17 mg KOH / g or more. On the other hand, when the solid content acid value is 40 mgKOH / g or less, the penetration of the developer into the interface with the substrate can be suppressed, and the pixel chipping can be further suppressed. The solid content acid value of the colored resin composition is more preferably 26 mg KOH / g or less. In order to develop such a low acid value colored resin composition efficiently, it is preferable to introduce a hydrophilic group such as ethylene oxide or propylene oxide, or to use a solvent having a boiling point exceeding 200 ° C. It is preferable to contain a residual solvent, etc.

Here, the solid content acid value of the colored resin composition can be measured by the neutralization titration method. In a Discup, 5.00 g of the coloring resin composition is diluted with 40.00 g of ethanol, and while stirring with a stirrer chip, while measuring pH with pH mater D51 manufactured by Horiba, Ltd., 0.1 mol / L KOH aqueous solution The dripping amount and pH are plotted, and the inflection point is taken as the neutralization point. On the other hand, the colored resin composition is weighed in an aluminum cup, and the solid content concentration of the colored resin composition is calculated from the weight after drying at 100 ° C. for 3 hours. The solid content acid value can be determined by the following equation from the weight of the solid content of the colored resin composition used for neutralization titration calculated from the solid content concentration of the colored resin composition and the amount of KOH dropped to the neutralization point .
Solid content acid value (mg KOH / g) = amount of KOH aqueous solution required up to the neutralization point (mL) x 5.611 (mg / mL) / solid weight of colored resin composition (g)
In addition, since a solid content acid value is a weighted average value of the acid value of each component of solid content in a coloring resin composition, when the acid value and content of each component are known, it may also be determined by calculation. it can. Moreover, solid content acid value can be adjusted to a desired range by adjusting the acid value and compounding quantity of each component.

  Next, the method for producing the colored resin composition of the present invention will be described. The colored resin composition of the present invention is C.I. I. Pigment green 59, C.I. I. Pigment Blue 16, an addition product, a binder resin, and an organic solvent are dispersed by a disperser to prepare a pigment dispersion, and then it is preferable to manufacture by adding and mixing other components as necessary. . It is more preferable to produce a colored resin composition by mixing a pigment dispersion and a dilution varnish in which other components are mixed. When the colored resin composition contains a dispersant, it is preferable to add the dispersant at the time of preparation of the pigment dispersion.

  Examples of the dispersing machine include a sand mill, a ball mill, a bead mill, a three-roll mill, and an attritor. Among these, the bead mill which is excellent in dispersion efficiency is preferable. As a dispersion bead used for a bead mill, a zirconia bead, an alumina bead, a glass bead is mentioned, for example. Among these, zirconia beads are preferred.

  Next, the color filter substrate of the present invention will be described. The color filter substrate of the present invention has green pixels formed from a cured product of the colored resin composition of the present invention. On a transparent substrate, a color filter substrate having a resin black matrix and red, green and blue pixels is preferable, and at least green pixels are formed from a cured product of the colored resin composition of the present invention. Furthermore, if necessary, an overcoat film may be provided, and a transparent conductive film may be provided on the overcoat film.

  Examples of the transparent substrate include glass substrates, plastic plates such as polyimide resins, acrylic resins, polyester resins, and polycarbonate resins, films, and the like. A glass substrate is preferred because of its high light transmittance, and excellent mechanical strength and dimensional stability, and a transparent glass substrate such as soda glass, non-alkali glass, borosilicate glass, quartz glass and the like is more preferred.

  As a material which forms a resin black matrix, the material containing binder resin, such as an acrylic resin and a polyimide resin, and a black pigment is mentioned, for example. As a black pigment, for example, C.I. I. Pigment black 7, carbon black, graphite, iron oxide, manganese oxide, titanium black and the like. Two or more of these may be contained, and pigments of other colors may be further contained. The black pigment may be surface-treated. The thickness of the resin black matrix is preferably 0.5 to 2 μm.

  At least the green pixel is formed from the cured product of the colored resin composition of the present invention, and the red pixel and the blue pixel are formed from the cured product of the colored resin composition containing a binder resin such as acrylic resin and polyimide resin and a pigment. Is preferred.

  Examples of pigments used for red pixels include C.I. I. Pigment red 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 209, 215, 216, 217, 220, 223, 224, 227, 228, 240, Red pigments such as 254, 255, 256, 257, 258, 260, 261, 264, 266, 267, 268, 269, 273, 274, 291; I. Pigment yellow 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 168, Yellow pigments such as C.I. I. Pigment orange 13, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71, and the like.

  Examples of pigments used for blue pixels include C.I. I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc., blue pigments, C.I. I. Pigment Violet 19, 23, 29, 30, 32, 37, 40, 50, and the like; Acid Red 59, 289; and coloring materials disclosed in JP-A-2011-032298.

  Examples of the overcoat film include films made of epoxy resin, acrylic epoxy resin, acrylic resin, siloxane resin, polyimide resin, silicon-containing polyimide resin, polyimide siloxane resin and the like.

  The coloring material in the pixels of the color filter substrate is subjected to surface polishing to remove other layers in contact with the pixels from the color filter substrate, and after the pixel sample is collected by a manipulator, analysis of the coloring materials in the coloring resin composition and It can be identified as well.

  As a transparent conductive film, metal oxide thin films, such as ITO, are mentioned, for example.

  The color filter substrate of the present invention may further have a fixed spacer. The fixed spacer is fixed to a specific place of the color filter substrate and in contact with the opposite substrate when the liquid crystal display device is manufactured. The fixed spacer holds a constant gap with the opposite substrate, and the gap is filled with a liquid crystal compound. By having the fixed spacer, it is possible to omit the process of dispersing the spherical spacer in the manufacturing process of the liquid crystal display device and the process of kneading the rod-like spacer in the sealing agent.

  In the color filter substrate of the present invention, the full width at half maximum of the transmission spectrum between wavelengths 490 and 570 nm in the green pixel is preferably 55 to 65 nm. When the green color purity of the display device is a constant value, the brightness can be improved by setting the half width of the peak between 490 nm and 570 nm of the green pixel of the color filter to 55 nm or more. On the other hand, by setting the half width of the peak to 65 nm or less, BT. The 2020 coverage can be further improved.

  Here, BT. The 2020 cover ratio is defined as three points (Red (0.708, 0.292), Green (0.170, 0.797), Blue (0.131, 0.s) defined in the (x, y) coordinate system. Red, Green, Blue when the coordinates of Green (0.170, 0.797) are replaced with the coordinates of the chromaticity of the green pixel in the display device of the present invention, where the area of the region enclosed by 046) is 100%. It refers to the area ratio of the overlap with the area surrounded by.

  BT. Since the 2020 cover ratio and the brightness Y of the green pixel are in a trade-off relationship, BT. The product of the 2020 coverage rate and the brightness Y of the green pixel can be used. BT. The higher the product of the 2020 coverage rate and the brightness Y of the green pixel, the better the balance of display performance. By setting the half width of the peak of the transmission spectrum between wavelengths 490 and 570 nm in the green pixel to 55 to 65 nm, BT. The 2020 cover ratio and the brightness Y of the green pixel can be improved in a more balanced manner.

  The peak wavelength between 490 and 570 nm and its half-width by measuring the transmission spectrum of 380 to 780 nm using a microspectrometer “LCF-100MA” manufactured by Otsuka Electronics Co., Ltd. for the green pixel in the color filter substrate Can be measured.

  For example, by using the cured product of the colored resin composition of the present invention as described above and setting the pixel film thickness to a preferable range described later, the half width of the peak can be easily adjusted to the above range.

  In the green pixel of the color filter substrate of the present invention, the chromaticity in the C light source defined by the CIE 1931 standard is preferably x = 0.070 to 0.210, y = 0.640 to 0.720. By setting x to 0.070 or more, the brightness Y can be improved. 0.164 or more of x is more preferable, and it enters inside a line connecting Green (0.170, 0.797) and Blue (0.131, 0.046) defined in the (x, y) coordinate system Therefore, the coverage can be increased. On the other hand, by setting x to 0.210 or less, BT. 2020 simple area ratio can be increased. 0.176 or less of x is more preferable, and it enters inside a line connecting Green (0.170, 0.797) and Blue (0.131, 0.046) defined in the (x, y) coordinate system Therefore, the coverage can be increased. Further, by setting y to 0.640 or more, BT. 2020 coverage can be increased. On the other hand, by setting y to 0.720 or less, the brightness Y can be improved.

  Here, BT. The 2020 simple area ratio refers to three points (Red (0.708, 0.292), Green (0.170, 0.797), Blue (0.131, 0) defined in the (x, y) coordinate system. Red, Green, and Green, when the coordinates of Green (0.170, 0.797) are replaced with the coordinates of the chromaticity of the green pixel in the display device of the present invention, where the area of the region surrounded by .046) is 100%. Indicates the area ratio of the area enclosed by Blue.

  The chromaticity x of the C light source based on the CIE 1931 standard by measuring the transmission spectrum of 380 to 780 nm using a microspectrometer “LCF-100MA” manufactured by Otsuka Electronics Co., Ltd. for the green pixel in the color filter substrate y, brightness Y can be measured.

  For example, by using the cured product of the colored resin composition of the present invention as described above and setting the pixel film thickness to a preferable range described later, the chromaticity can be easily adjusted to the above range.

  The thickness of the green pixel in the color filter substrate of the present invention is preferably 1.5 μm or more from the viewpoint of surface smoothness. On the other hand, the thickness of the green pixel is preferably 3 μm or less, more preferably 2.9 μm or less, from the viewpoint of adjusting the peak half value width and chromaticity of the transmission spectrum of the C light source to the above-mentioned preferable range to further suppress pixel loss. Preferably, it is 2.4 μm or less, more preferably 2.2 μm or less.

  The width of the pixel in the color filter substrate of the present invention is preferably 55 μm or more. Here, the width of the pixel refers to the width of the narrowest portion of the pixel. Since pixel defects in the display device are less likely to occur when the stripe pattern is thicker, pixel defects can be further suppressed by setting the pixel width to 55 μm or more. The color filter substrate of the present invention can be preferably used in a display device having a relatively large pixel width, such as a television application.

  Next, the method for producing a color filter substrate of the present invention will be described by taking a color filter substrate having a resin black matrix and red, green and blue pixels on a transparent substrate as an example.

  First, the colored resin composition is applied onto a substrate. As a coating method, for example, a method of coating a colored resin composition on a substrate using a spin coater, a bar coater, a blade coater, a roll coater, a die coater, an inkjet printing method, a screen printing method, etc. The method of immersing in inside, the method of spraying a coloring resin composition on a board | substrate, etc. are mentioned.

  After the colored resin composition is applied on a transparent substrate, it is preferable to form a coating film of the colored resin composition by air drying, heat drying, vacuum drying or the like.

  Next, when the colored resin composition has photosensitivity, a mask is placed on the coating film of the colored resin composition, and exposure is selectively performed by ultraviolet light or the like. As a light source, an ultra-high pressure mercury lamp, a chemical lamp, a high pressure mercury lamp etc. are mentioned, for example. Examples of the exposure device include methods such as proximity, mirror projection, and lens scan. Among these, the lens scan method is preferable from the viewpoint of accuracy.

  Thereafter, development is performed with an alkaline developer to form a pattern. Examples of the alkaline substance used for the alkaline developing solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, ammonia water, etc., ethylamine, n-propylamine etc. Primary amines, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyl diethylamine, organic alkalis such as tetramethyl ammonium hydroxide, and the like can be mentioned.

  Thereafter, the colored resin composition is cured by heat treatment of the obtained pattern to form a resin black matrix or a pixel. The heat treatment can be performed in air, in a nitrogen atmosphere, in vacuum, or the like. 150-350 degreeC is preferable and 180-250 degreeC of a heating temperature is more preferable. The heating time is preferably 0.5 to 5 hours, and may be heated continuously or stepwise. The patterning process is sequentially performed on each pixel of the black matrix and the three to six primary colors.

  Next, the display device of the present invention will be described. The display device of the present invention preferably includes the color filter substrate of the present invention and a backlight.

  The backlight has a function of causing almost white light to enter the color filter substrate. As a configuration of the backlight, for example, blue light is converted to white light by combining an element emitting white light in which a phosphor is chipped into blue LED on the entire screen, or by combining blue LED and a color conversion film. The configuration to be converted may be mentioned. As a backlight having the former configuration, for example, as a light emitting diode in which a blue LED and an inorganic phosphor are chipped (“NS2W364F”, trade name, manufactured by Nichia Corporation), “NSSW703B-HG” , Trade name, Nichia Chemical Co., Ltd.) and the like.

  The material of the backlight includes, for example, a two-wavelength (white) LED composed of a blue LED and a YAG phosphor, a three-wavelength (white) LED composed of a blue LED and a β-sialon, a KSF phosphor, a blue LED and γALON, a KSF fluorescence Inorganic phosphors such as three-wavelength (white) LEDs composed of organic compounds, pyridine-phthalimide described in JP-A-2002-348568, coumarin derivatives described in JP-A-2007-273440, JP-A-2002-317175 And organic phosphors such as dipyrromethene derivatives described in JP-A-2011-241160 and JP-A-2011-241160. As an inorganic fluorescent substance, what combined (beta) -sialon and KSF fluorescent substance is preferably used from the half value width of the peak of the emission spectrum in wavelength 490-570 nm being narrow. As the organic fluorescent substance, a dipyrromethene derivative is preferably used because the half width of the peak of the emission spectrum at a wavelength of 490 to 570 nm is narrow and the lifetime is long.

  The wavelength of the peak of the intensity at the wavelength of 490 to 570 nm of the backlight is preferably 510 to 530 nm. When the peak wavelength is 510 nm or more, color separation with blue is facilitated, and when the peak wavelength is 530 nm or less, color separation with red is facilitated.

  The half value width of the peak of the intensity at a wavelength of 490 to 570 nm of the backlight is preferably 31 to 50 nm. Luminance can be improved as the half value width of a peak is 31 nm or more, and color purity can be further improved as it is 50 nm or less.

Luminous intensity of the backlight, the visibility of the point of view of the display device, preferably 8,000 cd / ^{m 2} or more, more preferably 10,000cd / ^{m 2} or more, more preferably 15,000cd / ^{m 2} or more. On the other hand, from the viewpoint of light stability of the colorant is preferably 1,000,00cd / ^{m 2} or less, more preferably 50,000cd / ^{m 2} or less, more preferably 30,000cd / ^{m 2} or less.

The wavelength of the peak of the backlight at a wavelength of 490 to 570 nm and its half width use the emission spectrum of the backlight emitted at an output of 10000 cd / m ² using the LCD evaluation device LCD-720 manufactured by Otsuka Electronics Co., Ltd. It can measure by measuring.

  The backlight preferably further includes a color conversion film that converts incident light into light having a wavelength longer than that of the incident light. For example, when a blue LED is used as a light source, blue light can be converted to white light by having a color conversion film.

  The color conversion film is a film that converts incident light into light having a wavelength longer than that of the incident light. It is preferable to consist of a color conversion composition containing a compound represented by the following general formula (iii). By including the compound represented by the following general formula (iii), the half width of the peak of the intensity at a wavelength of 490 to 570 nm of the backlight can be reduced.

In the above general formula (iii), X represents C—R ¹⁵ or N. R ^{9 to} R ¹⁷ each independently represent hydrogen, an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a thiol group, an alkoxy group, an alkylthio group, an aryl ether group, Arylthio ether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, phosphine oxide group And an fused ring or an aliphatic ring formed between an amido group and an adjacent substituent. Said alkyl group, cycloalkyl group, heterocyclic group, alkeny group, cycloalkenyl group, alkynyl group, alkoxy group, alkylthio group, arylether group, arylthioether group, aryl group, heteroaryl group, carbonyl group, oxycarbonyl group, Some or all of the hydrogen atoms of the carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, bolyl group, amido group, phosphine oxide group may be substituted.

  The color conversion composition preferably contains a resin together with the compound represented by the general formula (iii).

  200 micrometers or less are preferable, as for the film thickness of a color conversion film, 100 micrometers or less are more preferable, and 50 micrometers or less are more preferable.

  Next, a method of manufacturing a display device of the present invention will be described by taking a liquid crystal display device as an example. First, on the opposite substrate, a liquid crystal alignment film subjected to rubbing treatment for liquid crystal alignment is provided on a drive element substrate having thin film transistor (TFT) elements, scanning lines, signal lines and transparent electrodes to obtain the opposite substrate. The color filter substrate of the present invention is subjected to rubbing treatment for liquid crystal alignment, made to face the above-mentioned opposite substrate, and bonded using a sealing material. Next, a liquid crystal compound is injected from the injection port provided in the seal portion into the gap between the opposing substrate and the color filter substrate, and then the injection port is sealed. Next, a liquid crystal display device can be obtained by attaching a backlight and mounting an IC driver or the like.

(Preparation of Resin Composition for Black Matrix)
150 g of carbon black (MA100 manufactured by Mitsubishi Chemical Corporation), 75 g of a polymer dispersant (by BYK Chemie “BYK” (registered trademark) 6919, 60% by weight solution), “Cyclomer” (registered trademark) P (ACA) Z 250 ( A slurry was prepared by mixing 100 g of a 45 wt% solution of dipropylene glycol monomethyl ether, an acid value of 110 mg KOH / g, and a molecular weight of 20,000, and 675 g of propylene glycol monomethyl ether acetate (PMA). The beaker containing the slurry is connected with a Dyno mill and a tube, and dispersion treatment is performed for 8 hours at a peripheral speed of 14 m / s using zirconia beads with a diameter of 0.5 mm as a medium, and a dispersion for black matrix (BMD-1) Was produced.

  BMD-1 56.54, "cyclomer" P (ACA) Z 250 3.14 g, DPHA monomer (Nippon Kayaku Co., Ltd. "Kayarad" (registered trademark) DPHA) 2.64 g, photopolymerization initiator ((stock 0.330 g of "ADEKA ARKRUZ" (registered trademark) NCI-831 (hereinafter NCI-831) manufactured by ADEKA, surfactant ("BYK" (registered trademark) -333 (hereinafter BYK-333) manufactured by BIC Chemie) 0. 04. g of a polymerization inhibitor (tertiary butyl catechol (TBC) manufactured by DIC Co., Ltd.) 0.01 g PMA 37.30 g was added to prepare a black matrix resin composition 1 (BM-1) for a black matrix.

(Preparation of red resin composition)
C. I. Pigment red 177 (Ciba Specialty Chemical Co., Ltd. “Chromoftal” red (registered trademark) A2B) 150 g, “BYK” 6919 75 g, “Cyclomer” P (ACA) Z 250 100 g, and PMA 675 g were mixed to prepare a slurry . The beaker containing the slurry is connected with a Dyno mill and a tube, and dispersion treatment is performed for 8 hours at a peripheral speed of 14 m / s using zirconia beads with a diameter of 0.5 mm as media, and a red dispersion liquid (RD-1) Made.

  RD-1 56.54, "cyclomer" P (ACA) Z 250 3.14 g, DPHA monomer 2.64 g, photopolymerization initiator (NCI-831) 0.330 g, surfactant (BYK-333) 0.04 g Then, 0.01 g of a polymerization inhibitor (TBC) and 37.30 g of PMA were added to prepare a red resin composition (R-1).

(Preparation of blue resin composition)
C. I. Pigment Blue 15: 6 (EP193 manufactured by DIC Corporation) 150 g of “BYK” 6919 75 g of “Cyclomer” P (ACA) Z 250 100 g of PMA 675 g were mixed to prepare a slurry. The beaker containing the slurry is connected with a Dyno mill and a tube, and dispersion treatment is performed for 8 hours at a peripheral speed of 14 m / s using zirconia beads with a diameter of 0.5 mm as media, and a blue dispersion liquid (BD-1) Made.

  BD-1 29.02, "cyclomer" P (ACA) Z 250 12.70 g, DPHA monomer 4.68 g, photopolymerization initiator (NCI-930) 0.585 g, surfactant (BYK-333) 0.04 g Then, 0.01 g of a polymerization inhibitor (TBC) and 52.96 g of PMA were added to prepare a blue resin composition (B-1).

(Preparation of Addition Product (F-1) of Metal Azo Compound Represented by General Formula (i) and / or Tautomer thereof and Compound Represented by General Formula (ii))
In 550 g of distilled water, 23.1 g (0.15 mol) of diazobarbituric acid and 19.2 g (0.15 mol) of barbituric acid were introduced. Next, 100 g of a 10% by weight aqueous potassium hydroxide solution is added dropwise, and the mixture is stirred for 90 minutes to prepare azobarbituric acid (0.3 mol), and after mixing with 750 g of distilled water, 38.7 g (0.3 mol) (Mole) of melamine, and an addition product (F) of an azo compound represented by the following structural formula and / or a tautomer thereof and a melamine wherein R ^{5 to} R ⁸ in the general formula (ii) are hydrogen -0) was obtained.

Next, 101.08 g (0.234 mol) of a 30 wt% aqueous nickel chloride solution and 29.98 g (0.066 mol) of a 30 wt% aqueous zinc chloride solution were mixed and added, and the mixture was stirred at 80 ° C. for 8 hours. The product is isolated by filtration, washed, dried at 120 ° C., ground in a mortar, metal azo compound of the general formula (i) and / or its tautomer and of the general formula (ii) An addition product (F-1) with the compound represented was obtained. F-1 was thermally decomposed with nitric acid, heated and dissolved with dilute nitric acid, and made constant. When Ni, Zn, Cu, Al, Fe and Co were measured using ICP emission spectrophotometer PS3520VDDII manufactured by Hitachi High-Tech Science Co., Ltd. and the metal ion content was determined, Ni ²⁺ and Zn ²⁺ in Me were obtained. The total content was 100 mol%, and Ni ²⁺ : Zn ²⁺ = 78: 22 (molar ratio).

(Preparation of Addition Product (F-2) of Metal Azo Compound Represented by General Formula (i) and / or Tautomer and Its Compound Represented by General Formula (ii))
30% by weight aqueous solution of nickel chloride (115.33 g 0.267 mol) and 30% by weight aqueous solution of zinc chloride (13.50 g 0.033 mol) in the addition product (F-0) obtained by the above method The mixture was added and stirred at 80 ° C. for 8 hours. The pigment is isolated by filtration, washed, dried at 120 ° C., ground in a mortar, metal azo compound of the general formula (i) and / or its tautomer and a table of the general formula (ii) The addition product (F-2) with the compound to be obtained was obtained. F-2 was thermally decomposed with nitric acid, heated and dissolved with dilute nitric acid, and made constant. The metal ion content was determined by the above method, and the total content of Ni ²⁺ and Zn ²⁺ in Me was 100 mol%, and Ni ²⁺ : Zn ²⁺ = 89: 11 (molar ratio).

(Preparation of Addition Product (F-3) of Metal Azo Compound Represented by General Formula (i) and / or Tautomer thereof and Compound Represented by General Formula (ii))
To the addition product (F-0) obtained by the above method, 30 wt% aqueous nickel chloride solution (86.83 g 0.201 mol) and 30 wt% aqueous zinc chloride solution (44.98 g 0.099 mol) The mixture was added and stirred at 80 ° C. for 8 hours. The pigment is isolated by filtration, washed, dried at 120 ° C., ground in a mortar, metal azo compound of the general formula (i) and / or its tautomer and a table of the general formula (ii) The addition product (F-3) with the compound to be obtained was obtained. F-3 was thermally decomposed with nitric acid, heated and dissolved with dilute nitric acid, and made constant. The metal ion content was determined by the above method, and the total content of Ni ²⁺ and Zn ²⁺ in Me was 100 mol%, and Ni ²⁺ : Zn ²⁺ = 67: 33 (molar ratio).

(Preparation of Addition Product (F-4) of Metal Azo Compound and / or Tautomer and Its Compound Represented by General Formula (ii))
A 30 wt% aqueous solution of nickel chloride (129.59 g, 0.3 mol) was added to the addition product (F-0) obtained by the above method, and the mixture was stirred at 80 ° C. for 8 hours. The pigment is isolated by filtration, washed, dried at 120 ° C., ground in a mortar, and the adduct of the metal azo compound and / or the tautomer thereof with the compound represented by the general formula (ii) ( F-4) was obtained. F-4 was thermally decomposed with nitric acid, heated and dissolved with dilute nitric acid, and made constant. The metal ion content was determined by the above method, and the total content of Ni ²⁺ and Zn ²⁺ in Me was 100 mol%, and Ni ²⁺ : Zn ²⁺ = 100: 0 (molar ratio).

(Preparation of Addition Product (F-5) of Metal Azo Compound and / or Tautomer and Its Compound Represented by General Formula (ii))
30% by weight aqueous solution of nickel chloride (116.63 g 0.27 mol) and 30% by weight aqueous solution of copper chloride (13.63 g 0.03 mol) in the addition product (F-0) obtained by the above method The mixture was added and stirred at 80 ° C. for 8 hours. The pigment is isolated by filtration, washed, dried at 120 ° C., ground in a mortar, and the adduct of the metal azo compound and / or the tautomer thereof with the compound represented by the general formula (ii) ( F-5) was obtained. F-5 was thermally decomposed with nitric acid, heated and dissolved with dilute nitric acid, and made constant. The metal ion content was determined by the above method, and the total content of Ni ²⁺ and Zn ^{2+ in} Me was 90 mol%, and Ni ²⁺ : Cu ²⁺ = 90: 10 (molar ratio).

(Preparation of Colorant Dispersion)
C. I. A slurry was prepared by mixing 150 g of C.I. Pigment Green 59 (FASTGEN Green C 100), 75 g of a polymer dispersant ("BYK" 6919), 100 g of a binder resin ("Adeka Acres" WR 301), and 675 g of PMA. The beaker containing the slurry is connected with a Dyno mill and a tube, and dispersion treatment is performed at a peripheral speed of 14 m / s for 8 hours using zirconia beads with a diameter of 0.5 mm as a medium, pigment green 59 dispersion (D-1) Was produced.

  Colorant dispersion liquid (D-2) to (D-1) in the same manner as (D-1) except that the types and addition amounts of the colorant, the polymer dispersant, the binder resin, and the organic solvent are changed as described in Table 1. (D-19) was obtained.

(Preparation of color filter substrate)
On a 30 cm × 35 cm non-alkali glass, a black matrix resin BM-1 was applied so as to give a film thickness of 1.5 μm after curing and vacuum drying. Exposure is performed with an i-line of 40 mJ / cm ² through a stripe photomask with a pixel pitch of 50 μm and a black matrix width of 5 μm, development is performed with a 0.3 wt% tetramethylammonium aqueous solution for 50 seconds, and heating is performed at 230 ° C. for 30 minutes Curing was performed to form a black matrix.

On it, red resin composition R-1 was applied so that film thickness might be set to 2.5 micrometers, and it vacuum-dried. It is exposed with i-line 40mJ / cm ² through a stripe photomask of 50μm width, developed with 0.3 wt% tetramethylammonium aqueous solution for 50 seconds, heat cured at 230 ° C for 30 minutes, pixel pitch 50μm The red pixel of the

Furthermore, the blue resin composition B-1 was apply | coated so that film thickness might be set to 2.5 micrometers, and it vacuum-dried. It is exposed with i-line 40mJ / cm ² through 50 μm wide stripe photomask, developed with 0.3 wt% tetramethylammonium aqueous solution for 50 seconds, heat cured for 30 minutes at 230 ° C, pixel pitch 50μm Blue pixels were formed.

Furthermore, the colored resin composition obtained by each Example and the comparative example was apply | coated on it, and it heat-dried at 90 degreeC for 10 minutes. The applied film thickness was such that the chromaticity y = 0.680. In Examples 1 to 31 and Comparative Example, 50 m width in Example 32, 45 m width in Example 32, 55 m width in Example 33, and 60 m width in Example 34 are exposed at i-line 100 mJ / cm ² through a stripe-shaped photomask. Then, development was carried out with a 0.3 wt% tetramethylammonium aqueous solution for 60 seconds, and heat curing was carried out at 230 ° C for 30 minutes to form green pixels having a pixel pitch of 45 to 60 μm.

  Thereafter, a transparent electrode is formed, and transmission spectrum, chromaticity, pixel film thickness, BT. 2020 cover rate, BT. A color filter substrate for 2020 simple area ratio and pixel missing evaluation was obtained.

On the other hand, the colored resin composition obtained in each Example and Comparative Example was applied onto a 10 cm × 10 cm non-alkali glass substrate, and dried by heating at 90 ° C. for 10 minutes. The applied film thickness was such that the chromaticity y = 0.680. It is exposed with i-line 100mJ / cm ² without photo mask, developed with 0.3 wt% tetramethylammonium aqueous solution for 60 seconds, heat cured at 230 ° C for 30 minutes to form green pixels, contrast A color filter substrate for evaluation was obtained.

(Backlight 1: Preparation of blue LED + β sialon phosphor + KSF phosphor)
Using a polyethylene container with a volume of 300 ml, 86% by weight of silicone resin OE-6630A / B (manufactured by Toray Dow Corning Co., Ltd.) and 7% by weight of β-sialon phosphor (GR-240 manufactured by Denka Co., Ltd.) KSF phosphor (Denka Co., Ltd. product, RE-315) was mixed in the ratio of 7 weight%. The resulting mixed solution is stirred / defoamed at 1000 rpm for 20 minutes using a planetary stirring / defoaming apparatus “Mazel Star” (registered trademark) KK-400 (manufactured by Kurashiki Spinning Co., Ltd.) to produce a resin for sheet production I got a liquid.

  The obtained resin solution for sheet preparation is coated on a polyethylene terephthalate film "Therapel" (registered trademark) BLK (made by Toray Film Co., Ltd.) using a slit die coater, heated at 130 ° C. for 2 hours, and dried. Thus, a phosphor sheet having a thickness of 200 μm was obtained. The obtained phosphor sheet was cut into pieces of 1 mm square using a dicing apparatus.

  After die bond paste EN-4900GC (made by Hitachi Chemical Co., Ltd.) was applied on the fragmented phosphor sheet, die bond paste was applied on the chip surface on a substrate on which 1 mm square flip chip type blue LED chips were mounted. The sheet was placed so that the surfaces were in contact and brought into close contact. The adhered phosphor sheet and the chip mounting substrate were heated at 100 ° C. for 1 minute using a hot plate to cure the die bond paste. Sealing agent OE-6630A / B (Toray Dow Corning Co., Ltd. product) was used for sealing, and the backlight 1 was obtained.

  When the obtained backlight 1 was evaluated by the method mentioned later, the peak wavelength in 490-570 nm of the emission spectrum was 540 nm, and the half value width was 55 nm.

(Backlight 2: Preparation of blue LED + β sialon phosphor + KSF phosphor)
Backlight 2 was obtained by the same method as the preparation of backlight 1 except that GR-SW 529Y manufactured by Denka Co., Ltd. was used instead of GR-240 manufactured by Denka Co., Ltd. as the β-sialon phosphor. When the obtained backlight 2 was evaluated similarly to the backlight 1, the wavelength of the peak in 490-570 nm of the emission spectrum was 528 nm, and the half value width was 48 nm.

(Backlight 3: preparation of blue LED + color conversion film)
Synthesis of Compound G-1 3,5-Dibromobenzaldehyde (3.0 g), 4-t-butylphenylboronic acid (5.3 g), tetrakis (triphenylphosphine) palladium (0) (0.4 g), potassium carbonate (2.0 g) was placed in a flask and purged with nitrogen. To this was added degassed toluene (30 mL) and degassed water (10 mL), and refluxed for 4 hours. The reaction solution was cooled to room temperature, and the organic layer was separated and washed with saturated brine. The organic layer was dried over magnesium sulfate and filtered, and the solvent was evaporated. The obtained reaction product was purified by silica gel column chromatography to obtain 3,5-bis (4-t-butylphenyl) benzaldehyde (3.5 g) as a white solid.

  3,5-Bis (4-t-butylphenyl) benzaldehyde (1.5 g) and 2,4-dimethylpyrrole (0.7 g) are added to the reaction solution, dehydrated dichloromethane (200 mL) and trifluoroacetic acid (1 drop) Was added and stirred for 4 hours under a nitrogen atmosphere. A solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (0.85 g) in dehydrated dichloromethane was added, and the mixture was further stirred for 1 hour. After completion of the reaction, boron trifluoride diethyl etherate (7.0 mL) and diisopropylethylamine (7.0 mL) are added and stirred for 4 hours, then water (100 mL) is further added and the mixture is stirred, and the organic layer is separated did. The organic layer was dried over magnesium sulfate and filtered, and the solvent was evaporated. The obtained reaction product was purified by silica gel column chromatography to obtain 0.4 g of a compound G-1 having the following structure (yield: 18%).

Synthesis of Compound R-1 A mixed solution of 300 mg of 4- (4-t-butylphenyl) -2- (4-methoxyphenyl) pyrrole, 201 mg of 2-methoxybenzoyl chloride and 10 ml of toluene under nitrogen stream at 120 ° C. for 6 hours Heated. After cooling to room temperature, it was evaporated. After washing with 20 ml of ethanol and vacuum drying, 260 mg of 2- (2-methoxybenzoyl) -3- (4-t-butylphenyl) -5- (4-methoxyphenyl) pyrrole was obtained.

  Next, 260 mg of 2- (2-methoxybenzoyl) -3- (4-t-butylphenyl) -5- (4-methoxyphenyl) pyrrole, 4- (4-t-butylphenyl) -2- (4-) A mixed solution of 180 mg of methoxyphenyl) pyrrole, 206 mg of methanesulfonic anhydride and 10 ml of degassed toluene was heated at 125 ° C. for 7 hours under a nitrogen stream. After cooling to room temperature, 20 ml of water was injected and extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, evaporated and dried in vacuo.

  Next, under nitrogen flow, 305 mg of diisopropylethylamine and 670 mg of boron trifluoride diethyl ether complex were added to a mixed solution of the obtained pyromethene body and 10 ml of toluene, and the mixture was stirred at room temperature for 3 hours. 20 ml of water were injected and extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, dried over magnesium sulfate and evaporated. After purification by silica gel column chromatography and vacuum drying, 0.27 g of reddish purple powder R-1 having the following structure was obtained.

  100 parts by weight of a silicone resin OE-6630A / B (manufactured by Toray Dow Corning Co., Ltd.) and 0.20 parts by weight of a compound G-1 are mixed, and then a planetary stirring / defoaming device "Mazerustar" (registered trademark) The composition G-1 was manufactured by stirring at 300 rpm for 1 hour using KK-400 (manufactured by Kurashiki Spinning Co., Ltd.).

  100 parts by weight of a silicone resin OE-6630A / B (manufactured by Toray Dow Corning Co., Ltd.) and 0.08 parts by weight of a compound R-1 are mixed, and then a planetary stirring / defoaming device "Mazel Star" (registered trademark) It stirred at 300 rpm for 1 hour using KK-400 (Kurashiki spinning Co., Ltd. product), and manufactured composition R-1.

  The obtained composition G-1 is coated on a stretched polyethylene terephthalate film ("Therapel" BLK, manufactured by Toray Film Co., Ltd.) using a bar coater, and dried by heating at 120 ° C for 5 minutes to obtain an average film thickness of 10 μm. A coating layer was formed. The composition R-1 was applied thereon using a bar coater, and dried by heating at 120 ° C. for 5 minutes to form a coating layer having an average film thickness of 10 μm. Thereafter, a diffusion film Texcell TDF127 (manufactured by Toray Advanced Materials Korea. Inc.) was laminated, followed by aging at 60 ° C. for 1 hour to obtain a color conversion film.

  A blue LED was attached to the obtained color conversion film to obtain a backlight 3 using the color conversion film. When the obtained backlight 3 was evaluated similarly to the backlight 1, the peak wavelength in 490-570 nm of an emission spectrum was 528 nm, and the half value width was 31 nm.

  The evaluation methods in the examples are as follows.

(The peak wavelength of the transmission spectrum between the wavelengths 490 to 570 nm of the green pixel and the half width of the peak, chromaticity x, y, Y)
About the green spectrum pixel of the transmission spectrum and color filter substrate for chromaticity measurement manufactured by the above method, the transmission spectrum of 380-780 nm is measured using Otsuka Electronics Co., Ltd. product microscopic differential light measurement device LCF-100MA, and it is based on CIE1931 standard The chromaticity (x, y, Y) in the C light source, and the peak wavelength and half width between 490 and 570 nm were measured.

(contrast)
Nitto Denko Polarizer ("NPF" (registered trademark)-G1220 DUN), for contrast evaluation on a backlight unit (FL8A-EX / 70) manufactured by Meitoku Kogyo Co., Ltd. using a hot cathode tube A color filter substrate and an analyzer (“NPF” -G1220DUN) manufactured by Nitto Denko Corporation are arranged in this order, and a polarizer and an analyzer are paralleled using a color luminance meter (BM-5A) manufactured by Topcon Corporation. The light transmittance (I1) and the light transmittance (I2) when the polarizer and the analyzer were orthogonal to each other were measured, and the contrast was calculated from the light transmittance ratio (I1 / I2).

(Pixel film thickness)
The film thickness of the part which measured the transmission spectrum using Otsuka Electronics Co., Ltd. product microspectrometer LCF-100MA was measured using the Tokyo Seimitsu product thickness meter "Surfcom" 1400D.

(BT. 2020 cover rate)
In the (x, y) coordinate system, BT. 100% of the area surrounded by 2020 defined three points (Red (0.708, 0.292), Green (0.170, 0.797), Blue (0.131, 0.046)) As red and blue are defined points, overlapping with the area surrounded by red, green and blue when replacing the green's coordinates with the chromaticity of the green pixel measured in each example and comparative example The area ratio was calculated.

(BT. 2020 simple area ratio)
In the (x, y) coordinate system, BT. 100% of the area surrounded by 2020 defined three points (Red (0.708, 0.292), Green (0.170, 0.797), Blue (0.131, 0.046)) As the red and blue are defined points, the area ratio of the area surrounded by red, green and blue when replacing the green's coordinates with the chromaticity of the green pixel measured in each example and comparative example Calculated.

(Pixel missing)
The green pixels of the color filter substrate prepared by the above-mentioned method are observed for a field of view of 5 cm × 5 cm under a condition of 50 × magnification using Nikon microscope OPTIPHOT 300, and the pixel chip is evaluated according to the following criteria did.
A: Chipping area is 0%
B: Chipping area is more than 0% and 0.01% or less C: Chipping area is more than 0.01% and 0.1% or less D: Chipping area is more than 0.1% and less than 1% E: Chipping area is 1 More than 20% or less F: Chipped area is more than 20%.

(The wavelength of the peak of the intensity at the wavelength of 490 to 570 nm of the backlight, half width)
The backlights 1 to 3 manufactured by the above-described method are turned on at an output of 10000 cd / m ^2, and the emission spectrum between wavelengths 490 to 570 nm is measured using the LCD evaluation device LCD-720 manufactured by Otsuka Electronics Co., Ltd. The peak wavelength and half width were measured.

(Display chromaticity x, y)
About the green pixel of the display obtained by Examples 35-37, the chromaticity x and the chromaticity y were measured using Otsuka Electronics Co., Ltd. LCD evaluation device LCD-720.

(Display area BT. 2020 simple area ratio)
In the (x, y) coordinate system, BT. 100% of the area surrounded by 2020 defined three points (Red (0.708, 0.292), Green (0.170, 0.797), Blue (0.131, 0.046)) Red and Blue are surrounded by Red, Green, and Blue when the coordinates of Green are replaced with the chromaticity x, y of the green pixel of the display measured in Examples 35 to 37 while the points are defined as Red and Blue. The area ratio of the area was calculated.

Example 1
4.736 g of the colorant dispersion D-1, 17.316 g of the colorant dispersion D-6, 25.309 g of the colorant dispersion D-11, and 1.111 g of WR 301 DPHA monomer (manufactured by Nippon Kayaku Co., Ltd. "Kayarad" ® DPHA Acid value: 0.1 mg KOH / g) 1.863 g, Photopolymerization initiator (ADEKA Corp. “ADEKA ARKLES” (registered trademark) NCI-831) 0.192 g, Chain transfer agent (Showa Denko Corporation "Kalens" (registered trademark) MT-PE1 0.021 g), adhesion improver (Shin-Etsu Chemical Co., Ltd. KBM-503) 0.160 g, surfactant (BICK Chemie "BYK" (registered) (Trademark)-333) 0.040 g, polymerization inhibitor (tertiary butyl catechol (TBC) manufactured by DIC) 0.009 g, PMA 7.243 g, dipropylene glycol It was added monomethyl ether acetate (DPMA) 42.001g, C. as a coloring material I. Pigment green 59, C.I. I. A green resin composition was prepared containing pigment blue 16 and an addition product at 10: 36.6: 53.4 (weight ratio). The content of the addition product relative to 100 parts by weight of pigment blue 16 was 146 parts by weight. The solid content acid number was 22.4 mg KOH / g. The compounding quantity of the photoinitiator was 1.33 weight% in solid content. The obtained green resin composition was evaluated by the method described above, Y = 8.3, x = 0.077, film thickness 2.96 μm, peak wavelength 506 nm, half width 38 nm, BT2020 simple area ratio 89.5%, BT2020 cover rate was 77.5%. The product of the BT 2020 cover ratio and the green pixel Y (cover ratio x brightness), which is an index of the balance between the cover ratio and the brightness, was 7.5. The pixel missing evaluation was E. The composition of the green resin composition and the evaluation results are shown in Table 2.

Examples 2 to 34, Comparative Examples 1 to 13
A green resin composition was produced in the same manner as in Example 1 except that the types and blending amounts of the respective components were changed as described in Tables 2 to 5. The results evaluated by the above-mentioned method are shown in Tables 6-13.

  In the colorant, C.I. I. Pigment green 59, C.I. I. Pigment Blue 16 and Examples 1 to 34 containing the addition product, have high color purity of y = 0.680, film thickness of 3 μm or less, and pixel chipping resistance having pixel chipping of E or more sufficient for practical use Was. Meanwhile, C.I. I. Pigment green 59 and Comparative Examples 1 to 4, C.I. I. The film thickness of each of Comparative Example 5 not containing pigment blue 16 was more than 3 μm, and the pixel chipping was insufficient of F. C. I. Pigment green 59, C.I. I. Pigment green 7 and C.I. I. Pigment green 58 and Comparative Examples 6 to 7, C.I. I. Pigment blue 16 instead of C.I. I. Pigment blue 15: 3 and C.I. I. Also in Comparative Examples 8 to 9 using Pigment Blue 60, the film thickness exceeded 3 μm in all cases, and the pixel chipping was insufficient of F. The film thickness of each of Comparative Examples 10 to 11 not containing an addition product exceeded 3 μm, and the pixel chipping was insufficient. Also in Comparative Examples 12 to 13 in which the metal ion content of the addition product is out of the range defined in the present invention, the film thickness exceeded 3 μm in all cases, and the pixel chipping was insufficient of F.

(Examples 1 to 8)
From Examples 1 to 8, C.I. I. It can be seen that the pixel chipping can be further suppressed by setting the content of the addition product to 150 to 1400 parts by weight with respect to 100 parts by weight of the pigment blue 16 content.

  Further, by setting x = 0.070-0.210 and y = 0.640-0.720, BT. It can be seen that the 2020 simple area ratio can be improved.

(Examples 13, 26-27)
From Examples 13 and 26 to 27, the pixel chipping can be further suppressed by setting the molar ratio of Ni ²⁺ and Zn ²⁺ (Ni ²⁺ : Zn ²⁺ ) in Me to 70:30 to 85:15. I understand.

(Examples 4, 10, 14, 17, 20, 23)
From Examples 4, 10, 14, 17, 20, 23, C.I. I. Pigment green 59, C.I. I. Pigment blue 16 and a total content of 100 parts by weight of the addition product, C.I. I. It is understood that the pixel chipping can be further suppressed by containing 20 to 60 parts by weight of pigment green 59.

(Examples 5, 11, 15, 18, 21, 24)
From Examples 5, 11, 15, 18, 21, 24 C.I. I. Pigment green 59, C.I. I. Pigment blue 16 and a total content of 100 parts by weight of the addition product, C.I. I. It is understood that the pixel chipping can be further suppressed by containing 20 to 60 parts by weight of pigment green 59.

(Example 3, 28-29, 31)
By setting the solid content acid value to 15 to 40 mg KOH / g from Examples 3, 28 to 29 and 31, pixel chipping can be further suppressed, and by setting the solid content acid value to 17 to 26 mg KOH / g It can be seen that the pixel missing can be further suppressed.

(Examples 9 to 12)
From Examples 9 to 12, by setting the half width of the peak of the transmission spectrum between the wavelengths 490 to 570 nm of the green pixel to 55 to 65 nm, BT. It can be seen that the product of the 2020 cover rate and the brightness Y is improved.

(Examples 17, 19 to 20, 22, 24 to 25)
From Examples 17, 19 to 20, 22, 24 to 25, by setting x = 0.164 to 0.176, y = 0.640 to 0.720, BT. It can be seen that the 2020 coverage can be improved.

(Examples 28, 30)
From Examples 28 and 30, it is understood that the pixel chipping can be further suppressed by setting the content of the photopolymerization initiator to 1.5% by weight or less in the solid content.

Example 35
(Fabrication of display device)
A TFT element, a transparent electrode and the like were formed on an alkali-free glass to prepare an array substrate. A polyimide alignment film was formed on each of the color filter substrate and the array substrate obtained in Example 14, and rubbing was performed. The sealing agent which knead | mixed the microrod on the array substrate was printed, and after spreading the bead spacer, the array substrate and the color filter substrate were bonded together. After injecting nematic liquid crystal (JNC Co., Ltd. “LIXON” (registered trademark) JC-5007LA) from the injection port provided in the seal portion, the polarizing film is placed on both sides of the liquid crystal cell so that the polarization axis is vertical. It stuck and obtained the liquid crystal panel. The back light 1 was attached to this liquid crystal panel as a back light source, and a TAB module, a printed circuit board and the like were mounted to manufacture a liquid crystal display. About the obtained liquid crystal display device, when it evaluated by the above-mentioned method, BT2020 simple area ratio of the display device was 88.6%. Other evaluation results are shown in Table 14.

Examples 36 to 37
A liquid crystal display was produced in the same manner as in Example 35 except that the type of backlight was changed as described in Table 14. The results evaluated by the aforementioned method are shown in Table 14.

(Examples 35 to 37)
From Example 35 to 37, by setting the peak wavelength at 490 to 570 nm of the backlight to 510 to 530 nm, the BT. It can be seen that the 2020 simple area ratio is improved.

  From Examples 36 and 37, when the backlight has a color conversion film, BT. It can be seen that the 2020 simple area ratio is improved.

  The colored resin composition of the present invention can be suitably used as a colored resin composition for forming the pixels of a color filter substrate preferably used in a display device.

Claims (13)

C. I. Pigment green 59,
C. I. Pigment blue 16,
An addition product of a metal azo compound represented by the following general formula (i) and / or a tautomer thereof and a compound represented by the following general formula (ii),
Colored resin composition containing binder resin.

(In the above general formula (i), R ¹ and R ² independently of each other represent OH or NHR ⁵ , and R ³ and R ⁴ independently of each other represent O or NR ⁵ , provided that R ⁵ is , Hydrogen or an alkyl group having 1 to 20 carbon atoms Me represents Ni ²⁺ , Zn ²⁺ , Cu ²⁺ , (Al ³⁺ ) _2/3 , Fe ²⁺ , (Fe ³⁺ ) _2/3 , Co ²⁺ or (Co ³⁺ ) _2/3 , provided that the total content of Ni ²⁺ and Zn ²⁺ in Me is 95 to 100 mol%, Cu ²⁺ , (Al ³⁺ ) _2/3 , Fe ²⁺ , (Fe ³⁺ ) _2/3 , the total content of Co ²⁺ and (Co ³⁺ ) _2/3 is 0 to 5 mol%, and the molar ratio of Ni ²⁺ and Zn ²⁺ (Ni ²⁺ : Zn ²⁺ ) is 1: 9 to 9: 1 In the above general formula (ii), ⁶ to R ⁸ each independently represent hydrogen or an alkyl having 1 to 20 carbon atoms.) Said C.I. I. The colored resin composition according to claim 1, wherein the addition product is contained in an amount of 150 to 1,400 parts by weight with respect to 100 parts by weight of pigment blue 16. Said C.I. I. Pigment green 59, C.I. I. Pigment Blue 16 and the total content of 100 parts by weight of the addition product I. The colored resin composition according to claim 1 or 2, which contains 20 to 60 parts by weight of pigment green 59. The colored resin composition according to any one of claims 1 to 3, which has a solid content acid value of 15 to 40 mg KOH / g. The colored resin composition according to any one of claims 1 to 4, further comprising a photopolymerization initiator in an amount of not more than 1.5% by weight based on the solid content. A color filter substrate having green pixels formed from a cured product of the colored resin composition according to any one of claims 1 to 5. The color filter substrate according to claim 6, wherein the film thickness of the green pixel is 1.5 to 3 m. The color filter substrate according to claim 6 or 7, wherein the half width of the peak of the transmission spectrum between the wavelengths 490 to 570 nm of the green pixel is 55 to 65 nm. The color filter according to any one of claims 6 to 8, wherein the chromaticity of the green pixel in the C light source defined by CIE 1931 is x = 0.070 to 0.210, y = 0.640 to 0.720. substrate. The color filter substrate according to any one of claims 6 to 9, wherein the width of the green pixel is 55 μm or more. A display device comprising the color filter substrate according to any one of claims 6 to 10 and a backlight. The display device according to claim 11, wherein a wavelength of a peak of intensity at a wavelength of 490 to 570 nm of the backlight is in a range of 510 to 530 nm. The backlight according to claim 12, which comprises a color conversion film comprising a color conversion composition containing a compound represented by the following general formula (iii), which converts incident light into light having a wavelength longer than that of incident light. Display device.

(In the above general formula (iii), X represents C—R ¹⁵ or N. R ^{9 to} R ¹⁷ each independently represent hydrogen, an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, cyclo Alkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, arylether group, arylthioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, oxycarbonyl group, Represents a fused ring or an aliphatic ring formed between a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxanyl group, a bolyl group, a phosphine oxide group, an amido group and an adjacent substituent. Group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, alkoxy group, al A hydrogen atom of a quilthio group, arylether group, arylthioether group, aryl group, heteroaryl group, carbonyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, phosphine oxide group Some or all may be substituted.)