JP2010097214A - Color filter substrate for liquid crystal display apparatus and liquid crystal display apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter substrate for a liquid crystal display apparatus which is obtained, by forming a thin film of a black matrix which contains a specific titanium nitride particle and has high OD (optical density) value, and layering a colored layer on the black matrix, in a picture frame light-shielding part area outside a display area and to provide a color filter, having high OD and high surface flatness and the liquid crystal display apparatus made to have superior display characteristics and high contrast by using the color filter. <P>SOLUTION: The color filter substrate for the liquid crystal display apparatus is obtained, by forming the black matrix and a pattern consisting of a plurality of colored layers on a transparent substrate; the black matrix is formed by using a black pigment-dispersed resin containing the titanium nitride particle and has ≤0.9 μm thickness in the display area; and the colored layer is layered on the black matrix in the picture frame light-shielding part area outside the display area. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a color filter substrate and a liquid crystal display device having high contrast and good display performance.

  The liquid crystal display device displays images and characters and performs information processing by using the electro-optic response of the liquid crystal. Specifically, the liquid crystal display device is used for large screens such as personal computers, monitors, and liquid crystal televisions. Is widely used for medium-sized and small-sized applications such as mobile phones, mobile terminals, and car navigation systems. Such a liquid crystal display device normally has a structure in which a liquid crystal layer is sandwiched between two substrates, and light and dark can be expressed by utilizing an electro-optical response that the liquid crystal layer exhibits with external application. Color display is also possible by using a color filter composed of pixels having color selectivity.

  Conventionally, a metal thin film using a chromium-based material has been used as the black matrix material, but in recent years, a resin black matrix made of a resin and a light shielding material has been used in terms of cost and environmental pollution. The resin black matrix is obtained by applying a black resin composition containing a resin and a light shielding material such as carbon black on a substrate and drying it to form a black film, which is finely patterned into a lattice pattern by a photolithography method. . For example, Patent Document 1 describes a resin black matrix in which carbon black is dispersed in a non-photosensitive polyimide resin.

  However, with the recent demand for thinner color filters, higher performance, and higher brightness of backlights used in liquid crystal display devices, there has been an increasing demand for higher OD values for resin black matrices. The resin black matrix had an insufficient OD value. In addition, when the resin black matrix is thick, the surface step generated by the color pixels on the resin black matrix becomes large, so that the flatness of the color filter is lowered and the liquid crystal orientation is disturbed. There is also a growing demand for computerization.

  As a method of forming a black matrix by reducing the surface level difference, for example, Patent Document 2 discloses a method of providing pixels with light shielding properties by stacking pixels. The method of stacking pixels is preferable because the surface level difference is small, but sufficient light-shielding performance cannot be obtained. Therefore, there is a problem that the contrast is reduced due to light leakage in the liquid crystal display device. In particular, there is a problem that light leakage from a light shielding portion outside the display area of the liquid crystal display device becomes a problem.

  A method for improving the light leakage of the light shielding part outside the display area by improving the light shielding property of the black matrix outside the display area of the liquid crystal display device has been studied. A method of improving the light shielding property by making the black matrix outside the display area into a laminated structure has been studied. For example, Patent Document 3 discloses a method of further laminating a black matrix on a black matrix outside the display area or laminating a black matrix and colored pixels. However, since the OD value is low and the OD value is low, black The problem was that the matrix became thicker.

  Although increasing the volume ratio of the light shielding material can achieve a high OD value and a thin film, the resin ratio in the resin black matrix is decreased and the adhesion between the resin black matrix and the glass is reduced, resulting in a resin black. There arises a problem that the matrix is peeled off and a problem that a sufficient resistance value cannot be obtained. Therefore, a light shielding material that achieves a higher OD value is required even with a small amount of content.

  As the light shielding material, carbon black, titanium black such as low-order titanium oxide and titanium oxynitride, metal oxides such as iron oxide, and other organic pigment mixed colors are used, but carbon black and titanium oxynitride are the mainstream. It has become.

Regarding carbon black, various attempts have been made for the purpose of obtaining a coating film having a high OD value. For example, Patent Document 4 is disclosed. In Patent Document 2, by defining the primary particle diameter of carbon black, DBP absorption amount, pH, and amine value and molecular weight of the organic compound used in combination, the OD value per film thickness of 1.0 μm is a resin black of 3.5. Although a matrix can be obtained, the OD value is not sufficient, and the resistance value is as low as 1 × 10 ⁶ or less, so that there is a problem that it cannot be used in applications where insulation is required.

  On the other hand, titanium oxynitride obtained by partially nitriding oxygen of titanium dioxide or titanium hydroxide is used for a resin black matrix having high resistance. In order to obtain a high OD value, it is important to perform nitriding so as not to contain white titanium dioxide, and various studies have been made (Patent Documents 5 and 6). In particular, Patent Document 4 describes that titanium oxynitride having a high degree of nitridation and a small crystallite diameter can be obtained by optimizing the heating and baking temperature at the time of nitriding and reducing titanium oxide. By using it, a resin black matrix having a sufficiently high OD value of 4.0 as the OD value per 0.8 μm thickness can be obtained. However, titanium oxynitride contains a large amount of alkali metals such as Na, K, Mg, Ca and the like derived from a production method such as nitridation reduction, which decreases the adhesion strength between the resin black matrix and the glass, and reduces the resistance value. It is a factor to reduce (Patent Document 7). For this reason, a step of removing alkali metals such as K and Na by ion exchange using ion exchange resin or pure water washing is required, which causes a problem of lowering productivity.

  On the other hand, titanium nitride is mentioned as another black pigment (Patent Document 8), and a technique using titanium nitride fine particles of 200 nm or less in solar radiation shielding is disclosed (Patent Document 9), but the near infrared region (800 The properties are optimized for the purpose of minimizing the transmittance at ˜2500 nm and the high transmittance in the visible light region, and minimizing the transmittance in the visible light region required as a black matrix, that is, the degree of blackness. Was not enough.

  Patent Document 10 discloses a titanium nitride film formed for black matrix use. However, since it is not applied and formed as a black composition, it has been difficult to easily form on a substrate.

Japanese Patent No. 3196638 (1st page, 9th to 11th page, Table 1) JP 2000-29014 A JP 10-170958 A JP 2004-292672 A JP 2005-514767 A JP 2006-209102 A Japanese Patent Laid-Open No. 2004-4651 JP-A 64-37408 JP 2005-179121 A JP-A-10-104663

  The present invention was devised in view of the drawbacks of the prior art. The object of the present invention is to form a black matrix having a high OD value containing specific titanium nitride particles as a thin film, and further outside the display area. It becomes possible to provide a color filter with higher OD and higher surface flatness. Further, by using this color filter, a liquid crystal display device having excellent display characteristics and high contrast can be obtained.

  As a result of intensive studies to solve the problems of the prior art, the present inventors have used specific titanium nitride particles as a light shielding material as follows, and formed a colored layer on the black matrix in the frame area outside the display area. It has been found that the problem of the present invention can be solved by laminating.

That is, the object of the present invention is achieved by the following configuration.
(1) A color filter substrate in which a black matrix and a plurality of colored layer patterns are formed on a transparent substrate, wherein the black matrix is a black pigment-dispersed resin containing titanium nitride particles, and the black matrix in the display region A color filter substrate for a liquid crystal display device, wherein the color filter substrate has a film thickness of 0.9 μm or less and a colored layer is laminated on a black matrix in a frame light shielding part region outside the display region.
(2) When the titanium nitride particles have CuKα rays as an X-ray source, the diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride particles is 42.5 ° or more and 42.8 ° or less. The color filter substrate for a liquid crystal display device according to (1), which is a black pigment.
(3) The crystallite size obtained from the half width of the peak derived from the (200) plane when CuKα rays of the titanium nitride particles are used as an X-ray source is 50 nm or less. Color filter substrate for liquid crystal display devices.
(4) The color filter substrate for a liquid crystal display device according to (1), wherein the colored layer laminated on the black matrix in the frame light shielding part region outside the display region is a red pixel.
(5) The color filter substrate for a liquid crystal display device according to any one of (1) to (4), wherein the optical density of the black matrix is 4.0 or more per 1 μm.
(6) The frame shading area of the portion where the black matrix in the display area has a thickness of 0.9 μm or less, the optical density of the black matrix in the display area is 3.6 or more, and the pixels outside the display area are stacked. The color filter substrate for a liquid crystal display device according to any one of (1) to (5), wherein the black matrix has an optical density of 4.2 or higher, which is higher than the optical density of the black matrix in the display region.
(7) The color filter substrate for a liquid crystal display device according to any one of (1) to (6), wherein the pixel resolution of the color filter is 150 ppi or more.
(8) A liquid crystal display device in which a liquid crystal compound is filled in a gap between the color filter substrate according to any one of (1) to (7) and a counter substrate.

  (9) A liquid crystal display device using the color filter substrate according to (8), wherein the liquid crystal display method is a horizontal electric field method.

  By using the black resin composition of the present invention, it is possible to obtain a color filter substrate having high light shielding properties, high resistance value, and high flatness. Further, by using the color filter substrate of the present invention, a liquid crystal display device having high contrast and excellent display performance can be obtained.

Sectional drawing which shows the structure of the color filter of this invention

Hereinafter, the present invention will be described in more detail.
The black resin composition of the present invention includes at least a light shielding material, a resin and a solvent, and uses titanium nitride particles having at least specific characteristics as a light shielding material for the black matrix, and laminates pixels on the black matrix outside the display area. It is necessary to.

The titanium nitride particles used as a light-shielding material in the present invention include titanium nitride as a main component and are usually low in titanium oxide TiO ₂ and Ti _n O _2n-1 (1 ≦ n ≦ 20) as subcomponents. It contains titanium oxynitride that can be expressed by titanium suboxide and TiN _x O _y (0 <x <2.0, 0.1 <y <2.0). The titanium nitride particles are characterized in that the diffraction angle 2θ of the peak derived from the (200) plane when CuKα rays are used as an X-ray source is 42.5 ° or more and 42.8 ° or less. By using physical particles as a light shielding material, the resin black matrix of the present invention can achieve a high OD value while keeping the concentration of the light shielding material in the black resin composition low. As a result, the resin black matrix of the present invention can ensure high adhesion. Further, since the resin black matrix of the present invention has a high OD value per film thickness, the film thickness is 1.0 μm or less at a practical OD value (4.0). As a result, even when a resin black matrix is used, it is possible to obtain a color filter having no practical problem in flatness without a protective film.

The X-ray diffraction spectrum of the titanium compound shows that when CuKα ray is used as the X-ray source, TiN has a peak derived from the (200) plane as the strongest peak, and 2θ = 42.5 ° in the vicinity of TiO and (200) plane of TiO. The peak derived from is seen in the vicinity of 2θ = 43.4 °. On the other hand, although not the strongest peak, the peak derived from the (200) plane of anatase TiO ₂ is in the vicinity of 2θ = 48.1 °, and the peak derived from the (200) plane of rutile TiO ₂ is 2θ = 39. Observed around 2 °. Therefore, a titanium compound having a crystal structure having nitrogen atoms and oxygen atoms has the strongest peak in the diffraction angle 2θ range of 42.5 ° to 43.4 °, and is in a crystalline state containing a large amount of oxygen atoms. The more the peak position is shifted to the higher angle side with respect to 42.5 °.

In order to exhibit the effect of the present invention, the peak diffraction angle 2θ derived from the (200) plane of the titanium nitride particles is preferably 42.5 ° or more and 42.8 ° or less. It is preferably 5 ° or more and less than 42.7 °. In the titanium oxynitride obtained by nitriding titanium oxide, the strongest peak is confirmed from 42.9 ° to 43.2 ° as the diffraction angle 2θ (Japanese Patent Laid-Open No. 2006-209102). It can be seen that the crystal structure is different from that of titanium nitride. When titanium oxide TiO ₂ is contained as an accessory component, the peak derived from anatase TiO ₂ (101) as the strongest peak is in the vicinity of 2θ = 25.3 ° and derived from rutile TiO ₂ (110). A peak is observed in the vicinity of 2θ = 27.4 °. However, since TiO ₂ is white and causes a reduction in the light shielding property of the black matrix, it is preferably reduced to such an extent that it is not observed as a peak.

  The crystallite size constituting the titanium nitride particles can be determined from the half width of the X-ray diffraction peak, and is calculated using the Scherrer equation shown in the following equations (1) and (2).

Here, K = 0.9, λ (0.15418 nm), β _e : half width of diffraction peak, β _o : correction value of half width (0.12 °). Where β, β _e and β _o are calculated in radians.

Titanium nitride particles used in the present invention contain TiN as a main component, and are usually noticeable when oxygen is mixed during the synthesis, particularly when the particle diameter is small, but partly due to oxidation of the particle surface, etc. Contains atoms. A smaller amount of oxygen is preferable because a higher OD value can be obtained, and it is particularly preferable not to contain TiO ₂ as a subcomponent. The oxygen atom content is 12% by weight or less, and more preferably 8% by weight or less.

  Titanium atom content is analyzed by ICP emission spectroscopy, nitrogen atom content is analyzed by inert gas melting-thermal conductivity method, and oxygen atom content is analyzed by inert gas melting-infrared absorption method. can do.

  In order to make the effect of the present invention remarkable, the crystallite size is preferably 50 nm or less, and more preferably 20 nm or more and 50 nm or less. By forming a black matrix using titanium nitride particles having a crystallite size of 50 nm or less, the transmitted light of the coating film exhibits a blue to violet color having a peak wavelength of 475 nm or less, and has a high light shielding property. A black matrix can be obtained. Further, since the transmittance of ultraviolet rays (particularly i-line (365 nm)) is higher than that of a conventional light-shielding material, even when a photosensitive black resin composition is used, film curing by light irradiation is sufficiently advanced, resulting in a high OD and shape. It is possible to form a good black matrix. Furthermore, it is preferable to use titanium nitride particles having a crystallite size of 20 nm to 50 nm in order to form a black matrix having a higher resistance value.

The specific surface area of the titanium nitride particles in the present invention can be determined by the BET method, and the value is preferably 5 m ² / g or more and 100 m ² / g or less, more preferably 10 m ² / g or more and 60 m ² / g or less. . Further, from the specific surface area obtained by the BET method, the particle diameter when the particles are assumed to be perfect spheres and the particle diameter is uniform can be obtained by the following equation (3).
Average particle diameter (nm) = 6 / (S × d × 1000) (3)
Here, S: specific surface area (m ² / g), d: density (g / cm ³ ), d = 5.24 (g / cm ³ ) for titanium nitride, d = 4 for titanium oxynitride 3 (g / cm ³ ).

  When the specific surface area is small, that is, the particle size is large, it is difficult to finely disperse the particles, the particles settle during storage, the flatness of the resin black matrix decreases, and the adhesion to glass This causes a problem of lowering. On the other hand, when the specific surface area is large, that is, when the particle diameter is small, the particles are likely to re-aggregate during dispersion, so that the dispersion stability tends to deteriorate, and when the resin black matrix is used, sufficient concealability as a light shielding material is obtained. This is not preferable because the OD value is lowered without being generated.

  A gas phase reaction method is generally used to synthesize titanium nitride, and examples include an electric furnace method and a thermal plasma method. The thermal plasma method has few impurities, has a uniform particle size, and has high productivity. The synthesis by is preferred. Examples of the method for generating thermal plasma include direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, hybrid plasma, and the like, and high frequency plasma in which impurities from the electrode are less mixed is more preferable. Specific methods for producing titanium nitride fine particles by the thermal plasma method include a method of reacting titanium tetrachloride and ammonia gas in a plasma flame (Japanese Patent Laid-Open No. 22221/1990), or evaporating titanium powder by high-frequency thermal plasma. A method of introducing nitrogen as a carrier gas and nitriding and synthesizing it in the cooling process (Japanese Patent Laid-Open No. 61-11140), a method of blowing ammonia gas into the peripheral edge of plasma (Japanese Patent Laid-Open No. 63-85007), and the like. However, the present invention is not limited to these, and the production method is not limited as long as titanium nitride particles having desired physical properties can be obtained. Various titanium nitride particles are commercially available, and a plurality of particles satisfying the diffraction angle and the oxygen atom amount defined in the present invention, and further satisfying the preferred crystallite size and specific surface area described above are also commercially available. ing. In the present invention, those commercially available products can be preferably used.

  In the present invention, in order to adjust the chromaticity of the black film, a part of the titanium nitride can be changed to another pigment within a range where the OD value does not decrease. As pigments other than titanium nitride, black organic pigments, mixed color organic pigments, inorganic pigments, and the like can be used. As the black organic pigment, carbon black, resin-coated carbon black, perylene black, aniline black, etc., and as the mixed color organic pigment, at least two kinds selected from red, blue, green, purple, yellow, magenta, cyan, etc. Inorganic pigments that have been pseudo-blackened by mixing pigments include graphite and fine metal particles such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, metal oxides, and composites. Examples thereof include oxides, metal sulfides, and metal nitrides. These may be used alone or in combination of two or more. In particular, if carbon black is used, the decrease in the OD value of the black coating can be minimized, and the resistance value, chromaticity, etc. of the black coating can be adjusted. That is, titanium nitride particles are high resistance, whereas carbon black has low resistance, so the resistance value of the black coating can be controlled by the mixing ratio of both. Moreover, if the surface-treated carbon black is used, the width of resistance value control of the black coating is further expanded. On the other hand, with regard to chromaticity, although depending on the crystallite size of the titanium nitride particles used, the transmitted color is generally blue, whereas the transmitted color of carbon black is red. Black without neutrality (neutral black) is obtained. When carbon black is used, its content can be appropriately selected and is not particularly limited, but is usually about 5 to 75% by weight with respect to the weight of the titanium nitride particles.

  As the resin used in the present invention, either photosensitive or non-photosensitive can be used. Specifically, an epoxy resin, an acrylic resin, a siloxane polymer resin, a polyimide resin, or the like is preferably used. In particular, acrylic resin or polyimide resin is excellent in terms of heat resistance of the coating film and storage stability of the black resin composition, and is preferably used.

  A polyimide resin is often used as a non-photosensitive resin, and is formed by heat-opening imidization of a polyamic acid as a precursor. A polyamic acid is generally obtained by subjecting a compound having an acid anhydride group and a diamine compound to an addition polymerization reaction at 40 to 100 ° C., and is usually represented by a repeating unit of a structural unit represented by the following general formula (4). . The structure of the polyimide precursor includes an amic acid structure represented by the following general formula (5), the following general formula (6) in which the amic acid structure is partially imide-cyclized, and the following general formula in which all imides are ring-closed. It is a polyimide precursor having both structures of the imide structure represented by (7).

Here, in the general formulas (4) to (7), R ₁ is a trivalent or tetravalent organic group having 2 to 22 carbon atoms, R ₂ is a divalent organic group having 1 to 22 carbon atoms, and n is 1 or 2.

  As a resin for black matrix obtained by imidizing a polyimide precursor, heat resistance and insulation are required, and therefore aromatic diamines and / or acid dianhydrides are generally preferably used.

  Examples of the aromatic diamine are as follows. Paraphenylenediamine, metaphenylenediamine, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, 4 , 4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) Benzene, 2,2-bis (trifluoromethyl) benzidine, 9,9'-bis (4-aminophenyl) fluorene 4,4'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine 2,4'-diamino Phenylamine, 4,4'-diaminodibenzylamine, 2,2'-diaminodibenzylamine, 3,4'-diaminodibenzylamine, 3,3'-diaminodibenzylamine, N, N'-bis- (4-amino-3-methylphenyl) ethylenediamine, 4,4′-diaminobenzanilide, 3,4′-diaminobenzanilide, 3,3′-diaminobenzanilide, 4,3′-diaminobenzanilide, 2, 4'-diaminobenzanilide, N, N'-p-phenylenebis-p-aminobenzamide, N, N'-p-phenylenebis-m-aminobenzamide, N, N'-m-phenylenebis-p-amino Benzamide, N, N'-m-phenylenebis-m-aminobenzamide, N, N'-dimethyl-N, N'-p-phenylenebis-p-amino N'Namide, N, N'-dimethyl-N, N'-p-phenylenebis-m-aminobenzamide, N, N'-diphenyl-N, N'-p-phenylenebis-p-aminobenzamide, N, N ' -Diphenyl-N, N'-p-phenylenebis-m-aminobenzamide and the like can be mentioned, and one or more of them can be used in combination. More preferably, at least part of the diamine component is paraphenylenediamine, metaphenylenediamine, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl. It is preferably one or a mixture of two or more selected from sulfone, 4,4′-diaminodiphenylsulfone, 9,9′-bis (4-aminophenyl) fluorene, and 4,4′-diaminobenzanilide. .

  On the other hand, examples of the aromatic tetracarboxylic acid include 4,4′-oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 3, 4,9,10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-paraterphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-metaterphenyl Tetracarboxylic dianhydride etc. are mentioned. More preferably, 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-benzophenone tetracarboxylic dianhydride, or pyromellitic dianhydride is used. Further, when a fluorine-based tetracarboxylic dianhydride is used, a polyimide precursor composition that can be converted into a polyimide having good transparency in a short wavelength region can be obtained. Specific examples thereof include 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride and the like. One or two or more of these aromatic tetracarboxylic dianhydrides can be used in combination.

  Furthermore, if necessary, an acid anhydride such as maleic anhydride or phthalic anhydride may be added as a terminal blocking agent. In addition to aromatic compounds, Si-based acid anhydrides and / or diamines are preferably used for the purpose of improving adhesion to inorganic materials such as glass plates and silicon wafers. In particular, when a siloxane diamine typified by bis-3- (aminopropyl) tetramethylsiloxane is used, the adhesion to an inorganic substrate can be improved. Siloxane diamine is usually used in an amount of 1 to 20 mol% in the total diamine. If the amount of siloxane diamine is too small, the effect of improving adhesiveness will not be exhibited, and if it is too large, the heat resistance will be reduced, or the adhesion to the substrate as a dry coating film when photolithography will be too strong, and alkali development will be possible. The problem of remaining on the substrate occurs.

  In addition, the use of an alicyclic compound as a part of acid dianhydride and / or diamine for improving optical properties such as low birefringence does not hinder the present invention. The alicyclic compound may be a known one. Specific examples include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, Bicyclo [2.2.1] heptane-2-endo-3-endo-5-exo-6-exo-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane -2-exo-3-exo-5-exo-6-exo-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6- Tetracarboxylic dianhydride, decahydro-dimethananaphthalenetetracarboxylic dianhydride, bis [2- (3-aminopropoxy) ethyl] ether, 1,4-butanediol-bis (3-aminopropyl) ether Ter 3,9-bis (3-amino (Lopyl) -2,4,8,10-tetraspiro-5,5-undecane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis (3-aminopropoxy) ethane, triethylene glycol-bis (3-aminopropyl) ether, polyethylene glycol-bis (3-aminopropyl) ether, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro-5,5-undecane, 1, 4-Butanediol-bis (3-aminopropyl) ether or the like is used.

  The synthesis of the polyimide precursor is generally performed by reacting tetracarboxylic dianhydride and diamine in a polar organic solvent. At this time, the polymerization degree of the polyamic acid obtained can be adjusted by the mixing ratio of tetracarboxylic dianhydride and diamine. As the solvent, amide polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide are used, and lactone is used to enhance the dispersion effect of the pigment as a light shielding material. Also preferred is a solvent comprising a main component or a lactone alone. Here, the solvent containing lactones as a main component refers to a solvent that is a mixed solvent and has a maximum weight ratio of the total amount of lactone solvents in the mixed solvent to the total solvent. Lactones are aliphatic cyclic esters having 3 to 12 carbon atoms. Specific examples include, but are not limited to, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and the like. In particular, γ-butyrolactone is preferable from the viewpoint of solubility of the polyimide precursor. Examples of solvents other than lactones include, in addition to the above amide polar solvents, for example, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, propylene glycol mono-methyl ether. Propylene glycol mono-methyl ether acetate, dipropylene glycol mono-methyl ether, tripropylene glycol mono-methyl ether, propylene glycol mono-tertiary-butyl ether Ter, isobutyl alcohol, isoamyl alcohol, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, methyl carbitol, methyl carbitol acetate, ethyl carbitol, ethyl carbitol acetate, etc. But not limited to

  An acrylic resin is often used as a photosensitive resin, and is composed of at least an acrylic polymer, a photopolymerizable monomer, and a photopolymerization initiator. These quantitative ratios are usually 10/90 to 90/10 as the weight composition ratio of the acrylic polymer and the photopolymerizable monomer, and 1 to the weight sum of the polymer and the monomer as the addition amount of the photopolymerization initiator. About 20% by weight.

  As the acrylic polymer, an acrylic polymer having a carboxyl group is preferably used. As the acrylic polymer having a carboxyl group, a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound can be preferably used. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid and the like.

  These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. Specific examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, methacryl Isopropyl acrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate N-pentyl acrylate, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate and other unsaturated carboxylic acid alkyl esters, styrene, p-methyls Rene, aromatic vinyl compounds such as o-methylstyrene, m-methylstyrene and α-methylstyrene, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, aliphatic conjugated dienes such as 1,3-butadiene and isoprene, acryloyl groups at the terminals, Alternatively, polystyrene having a methacryloyl group, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and the like can be mentioned. Not shall. In particular, a quaternary copolymer selected from methacrylic acid and / or acrylic acid and methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, and styrene has an average molecular weight Mw of 2,000 to 100,000, an acid value of 70 to 150 (mgKOH / The polymer g) is preferred from the viewpoint of solubility in an alkali developer. Outside this range, the dissolution rate in the alkaline developer is undesirably lowered or increased too much.

  Further, when an acrylic polymer having an ethylenically unsaturated group in the side chain is used, the sensitivity at the time of exposure and development is improved, so that it can be preferably used. As an ethylenically unsaturated group, an acryl group and a methacryl group are preferable. Such an acrylic polymer can be subjected to an addition reaction of an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group to a carboxyl group of an acrylic (co) polymer having a carboxyl group.

  Specific examples of the acrylic polymer having an ethylenically unsaturated group in the side chain include a copolymer described in Japanese Patent No. 3120476, JP-A-8-262221, or a commercially available acrylic polymer. Examples thereof include curable resin “Cyclomer (registered trademark) P” (Daicel Chemical Industries, Ltd.), alkali-soluble cardo resin, and the like. In particular, an acrylic polymer having an ethylenically unsaturated group in the side chain and an average molecular weight (Mw) of 2,000 to 100,000 (measured by gel permeation chromatography using tetrahydrofuran as a carrier, and using a standard polystyrene calibration curve) The polymer having an acid value of 70 to 150 (mg KOH / g) is most preferable from the viewpoints of photosensitive characteristics, solubility in an ester solvent, and solubility in an alkali developer.

  As the monomer, a polyfunctional or monofunctional acrylic monomer or oligomer can be used. Examples of the polyfunctional monomer include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (meth) acrylate, anhydrous Phthalic acid propylene oxide (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin-modified epoxy di (meth) acrylate, alkyd-modified (meth) acrylate, Japanese Patent No. 3621533 and Japanese Patent Application Laid-Open No. 8-278630 Or full propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol Nord A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di Pentaerythritol penta (meth) acrylate, 2,2-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] propane, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] methane, bis [ 4- (3-acryloxy-2-hydroxypropoxy) phenyl] sulfone, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] ether, 4,4′-bis [4- (3-acryloxy) -2-hydroxypropoxy) phenyl] cyclohexane, 9,9-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3-methyl-4- (3-acryloxy-2) -Hydroxypropoxy) phenyl] fluorene, 9,9-bis [3-chloro-4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, biscresol full Examples include orange acrylate and biscresol full orange methacrylate. These can be used alone or in combination.

  By selecting and combining these polyfunctional monomers and oligomers, it is possible to control the sensitivity and processability characteristics of the resist. In particular, in order to increase sensitivity, it is desirable to use a compound having 3 or more, more preferably 5 or more functional groups, and dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable. When using a pigment that absorbs ultraviolet rays effective for photocrosslinking, such as resin BM, in addition to dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate, the molecule contains many aromatic rings. The combined use of (meth) acrylate having a fluorene ring having high water repellency is more preferable because the pattern can be controlled to a desired shape during development. It is preferable to use a mixture of 10 to 60 parts by weight of dipentaerythritol hexa (meth) acrylate and / or dipentaerythritol penta (meth) acrylate and 90 to 40 parts by weight of (meth) acrylate having a fluorene ring as a monomer.

  The photopolymerization initiator is not particularly limited, and is a benzophenone compound, an acetophenone compound, an oxanthone compound, an imidazole compound, a benzothiazole compound, a benzoxazole compound, an oxime ester compound, a carbazole compound, a triazine compound, Known materials such as inorganic photopolymerization initiators such as phosphorus compounds and titanates can be used. For example, benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl Ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane, Ciba Specialty Chemical “Irgacure (registered trademark)” 369, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, Ciba Specialty Chemical Co., Ltd. CGI-113 2- [4-Methylbenzyl] -2-dimethylamino-1- (4-morpholinophenyl) -butanone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methyl Anthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4 , 5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, Ciba Specialty Chemicals Co., Ltd. “Irgacure (registered trademark)” OXE01 1,2-octanedione, 1- [4 -(Phenylthio) -2- (O-benzoyl) Oxime)], an ethanone that is CGI-242, Ciba Specialty Chemical Co., Ltd., 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O— Acetyloxime), 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl) -s-triazine, “Adeka (registered trademark) optomer” N, which is a carbazole-based compound manufactured by Asahi Denka Kogyo Co., Ltd. -1818, N-1919 and the like. These photopolymerization initiators can be used in combination of two or more. In particular, N, N′-tetraethyl-4,4′-diaminobenzophenone and Ciba Specialty Chemicals Co., Ltd. “Irgacure (registered trademark)” 369 or Ciba Specialty Chemical Co., Ltd. CGI-113 and Asahi Denka Kogyo Co., Ltd. “ADEKA (registered trademark) Optmer” N-1818, N-1919 or Ciba Specialty Chemical Co., Ltd. CGI-242 Use of three types of carbazole compounds in combination is preferable because a photosensitive resin composition having high sensitivity and good pattern shape can be obtained.

  In the case of using any of a polyimide resin and an acrylic resin, an adhesion improver can be added for the purpose of improving the adhesion to an inorganic substance such as a glass plate or a silicon wafer. As the adhesion improving agent, a silane coupling agent or a titanium coupling agent can be used. The addition amount of the adhesion improver is usually about 0.2 to 20% by weight based on the weight of the polyimide resin or acrylic resin.

  In the black composition of the present invention, a polymer dispersant can be added for the purpose of improving the dispersion stability of the light shielding material. As the polymer dispersant, a polyethyleneimine polymer dispersant, a polyurethane polymer dispersant, a polyallylamine polymer dispersant, or the like can be suitably used. These polymer dispersants are preferably added to such an extent that the photosensitivity and adhesion are not lowered, and the addition amount is usually about 1 to 40% by weight with respect to the light shielding material.

  In the black composition of the present invention, the weight composition ratio of the light shielding material / resin component is preferably in the range of 75/25 to 40/60 in order to obtain a black film having a high resistance and a high OD value. Moreover, it is more preferable that the weight composition ratio of the light shielding material / resin component is in the range of 75/25 to 60/40 in terms of the balance of adhesion, pattern workability, and OD value. Here, the resin component is the total of the polymer, monomer or oligomer and the polymer dispersant. If the amount of the resin component is too small, the adhesion of the black film to the substrate becomes poor. Conversely, if the amount of the light shielding material is too small, the optical density per unit thickness (OD value / μm) is lowered, causing a problem.

  The solvent used in the black resin composition of the present invention is not particularly limited, and water and an organic solvent can be used in accordance with the dispersion stability of the pigment to be dispersed and the solubility of the resin to be added. The organic solvent is not particularly limited, and esters, aliphatic alcohols, (poly) alkylene glycol ether solvents, ketones, amide polar solvents, lactone polar solvents, and the like are used. These can be used alone or in combination of two or more. Mixing with other solvents is also preferably used.

  As described above, it is particularly preferable to use a polyimide or acrylic resin as the resin in the present invention. Therefore, it is preferable to use a solvent that dissolves these resins as the solvent. Specifically, particularly when the resin is a polyimide resin, a solvent for dissolving the precursor polyamic acid, that is, N-methyl-2-pyrrolidone (boiling point 202 ° C.), N, N-dimethylacetamide ( Amide polar solvents such as N, N-dimethylformamide (boiling point 153 ° C.), β-propiolactone (boiling point 155 ° C.), γ-butyrolactone (boiling point 204 ° C.), γ-valerolactone (boiling point 207) ° C), δ-valerolactone (boiling point 58 ° C), γ-caprolactone (boiling point 100 ° C), ε-caprolactone (boiling point 96 ° C), and the like can be preferably used.

  Specific esters include benzyl acetate (bp 214 ° C.), ethyl benzoate (bp 213 ° C.), methyl benzoate (bp 200 ° C.), diethyl malonate (bp 199 ° C.), 2-ethylhexyl acetate (bp 199 ° C.) 2-butoxyethyl acetate (boiling point 192 ° C.), 3-methoxy-3-methyl-butyl 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-3-ethoxypropionate (boiling point 170 ° C.), 2-ethylbutyl acetate (boiling point 162 ° C.), Isopentyl propionate (boiling point 160 ° C), propylene glycol Examples include, but are not limited to, coal monomethyl ether propionate (boiling point 160 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), pentyl acetate (boiling point 150 ° C.), propylene glycol monomethyl ether acetate (boiling point 146 ° C.). Not.

  Other solvents than the above 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.), mono Ethyl ether (boiling point 135 ° C), methyl carbitol (boiling point 194 ° C), ethyl carbitol (202 ° C), propylene glycol monomethyl ether (boiling point 120 ° C), propylene glycol monoethyl ether (boiling point 133 ° C), propylene glycol tertiary (Poly) alkylene glycol ether solvents such as butyl ether (boiling point 153 ° C.), dipropylene glycol monomethyl ether (boiling point 188 ° C.), aliphatic esters other than the above, for example , Ethyl acetate (boiling point 77 ° C), butyl acetate (boiling point 126 ° C), isopentyl acetate (boiling point 142 ° C), butanol (boiling point 118 ° C), 3-methyl-2-butanol (boiling point 112 ° C), 3-methyl -3- aliphatic alcohols such as methoxybutanol (boiling point 174 ° C), ketones such as cyclopentanone and cyclohexanone, xylene (boiling point 144 ° C), ethylbenzene (boiling point 136 ° C), solvent naphtha (petroleum fraction: boiling point 165 It is also possible to use a solvent such as (˜178 ° C.).

  Furthermore, since application by a die coating apparatus has become mainstream with an increase in the size of the substrate, it is preferable to use a mixed solvent of two or more components in order to achieve appropriate volatility and drying properties. When the boiling points of all the solvents constituting the mixed solvent are 150 ° C. or less, film thickness uniformity cannot be obtained, the film thickness of the coating end part is increased, and the pigment is applied to the base part for discharging the coating liquid from the slit. Aggregates are formed, causing many problems that streaks occur in the coating film. On the other hand, when the mixed solvent contains a large amount of solvent having a boiling point of 200 ° C. or higher, the surface of the coating film becomes sticky and sticking occurs. Therefore, a mixed solvent containing 30 to 75% by mass of a solvent having a boiling point of 150 ° C. or higher and 200 ° C. is desirable.

  In addition, a surfactant can be added to the black resin composition of the present invention for the purpose of preventing coating properties, smoothness of the colored coating, and Benard cell. The addition amount of the surfactant is usually 0.001 to 10% by mass, preferably 0.01 to 1% by mass of the pigment. If the amount added is too small, the coating properties, smoothness of the colored coating and Benard cell are not effective, and if too large, the physical properties of the coating film may be poor. Specific examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, lauryldimethylamine oxide, Amphoteric surfactants such as lauryl carboxymethyl hydroxyethyl imidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate, and silicones based on polydimethylsiloxane Surfactants, fluorosurfactants and the like can be mentioned. In the present invention, the surfactant is not limited to these, and one or more surfactants can be used.

  In the black resin composition of the present invention, the solid content concentration of the resin component (including additives such as monomers, oligomers and photopolymerization initiators) and the light shielding material is 2% or more from the viewpoint of coating properties and drying properties. It is preferably 30% or less, and more preferably 5% or more and 20% or less. Therefore, the black composition of the present invention preferably consists essentially of a solvent, a resin component and a light shielding material, and the total amount of the resin component and the light shielding material is preferably 2% or more and 30% or less, more preferably 5% or more and 20% or less, and the balance is the solvent. As described above, a surfactant may be further contained at the concentration described above.

  In the black resin composition in the present invention, a method of dispersing a pigment directly in a resin solution using a disperser, or a pigment dispersion is prepared by dispersing a pigment in water or an organic solvent using a disperser, Thereafter, it is manufactured by a method of mixing with a resin solution. The method for dispersing the pigment is not particularly limited, and various methods such as a ball mill, a sand grinder, a three-roll mill, and a high speed impact mill can be used, but a bead mill is preferred from the viewpoint of dispersion efficiency and fine dispersion. As the bead mill, a coball mill, a basket mill, a pin mill, a dyno mill, or the like can be used. As the beads of the bead mill, titania beads, zirconia beads, zircon beads and the like are preferably used. The bead diameter used for dispersion is preferably 0.01 mm to 5.0 mm, more preferably 0.03 mm to 1.0 mm. When the primary particle diameter of the pigment and the secondary particles formed by agglomeration of the primary particles are small, it is preferable to use fine dispersed beads of 0.03 mm or more and 0.10 mm or less. In this case, it is preferable to disperse using a bead mill having a centrifugal separator capable of separating fine dispersion beads and dispersion. On the other hand, when dispersing a pigment containing coarse particles of about submicron, it is preferable to use dispersed beads of 0.10 mm or more because sufficient pulverization force can be obtained and the pigment can be finely dispersed.

  The resin black matrix obtained from the black resin composition of the present invention is more excellent in surface flatness of the color filter substrate as the film thickness is thinner.

  The optical density (optical density, OD value) of the resin black matrix obtained from the black resin composition of the present invention is 4.0 or more per 1.0 μm film thickness in the visible light range of 380 to 700 nm. is necessary. When the OD per 1 μm of film thickness is less than 4.0, the film thickness must be increased in order to obtain sufficient light shielding properties. The higher the light shielding performance of the resin black matrix and the higher the OD value per unit film thickness, the more preferable the resin black matrix can be made thinner.

  As the color filter substrate, the resin black matrix in the display region has an OD value of preferably 3.6 or more, and more preferably 4.0 or more. The OD value of the resin black matrix outside the display area is required to be 3.6 or more, preferably 4.0 or more, and more preferably 4.3 or more. Outside the display area, the alignment of the liquid crystal may be partially disturbed due to the influence of a sealing agent, etc., and it is difficult to control the light transmittance with the voltage applied to the liquid crystal, and light leakage that cannot block the light with the liquid crystal There is a part. Outside the display area where light leakage occurs, it is necessary to increase the OD value in order to block light with resin black.

The OD value is measured using a microspectroscope (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) and can be obtained from the following relational expression (8).
OD value = log ₁₀ (I ₀ / I) (8)
Here, I _{0 is} incident light intensity, and I is transmitted light intensity.

The volume resistance value ρ (Ω · cm) of the resin black matrix obtained from the black resin composition of the present invention is preferably 10 ⁶ (Ω · cm) or more, and more preferably 10 ⁸ (Ω · cm) or more. It is preferable. The volume resistance value is measured by the three-terminal method with a guard ring, and can be obtained by the following relational expression (9).
Volume resistance value ρ (Ω · cm) = (V / I) × (s / d) (9)
Here, V: applied voltage (V), I: flowing current (A), s: electrode area (cm ² ), d: coating thickness (μm).

The adhesion strength between the resin black matrix obtained from the black resin composition of the present invention and the substrate is preferably 6.0 MPa or more when the contact area with the substrate is 5 mm ² , more preferably 8 It is preferably 0.0 MPa or more. If the adhesion strength with the substrate is less than 6.0 MPa, there arises a problem that the resin black matrix is peeled off from the glass.

  In the present invention, a color filter substrate can be manufactured by forming colored pixels after forming the resin black matrix on the substrate using the resin black matrix described above.

  The colored pixel usually has three colors of red (R), green (G), and blue (B), and has selective transmission with respect to the wavelength of light.

  The liquid crystal display device is preferable because the display quality is improved as the color reproduction range is improved. The color reproduction range is represented by the NTSC standard (National Television System Committee). The chromaticity coordinates (x, y) in the XYZ color system chromaticity diagrams for NTSC red, green, and blue jobs are red (0.670, 0.330) and green (0.210, 0.710), respectively. , Blue (0.140, 0.080). The color reproduction range of CRT (Cathode Ray Tube) is about 70% of the NTSC ratio, and the color reproduction range of the liquid crystal display device is preferably CRT or more.

  A liquid crystal display device with an expanded color reproduction range can be produced by darkening the pixels of the color filter. As a method of darkening pixels, there is a method of increasing the pigment concentration of the pigment / resin composition ratio of the color filter paste. When the color filter paste is non-photosensitive, increasing the pigment concentration decreases the resin content, and the strength of the pixel as a coating film decreases. The non-photosensitive resin is laminated with a positive resist and photolithographically processed. However, if the film strength of the pixel is reduced, the positive resist is applied in a process such as a lamination coating process, a development process, or a positive resist peeling process. There is a limit in increasing the pigment concentration because the liquid causes a problem that the pixel is cracked or missing. When the pixel is a photosensitive resin, if the pigment concentration is increased, the resin component is decreased and the photosensitivity is lowered, so that the pixel is not photocured or a large amount of light needs to be applied, resulting in a decrease in productivity.

  On the other hand, there is a method of increasing the pixel film thickness without increasing the pigment / resin composition ratio as a method of darkening the pixel without increasing the pigment concentration. Since it is difficult to form a uniform pattern when the film thickness of the pixel is large, the pixel film thickness is generally 5 μm or less.

  In general, a black matrix is formed on the substrate before pixel formation, and light leakage of the backlight in the display area is prevented by forming a part of the colored pixels so as to overlap the resin black matrix. . The resolution of the liquid crystal display device is expressed by ppi (Pixel Per Inch), and is expressed by how many pixels each of which has three colors of red, blue, and green in one inch. The higher the resolution, the better the liquid crystal display quality, but the smaller the pixels, so that it becomes difficult to produce uniformly. For example, at a resolution of 150 ppi, the pixel pitch is 169.3 μm, and the width of each red, blue, and green sub-pixel is 56.4 μm. As the resolution increases, the pixels become smaller and the light transmitting area of the pixels becomes smaller. Therefore, it is necessary to reduce the width of the resin black matrix and increase the aperture ratio. For this reason, in a high-resolution liquid crystal display device of 150 ppi or more, the black matrix width is preferably 10 μm or less, and more preferably 8 μm or less. When a thick film is processed in a narrow black matrix, the black matrix is peeled off or missing during the development process, so that there is a high possibility that a defective product will be generated. Therefore, the thickness of the black matrix is preferably 0.9 μm or less, and more preferably 0.7 μm or less. As described above, in a high-resolution liquid crystal display device, a black matrix having a width as narrow as 10 μm or less and a film thickness as thin as 0.9 μm or less requires a higher OD black matrix.

  If the step on the surface in the liquid crystal display region is large, the colored pixels are not flattened, resulting in poor alignment of the liquid crystal and light leakage. When light leakage occurs, the contrast is lowered due to light leakage when black display is performed on the liquid crystal display device, and the display quality is lowered.

  If the thickness of the resin black matrix is large, the surface flatness deteriorates and the contrast is lowered. Therefore, the thickness of the resin black matrix is preferably 0.9 μm or less, and more preferably 0.7 μm or less. preferable.

  When the film thickness of the resin black matrix is reduced, the OD of the black matrix outside the display area becomes insufficient, and the display quality deteriorates. In the present invention, a method is proposed in which pixels are stacked on a resin black matrix outside the display area to increase the OD outside the display area. As the pixels to be stacked have a smaller luminous transmittance (Y), the light shielding property is improved. Therefore, the pixels to be stacked outside the display region are preferably red or blue. The green pixel has a large Y and is not suitable for a pixel stacked on a black matrix outside the display area.

  The resin black matrix using the titanium nitride of the present invention as a light shielding agent has a slightly high transmittance on the short wavelength side in visible light, and the transmitted light is bluish. For this reason, it is preferable to stack red pixels having a low short wavelength transmittance in visible light because the effect of increasing the light shielding property of the non-display area is high.

An example of a method for producing the resin black matrix of the present invention is shown below.
As a method of applying the black resin composition on the substrate, a dipping method, a roll coater method, a spinner method, a die coating method, a method using a wire bar, a method of immersing the substrate in a solution, a solution Various methods such as spraying on the substrate can be used. The substrate is not particularly limited, and quartz glass, borosilicate glass, aluminosilicate glass, inorganic glass such as soda lime glass coated with silica on the surface, organic plastic film or sheet are preferably used. In addition, when coating on a substrate, if the substrate surface is treated with an adhesion aid such as a silane coupling agent, an aluminum chelating agent, or a titanium chelating agent, the adhesion between the black matrix coating and the substrate can be improved. it can.

  After the black resin fat composition is applied to the transparent substrate by the method as described above, it is dried and cured by air drying, heat drying, vacuum drying or the like to form a dry film. In order to suppress drying unevenness and transport unevenness when forming the coating film, it is preferable to heat cure after the substrate coated with the coating liquid is dried under reduced pressure with a vacuum dryer equipped with a heating device.

  The coating film thus obtained is usually patterned using a method such as photolithography. That is, when the resin is a non-photosensitive resin, after forming a photoresist film thereon, and when the resin is a photosensitive resin, the resin is left as it is or after an oxygen blocking film is formed. Exposure development is performed to obtain a desired pattern. Then, if necessary, after removing the photoresist or the oxygen barrier film, the resin black matrix is obtained by heating and curing. Although thermosetting conditions differ with resin, when obtaining polyimide-type resin from a polyimide precursor, it is common to heat at 200-350 degreeC normally for 1 to 60 minutes.

  The pigment used for the pixel of the color filter of the present invention is not particularly limited, but a pigment excellent in light resistance, heat resistance and chemical resistance is desirable. When specific examples of typical pigments are indicated by color index (CI) numbers, the following are preferably used, but they are not limited to these.

  Examples of red pigments include pigment red (hereinafter abbreviated as PR) 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR177, PR179, PR180, PR190, PR192, PR209, PR215, PR216, PR217. PR220, PR223, PR224, PR226, PR227, PR228, PR240, PR254, etc. are used.

  Examples of orange pigments include pigment orange (hereinafter abbreviated as PO) 13, PO31, PO36, PO38, PO40, PO42, PO43, PO51, PO55, PO59, PO61, PO64, PO65, PO71, and the like.

Examples of yellow pigments include pigment yellow (hereinafter abbreviated as PY) PY12, PY13, PY14, PY17, PY20, PY24, PY83, PY86, PY93, PY94, PY95, PY109, PY110, PY117, PY125, PY129, PY137, PY138. , PY139, PY147, PY148, PY150, PY153, PY154, PY166, PY168, PY173, PY180, PY185, and the like are used.
Examples of purple pigments include pigment violet (hereinafter abbreviated as PV) 19, PV23, PV29, PV30, PV32, PV36, PV37, PV38, PV40, and PV50.

  Examples of blue pigments include pigment blue (hereinafter abbreviated as PB) 15, PB15: 3, PB15: 4, PB15: 6, PB22, PB60, and PB64.

  Examples of green pigments include pigment green (hereinafter abbreviated as PG) 7, PG10, and PG36.

These pigments may be subjected to surface treatment such as rosin treatment, acidic group treatment, basic treatment, etc., if necessary, and a pigment derivative may be added as a dispersant.
Although there is no restriction | limiting in particular in the matrix resin used for the pixel of the color filter of this invention, Acrylic resin, polyvinyl alcohol, polyamide, a polyimide, etc. can be used. It is preferable to use a pigment-dispersed resin film as a pixel from the viewpoint of simplicity of the manufacturing process, heat resistance, and light resistance. From the viewpoint of ease of pattern formation, it is preferable to use a photosensitive acrylic resin in which a pigment is dispersed. However, it is preferable to use a pigment-dispersed polyimide film from the viewpoint of heat resistance and chemical resistance.

  As a process for producing the color filter substrate of the present invention, when a resin black matrix is used for a color filter for liquid crystal display, as a normal production process, for example, as shown in Japanese Patent Publication No. 2-1311, first, it is transparent. A black matrix, and then pixels having color selectivity of red (R), green (G), and blue (B) are formed on the substrate, and an overcoat film is formed thereon as necessary. Specific materials of the pixel include an inorganic film whose film thickness is controlled so as to transmit only arbitrary light, and a colored resin film in which dyeing, dye dispersion, or pigment dispersion is performed. Further, the pixel formation order can be arbitrarily changed as necessary. Further, if necessary, a transparent conductive film can be formed after forming the three primary color layers or after forming the overcoat film on the three primary color layers. An oxide thin film such as ITO is employed as the transparent conductive film, and an ITO film of about 0.1 μm is usually formed by sputtering or vacuum deposition.

  A spacer fixed on the color filter for a liquid crystal display device of the present invention may be formed. The fixed spacer is fixed to a specific location of a substrate for a liquid crystal display device as disclosed in JP-A-4-318816, and is in contact with a counter substrate when the liquid crystal display device is manufactured. As a result, a constant gap is maintained between the counter substrate and liquid crystal is injected between the gaps. By arranging the fixed spacer, it is possible to omit the step of dispersing the spherical spacer in the manufacturing process of the liquid crystal display device and the step of kneading the rod-shaped spacer in the sealing agent.

  The fixed spacer is formed by a method such as photolithography, printing, or electrodeposition. Since the spacer can be easily formed at the designed position, it is preferable to form the spacer by photolithography. The spacer may be formed in a laminated structure at the same time as the R, G, and B pixels are manufactured, or may be formed after the R, G, and B pixels are manufactured.

  In the present invention, since the resin black matrix can be formed into a thin film as described above, the color pixel height mounted on the black matrix is reduced, and a color with high flatness is obtained without forming an overcoat film. A filter can be produced. However, when higher flatness is required, or when flattening holes and steps processed in color pixels, and for the purpose of preventing elution of components contained in color pixels into the liquid crystal layer, an overcoat film is used. It is preferable to form. Examples of the material for the overcoat film include an epoxy film, an acrylic epoxy film, an acrylic film, a siloxane polymer film, a polyimide film, a silicon-containing polyimide film, and a polyimidesiloxane film. The overcoat film may be formed after the resin black matrix is formed, after the pixel is formed, or after the fixed spacer is arranged. The thickness of the overcoat after heat-curing, when applied on an uneven substrate, is thicker at the concave portion (lower portion than the surroundings) and thinner at the convex portion (higher than the surrounding portion) due to the leveling property of the overcoat agent. Tend to be. Although there is no restriction | limiting in particular in the thickness of the overcoat in this invention, 0.01-5 micrometers, Preferably it is 0.03-4 micrometers, More preferably, it is 0.04-3 micrometers.

  The present invention further provides a liquid crystal display device comprising the color filter of the present invention. The liquid crystal display device of the present invention includes the color filter of the present invention, an electrode substrate disposed to face the color filter, a liquid crystal alignment film provided on the color filter and the electrode substrate, and A spacer for ensuring a space between the liquid crystal alignment films and a liquid crystal filled in the space are provided.

The color filter substrate of the present invention can be used for all liquid crystal display devices. However, since the resin black matrix using titanium nitride as a light-shielding agent has a high volume resistance, it is suitable for a horizontal electric field type liquid crystal display device. It can be preferably used. In a horizontal electric field type liquid crystal display device, if the volume resistance of the color filter is high, the liquid crystal driving voltage leaks to the color filter substrate, and the intended liquid crystal display cannot be performed, resulting in display unevenness.
Examples of the horizontal electric field type liquid crystal display method include, but are not limited to, an IPS (In Plane Switching) method and an AFFS (Advanced Fried Field Switching) method.

  An example of the liquid crystal display device produced using this color filter will be described. The color filter and the electrode substrate are bonded to each other through a liquid crystal alignment film that has been subjected to a rubbing treatment for liquid crystal alignment provided on the substrate and a spacer for maintaining a cell gap. Note that a thin film transistor (TFT) element, a thin film diode (TFD) element, a scanning line, a signal line, or the like can be provided over the electrode substrate, whereby a TFT liquid crystal display device or a TFD liquid crystal display device can be manufactured. Next, after injecting liquid crystal from the injection port provided in the seal portion, the injection port is sealed. Next, a liquid crystal display device is completed by mounting an IC driver or the like.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example and a comparative example, this invention is not limited to a following example.

<Evaluation method>
"X-ray diffraction"
X-ray diffraction was measured by a wide-angle X-ray diffraction method (RU-200R manufactured by Rigaku Corporation) with a powder sample packed in an aluminum standard sample holder. As measurement conditions, the X-ray source is CuKα ray, the output is 50 kV / 200 mA, the slit system is 1 ° -1 ° -0.15 mm-0.45 mm, the measurement step (2θ) is 0.02 °, and the scan speed is It was 2 ° / min.

  The diffraction angle of the peak derived from the (200) plane observed near the diffraction angle 2θ = 46 ° was measured. Further, from the half width of the peak derived from the (200) plane, the crystallite size constituting the particle was determined using the Scherrer equation of the above-described equations (1) and (2).

"Composition analysis"
The content of titanium atoms was measured by ICP emission spectroscopic analysis (ICP emission spectroscopic analyzer SPS3000 manufactured by Seiko Instruments Inc.).

  The content of oxygen atoms and nitrogen atoms was measured using (Horiba oxygen / nitrogen analyzer EMGA-620W / C), and the oxygen atoms were converted into inert gas by infrared gas absorption-infrared absorption method. The nitrogen atom was determined by the method.

[OD value]
The resin black matrix was formed on the alkali-free glass with the film thickness described in the Examples, and the value was obtained from the above formula (8) using a microspectroscope (MCPD2000 manufactured by Otsuka Electronics).

"Specific surface area"
The specific surface area of the pigment is the adsorption isotherm at a liquid nitrogen temperature (77 K) of N ₂ gas after vacuum degassing at 100 ° C. using a high-precision fully automatic gas adsorption device (“BELSORP” 36) manufactured by Nippon Bell Co., Ltd. The isotherm was analyzed by the BET method to determine the specific surface area. Further, from the value of the specific surface area, the BET equivalent particle diameter was obtained using the above-described formula (3). At this time, the titanium nitride value d = 5.24 (g / cm ³ ) is used as the specific gravity for the titanium nitride particles, and the specific gravity d = 4.30 (g / cm ³ ) is used for the titanium oxynitride sample. It was.

"Black matrix missing"
A resin black matrix having a target film thickness of 1.1 μm to 0.7 μm was formed on alkali-free glass, and photolithography was performed so that the width of the resin black matrix was 6 μm and the lattice spacing was 50 μm. This substrate was visually and microscopically observed to determine whether or not there was a missing resin black matrix.

Synthesis of polyamic acid 4,4'-diaminophenyl ether (0.30 molar equivalent), paraphenylenediamine (0.65 molar equivalent), bis (3-aminopropyl) tetramethyldisiloxane (0.05 molar equivalent) Charged together with 850 g of γ-butyrolactone and 850 g of N-methyl-2-pyrrolidone, 3,3 ′, 4,4′-oxydiphthalcarboxylic dianhydride (0.9975 molar equivalent) was added, and 3 hours at 80 ° C. Reacted. Maleic anhydride (0.02 molar equivalent) was added and further reacted at 80 ° C. for 1 hour to obtain a polyamic acid A-1 (polymer concentration 20% by weight) solution.

  4,4′-diaminophenyl ether (0.95 molar equivalent) and bis (3-aminopropyl) tetramethyldisiloxane (0.05 molar equivalent) were charged together with 1700 g (100%) of γ-butyrolactone, Anhydride (0.49 molar equivalent) and benzophenonetetracarboxylic dianhydride (0.50 molar equivalent) were added and reacted at 80 ° C. for 3 hours. Maleic anhydride (0.02 molar equivalent) was added and further reacted at 80 ° C. for 1 hour to obtain a polyamic acid A-2 (polymer concentration 20% by weight) solution.

Synthesis of acrylic polymer After synthesizing methyl methacrylate / methacrylic acid / styrene copolymer (weight composition ratio 30/40/30) by the method described in Example 1 of Japanese Patent No. 3120476, 40 parts by weight of glycidyl methacrylate was added. Then, reprecipitation with purified water, filtration, and drying were performed to obtain an acrylic polymer (P-1) powder having characteristics of an average molecular weight (Mw) of 40,000 and an acid value of 110 (mgKOH / g).

Synthesis of adhesion improver 24.8 g (0.1 mol) of 3-bis (3-aminopropyl) tetramethyldisiloxane, 56.9 g (0.4 mol) of glycidyl methacrylate and 0.08 g of polymerization inhibitor hydroquinone monomethyl ether After being charged into a flask and reacted at 55 ° C. for 4 hours with stirring, 81.7 g of propylene glycol monomethyl ether acetate was added, diluted to a concentration of 50% by mass, and further reacted at 55 ° C. for 2 hours. A solution (AP-1) was obtained.

Example 1
Production of Resin Black Paste The diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride reagent (Sample 1, Wako Pure Chemical Industries, Ltd., titanium nitride 50 nm) is 42.57 °, from the half-value width of this peak The obtained crystallite size was 44.6 nm. As a result of composition analysis, the titanium content was 74.3% by weight, the nitrogen content was 20.3% by weight, and the oxygen content was 2.94% by weight. Further, no X-ray diffraction peak attributed to TiO ₂ was observed. Table 1 shows the characteristics of titanium nitride.

  Sample 1 (96 g) was charged with polyamic acid solution A-1 (120 g), γ-butyrolactone (114 g), N-methyl-2pyrrolidone (538 g), and 3 methyl-3-methoxybutyl acetate (132 g) in a tank. Stirring was carried out for 1 hour with a mixer (manufactured by Special Machine) to obtain Preliminary Dispersion 1. Thereafter, the preliminary dispersion 6 is supplied to Dynomill KDL (manufactured by Shinmaru Enterprises) filled with 85% 0.40 mmφ zirconia beads (manufactured by Toray Industries, Inc., Treceram beads), and dispersed for 4 hours at a rotational speed of 11 m / s. And a pigment dispersion 1 having a solid content concentration of 12% by weight and a pigment / resin (weight ratio) of 80/20 was obtained.

  To this pigment dispersion 1 (728 g), polyamic acid A-1 (63 g), γ-butyrolactone (82 g), N-methyl-2-pyrrolidone (87 g), 3 methyl-3 methoxybutyl acetate (39 g), surface activity Agent LC951 (manufactured by Enomoto Kasei Co., Ltd., 1 g) was added to obtain a black resin composition BM-1 having a total solid concentration of 10% by weight and a pigment / resin (weight ratio) = 70/30. Similarly, a black resin composition BM-2 having a pigment / resin (weight ratio) of 75/25 was obtained.

Preparation of non-photosensitive color paste Pigment Red PR254, 1.80 g (40 wt%), Pigment Red PR177, 2.70 g (60 wt%), polyamic acid (A-1) 22.5 g and γ-butyrolactone 42.8 g, 3 20.2 g of -methoxy-3-methyl-1-butanol was charged together with 90 g of glass beads, and after dispersing for 5 hours at 7000 rpm using a homogenizer, the glass beads were filtered and removed. In this way, a red dispersion 5% solution (PR-1) was obtained.

  A solution obtained by diluting 8.0 g of polyamic acid solution (A-1) with 42.0 g of γ-butyrolactone was added to and mixed with 50.0 g of dispersion (PR-1) to obtain a red color paste (R-1). Similarly, green paste (G-1) and blue paste (B-1) were obtained at the ratio of pigments shown in Table 2.

The black resin composition BM-1 was applied on a non-alkali glass (Corning “EAGLE XG”) substrate with a curtain flow coater so that the film thickness after curing was 0.9 μm, and at 80 ° C. and 10 ⁻¹ Torr. Vacuum dried for 2 minutes. Then, it was semi-cured in an oven at 140 ° C. for 20 minutes, a positive photoresist (“LC-100” manufactured by Rohm and Haas Electronic Materials Co., Ltd.) was applied with a spinner, and prebaked at 120 ° C. for 3 minutes with a hot plate. Through a photomask designed to have a black matrix of 168 μm in length and 56 μm in width and 6 μm in width and a frame area with a width of 2 mm outside the display area, a UV exposure machine (“MAP” manufactured by Dainippon Kaken Co., Ltd.) -1200 L "), and was exposed at an exposure amount of 100 mJ / cm ² at 365 nm. After exposure, the positive resist was developed and the polyimide precursor was etched simultaneously by dipping in a 2.38%, 23 ° C. tetramethylammonium hydroxide aqueous solution for 60 seconds, and then washed with pure water. Next, the positive resist was peeled off with methyl cellosolve acetate. Furthermore, it was cured in an oven at 300 ° C. for 30 minutes. Thus, a black matrix having a thickness of 0.9 μm and a width of 6 μm was produced.

Production of Pixels Red paste containing a non-photosensitive resin so that the chromaticity (x, y) when passing through a C light source on a glass substrate on which a black matrix is patterned is (0.657, 0.319) (R-1) was applied onto a glass substrate with a spinner and semi-cured in an oven at 140 ° C. for 20 minutes. On top of this, a positive photoresist (“LC-100” manufactured by Rohm and Haas Electronic Materials Co., Ltd.) was applied with a spinner and prebaked on a hot plate at 120 ° C. for 3 minutes. An ultraviolet exposure machine ("MAP" manufactured by Dainippon Kaken Co., Ltd.) is passed through a photomask in which the pixel formation location is shielded so as to form red pixels in the red pixel formation portion within the display region and the frame portion outside the display region. -1200 L "), and was exposed through a photomask at an exposure amount of 100 mJ / cm ² at 365 nm. After exposure, the positive resist was developed and the polyimide precursor was etched simultaneously by dipping in a 2.38%, 23 ° C. tetramethylammonium hydroxide aqueous solution for 60 seconds, and then washed with pure water. Next, the positive resist was peeled off with methyl cellosolve acetate. Furthermore, it was cured at 260 ° C. for 30 minutes to convert to polyimide, and red pixels were formed in the frame area inside and outside the display area. The film thickness of the red pixel was 2.0 μm.

Next, a blue paste (B-1) containing a non-photosensitive resin is used with a spinner so that the finished chromaticity (x, y) when passing through a C light source is (0.141, 0.068). It apply | coated on the glass substrate and semi-cured for 20 minutes at 130 degreeC in oven. On top of this, a positive photoresist (“LC-100” manufactured by Rohm and Haas Electronic Materials Co., Ltd.) was applied with a spinner and prebaked on a hot plate at 120 ° C. for 3 minutes. Using a UV exposure machine (“MAP-1200L” manufactured by Dainippon Kaken Co., Ltd.) through a photomask whose pixel formation location is shielded so as to form blue pixels in the blue pixel formation portion in the display area, It exposed with the exposure amount of 100 mJ / cm < ² > of 365 nm through the mask. After exposure, the positive resist was developed and the polyimide precursor was etched simultaneously by dipping in a 2.38%, 23 ° C. tetramethylammonium hydroxide aqueous solution for 60 seconds, and then washed with pure water. Next, the positive resist was peeled off with methyl cellosolve acetate. Furthermore, it was cured at 260 ° C. for 30 minutes, and converted to polyimide to form blue pixels. The film thickness of the blue pixel was 2.0 μm.

Next, a green paste (G-1) containing a non-photosensitive resin is applied to a glass substrate with a spinner so that the finished chromaticity (x, y) when passing through a C light source is (0.287, 0.577). It was applied on top and semi-cured in an oven at 130 ° C. for 20 minutes. On top of this, a positive photoresist (“LC-100” manufactured by Rohm and Haas Electronic Materials Co., Ltd.) was applied with a spinner and prebaked on a hot plate at 120 ° C. for 3 minutes. Using a UV exposure machine (“MAP-1200L” manufactured by Dainippon Kaken Co., Ltd.) through a photomask whose pixel formation location is shielded so as to form green pixels in the green pixel formation portion in the display area, It exposed with the exposure amount of 100 mJ / cm < ² > of 365 nm through the mask. After exposure, the positive resist was developed and the polyimide precursor was etched simultaneously by dipping in a 2.38%, 23 ° C. tetramethylammonium hydroxide aqueous solution for 60 seconds, and then washed with pure water. Next, the positive resist was peeled off with methyl cellosolve acetate. Furthermore, it was cured at 260 ° C. for 30 minutes and converted to polyimide to form a green pixel. The film thickness of the green pixel was 2.0 μm.

An overcoat layer having a thickness of 2 μm was formed on the pixel film thus obtained, and an ITO film was further sputtered thereon to a thickness of 0.1 μm.
Table 3 shows the OD values of the black matrix of the portion of the color filter substrate thus obtained where the red pixels are laminated and the portion where the red pixels are not laminated.

  The OD value of the portion where the red pixel is not laminated is 4.18, and the OD value of the portion where the red pixel outside the display region is laminated is 4.95.

  Table 4 shows the transmissive area chromaticity of the C light source in the display area of the color filter substrate.

  The contrast of the obtained color filter substrate was 4200, the OD of the black matrix of the frame was 4.95, and light leakage was so small that it could be ignored. The surface roughness difference of this color filter was 0.28 μm, and the flatness was good.

The volume resistance value of the black matrix of Example 1 was as high as 1.1 × 10 ¹² Ω · cm.

Example 2
A black matrix and a color filter were prepared in the same manner as in Example 1 except that BM-2 was used as the black resin composition and the thickness of the black matrix was 0.7 μm.

  The contrast of the obtained color filter substrate was 4400, the OD of the black matrix of the frame was 4.52, and the light leakage was so small that it could be ignored. The surface roughness difference of this color filter was 0.15 μm, and the flatness was good.

Example 3
BM-2 was used as the black resin composition, the film thickness of the black matrix was 0.7 μm, the black matrix was a matrix with a pitch of 84 μm in length and 28 μm in width and had a frame area with a width of 2 mm outside the display area. A black matrix and a color filter were produced in the same manner as in Example 1 except that the exposure was performed through the designed photomask.

  The contrast of the obtained color filter substrate was 4000, the OD of the black matrix of the frame was 4.52, and the light leakage was so small that it could be ignored. The surface unevenness of the color filter was 0.18 μm, and the flatness was good.

Example 4
The color filter is the same as in the first embodiment except that the red pixel is formed only in the red pixel forming portion in the display region and the blue pixel is formed in the blue pixel forming portion in the display region and the frame portion outside the display region. Was made.

  The contrast of the obtained color filter substrate was 4200, the OD of the black matrix of the frame was 4.74, and the light leakage was so small that it could be ignored. The surface roughness difference of this color filter was 0.26 μm, and the flatness was good.

Comparative Example 1
A color filter was produced in the same manner as in Example 1 except that the red pixel was formed only in the red pixel forming portion in the display area and the red pixel on the frame outside the display area was not formed.

  The contrast of the obtained color filter substrate was 3400, the OD of the frame black matrix was 4.18, and the OD value was insufficient. The surface roughness difference of this color filter was 0.26 μm, and the flatness was good.

Comparative Example 2
A black matrix and a color filter were produced in the same manner as in Example 1 except that the thickness of the black matrix was 1.1 μm.

  The contrast of the obtained color filter substrate was 3500, the OD of the black matrix of the frame was 5.70, and light leakage was so small that it could be ignored. The surface unevenness difference of this color filter was 0.45 μm, and the flatness was not good.

Comparative Example 3
A black matrix was prepared in the same manner as in Example 1 except that the black matrix was formed of a black resin having a pigment / resin (weight ratio) of 80/20 as the black resin composition, and the thickness of the black matrix was 0.7 μm. did.
The obtained black matrix was defective because it was partially missing in the display area.

Example 5
Titanium nitride sample 1 (200 g), acrylic polymer (P-1) 3-methyl-3-methoxybutanol 45 wt% solution (100 g), and propylene glycol tertiary butyl ether (700 g) were charged into a tank and homomixer (special And pre-dispersion liquid 12 was obtained. Thereafter, the preliminary dispersion 13 was supplied to an ultra apex mill (manufactured by Kotobuki Industries Co., Ltd.) equipped with a centrifugal separator filled with 70% 0.05 mmφ zirconia beads (manufactured by Nikkato, YTZ ball), and rotated at 8 m / s for 2 hours. Dispersion was performed to obtain a pigment dispersion 12 having a solid content concentration of 24.5% by weight and a pigment / resin (weight ratio) = 82/18.

  This pigment dispersion 12 (525.8 g) was mixed with bisphenoxyethanol full orange acrylate in 50% by weight propylene glycol monomethyl ether acetate (27.0 g), and dipentaerythritol hexaacrylate as a polyfunctional monomer (DHPA manufactured by Nippon Kayaku Co., Ltd.). ) Propylene glycol monomethyl ether acetate solution (27.0 g), “Irgacure” 369 (14.7 g) as a photopolymerization initiator, Asahi Denka Kogyo Co., Ltd. “Adeka (registered trademark) Optomer” N-1919 ( 4.0 g) and N, N′-tetraethyl-4,4′-diaminobenzophenone (1.5 g), 8.57 g of AP-1 (50 wt% solution) as an adhesion improver, propylene as a silicone surfactant Glycol monomethyl ether acetate A solution prepared by dissolving a 0% by weight solution (3.6 g) in 3-methyl-3-methoxy-butyl acetate (374.8 g) and propylene glycol monomethyl ether acetate (14.4 g) was added, and the total solid concentration was 18 wt. %, Pigment / resin (weight ratio) = 67.5 / 22.5, black resin composition BM-3 was obtained. Similarly, a black resin composition BM-4 having a pigment / resin (weight ratio) = 75/25 was obtained.

The black resin composition BM-1 was applied on a non-alkali glass (Corning “EAGLE XG”) substrate with a curtain flow coater so that the film thickness after curing was 0.9 μm, and at 40 ° C. and 10 ⁻¹ Torr. Vacuum dried for 1 minute. Then, it prebaked at 90 degreeC for 10 minutes in oven. Through a photomask designed to have a black matrix of 168 μm in length and 56 μm in width and 6 μm in width and a frame area with a width of 2 mm outside the display area, a UV exposure machine (“MAP” manufactured by Dainippon Kaken Co., Ltd.) -1200 L "), and was exposed at an exposure amount of 100 mJ / cm ² at 365 nm. After exposure, the film was immersed in a 0.1%, 23 ° C. aqueous tetramethylammonium hydroxide solution for 60 seconds for development, and then washed with pure water. Next, it was post-baked at 230 ° C. for 30 minutes in an oven. Thus, a black matrix having a thickness of 0.9 μm and a width of 6 μm was produced.

Production of Pixels Red paste containing a non-photosensitive resin so that the chromaticity (x, y) when passing through a C light source on a glass substrate on which a black matrix is patterned is (0.657, 0.319) (R-1) was applied onto a glass substrate with a spinner and semi-cured in an oven at 140 ° C. for 20 minutes. On top of this, a positive photoresist (“LC-100” manufactured by Rohm and Haas Electronic Materials Co., Ltd.) was applied with a spinner and prebaked on a hot plate at 120 ° C. for 3 minutes. An ultraviolet exposure machine ("MAP" manufactured by Dainippon Kaken Co., Ltd.) is passed through a photomask in which the pixel formation location is shielded so as to form red pixels in the red pixel formation portion within the display region and the frame portion outside the display region. -1200 L "), and was exposed through a photomask at an exposure amount of 100 mJ / cm ² at 365 nm. After exposure, the positive resist was developed and the polyimide precursor was etched simultaneously by dipping in a 2.38%, 23 ° C. tetramethylammonium hydroxide aqueous solution for 60 seconds, and then washed with pure water. Next, the positive resist was peeled off with methyl cellosolve acetate. Furthermore, it was cured at 260 ° C. for 30 minutes to convert to polyimide, and red pixels were formed in the frame area inside and outside the display area. The film thickness of the red pixel was 2.0 μm.

Next, a blue paste (B-1) containing a non-photosensitive resin is used with a spinner so that the finished chromaticity (x, y) when passing through a C light source is (0.141, 0.068). It apply | coated on the glass substrate and semi-cured for 20 minutes at 130 degreeC in oven. On top of this, a positive photoresist (“LC-100” manufactured by Rohm and Haas Electronic Materials Co., Ltd.) was applied with a spinner and prebaked on a hot plate at 120 ° C. for 3 minutes. Using a UV exposure machine (“MAP-1200L” manufactured by Dainippon Kaken Co., Ltd.) through a photomask whose pixel formation location is shielded so as to form blue pixels in the blue pixel formation portion in the display area, It exposed with the exposure amount of 100 mJ / cm < ² > of 365 nm through the mask. After exposure, the positive resist was developed and the polyimide precursor was etched simultaneously by dipping in a 2.38%, 23 ° C. tetramethylammonium hydroxide aqueous solution for 60 seconds, and then washed with pure water. Next, the positive resist was peeled off with methyl cellosolve acetate. Furthermore, it was cured at 260 ° C. for 30 minutes, and converted to polyimide to form blue pixels. The film thickness of the blue pixel was 2.0 μm.

Next, a green paste (G-1) containing a non-photosensitive resin is applied to a glass substrate with a spinner so that the finished chromaticity (x, y) when passing through a C light source is (0.287, 0.577). It was applied on top and semi-cured in an oven at 130 ° C. for 20 minutes. On top of this, a positive photoresist (“LC-100” manufactured by Rohm and Haas Electronic Materials Co., Ltd.) was applied with a spinner and prebaked on a hot plate at 120 ° C. for 3 minutes. Using a UV exposure machine (“MAP-1200L” manufactured by Dainippon Kaken Co., Ltd.) through a photomask whose pixel formation location is shielded so as to form green pixels in the green pixel formation portion in the display area, It exposed with the exposure amount of 100 mJ / cm < ² > of 365 nm through the mask. After exposure, the positive resist was developed and the polyimide precursor was etched simultaneously by dipping in a 2.38%, 23 ° C. tetramethylammonium hydroxide aqueous solution for 60 seconds, and then washed with pure water. Next, the positive resist was peeled off with methyl cellosolve acetate. Furthermore, it was cured at 260 ° C. for 30 minutes and converted to polyimide to form a green pixel. The film thickness of the green pixel was 2.0 μm.

An overcoat layer having a thickness of 2 μm was formed on the pixel film thus obtained, and an ITO film was further sputtered thereon to a thickness of 0.1 μm.
As shown in Table 3, the OD value of the black matrix of the portion where the red pixels of the color filter substrate thus obtained are laminated and the portion where the red pixels are not laminated is shown in Table 3. The OD value was 4.65, and the OD value of the portion where the red pixels outside the display area were stacked was 5.42.

  Table 4 shows the transmissive area chromaticity of the C light source in the display area of the color filter substrate.

  The contrast of the obtained color filter substrate was 4300, and the light leakage of the black matrix of the frame was so small that it could be ignored. The surface roughness difference of this color filter was 0.27 μm, and the flatness was good.

Example 6
A black matrix and a color filter were produced in the same manner as in Example 5 except that the thickness of the black matrix was 0.7 μm.

  The contrast of the obtained color filter substrate was 4600, the OD of the black matrix of the frame was 4.39, and the light leakage was so small that it could be ignored. The surface roughness difference of this color filter was 0.13 μm, and the flatness was good.

Example 7
A black matrix and a color filter were produced in the same manner as in Example 5 except that BM-4 was used as the black resin composition and the thickness of the black matrix was 0.7 μm.

  The contrast of the obtained color filter substrate was 4550, the OD of the black matrix of the frame was 4.79, and light leakage was so small that it could be ignored. The surface roughness difference of this color filter was 0.13 μm, and the flatness was good.

Example 8
BM-4 was used as the black resin composition, the thickness of the black matrix was 0.7 μm, the black matrix was a matrix with a pitch of 84 μm in length and 28 μm in width and had a frame area with a width of 2 mm outside the display area. A black matrix and a color filter were produced in the same manner as in Example 5 except that the exposure was performed through the designed photomask.

  The contrast of the obtained color filter substrate was 4200, the OD of the black matrix of the frame was 4.52, and the light leakage was so small that it could be ignored. The surface roughness difference of this color filter was 0.16 μm, and the flatness was good.

Example 9
The color filter is the same as in Example 5 except that the red pixels are formed only in the red pixel forming portion in the display area and the blue pixels are formed in the blue pixel forming portion in the display area and the frame portion outside the display area. Was made.

  The contrast of the obtained color filter substrate was 4300, the OD of the black matrix of the frame was 5.21, and the light leakage was so small that it could be ignored. The surface roughness difference of this color filter was 0.26 μm, and the flatness was good.

Comparative Example 4
“13-MC” (Sample 2, manufactured by Mitsubishi Materials Corporation) was used as a commercially available titanium black pigment, the thickness of the black matrix was set to 1.0 μm, and red pixels were formed in the display area. A black matrix and a color filter were produced in the same manner as in Example 5, except that the red pixels were not formed on the frame outside the display area.

The diffraction angle 2θ of the peak derived from the (200) plane of Sample 2 was 42.91 °, and the crystallite size determined from the half width of this peak was 29.6 nm. As a result of composition analysis, the titanium content was 70.3% by weight, the nitrogen content was 17.8% by weight, and the oxygen content was 10.3% by weight. In addition, X-ray diffraction peaks attributed to TiO ₂ were observed at 25.28 ° and 27.44 °. The contrast of the obtained color filter substrate was 2800, the OD of the black matrix of the frame was 3.29, the OD in the display area was 3.29, the OD value was insufficient, and the contrast was Declined.

Comparative Example 5
A black matrix and a color filter were prepared in the same manner as in Example 5 except that Sample 2 was used as the titanium black pigment and the thickness of the black matrix was 1.0 μm.

  The contrast of the obtained color filter substrate was 3000, the OD of the black matrix of the frame was 3.90, the OD in the display area was 3.29, the OD value was insufficient, and the contrast was lowered. .

Comparative Example 6
A black matrix and a color filter were produced in the same manner as in Example 5 except that the thickness of the black matrix was 1.1 μm.

  The contrast of the obtained color filter substrate was 3500, the OD of the black matrix of the frame was 6.10, and the light leakage was negligibly small, but the surface unevenness difference of this color filter was 0.44 μm, Since the flatness was not good, the contrast was lowered.

Preparation of Liquid Crystal Display Device After the obtained color filter was washed with a neutral detergent, an alignment film made of polyimide resin was applied by a printing method and heated on a hot plate at a temperature of 250 ° C. for 10 minutes. The film thickness was 0.07 μm. Thereafter, the color filter substrate was rubbed, and the sealing agent was applied by a dispensing method and heated on a hot plate at 90 ° C. for 10 minutes. On the other hand, a circular photospacer having a height of 4 μm and a width of 12 μm was formed on the TFT on a substrate on which an AFFS TFT array, which is a lateral electric field method, was formed on glass, for adjusting the liquid crystal cell gap. The TFT substrate was washed in the same manner, and then an alignment film was applied and heated. The sealant was applied to the color filter substrate coated with the sealant and heated at 160 ° C. for 90 minutes while being pressurized in an oven to cure the sealant. This cell was allowed to stand for 4 hours at a temperature of 120 ° C. and a pressure of 13.3 Pa. Subsequently, after being left for 0.5 hour in nitrogen, liquid crystal injection was performed again under vacuum. Liquid crystal injection was performed by placing the cell in a chamber and reducing the pressure to 13.3 Pa at room temperature, and then immersing the liquid crystal injection port in liquid crystal and returning to normal pressure using nitrogen. After the liquid crystal injection, the liquid crystal injection port was sealed with an ultraviolet curable resin. Next, a polarizing plate was attached to the outside of the two glass substrates of the cell to complete the cell. Furthermore, the obtained cell was modularized and the liquid crystal display device 1 was completed. As a result of observing the obtained liquid crystal display device 1, it was found that there was no display defect. Further, since the resin black matrix has a high light shielding property, the contrast was good. Similarly, 100 liquid crystal display devices were produced. However, since the adhesion of the resin black matrix was high, no defects such as peeling of the seal portion at the time of liquid crystal injection occurred.

  The color filter substrate of the present invention can be used for a liquid crystal display device.

1: Substrate 2: Resin black matrix 3R: Red pixel 3B: Blue pixel 3G: Green pixel 4: Frame black matrix 5: Display area 6: Non-display area

Claims (9)

A color filter substrate in which a black matrix and a plurality of colored layers are formed on a transparent substrate, wherein the black matrix is a black pigment-dispersed resin containing titanium nitride particles, and the thickness of the black matrix in the display area is A color filter substrate for a liquid crystal display device, wherein a color layer is laminated on a black matrix of 0.9 μm or less and outside the display region in a frame light shielding part region. When the titanium nitride particles have CuKα rays as an X-ray source, the peak diffraction angle 2θ derived from the (200) plane of the titanium nitride particles is 42.5 ° or more and 42.8 ° or less. The color filter substrate for a liquid crystal display device according to claim 1. 3. The color for a liquid crystal display device according to claim 1, wherein a crystallite size obtained from a half width of a peak derived from a (200) plane when CuKα rays of the titanium nitride particles are used as an X-ray source is 50 nm or less. Filter substrate. The color filter substrate for a liquid crystal display device according to claim 1, wherein the colored layer laminated on the black matrix in the frame light shielding portion region outside the display region is a red pixel. The optical density of the black matrix is 4.0 or more per 1 μm.
5. A color filter substrate for a liquid crystal display device according to any one of items 1 to 4. The black matrix in the frame shading region of the portion where the black matrix in the display region has a thickness of 0.9 μm or less, the optical density of the black matrix in the display region is 3.6 or more, and the pixels outside the display region are stacked. The color filter substrate for a liquid crystal display device according to any one of claims 1 to 5, wherein the optical density of the liquid crystal display device is 4.2 or higher, which is higher than the optical density of the black matrix in the display region. The color filter substrate for a liquid crystal display device according to any one of claims 1 to 6, wherein the pixel resolution of the color filter is 150 ppi or more. A liquid crystal display device in which a liquid crystal compound is filled in a gap between the color filter substrate according to claim 1 and a counter substrate. The liquid crystal display device according to claim 8, wherein the liquid crystal display method is a horizontal electric field method.

Images