JP2014215589A - Black matrix substrate, color filter substrate and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black matrix substrate for a liquid crystal display device, being a thin film, having high optical concentration and low reflective index, adjusting reflection chromaticity to a cyan color to cancel reddish coloring resulting from a liquid crystal display device, and capable of imparting a sense of unity with an outer frame part when not lighting.SOLUTION: A black matrix substrate 30 is formed by laminating a plurality of light-shielding layers 2 having different optical concentration on a transparent substrate 1. The light-shielding layers having different optical concentration are laminated on the transparent substrate in an order of a low optical concentration light-shielding layer 21, and a high optical concentration light-shielding layer 22. The low optical concentration light-shielding layer 21 is formed using a black photosensitive resin composition containing one or more types of orange pigment or one or more types of yellow pigment, or one or more types of orange pigment and one or more types of yellow pigment. The optical concentration of the low optical concentration light-shielding layer 21 is 0.3 or lower.

Description

  The present invention relates to a black matrix substrate used for a color filter of a liquid crystal display device.

  A color filter is an indispensable component for colorization of a liquid crystal display device that has been applied in various fields in recent years. The color filter is obtained by providing colored pixels such as red, green, and blue on a transparent substrate such as glass. A light shielding layer (black matrix) is generally provided between the colored pixels in order to improve the contrast and to prevent malfunction caused by light of the TFT element provided on the counter substrate in the liquid crystal display device. .

  As a method for forming the light shielding layer, a method of etching a metal chromium thin film has been used. However, due to the problem of cost and environmental load, replacement with a photolithography method using a black photosensitive resin composition containing a light shielding material has progressed. It is out.

  Formation of the black matrix by the photolithography method using the black photosensitive resin composition is performed as follows. First, a black photosensitive resin composition coating film is formed on a transparent substrate by spin coating or slit coating. After drying and heat treatment as necessary, exposure processing is performed through a photomask having a predetermined pattern. Subsequently, a black matrix can be formed on the transparent substrate by removing an unexposed portion by a development process and performing a heat hardening process.

  The properties required for the light-shielding layer include light-shielding properties, resolution, insulation, etc. In recent years, it is a new technology to control the hue (reflection chromaticity) of reflected light and the reflected light (reflectance) itself. It has emerged as an issue. This is because, among the members constituting the color filter, the reflected light of the black matrix having a relatively high reflectance and the appearance of the black liquid crystal display device when the reflection chromaticity is not turned on are affected.

  Light incident on the liquid crystal display device when not lit is reflected by the polarizing plate. However, part of the light transmitted through the polarizing plate is reflected by the color filter substrate and the TFT element. At this time, among the color filter substrates, the reflectance of the black matrix substrate is high, and the reflection at the interface between the black matrix and the transparent substrate occupies a large proportion, and the demand for reducing the reflectance of the black matrix has increased. Yes.

  Further, the color when not lit reflects the reflection chromaticity of each member such as a TFT element, a liquid crystal, a polarizing plate, and a color filter constituting the liquid crystal display. The black reflection chromaticity of the liquid crystal display device shifts to red (the a * and b * values in the CIE Lab color space display system are shifted in the positive direction), resulting in reddish black. Is a problem.

  In particular, when incorporated in a mobile device, there is a problem that the sense of unity is impaired due to the difference in reflectance and reflection chromaticity with an outer frame portion called a bezel.

  An attempt is made to reduce the reflectance by forming a light-shielding layer in which two layers having different optical densities are laminated by the technique described in Patent Document 1. However, the reflectivity is certainly lowered, but the reflection chromaticity is not mentioned at all.

As an attempt to adjust the reflection chromaticity of the light shielding layer, the following Patent Document 2 discloses that neutral black is obtained by using a light shielding layer in which a pigment such as blue or purple is added as a complementary color pigment in addition to a light shielding agent and a resin. A proposal has been made.

  Patent Document 3 proposes to obtain neutral black by using carbon black and titanium oxynitride in combination.

  Patent Document 4 discloses titanium nitride and C.I. I. Pigment red 254, C.I. I. Pigment red 177, C.I. I. A proposal has been made to obtain neutral black by using at least one red pigment selected from CI Pigment Red 179 in combination.

  Although these proposals are effective for each of the reflection chromaticity and the reflectance, there is no description about achieving both the reflection chromaticity and the reflectance.

International Publication No. 10/070929 Japanese Patent No. 286139 JP-A-2005-75965 JP2011-227467A

  The present invention has been made in view of such circumstances. The thin film has high optical density, low reflectance, and the reflection chromaticity is adjusted to a cyan color to cancel reddish coloring caused by the liquid crystal display device. Another object of the present invention is to provide a black matrix substrate for a liquid crystal display device that can provide a sense of unity with the outer frame when not lit.

As a means for solving the above problems, the invention according to claim 1 is a black matrix substrate formed by laminating a plurality of light shielding layers having different optical densities on a transparent substrate,
The light shielding layers having different optical densities are laminated on the transparent substrate in the order of a low optical density light shielding layer and a high optical density light shielding layer,
The low optical density light shielding layer is formed using a black photosensitive resin composition having one or more kinds of orange pigments or one or more kinds of yellow pigments, or one or more kinds of orange pigments and one or more kinds of yellow pigments. And a black matrix substrate in which the optical density of the low optical density light-shielding layer is 0.3 or less.

  In the invention according to claim 2, the a * and b * values in the CIE Lab color space display system of the light shielding layer measured from the transparent substrate side are a * <− 0.5 or b * <− 0.5. The black matrix substrate according to claim 1, wherein a * <− 0.5 and b * <− 0.5.

  The invention according to claim 3 is the black matrix substrate according to claim 1 or 2, wherein the reflectance of the light shielding layer measured from the transparent substrate side is 0.8 or less.

  The invention according to claim 4 is characterized in that the sum of the optical densities of the light shielding layers having different optical densities is 4.0 or more, and the black matrix according to any one of claims 1 to 3 It is a substrate.

  In the invention according to claim 5, the yellow pigment contained in the black photosensitive resin composition is Pigment Yellow 139 or C.I. I. The black matrix substrate according to claim 1, which is Pigment Yellow 150.

  The invention according to claim 6 is the black matrix substrate according to any one of claims 1 to 5, wherein the orange pigment contained in the black photosensitive resin composition is Pigment Orange 71. It is.

  The invention according to claim 7 is a color filter substrate using the black matrix substrate according to any one of claims 1 to 6.

  The invention according to claim 8 is a liquid crystal display device using the color filter substrate according to claim 7.

  By using the black photosensitive resin composition of the present invention, a black matrix substrate in which the reflectance is reduced and the reflection chromaticity a * and b * is minus can be obtained. By using the color filter provided with the black matrix substrate, a neutral black without coloring when the liquid crystal display device is not turned on can be obtained by canceling the reddish coloring caused by the TFT element and the liquid crystal composition.

It is the schematic cross section which showed an example of the color filter structure using the black matrix board | substrate of this invention. It is the schematic cross section which showed an example of the black matrix board | substrate structure of this invention. It is the schematic cross section which showed an example of the liquid crystal display device structure of this invention.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the color filter of the present invention. In the color filter of FIG. 1, a light shielding layer 2 comprising a low optical density light shielding layer 21 and a high optical density light shielding layer 22 is formed on a transparent substrate 1, and the light shielding layer 2 in the black matrix substrate shown in FIG. Red, green, and blue colored pixels 3 are formed in the openings. A transparent protective film (not shown) may be provided on the colored pixels 3 as necessary.

  FIG. 3 is a schematic cross-sectional view showing an example of the configuration of the liquid crystal display device of the present invention. The liquid crystal display device shown in FIG. 3 includes an array substrate 10 and a color filter substrate that are arranged to face each other, and a liquid crystal compound 4 is sealed between them. Examples of liquid crystal compounds include TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertically Aligned) and OCB (Optically Compensated B). It is possible to use.

<Black photosensitive resin composition>
The light shielding layer 2 of the present invention is formed using two types of black photosensitive resin compositions having different optical densities. Hereinafter, the black photosensitive resin composition having a low optical density is referred to as “low optical density light shielding material”, and the black photosensitive resin composition having a high optical density is referred to as “high optical density light shielding material”. Both the low optical density light-shielding material and the high optical density light-shielding material are photosensitive resin compositions containing at least a resin, a polymerizable monomer, a photopolymerization initiator, and a solvent, and contain at least one of a yellow pigment and an orange pigment. It is characterized by doing. In addition to this, in the low optical density light shielding material, the optical density around 1 μm of the thickness of the light shielding layer 2 is in the range of 0 to 1.0 or less, and in the high optical density light shielding material, the optical density of the light shielding layer 2 around 1 μm in thickness. What added the black pigment in the range from which a density | concentration becomes 2.5 or more is used.

<Black pigment>
As the black pigment used in the present invention, carbon black is preferable. As carbon black, any of lamp black, acetylene black, thermal black, channel black, furnace black and the like may be used.

  Specific examples of black pigments that can be used include titanium nitride, titanium nitride oxide, etc., but the reflection chromaticity of titanium nitride and titanium nitride oxide is more pronounced reddish than carbon black. It is preferable to use carbon black in the present invention which aims to obtain a reflection spectrum which is flat in the visible light region.

  The content of the black pigment in the low optical density light shielding material is preferably less than 20% by weight, more preferably 15% by weight or less in the solid content. When content is 25 weight% or more, the reflectance of the light shielding layer 2 formed will become high. Further, the content of the yellow pigment and the orange pigment is preferably 100% by weight or less with respect to the black pigment in the solid content.

  The content of the black pigment in the high optical density light-shielding material is preferably 40 to 56% by weight, more preferably 42 to 54% by weight in the solid content of the black photosensitive resin composition. When the content is 40% by weight or less, the light shielding property of the formed light shielding layer 2 is insufficient. On the other hand, when the content is 56% by weight or more, the sensitivity of the black photosensitive resin composition is insufficient, and the adhesion of the light shielding layer 2 is lowered. The optical density of the high optical density light-shielding layer can be 4 or more, preferably 5 or more.

  The reflection color of the light shielding layer 2 can be adjusted by adding a pigment to the black photosensitive resin composition. The black photosensitive resin composition of the present invention is characterized by containing at least one of a yellow pigment and an orange pigment as a pigment. By adding a yellow pigment, the b * value can be reduced while maintaining the a * value in the CIE Lab color space display system. Further, by adding an orange pigment, both the a * value and the b * value can be made negative. Therefore, by using these alone or in combination, it is possible to adjust the reflection chromaticity of the black matrix to an arbitrary chromaticity in the cyan direction.

  Specific examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100 , 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 144, 146 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 1 3,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 etc. but, among them C. I. Pigment Yellow 139 or Pigment Yellow 150 is preferable.

  Specific examples of orange pigments include C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73 and the like. I. Pigment Orange 71 is good.

<Resin>
Resins include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and other alkyl acrylates or alkyl methacrylates, cyclic cyclohexyl acrylate or methacrylate, hydroxyethyl acrylate or methacrylate, styrene, etc. Among these, a resin having a molecular weight of about 5000 to 100,000, which is synthesized using about 3 to 5 types of monomers, can be preferably used.

In addition, as a resin in which an unsaturated double bond is added to a part of an acrylic resin, a compound such as the above acrylic resin, isocyanate ethyl acrylate having at least one vinyl group and an isocyanate group, or methacryloyl isocyanate is reacted. The photosensitive copolymer having an acid value of 50 to 150 can be preferably used from the viewpoints of heat resistance, developability and the like. Furthermore, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, polycarboxylic acid glycidyl ester, polyol polyglycidyl ester, aliphatic or cycloaliphatic epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, Ordinary photopolymerizable resins such as epoxy (meth) acrylate obtained by reacting an epoxy resin such as a dihydroxybenzene type epoxy resin and (meth) acrylic acid, or a cardo resin can also be used.

<Polymerizable monomer>
Examples of the photopolymerizable monomer include ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol. Di (meth) acrylate, hexane di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, glycerin tetra (meth) acrylate, tetratrimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( Data) acrylate, dipentaerythritol hexa (meth) acrylate and the like, these components are used alone or as a mixture. Various modified (meth) acrylates, urethane (meth) acrylates, and the like can also be used. Among these, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate, which have a small double bond equivalent and can achieve high sensitivity, are preferably used.

  As content of a photopolymerizable monomer, it is preferable that it is 5 to 20 weight% in solid content of a black photosensitive resin composition, More preferably, it is the range of 10 to 15 weight%. When the content of the photopolymerizable monomer is within this range, the sensitivity and development speed of the black photosensitive resin composition can be adjusted to a level suitable for production. When the content of the photopolymerizable monomer is 5% by weight or less, the sensitivity of the black photosensitive resin composition is insufficient.

<Photopolymerization initiator>
Conventionally known compounds can be appropriately used as a photopolymerization initiator, but an oxime ester compound that can achieve high sensitivity even when used in a black photosensitive resin composition that does not transmit light is used. Is preferred.

  Specific examples of the oxime ester compound include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9. -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone (both manufactured by BASF Japan Ltd.) and the like.

  The content of the photopolymerization initiator represented above is preferably 1 to 10% by weight, more preferably 2 to 5% by weight, based on the solid content of the black photosensitive resin composition. When the content of the photopolymerization initiator is 1% by weight or less, the sensitivity of the black photosensitive resin composition is insufficient. On the other hand, when the content of the photopolymerization initiator is 10% by weight or more, the pattern line width of the light shielding layer 2 is too thick.

  In the black photosensitive resin composition of the present invention, other photopolymerization initiators can be used in combination with the photopolymerization initiator represented above. Other photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Acetophenone compounds such as butan-1-one, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenyl Benzophenone compounds such as nzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2- Thioxanthone compounds such as chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6- Bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6 -Triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine and other triazine compounds, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenyl Phosphine compounds such as phosphine oxide, 9,10-phenanthrenequinone, camphorquinone, ethyl anthrac Non-quinone compounds, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds, and the like are used. These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. The content of the other photopolymerization initiator is preferably 0.1 to 1% by weight, more preferably 0.2 to 0.5% by weight in the solid content of the black photosensitive resin composition. is there.

<Solvent>
Solvents include methanol, ethanol, ethyl cellosolve, ethyl cellosolve acetate, diglyme, cyclohexanone, ethylbenzene, xylene, isoamyl acetate, n amyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol mono Ethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, triethylene glycol, Liethylene glycol monomethyl ether, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether, triethylene glycol monoethyl ether acetate, liquid polyethylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether , Dipropylene glycol monoethyl ether acetate, lactic acid ester, ethyl ethoxypropionate and the like.

<Other additives>
In the black photosensitive resin composition of the present invention, a surfactant for further improving the coating property, a silane coupling agent for improving the adhesion to the transparent substrate 1 and the like can be used in combination.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

  As silane coupling agents, vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, epoxy silanes such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyldimethoxysilane, Methacrylsilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, N- Aminosilanes such as phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrieth Isocyanate silanes such as Shishiran like.

<Black matrix substrate>
The black matrix substrate 30 of the present invention comprises a low optical density light-shielding layer formed on the transparent substrate using the black photosensitive resin composition of the present invention and a high optical density light-shielding layer formed thereon. It comprises two layers having different optical densities.

  The black matrix substrate 30 of the present invention has a reflectance measured from the transparent substrate 1 side of 0.8 or less, and the a * and b * values of the light shielding layer 2 in the CIE Lab color space display system are a * <− 0. 5 or b * <− 0.5 or a * <− 0.5 and b * <− 0.5. Thereby, it is possible to improve red / yellow tint when the liquid crystal display device is not lit.

  The thickness of the light shielding layer 2 is preferably 0.2 to 0.5 μm for the low optical density light shielding layer 21.

  The high optical density light-shielding layer 22 is preferably 0.90 to 1.50 μm.

  When the film thickness of the light shielding layer 2 is 0.8 μm or less, the light shielding property is insufficient. On the other hand, when the film thickness of the black matrix is 1.6 μm or more, the flatness of the color filter is impaired and liquid crystal alignment failure is likely to occur.

The substrate on which the light shielding layer 2 is formed preferably has a certain transmittance with respect to visible light, and more preferably has a transmittance of 80% or more. Examples thereof include various glass substrates such as quartz glass, borosilicate glass, and aluminosilicate glass, and various plastic substrates such as polyester resin and polyolefin resin.

  The formation of the light shielding layer 2 is performed as follows. A coating film of the black photosensitive resin composition is formed on the transparent substrate 1 by a coating method such as spray coating, spin coating, slit coating, or roll coating.

  After removing the residual solvent in the coating film by drying under reduced pressure and pre-baking treatment, the entire coating film is exposed. As the exposure light source, a conventionally known plateau such as an ultra-high pressure mercury lamp, a xenon lamp, or a carbon arc can be used. Thereby, the low optical density light shielding layer 21 can be obtained.

  A black photosensitive resin composition for forming the high optical density light shielding layer 22 on the low optical density light shielding layer 21 is formed by a coating method such as spray coating, spin coating, slit coating, roll coating or the like.

  After removing the residual solvent in the coating film by drying under reduced pressure and pre-baking treatment, exposure is performed through a photomask having a predetermined pattern. As the exposure light source, a conventionally known light source such as an ultrahigh pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used.

  Next, it develops using the developing solution which consists of alkaline aqueous solution. Examples of the developer comprising the alkaline aqueous solution include a potassium carbonate aqueous solution, a sodium carbonate aqueous solution, or a sodium hydrogen carbonate aqueous solution, and those obtained by adding an appropriate surfactant to these aqueous solutions. After the development, the substrate is washed with water, dried and baked to obtain a black matrix substrate on which a black matrix pattern having a plurality of pixel openings is formed. The opening shape is a polygonal pixel shape having at least two sides parallel to each other, and examples thereof include a rectangle, a parallelogram, and a dogleg shape.

<Color filter>
The color filter of the present invention includes the black matrix substrate 30 and red, green, and blue colored pixels 3 formed in the opening of the light shielding layer 2.

  Examples of red pigments used for forming red pixels include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264 272, 279 and the like. It is also possible to use a yellow pigment and an orange pigment in combination in order to adjust the hue of the red pixel.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100 , 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 144, 146 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 1 3,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, and the like.

  Examples of orange pigments include C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73 and the like.

  Examples of the green pigment for forming the green pixel include C.I. I. Pigment Green 7, 10, 36, 37, 58 and the like. It is also possible to use a yellow pigment in combination to adjust the hue of the green pixel. As a yellow pigment, what was illustrated as a yellow pigment which can be used together in order to adjust the hue of a red pixel can be used suitably.

  Examples of blue pigments for forming blue pixels include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and the like. Further, a purple pigment can be used in combination to adjust the hue of the blue pixel. Specific examples of purple pigments include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like.

  The color filter is manufactured as follows. On the black matrix substrate 30, a coating film of a colored photosensitive resin composition containing a pigment corresponding to each colored pixel of the color filter is formed. After drying, exposure is performed through a photomask having a pattern corresponding to the opening of the light shielding layer 2. The colored pixels 3 can be formed in the openings of the light shielding layer 2 by removing the unexposed portions by development and then baking. By performing a series of operations using a colored photosensitive resin composition containing, for example, red, green, and blue color materials, a color filter having red, green, and blue pixels can be manufactured.

<Liquid crystal display device>
On the array substrate 5, active elements for driving liquid crystal such as TFT elements 5 and MIM (metal / insulating film / metal) are formed.

  As the TFT element 5, various TFTs that use amorphous silicon or a polysilicon thin film, those that use a transparent oxide semiconductor, or those that use carbon nanotubes have been proposed.

  A transparent electrode 6 layer made of ITO, for example, is formed thereon. An alignment film 7 is provided on the transparent electrode 6 layer. A polarizing plate 9 is formed on the outer surface of the transparent substrate 1.

  The color filter of the present invention is formed on the inner surface of the transparent substrate 1. A transparent protective film 8 is formed so as to cover the color filter 12, and further, a transparent electrode 6 layer made of, for example, ITO is formed thereon, and an alignment film 7 is provided to cover the transparent electrode 6 layer. Yes. A polarizing plate 9 is formed on the outer surface of the transparent substrate 1. A backlight unit is provided below the polarizing plate 9.

  In the liquid crystal display device of the present invention, since the reflectance of the light shielding layer 2 of the color filter is low and the reflected light is bluish, the redness caused by the reflected light of the TFT element 5 can be offset. Black color with a sense of unity with the bezel is obtained when lit.

<Low optical density light shielding material 1>
Bisphenol fluorene type epoxy resin 11.91g
(V259-ME solid content 56.1% manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
Dipentaerythritol hexaacrylate 1.97g
(Aronix M402 manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator (OXE-02 manufactured by BASF Japan Ltd.) 0.99 g Carbon black dispersion 10.75 g
(Propylene glycol monomethyl ether acetate
Solid content 24.43%, pigment concentration in solid content 79.98% by weight),
Yellow Pigment Yellow 139 7.05 g
(Solid content 23.90%, pigment concentration in solid content 62.34%)
Leveling agent solution (BYK-Chemie BYK-323 (1% solution)) 1.00 g Propylene glycol monomethyl ether acetate 70.62 g
And stir well,
100 g of low optical density light shielding material 1 (solid content 14.0%, carbon black pigment 15.0
% By weight, 7.5% by weight of yellow pigment, and an optical density of 1.0 / μm).

<Low optical density light shielding material 2>
Bisphenol fluorene type epoxy resin 9.44g
(V259-ME manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .: solid content 56.1%)
Dipentaerythritol hexaacrylate 1.78g
(Aronix M402 manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator (OXE-02 manufactured by BASF Japan Ltd.) 0.89 g Carbon black dispersion 10.75 g
(Propylene glycol monomethyl ether acetate
(Solid content 24.43%, pigment concentration in solid content 79.98% by weight)
Yellow pigment Pigment Yellow 139 14.10 g
(Solid content 23.90%, pigment concentration in solid content 62.34%)
Leveling agent liquid (BYK-Chemie BYK-323 (1% solution)) 1.00 g propylene glycol monomethyl ether acetate 62.05 g was added and stirred well.
100 g (solid content: 14.0%, carbon black pigment: 15.0% by weight, yellow pigment: 15.0% by weight, optical density: 1.0 / μm) was obtained.

<Low optical density light shielding material 3>
Bisphenol fluorene type epoxy resin 11.93g
(“V259-ME” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. 56.1% solids)
Dipentaerythritol hexaacrylate 1.97g
(Aronix M402 manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator (OXE-02 manufactured by BASF Japan) 0.99 g Carbon black dispersion 10.75 g
(Propylene glycol monomethyl ether acetate
(Solid content 24.43%, pigment concentration in solid content 79.98% by weight)
Orange pigment Pigment Orange 71 7.00 g
(Solid content 23.90%, pigment concentration in solid content 62.76%)
Leveling agent solution (BYK-Chemie BYK-323 (1% solution)) 1.00 g propylene glycol monomethyl ether acetate 66.36 g was added and stirred well.
100 g of the low optical density light shielding material 3 (solid content: 14.0%, carbon black pigment: 15.0
Weight%, orange pigment 7.5 weight% optical density 1.0 / μm).

<Low optical density light shielding material 4>
Bisphenol fluorene type epoxy resin 9.48g
(V259-ME solid content 56.1% made by Nippon Steel & Sumikin Chemical Co., Ltd.)
Dipentaerythritol hexaacrylate 1.78g
(Aronix M402 manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator (OXE-02 manufactured by BASF Japan Ltd.) 0.89 g Carbon black dispersion 10.75 g
(Propylene glycol monomethyl ether acetate
(Solid content 24.43%, pigment concentration in solid content 79.98% by weight)
Orange pigment Pigment Orange 71 14.00 g
(Solid content 23.90%, pigment concentration in solid content 62.76%)
Leveling agent solution (BYK-Chemie BYK-323 (1% solution) 1.00 g propylene glycol monomethyl ether acetate 62.10 g was added and stirred well.
100 g of low optical density light shielding material 4 (solid content: 14.0%, carbon black pigment: 15.0
% By weight, orange pigment 15.0% by weight, optical density 1.0 / μm).

<Low optical density light shielding material 5>
Bisphenol fluorene type epoxy resin 11.92g
(V259-ME solid content 56.1% manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
Dipentaerythritol hexaacrylate 1.97g
(Aronix M402 manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator (OXE-02 manufactured by BASF Japan) 0.99 g Carbon black dispersion 10.75 g
(Propylene glycol monomethyl ether acetate
(Solid content 24.43%, pigment concentration in solid content 79.98% by weight)
Yellow pigment Pigment Yellow 150 7.05 g
(Solid content 23.90%, pigment concentration in solid content 62.34%)
Orange pigment Pigment Orange 71 7.00 g
(Solid content 23.90%, pigment concentration in solid content 62.76%)
Leveling agent solution (BYK-Chemie BYK-323 (1% solution)) 1.00 g propylene glycol monomethyl ether acetate 59.32 g was added and stirred well.
100 g (solid content 14.0%, carbon black pigment 15.0% by weight, yellow pigment 7.5% by weight, orange pigment 7.5% by weight optical density 1.0 / μm) is obtained. It was.

<Low optical density light shielding material 6>
Bisphenol fluorene type epoxy resin 14.39g
(“V259-ME” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. 56.1% solids)
Dipentaerythritol hexaacrylate 2.16g
(Aronix M402 manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator (OXE-02 manufactured by BASF Japan) 1.08 g Carbon black dispersion 10.75 g
(Propylene glycol monomethyl ether acetate
(Solid content 24.43%, pigment concentration in solid content 79.98% by weight)
Leveling agent solution (BYK-Chemie BYK-323 (1% solution)) 1.00 g propylene glycol monomethyl ether acetate 70.62 g was added and stirred well.
100 g of low optical density light shielding material 6 (solid content: 14.0%, carbon black pigment: 15.0
Wt%, optical density 1.0 / μm).

<Low optical density light shielding material 7>
Bisphenol fluorene type epoxy resin 9.37g
(V259-ME solid content 56.1% made by Nippon Steel & Sumikin Chemical Co., Ltd.)
Dipentaerythritol hexaacrylate 1.78g
(Aronix M402 manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator (OXE-02 manufactured by BASF Japan Ltd.) 0.89 g Carbon black dispersion 10.75 g
(Propylene glycol monomethyl ether acetate, solid content: 24.43%, pigment concentration in solid content: 79.98% by weight)
Green pigment C.I. I. Pigment Green58 16.15g
(Solid content 21.10%, pigment concentration in solid content 61.61%)
Leveling agent solution (BYK-Chemie BYK-323 (1% solution)) 1.00 g propylene glycol monomethyl ether acetate 60.06 g was added and stirred well.
100 g of low optical density light-shielding material 7 (solid content: 14.0%, carbon black pigment: 15.0
% By weight, green pigment 15.0% by weight, optical density 1.0 / μm).

<Low optical density light shielding material 8>
Bisphenol fluorene type epoxy resin 9.07g
(V259-ME solid content 56.1% manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
Dipentaerythritol hexaacrylate 1.78g
(Aronix M402 manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator (OXE-02 manufactured by BASF Japan) 0.89 g Carbon black dispersion 10.75 g
(Propylene glycol monomethyl ether acetate, solid content: 24.43%, pigment concentration in solid content: 79.98% by weight)
Purple pigment C.I. I. Pigment Violet 23 17.34 g
(Solid content 20.60%, pigment concentration in solid content 58.74%)
Leveling agent solution (BYK-Chemie BYK-323 (1% solution)) 1.00 g propylene glycol monomethyl ether acetate 59.15 g was added and stirred well.
100 g of low optical density light shielding material 8 (solid content: 14.0%, carbon black pigment: 15.0
% By weight, purple pigment 15.0% by weight, optical density 1.0 / μm).

<Adjustment of high optical density light shielding material>
Bisphenol fluorene type epoxy resin 4.07g
(V259-ME solid content 56.1% manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
Dipentaerythritol penta / hexaacrylate mixture 1.49g
(KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization initiator (NCI-831 manufactured by ADEKA) 0.53 g Carbon black dispersion 37.33 g
(Propylene glycol monomethyl ether acetate, solid content: 26.0%, pigment concentration in solid content: 75.0% by weight)
Add 56.59 g of propylene glycol monomethyl ether acetate and stir well.
100 g (solid content 14.0%, carbon black pigment 52% by weight, optical density 3.8 / μm) of a high optical density light-shielding material was obtained.

A coating film of the low optical density light-shielding material 1 was formed on a glass substrate (“EAGLE XG” manufactured by Corning) by spin coating. After drying, it was pre-baked on a hot plate at 90 ° C. for 1 minute. At this time, the number of revolutions during coating was adjusted so that the film thickness after pre-baking was 0.2 μm. Next, the whole coating film of the low optical density material was irradiated with 5 mJ / cm ² of ultraviolet light using an ultrahigh pressure mercury lamp (illuminance 26 mW / cm ² ). Subsequently, the coating film of the high optical density light-shielding material was formed on the coating film of the low optical density agent by spin coating. At this time, the film thickness was adjusted so that the optical density of the light shielding layer 2 obtained after firing was 4.0. After drying, it was pre-baked for 30 seconds on a 90 ° C. hot plate, and then baked for 60 minutes in a 230 ° C. clean oven to prepare a black matrix substrate 1.

  In the low optical density light-shielding material 1 in Example 1, the amount of yellow pigment Pigment Yellow 139 added was doubled. A black matrix substrate 2 was produced under the same conditions except that the light density light-shielding material 2 was used (or the addition amount was doubled instead of Pigment Yellow ΔΔ).

  A black matrix substrate 3 was produced under the same conditions except that the yellow pigment of the low optical density light-shielding material 1 in Example 1 was changed to the low optical density light-shielding material 3 in place of Pigment Orange 71 which is an orange pigment.

  A black matrix substrate 4 was produced under the same conditions except that the low optical density light shielding material 4 in which the addition amount of the orange pigment Pigment Orange 71 of the low optical density light shielding material 3 in Example 3 was doubled was used.

  A black matrix substrate 5 was produced under the same conditions except that the low optical density light-shielding material 5 was obtained by using both a yellow pigment and an orange pigment as the additive pigment of the low optical density light-shielding material 1 in Example 1.

<Comparative Example 1>
A black matrix substrate 6 was produced under the same conditions except that the low optical density light-shielding material 1 in Example 1 was changed to a low optical density light-shielding material 6 containing no yellow pigment or orange pigment.

<Comparative example 2>
A black matrix substrate 7 was produced under the same conditions except that the low optical density light-shielding material 1 in Example 1 was changed to a low optical density light-shielding material 7 using a green pigment instead of a yellow pigment or an orange pigment.

<Comparative Example 3>
A black matrix substrate 8 was produced under the same conditions except that the low optical density light-shielding material 1 in Example 1 was changed to a low optical density light-shielding material 8 using a purple pigment instead of a yellow pigment or an orange pigment.

<Comparative example 4>
The same low optical density light-shielding material 1 as in Example 1 is formed so that the film thickness after pre-baking is 0.4 μm, and further, a high optical density light-shielding material is laminated and the optical density of the light-shielding layer obtained after firing is A black matrix substrate 9 was produced under the same conditions except that the film thickness was adjusted to 4.2.

<Comparative Example 5>
The same low optical density light-shielding material 1 as in Example 1 is formed so that the film thickness after pre-baking is 0.7 μm, and further, a high optical density light-shielding material is laminated and the optical density of the light-shielding layer obtained after firing is A black matrix substrate 10 was produced under the same conditions except that the film thickness was adjusted to 4.5.

<Reflection evaluation>
The reflection chromaticity from the glass surface of the prepared black matrix substrate 30 was measured with a spectrophotometer (U-4000 manufactured by Hitachi, Ltd.). Measurement conditions were as follows: light source: D65, measurement wavelength region: 300 to 800 nm, scan speed: 300 nm / mim, sampling interval: 1.0 nm, slit width: 4.0 nm.

  The reflectance was measured by the above spectrophotometer. The luminous reflectance Y in the XYZ color system measured from the transparent substrate 1 side using a C light source was taken as the reflectance value, and the reflective chromaticity was taken as the a * and b * values in the CIE Lab color space display system.

  The evaluation results are shown in Table 1.

As shown in Examples 1 to 5, by adding a yellow pigment or an orange pigment, the a * and b * values of the light shielding layer in the CIE Lab color space display system are a * <− 0.5 or b * <− 0.5. Alternatively, a * <− 0.5 and b * <− 0.5, the reflection chromaticity can be adjusted to cyan, and the reflectance is also a value of 0.8 or less. The taste coloring could be offset. On the other hand, in Comparative Example 1 containing no color pigment, Comparative Example 2 containing a green pigment, and Comparative Example 3 containing a purple pigment, the reflectance was a value of 0.8 or less. Since both of the results showed positive values, the reddish coloring caused by the liquid crystal display device could not be offset, and a sense of unity with the outer frame portion could not be obtained when not lit.

  Comparative Example 4 and Comparative Example 5 contain an orange pigment, but the low optical density light-shielding layer 21 is thick and has a high optical density of 0.4 and 0.7, a reflectance of 0.9, and 1. It became a value exceeding 1 and 0.8.

  By using the black photosensitive resin composition of the present invention, the black matrix substrate 30 in which the reflectance is reduced and the reflection chromaticity a * and b * is minus is obtained. By using the color filter provided with the black matrix substrate 30, a neutral black color can be obtained when the liquid crystal display device is not turned on, canceling the reddish coloring caused by the TFT element 5 and the liquid crystal composition.

1 ... transparent substrate 2 ... light shielding layer (black matrix)
DESCRIPTION OF SYMBOLS 3 ... Colored pixel 4 ... Liquid crystal layer 5 ... TFT element 6 ... Transparent electrode 7 ... Alignment film 8 ... Transparent protective film 9 ... Polarizing plate 10 ... Array substrate 21 ... Low optical density light shielding layer 22 ... High optical density light shielding layer 30 ... Black matrix substrate

Claims (8)

A black matrix substrate formed by laminating a plurality of light shielding layers having different optical densities on a transparent substrate,
The light shielding layers having different optical densities are laminated on the transparent substrate in the order of a low optical density light shielding layer and a high optical density light shielding layer,
The low optical density light-shielding layer is formed using one or more kinds of orange pigments or one or more kinds of yellow pigments, or a black photosensitive resin composition having one or more kinds of orange pigments and one or more kinds of yellow pigments. And a black matrix substrate in which the optical density of the low optical density light-shielding layer is 0.3 or less.   The a * and b * values in the CIE Lab color space display system of the reflection density of the low optical density light-shielding layer measured from the transparent substrate side are a * <− 0.5 or b * <− 0.5, or a * The black matrix substrate according to claim 1, wherein <−0.5 and b * <− 0.5.   The black matrix substrate according to claim 1 or 2, wherein the reflectance of the low optical density light-shielding layer measured from the transparent substrate side is 0.8 or less.   The black matrix substrate according to any one of claims 1 to 3, wherein the sum of the optical densities of the light shielding layers having different optical densities is 4.0 or more.   The yellow pigment contained in the black photosensitive resin composition is Pigment Yellow 139 or C.I. I. The black matrix substrate according to claim 1, which is Pigment Yellow 150.   6. The black matrix substrate according to claim 1, wherein the orange pigment contained in the black photosensitive resin composition is Pigment Orange 71. 7.   A color filter substrate using the black matrix substrate according to claim 1.   A liquid crystal display device using the color filter substrate according to claim 7.