JP2017211744A - Color filter substrate and display device using the same - Google Patents

Abstract

[Problem] To provide a color filter substrate in which a touch panel electrode based on a light-shielding metal film is formed on the back surface of a transparent substrate on which a color filter is formed, the touch panel electrode having low reflectance over the visible light range of external light, small reddish/yellowish chromaticity, and excellent impact resistance, and a touch panel integrated display device using the same. [Solution] The touch panel electrode is a color filter substrate comprising an adhesive layer, a metal layer, a black anti-reflection layer, and an electrode protection layer, in this order, on a transparent substrate, the black anti-reflection layer having an optical density of 3.0 (/μm) or more and containing a black pigment or black dye, a reflectance adjuster, and a reflection color adjuster, the reflectance adjuster being one selected from silica fine particles, magnesium fluoride fine particles, and cryolite fine particles, the reflection color adjuster being one selected from a yellow pigment, a red pigment, a yellow dye, and a red dye, and the electrode protection layer being made of a transparent resin composition having a pencil hardness of 4H or more. [Selected Figure] Figure 1

Description

  The present invention relates to a color filter substrate with a touch panel electrode and a touch panel integrated display device using the same.

  In recent years, a touch panel has been adopted as an operation unit of an electronic device such as a mobile phone or a portable information terminal. The touch panel detection method includes a resistance film method, a capacitance method, an ultrasonic method, and an optical method. Capacitive touch panels have high optical characteristics (transmittance) and are superior to resistive film systems in terms of durability and operating temperature characteristics, and are therefore being developed especially for high-reliability applications such as in-vehicle use. .

  The touch panel is a position input device used in combination with a display panel using liquid crystal or organic EL. The capacitive touch panel has a plurality of electrodes extending in the X direction and the Y direction, detects a change in electrostatic capacitance of an electrode that is in contact with or close to a finger or a nib as a change in a weak current amount, and is in a contacted position. The specified content is received as an input signal, and the display panel is driven.

  The plurality of electrodes are formed as transparent electrodes in a display region using a material such as ITO (Indium Tin Oxide) having electrical conductivity and transparency, and X is interposed through an insulating region such as a transparent substrate. It is arranged in stripes or arrays in the direction and the Y direction.

  In order to further reduce the thickness and weight of electronic devices, a touch panel integrated display device in which a touch panel and a display panel are bonded and combined has been proposed (for example, Patent Document 1).

  In the touch panel integrated display device, in the method of forming the electrode for the touch panel on the back surface of the transparent substrate on which the color filter in the liquid crystal display panel is formed, the transparent substrate is thinned using hydrofluoric acid after bonding. An electrode is formed later. For this reason, it is not possible to perform high-temperature heat treatment that affects the liquid crystal or alignment film in the liquid crystal panel during electrode formation, and the resistance value is lowered because sufficient annealing cannot be performed on transparent electrodes such as ITO. It becomes difficult to cope with the increase in the screen size of the display device.

  Therefore, a technique is disclosed that uses a light-shielding metal film such as Cu (hereinafter referred to as a metal film as appropriate) as an electrode material that can replace ITO due to cost problems and to improve conductivity (for example, Patent Document 2). ).

Special table 2009-540374 JP 2011-028699 A JP 2013-004076 A

  However, the touch panel using a light-shielding metal pattern as an electrode is more advantageous in terms of conductivity than the case where an ITO pattern is used as an electrode. Therefore, there is a problem that the electrode pattern is easily visible to the user, and the visibility of the display image when integrated as a display device is lowered. Therefore, an attempt is made to suppress the reflection of wiring due to external light by laminating an interference film on the metal film using a sputtering method, applying a blackening treatment to the light shielding metal (for example, Patent Document 3), or laminating a black matrix. However, the reflectivity has not been greatly improved.

In addition, as the design becomes an increasingly important appeal point in products using display devices, attention is also focused on the reflection color. When the light-shielding metal film pattern is used as an electrode, the reflection chromaticity of the metal film surface is reddish / yellowish (that is, the a ^* and b ^* values in the CIE Lab color space display system are shifted in the plus direction. Therefore, there is a problem that the display device is colored reddish / yellowish. In addition, since the metal film does not have sufficient hardness and impact resistance, there is a concern that the yield may decrease due to impact during transportation or peeling of the wiring in the next process.

  The present invention has been made in view of the above problems, and its object is to form a touch panel electrode based on a light-shielding metal film on the back surface of a transparent substrate on which a color filter in a display panel is formed. In the color filter substrate, the reflectance of the outside light of the touch panel electrode is low and difficult to be visually recognized by the user, and thus the visibility of the display image is increased, and the red / yellowish chromaticity is small, A color filter substrate having excellent impact resistance and a touch panel integrated display device using the same are provided.

In order to solve the above-mentioned problem, the present invention described in claim 1 is a color filter substrate including a color filter on a first surface of a transparent substrate and a touch panel electrode on a second surface,
The touch panel electrode includes an adhesive layer, a metal layer, a black reflection suppression layer, and an electrode protective layer in this order on the transparent substrate.
The adhesive layer, the metal layer, and the black antireflection layer are patterned,
The black antireflection layer has an optical density (OD) of 3.0 (/ μm) or more per unit film thickness, and the black antireflection layer comprises a black pigment and / or black dye, a reflectance adjusting agent, and a reflecting color adjusting agent. And at least
The reflectance adjusting agent is at least one selected from silica fine particles, magnesium fluoride fine particles, cryolite (sodium hexafluoroaluminate) fine particles,
The reflection color adjusting agent is at least one selected from a yellow pigment, a red pigment, a yellow dye, and a red dye,
The electrode protective layer contains at least a polymerizable polyfunctional monomer, a binder resin, a thermal polymerization initiator or a photopolymerization initiator, and comprises a transparent resin composition having a pencil hardness of 4H or more,
The luminous reflectance in the XYZ color system viewed from the electrode protective layer side of the touch panel electrode is 5.0% or less, and the a ^* and b ^* values in the CIELab color space display system are −0.5 <a ^*. <+0.5 and −0.5 <b ^* <+ 0.5.

  According to a second aspect of the present invention, in the color filter substrate according to the first aspect, the adhesive layer contains indium, and the metal layer is a copper layer, a copper alloy layer, or both. Is.

  The present invention described in claim 3 is the color filter substrate according to claim 1, wherein the black pigment is at least one selected from carbon black and titanium nitride. .

  The present invention according to claim 4 provides the color filter substrate according to any one of claims 1 to 3, wherein the black dye is aniline black.

  In the present invention according to claim 5, the reflection color adjusting agent is a yellow pigment C.I. I. Pigment Yellow 139, yellow dye C.I. I. Solvent Yellow 83, red pigment C.I. I. Pigment Red 177, red dye C.I. I. The color filter substrate according to claim 1, wherein the color filter substrate is at least one selected from Solvent Red 124.

  According to a sixth aspect of the present invention, there is provided a display device comprising the color filter substrate according to any one of the first to fifth aspects.

  According to the color filter substrate with a touch panel electrode of the present invention, since the touch panel electrode is made of a suitable material / configuration based on a metal film, the reflectance of the external light of the touch panel electrode over the visible light region is low and is visually recognized by the user. Therefore, the color filter substrate has high visibility, high redness / yellowish chromaticity, excellent design, and excellent impact resistance. As a result, it becomes possible to contribute to the improvement of the yield of the touch panel integrated liquid crystal display device and the increase in the screen size.

It is a schematic cross section of the color filter substrate of the first embodiment of the present invention. It is the partial expanded view of the touch-panel electrode part of FIG. 1, and the schematic cross section for demonstrating the luminous reflectance of a touch-panel electrode and a ^* , b ^* measurement in an Example. It is a schematic cross section of the color filter substrate of the second embodiment of the present invention. It is a schematic cross section of the display device of the third embodiment of the present invention using the color filter substrate of the first embodiment of the present invention. It is a schematic cross section of the display device of the fourth embodiment of the present invention using the color filter substrate of the second embodiment of the present invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as appropriate. In addition, the same code | symbol is attached | subjected about the same component unless there is a reason for convenience, and the overlapping description is abbreviate | omitted. Further, in the drawings used in the following description, in order to make the features easy to understand, the portions that become the features may be shown in an enlarged manner, and the dimensional ratios of the respective components are not necessarily the same as the actual ones. The embodiments will be described as examples of the color filter substrate of the present invention or a liquid crystal display device using the same, but the color filter substrate of the present invention can also be applied to other display devices such as an organic EL display device. It is.

[Color Filter Substrate of First Embodiment]
FIG. 1 is a schematic cross-sectional view of a color filter substrate according to a first embodiment of the present invention. The color filter substrate 100 includes a color filter 2 including a black matrix (BM) and colored pixels (R: red layer, G: green layer, B: blue layer) on the first surface of the transparent substrate 1, and further includes a protective layer. The transparent resin layer 8 is provided as an insulating layer. The touch panel electrode 3 is provided on the second surface, and the touch panel electrode 3 is formed by laminating an adhesive layer 4 and a metal layer 5 in order from the side close to the transparent substrate 1. A black antireflection layer 6 is formed on the side surface of each of these layers, and these layers are patterned into a plurality of linear patterns arranged in parallel in a plan view. The arrangement of the touch panel electrodes 3 is arranged in a stripe pattern shape in the Y direction perpendicular to the paper surface. Further, an electrode protective layer 7 is formed so as to cover the touch panel electrode 3 (see also FIG. 2).

[Color Filter Substrate of Second Embodiment]
FIG. 3 is a schematic cross-sectional view of a color filter substrate according to the second embodiment of the present invention. The difference from the color filter substrate of the first embodiment is that the transparent electrode 9 is formed on the transparent resin layer 8. A stripe pattern of the transparent electrode 9 is formed on the transparent resin layer 8 so as to be orthogonal to the touch panel electrode 3.

  Since the difference due to the transparent electrode 9 appears after the display device of the present invention described later, the following description of the color filter substrate of the present invention is common to the first embodiment and the second embodiment.

In order to secure a reflectance such that the touch panel electrode is not visible, the OD of the touch panel electrode is 3.0 (/ μm) or more per unit film thickness, and from the electrode protective layer side of the touch panel electrode The viewed reflectance in the XYZ color system is 5.0% or less, and the a ^* and b ^* values in the CIELab color space display system are −0.5 <a ^* <+ 0.5 and −0.5 <. b ^* <+ 0.5.

[Touch panel electrode]
Hereinafter, elements constituting the touch panel electrode 3 will be described. The touch panel electrode 3 should be called the first touch panel electrode in contrast with the second touch panel electrode shown in the description of the display device of the present invention to be described later, but is simply called the touch panel electrode for convenience.

(Black pigment or black dye contained in the black antireflection layer)
Examples of the black pigment or black dye contained in the black resin composition serving as the black antireflection layer include organic pigments such as carbon black, graphite, aniline black, and cyanine black, and inorganic pigments such as titanium oxide, titanium nitride, and iron oxide. However, carbon black having excellent light shielding properties is particularly preferable.

  As content of a black pigment or black dye, it is preferable that it is 4-60 mass% in solid content of a black resin composition, More preferably, it is the range of 10-55 mass%. When the content of the black pigment is 4% by mass or less, a sufficient black color cannot be obtained, the reflection of the underlying metal film is large, and the visibility is lowered, which is not suitable for practical use. On the other hand, when the content of the black pigment is 60% by mass or more, the linearity of the pattern and the film surface shape tend to deteriorate.

(Reflectance adjusting agent contained in the black antireflection layer)
As the reflectance adjusting agent, low refractive index compounds such as silica fine particles, magnesium fluoride fine particles, cryolite (sodium hexafluoroaluminate) fine particles can be appropriately used for reducing the reflectivity. From the viewpoint, it is preferable to use silica fine particles.

  The content of the reflectance adjusting agent including silica fine particles, magnesium fluoride fine particles, cryolite (sodium hexafluoroaluminate) fine particles is preferably 1 to 30% by mass in the solid content of the black resin composition, more preferably 2 to 2. 25% by mass. When the content is 1% by mass or less, the reflectance reducing ability is insufficient. On the other hand, when content is 30 mass% or more, the ratio for which a black pigment or black dye accounts in solid content of a black photosensitive resin composition falls, and light-shielding property is insufficient.

(Reflection color adjusting agent contained in the black antireflection layer)
About a reflective color adjusting agent, it is possible to adjust the reflective color of a black reflection suppression layer by adding a color pigment or a coloring dye to the said black resin composition. As the coloring pigment or coloring dye, conventionally known compounds such as yellow pigments, yellow dyes, red pigments and red dyes can be used as appropriate. I. Pigment Yellow 139, C.I. I. Solvent Yellow 83, C.I. I. PigmentRed 177, C.I. I. It is preferable to use SolventRed124. C. I. Pigment Yellow 139, C.I. I. By adding Solvent Yellow 83, it is possible to make the b ^* value minus while maintaining the a ^* value in the CIE Lab color space display system. On the other hand, C.I. I. PigmentRed 177, C.I. I. By adding SolventRed 124, the a ^* value can be minus while maintaining the b ^* value. Therefore, by using both together, it is possible to adjust the reflection chromaticity of the black reflection suppression layer to neutral chromaticity. In addition, C.I. I. Pigment Yellow 139, C.I. I. Solvent Yellow 83, C.I. I. PigmentRed 177, C.I. I. Since SolventRed 124 has a strong coloring power, it is possible to greatly shift the a ^* and b ^* values of the black antireflection layer by adding a small amount. Therefore, it is possible to suppress the addition concentration of carbon black or the like, which is a black reflection suppression layer, and to increase the adjustment range of the patterning property by adjusting the clear component. C. I. Pigment Yellow 139, C.I. I. Solvent Yellow 83, C.I. I. PigmentRed 177, C.I. I. The content of the coloring pigment or coloring dye containing SolventRed124 is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, based on the solid content of the black resin composition. When the content is 1% by mass or less, the amount of shift in reflection chromaticity is insufficient. On the other hand, when content is 30 mass% or more, the ratio for which carbon black accounts in solid content of a black photosensitive resin composition falls, and light-shielding property is insufficient.

  The coloring pigment or coloring dye added to the black resin composition is C.I. I. Pigment Yellow 139, C.I. I. Solvent Yellow 83, C.I. I. PigmentRed 177, C.I. I. Colored pigments or colored dyes other than SolventRed 124 can also be used as appropriate.

  Examples of red pigments include C.I. I. PigmentRed 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 178 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264 269, 272, 279 and the like.

  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, 144, 146, 147 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 1 4,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, and the like.

  Specific examples of the red dye include C.I. I. SolventRed 1, 2, 3, 4, 8, 16, 17, 18, 19, 23, 24, 25, 26, 27, 30, 33, 35, 41, 43, 45, 48, 49, 52, 68, 69 72, 73, 83: 1, 84: 1, 89, 90, 90: 1, 91, 92, 106, 109, 110, 118, 119, 122, 125, 127, 130, 132, 135, 141, 143 145, 146, 149, 150, 151, 155, 160, 161, 164, 164: 1, 165, 166, 168, 169, 172, 175, 179, 180, 181, 182, 195, 196, 197, 198 , 207, 208, 210, 212, 214, 215, 218, 222, 223, 225, 227, 229, 230, 233, 234, 235, 236, 23 8, 239, 240, 241, 242, 243, 244, 245, 247, 248, C.I. I. Acid Red 6, 11, 26, 60, 88, 111, 186, 215, C.I. I. Basic Red 1, 2, 13, 14, 22, 27, 29, 39, C.I. I. DirectRed 4, 23, 31, 75, 76, 79, 80, 81, 83, 84, 149, 224, C.I. I. SulfurRed 5, 6, 7, C.I. I. Reactive Red 8, 22, 46, 120, C.I. I. Disperse Red 4, 11, 54, 55, 58, 65, 73, 127, 129, 141, 196, 210, 229, 354, 356 and the like.

  Specific examples of yellow dyes include C.I. I. Solvent Yellow 2, 3, 7, 12, 13, 14, 16, 18, 19, 21, 25, 25: 1, 27, 28, 29, 30, 33, 34, 36, 42, 43, 44, 47, 56 62, 72, 73, 77, 79, 81, 82: 1, 88, 89, 90, 93, 94, 96, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135 141, 143, 145, 146, 157, 160: 1, 161, 162, 163, 167, 169, 172, 174, 175, 176, 179, 180, 181, 182, 183, 184, 185, 186, 187 189, 190, 191, C.I. I. Acid Yellow 17, 23, 25, 36, 38, 42, 44, 72, 78, C.I. I. Basic Yellow 11, 23, 25, 28, 41, C.I. I. Direct Yellow 26, 27, 28, 33, 44, 50, 86, 142, C.I. I. Sulfur Yellow 4, C.I. I. Vat Yellow 2, 12, 20, 33, C.I. I. Reactive Yellow 1, 2, 4, 14, 16, C.I. I. Disperse Yellow 3, 4, 5, 7, 23, 33, 42, 60, 64 and the like.

  The black resin composition for forming the black antireflection layer 6 of the color filter substrate of the present invention includes a polymerizable polyfunctional monomer, a binder in addition to the above-described black pigment or black dye, reflectance adjusting agent, and reflecting color adjusting agent. Contains resin, thermal polymerization initiator or photopolymerization initiator.

(Polymerizable polyfunctional monomer contained in the black antireflection layer)
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, pentafunctional / 6 functional monomers capable of suppressing the amount of line width shift in the post-baking step, specifically, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferably used.

  As content of a photopolymerizable monomer, it is preferable that it is 5-20 mass% in solid content of a black resin composition, More preferably, it is the range of 10-15 mass%. When the content of the photopolymerizable monomer is within this range, the sensitivity and development speed of the black resin composition can be adjusted to a level suitable for production. When the content of the photopolymerizable monomer is 5% by mass or less, the sensitivity of the black resin composition is insufficient. On the other hand, when the content of the photopolymerizable monomer is 20% by mass or more, the linearity of the pattern is deteriorated and an inversely tapered shape is easily obtained.

(Binder resin contained in the black antireflection layer)
Binder resins include alkyl acrylate or alkyl methacrylate such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, cyclic cyclohexyl acrylate or methacrylate, hydroxyethyl acrylate or methacrylate, styrene A resin having a molecular weight of about 2000 to 10000 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, novolak type epoxy resin, polycarboxylic acid glycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic 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.

(Thermal polymerization initiator or photopolymerization initiator contained in the black antireflection layer)
As the thermal polymerization initiator or photopolymerization initiator, conventionally known compounds such as azonitrile, azoester, and azoamide can be appropriately used as the thermal polymerization initiator. In order to avoid reactive substances, it is preferable to use azoamidine or azoimidazolium compounds.

  Examples of the azoamidine and azoimidazolium compounds include VA-061, VA-057, V-50, VA-046B, and VA-044 (Wako Pure Chemical Industries, Ltd.).

  The content of the thermal polymerization initiator is preferably 0.1 to 10% by mass in the solid content of the black resin composition, and more preferably in the range of 0.2 to 5% by mass. When the content of the thermal polymerization initiator is 0.2% by mass or less, the black resin composition is insufficiently cured. On the other hand, when the content of the thermal polymerization initiator is 10% by mass or more, a pattern residue is generated on the glass.

  As the photopolymerization initiator, conventionally known compounds can be used as appropriate, but it is preferable to use an oxime ester compound that can achieve high sensitivity even when used in a black resin composition that does not transmit light.

  Examples of the oxime ester compounds include Irgacure OXE01, Irgacure OXE02 (trade names, both manufactured by BASF Japan), NCI-831 (trade names, manufactured by ADEKA), and the like.

  It is preferable that content of a photoinitiator is 0.5-20 mass% in solid content of the said black resin composition, More preferably, it is the range of 0.5-15 mass%. When the content of the photopolymerization initiator is 0.5% by mass or less, the sensitivity of the black resin composition is insufficient. On the other hand, when the content of the photopolymerization initiator is 20% by mass or more, the pattern line width becomes too thick.

  In the black resin composition of the present invention, other photopolymerization initiators can be used in combination with the oxime ester-based compound. 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-phenylbenzoate Benzophenone compounds such as zophenone, 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, triazine compounds such as 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine Phosphine compounds such as oxide, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquino Quinone compounds such as borate compounds, carbazole compounds, imidazole compounds, titanocene compounds and the like. 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 mass in the solid content of the black resin composition, more preferably 0.2 to 0.5% by mass.

(Other additives for black antireflection layer)
The black resin composition for forming the black antireflection layer 6 of the color filter substrate of the present invention includes a surfactant for further improving the coating property, and a silane coupling for improving the adhesion to the substrate. An agent, a thiol compound, a polymerization inhibitor 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.

  The silane coupling agent may have a solid content ratio of 0.1 to 10% by mass, preferably 0.2 to 5% by mass, of the black resin composition. If the amount of the alkoxysilyl group, silanol group, silanol condensation group or the like is too large, a development residue of the black resin composition is generated on the glass surface during photo patterning. As the silane coupling agent, 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, mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrieth Isocyanate silanes such as Shishiran like.

  As the polymerization inhibitor, a hydroquinone polymerization inhibitor which is excellent in compatibility with the black resin composition and the alkali developer and has a slight influence on the exposure sensitivity level itself is preferably used. Specifically, hydroquinone, tert-butylhydroquinone, 2,5-bis (1,1-dimethylbutyl) hydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, etc. are used. . In addition, catechol-based polymerization inhibitors such as catechol and tert-butylcatechol can also be used. By adding a polymerization inhibitor, it is possible to significantly suppress the increase in line width due to diffracted light that becomes a barrier when forming a fine line by the proximity exposure method. In addition, since it is hardly affected by diffracted light, the curability of the pattern edge is excellent, and the line width change due to development variations can be reduced. It is preferable that the addition amount of a polymerization inhibitor is 0.01-0.5 mass% in solid content of the said black resin composition, More preferably, it is the range of 0.02-0.15 mass%. By combining the effects of the above-described photopolymerization initiator or thermal polymerization initiator with the effects of the polymerization inhibitor, it becomes possible to accurately form a pattern having a line width of 5 μm or less.

  When the polyfunctional thiol is used together with a photopolymerization initiator, it generates a thiyl radical that acts as a chain transfer agent and hardly undergoes polymerization inhibition by oxygen in the radical polymerization process after light irradiation. Therefore, when the polyfunctional thiol is further contained, the black resin composition becomes more sensitive. In particular, polyfunctional aliphatic thiols in which SH groups are bonded to aliphatic groups such as methylene and ethylene groups are preferred. Examples of the polyfunctional aliphatic thiol bonded to the aliphatic group include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycol. Rate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthio Propionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazi And 2- (N, N- dibutylamino) -4,6-dimercapto--s- triazine. Among these, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate and pentaerythritol tetrakisthiopropionate are preferable. These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types.

  The content of the polyfunctional thiol is determined so that the effect as a chain transfer agent is sufficiently exhibited and the developability and adhesion are not impaired. It is preferable that content of polyfunctional thiol is 0.5-5.0 mass% in solid content of the said black resin composition, More preferably, it is the range of 1.0-3.0 mass%.

  Other 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 monoethyl 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 , Triethylene 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 Examples include glycol monoethyl ether, dipropylene glycol monoethyl ether acetate, lactic acid ester, and ethyl ethoxypropionate.

(Method for forming black reflection suppression layer)
The black reflection suppression layer is formed as follows.
First, a coating film of the black resin composition is formed on a substrate 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, 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 high pressure mercury lamp, a xenon lamp, an arc lamp, or an LED-UV 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 on which a predetermined pattern is formed can be obtained by washing with water, drying and baking.

  The exposure is not necessarily required, and a black pattern can be selectively obtained on the metal wiring by omitting exposure and performing only the development.

  The thickness of the black antireflection layer to be formed is preferably 1.0 to 2.0 μm. When the film thickness is less than 1.0 μm, the anti-reflection property that is the original function is insufficient. When the film thickness is larger than 2.0 μm, the line width variation is deteriorated from the viewpoint of patterning property.

(Metal layer)
The metal forming the touch panel electrode 3 is copper or a copper alloy. In the case of a copper thin film or a copper alloy thin film, if the thickness of the touch panel electrode 3 is 100 nm or more, or 150 nm or more, the touch panel electrode 3 hardly transmits visible light. Therefore, the metal wiring according to the present embodiment can obtain a sufficient light shielding property when the thickness of the touch panel electrode 3 is, for example, about 100 to 300 nm.

  As the touch panel electrode 3, an alkali-resistant metal film can be applied. The case where alkali resistance is required is, for example, the case where there is a development step using an alkali developer in the subsequent step. Specifically, for example, a color filter or a black matrix is formed. Even when the terminal portion is formed on the metal wiring, alkali resistance is necessary. Chromium has alkali resistance and can be applied as the touch panel electrode 3. However, the resistance value is large, and chromium ions generated in the manufacturing process are harmful, so that it is difficult to apply to actual production. Copper or copper alloy is desirable as the touch panel electrode 3 from the viewpoint of a low resistance value. Copper or copper alloy is desirable as the touch panel electrode 3 because of its good conductivity.

  The touch panel electrode 3 can contain an alloy element having a triatomic composition percentage (hereinafter referred to as “at%”) or less as a copper alloy. As the alloy element, one or more elements can be selected from magnesium, calcium, titanium, molybdenum, indium, tin, zinc, aluminum, beryllium, and nickel. Copper alloying can suppress copper diffusion and improve heat resistance as a copper alloy. Addition of an alloy element of 3 at% or more increases the resistance value of the touch panel electrode 3. When the resistance value of the touch panel electrode 3 is increased, it is not preferable because the drive voltage waveform rounding and signal delay related to touch detection occur.

(Adhesive layer)
The role of the adhesive layer 4 containing indium is mainly to improve the adhesion with the color filter substrate. Copper, copper alloys, or their oxides and nitrides generally have poor adhesion to a transparent substrate such as glass or a black layer that is a dispersion of a black color material, and have a problem of peeling at the interface. In addition, steel, copper alloys, or their oxides and chambers usually have unstable electrical connections and lack reliability. For example, copper oxide or copper sulfide formed over time on a copper surface is close to an insulator and causes a problem in electrical mounting.

  The adhesion layer 4 containing indium can be selected from a conductive metal oxide containing indium or a copper indium alloy containing 0.5 at% to 40 at% of metal indium with respect to copper. By increasing the amount of indium in the copper indium alloy, the formation of copper oxide that is easily formed on the surface of the adhesive layer 4 can be suppressed, and electrical contact can be facilitated. In the case of a copper indium alloy, an alloy containing 40 at% or more of metal indium may be used. However, since indium is expensive, it is not preferable to contain a large amount of indium for economic reasons. Further, since it has a heat resistance of up to 500 ° C. with metallic indium being 40 at% or less, it can be used as a metal wiring of an array substrate. Indium has a larger atomic weight than copper, and is more likely to be combined with oxygen than copper, and the surface of the copper indium alloy is more likely to form indium oxide than copper oxide. The copper indium alloy can suppress copper diffusion, void formation, bridge formation, and the like, which are problems when copper is used alone.

  As the conductive metal oxide containing indium, a mixed oxide of indium oxide and tin oxide called ITO, or a mixed oxide of indium oxide and zinc oxide can be used. It is not necessary to limit to these metal oxides, and a mixed oxide in which a small amount of other metal oxides such as titanium oxide, zirconium oxide, hafnium oxide, cerium oxide and the like are further added may be used. “Indium-containing” means that in the case of a mixed oxide, 51 wt% to 99 wt% of indium oxide in the mixed oxide is considered in consideration of the electrical contact on the surface of the mixed oxide, that is, the electrical connection. it can.

  Since indium can be a metal and an oxide, it can greatly improve the tightness of the color filter base material such as acrylic resin, transparent substrates such as glass, or inorganic films such as silicon oxide and silicon nitride. It can be used as a base material for an adhesive layer at the interface between a metal film of copper or copper alloy and a black layer, or a transparent substrate or an inorganic insulating layer.

  The adhesive layer containing indium can be formed by a technique such as sputtering. In the case of forming an adhesive layer containing indium, oxygen gas can be introduced in addition to argon during sputtering.

[Electrode protective layer]
The electrode protective layer 7 used in the present invention is composed of a transparent resin composition containing at least (G) a photopolymerization initiator, (H) a polymerizable polyfunctional monomer, and (I) a silane coupling agent. Resins, solvents and additives can be included.

  Examples of the (G) photopolymerization initiator used in the electrode protective layer 7 of the present invention include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, and 1- (4-isopropylphenyl) -2-hydroxy. Acetophenone compounds such as -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4 Benzophenone compounds such as '-methyldiphenyl sulfide, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 -Diisopropylthioxanthone, thioxanthone compounds such as 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- (na To-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, 1,2-octanedione, 1- [4- ( Oxime ester systems such as phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine Compounds, phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 9,10-phenanthrenequinone, potassium Fakinon, quinone-based compounds such as ethyl anthraquinone, borate compounds, carbazole compounds, imidazole compounds, but titanocene compounds and the like, from the viewpoint of curability and transmittance, acetophenone compounds and phosphine compounds.

  The amount of the photopolymerization initiator used is preferably 0.5 to 50% by mass, more preferably 3 to 30% by mass, based on the total solid content of the colored composition.

  As the (H) polymerizable polyfunctional monomer used in the electrode protective layer 7 of the present invention, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (Meth) acrylate, β-carboxyethyl (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) ) Acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) ) Various acrylates and methacrylates such as acrylate, caprolactone-modified dipentaerythritol hexaacrylate, urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, etc. And the like. These can be used alone or in admixture of two or more.

  From the viewpoint of adjusting the acid value, it is preferable that at least one of the polymerizable polyfunctional monomers contains a carboxyl group. As the polymerizable polyfunctional monomer containing a carboxyl group, Aronix M-5300, M-5400, M-510, M-520 (above, manufactured by Toagosei Co., Ltd.), NK ester A-SA (produced by Shin-Nakamura Chemical Co., Ltd.) Etc.

  (I) Silane coupling agent is added to the electrode protective layer 7 of the present invention as an adhesion-imparting agent. Examples of silane coupling agents that can be used in the present invention include KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-502, KBM-503, KBE-502, KBE-503, KBM- 5103, KBM-802, KBM-803, KBE-9007 (manufactured by Shin-Etsu Silicone), Z-6011, Z-6020, Z-6030, Z-6040, Z-6043, Z-6094, Z-6519 ( As mentioned above, Toray Dow Corning Co., Ltd.) and the like can be mentioned. The silane coupling agent can be contained in an amount of 0.1 to 30% by mass or less based on the total amount of the transparent resin composition.

  The acid value of the transparent resin composition of the present invention is preferably 0.5 to 2.0 mgKOH / g. If the acid value is lower than 0.5 mgKOH / g, sufficient adhesion to a transparent substrate having a polar hydroxyl group cannot be obtained sufficiently, and if the acid value is higher than 2.0 mgKOH / g, the stability of the transparent resin composition Or corrosion of the electrode. The acid value is measured by a titration method using a burette and an indicator.

[Display Device of Third Embodiment]
FIG. 4 is a schematic cross-sectional view of a display device according to the third embodiment of the present invention, using the color filter substrate of the first embodiment of the present invention. This embodiment is an embodiment in the case of a so-called horizontal electric field type liquid crystal display device.

  In FIG. 4, an active element (TFT, not shown) is disposed on the array substrate 10, and the active element is a metal wiring (hereinafter referred to as a second touch panel) that runs in parallel with a gate wiring (not shown). Called an electrode 17). The gate wiring and the second touch panel electrode 17 are formed of the same metal material and configuration in the same process, but are electrically independent. The display driving metal wiring is composed of a gate wiring and a source wiring.

  The liquid crystal of the liquid crystal layer 30 is aligned horizontally on the surface of the array substrate 10. The liquid crystal is driven by a fringe electric field generated between the pixel electrode 15 and the common electrode 16. This liquid crystal driving method is called FFS (Fringe Field Switching) or IPS (In Plane Switching), that is, a horizontal electric field method. The common electrode 16 is formed of a transparent conductive film such as ITO. A transparent substrate 14 which is a glass substrate having the same thermal expansion coefficient as that of the color filter substrate is usually applied to the array substrate 10.

  Capacitance for touch sensing is formed between the touch panel electrode 3 and the second touch panel electrode 17. In the configuration in FIG. 4, the liquid crystal driving of the common electrode 16 and the driving of the second touch panel electrode 17 in touch sensing may be performed in a time division manner, or the driving of the second touch panel electrode 17 is a liquid crystal driving. You may drive with a different frequency. The second touch panel electrode 17 can be used as a drive electrode (scanning electrode) or a detection electrode. The pixel electrode 15 and the common electrode 16 are formed on any one of the insulating layers 11, 12, and 13.

[Display Device of Fourth Embodiment]
FIG. 5 is a schematic cross-sectional view of a display device according to a fourth embodiment of the present invention, using the color filter substrate of the second embodiment of the present invention. This embodiment is an embodiment in the case of a so-called vertical electric field type liquid crystal display device.

  The liquid crystal display device of FIG. 5 has a configuration in which an array substrate 20 including a color filter substrate 200 and an active element (TFT, not shown) is bonded via a liquid crystal layer 40. The transparent electrode 9 disposed on the color filter substrate 200 serves both as a second touch panel electrode and a liquid crystal common electrode (liquid crystal drive electrode).

  In the liquid crystal display device of this embodiment, the liquid crystal layer 40 is driven by applying a liquid crystal driving voltage between the transparent electrode 9 as a common electrode and the pixel electrode 25 provided on the array substrate 20. To do. Since a voltage is applied in the thickness direction (vertical direction = Z direction) of the liquid crystal layer 40 and the transparent substrate 24, this is a liquid crystal driving method called a vertical electric field method.

  In FIG. 5, the touch panel electrodes 3 are arranged in a stripe pattern shape in the Y direction perpendicular to the paper surface. The transparent electrode 9 disposed on the transparent resin layer 8 is similarly provided in a stripe pattern shape in the X direction, and the touch panel electrode 3 and the transparent electrode 9 are orthogonal to each other via the transparent resin layer 8 which is a dielectric. .

  In the present embodiment, the transparent electrode 9 is a common electrode, for example, serves as a detection electrode of the second touch panel electrode, and the touch panel electrode 3 can be used as a drive electrode in touch sensing. An approximately constant capacitance is formed between the touch panel electrode 3 and the transparent electrode 9, but the capacitance at that portion changes due to the contact or proximity of a pointer such as a finger, and the touch position is detected.

  If the touch panel electrode 3 is a drive electrode for touch sensing and the transparent electrode 9 is a detection electrode, the touch sensing drive condition and the liquid crystal drive condition (frequency, voltage, etc.) can be made different. By making the drive frequency of touch sensing different from the drive frequency of liquid crystal, it can be made less susceptible to the influence of the drive. For example, the driving frequency of touch sensing can be several kHz to several tens of kHz, and the liquid crystal driving frequency can be 60 Hz to 240 Hz. Furthermore, the touch sensing drive and the liquid crystal drive can be time-shared. When the touch panel electrode 3 is used as a drive electrode, the scanning frequency of capacitance detection can be arbitrarily adjusted according to the required input speed of touch.

  Or it is good also as a drive electrode which replaces the drive electrode and detection electrode in touch sensing, and applies the voltage with a fixed frequency for the transparent electrode 9. Note that the voltage (AC signal) applied to the drive electrode in touch sensing or liquid crystal drive may be an inversion drive system that inverts positive and negative voltages. Touch sensing and liquid crystal driving may be time-division or may not be time-division.

(Other elements of the display device)
In the display device according to the third and fourth embodiments of FIGS. 4 and 5, optical films 18, 19 serving as polarizing plates and retardation plates are formed on the upper surface of the electrode protective layer 7 and the rear surfaces of the transparent substrates 14, 24. 28, 29 can be provided. In some cases, a separate adhesive layer can be provided between these layers.

  Moreover, although not shown in figure, the cover glass used as the member which is a transparent front board and is touched by the user is provided in the outermost surface by the side of the visual recognition of the display apparatus of FIG. 4, FIG. The cover glass surface can be provided with a scattering prevention film made of a decorative layer or a resin material. The decoration layer is formed of one or more layers, and imparts design to the display device and plays a role of hiding wiring provided on the peripheral edge of the touch panel. Preferably, it is formed on one surface of the cover glass using a light-shielding film containing a pigment and absorbing visible light. The method for forming the decorative layer can be selected from photolithography, screen printing, and the like.

[Transparent substrate]
The color filter substrate of the present invention and the transparent substrate used in a display device using the same preferably have a certain transmittance with respect to visible light, and more preferably have a transmittance of 80% or more. Can do. Generally, it may be one used in a liquid crystal display device, and examples thereof include a plastic substrate such as PET and glass, but a glass substrate is usually used. When using a black matrix, it is sufficient to use a metal thin film such as chromium or a light-shielding resin pattern on the transparent substrate in advance by a known method. A pattern made of a conductive resin is preferably used.

[Colored pixels (color filter)]
Hereinafter, the colored pixels constituting the color filter substrate of the present invention will be described.

(Method for forming colored pixels)
As a method for producing the colored pixels on the transparent substrate, any method such as a known ink jet method, printing method, photolithography method, etching method or the like may be used. However, considering high definition, controllability and reproducibility of spectral characteristics, etc., a colored composition in which a pigment is dispersed in a transparent resin together with a photoinitiator and a polymerizable monomer in a suitable solvent is formed on a transparent substrate. A photolithographic method is preferred in which a colored layer is formed by coating and forming, and a step of forming a pixel of one color by pattern exposure and development of the colored layer is repeated for each color.

  By repeating the above-described series of steps by changing the color composition and pattern as many times as necessary, it is possible to obtain a colored pattern in which a necessary number of colors are combined, that is, a pixel of a plurality of colors. In addition to the combination of red, green, blue (RGB), yellow, magenta, and cyan (YMC), and mixed systems of the pixels of a plurality of colors, transparent pixels for luminance adjustment can be applied.

  The colored pixels constituting the pixels included in the color filter substrate of the present invention follow, for example, the following method when a colored composition is prepared and formed by photolithography. A pigment serving as a colorant is dispersed in a suitable solvent together with a photoinitiator and a polymerizable monomer in a transparent resin. There are various methods such as mill base, three rolls, jet mill and the like, and there are no particular limitations.

(Coloring composition forming colored pixels)
Specific examples of organic pigments that can be used in the colored composition forming the colored pixels of the color filter substrate of the present invention are indicated by color index numbers.

  Examples of red coloring compositions for forming red pixels include C.I. I. PigmentRed 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, 242, 246, 254, 255 Red pigments such as H.264, 269, 272, and 279 can be used. A yellow pigment and an orange pigment can be used in combination with the red coloring composition.

  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, 17 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.

  Green coloring compositions for forming green pixels include C.I. I. Green pigments such as Pigment Green 7, 36, and 58 can be used. The green coloring composition can be used in combination with the same yellow pigment as the red coloring composition.

  The blue coloring composition for forming a blue pixel includes C.I. I. Pigment Blue 15: 3, 15: 4 blue pigment, C.I. I. In addition to the purple pigment of Pigment Violet 23, other pigments can be used in combination as appropriate.

  In addition, in combination with the above organic pigments, in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness, inorganic pigments should be used in combination as long as the liquid crystal resistance is not lowered. Is also possible. Inorganic pigments include yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green and other metal oxide powders, metal sulfide powders, metal powders, etc. Can be mentioned. Furthermore, for color matching, a dye can be contained within a range that does not deteriorate liquid crystal resistance and heat resistance.

  The transparent resin used for the coloring composition is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin. In the transparent resin, if necessary, a monomer or oligomer that is a precursor thereof and is cured by irradiation with radiation to form a transparent resin can be used alone or in combination of two or more.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. In addition, linear polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer can be obtained from (meth) acrylic compounds having hydroxyl groups such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  A polymerizable monomer or oligomer is used as the photocrosslinking agent. Polymerizable monomers and oligomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meta ) Acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, penta Erythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neope N-glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, Various acrylic esters and methacrylic esters such as caprolactone-modified dipentaerythritol hexaacrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. These can be used alone or in admixture of two or more.

  The addition amount is preferably as long as it does not impair applicability and development suitability, and is about 20 to 80% by mass, more preferably about 50 to 70% by mass, based on the total solid content of the colored composition. is there. If the addition amount is less than this range, the cross-linkability is insufficient and the liquid crystal resistance is deteriorated. If the addition amount is more than this range, unevenness and pinholes are likely to occur when the colored composition is applied, and the applicability is remarkably deteriorated. The liquid solubility is remarkably lowered and the development suitability is poor.

  When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the coloring composition.

  As photopolymerization initiators, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone compounds such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl Benzoin compounds such as dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3 Benzophenone compounds such as 3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4- Thioxanthone compounds such as 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 (trichloro) Methyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, Triazine compounds such as 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], Oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, bis (2,4,6-trimethylbenzoyl) phenyl Phosphine compounds such as phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquino Quinone compounds such as borate compounds, carbazole compounds, imidazole compounds, titanocene compounds and the like. These photopolymerization initiators can be used alone or in combination.

  The amount of the photopolymerization initiator used is preferably 0.5 to 50% by mass, more preferably 3 to 30% by mass, based on the total solid content of the colored composition.

  Further, as sensitizers, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-Ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethyl) Amine-based compounds such as amino) benzophenone can also be used in combination. These sensitizers can be used alone or in combination.

  The amount of the sensitizer used is preferably 0.5 to 60% by mass, more preferably 3 to 40% by mass based on the total amount of the photopolymerization initiator and the sensitizer.

  Furthermore, the coloring composition can contain a polyfunctional thiol that functions as a chain transfer agent.

  The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, tris (2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-to Azine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine. These polyfunctional thiols can be used alone or in combination.

  The amount of the polyfunctional thiol used is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on the total solid content of the colored composition. If it is less than 0.1% by mass, the effect of adding a polyfunctional thiol is insufficient, and if it exceeds 30% by mass, the sensitivity is too high and the resolution is lowered.

  Moreover, a thermal crosslinking agent can also be added as needed. Examples of the thermal crosslinking agent include melamine resin and epoxy resin.

  Examples of the melamine resin include alkylated melamine resins (methylated melamine resin, butylated melamine resin, etc.), mixed etherified melamine resins, and the like, which may be a high condensation type or a low condensation type. Any of these may be used alone or in admixture of two or more. Moreover, an epoxy resin can also be mixed and used as needed.

  Examples of the epoxy resin include glycerol / polyglycidyl ether, trimethylolpropane / polyglycidyl ether, resorcin / diglycidyl ether, neopentyl glycol / diglycidyl ether, 1,6-hexanediol / diglycidyl ether, ethylene glycol (polyethylene). Glycol) and diglycidyl ether. Also about these, it can use individually or in mixture of 2 or more types.

  The coloring composition can contain an organic solvent as necessary. Examples of the organic solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination.

  Hereinafter, the present invention will be specifically described with reference to preparation of an evaluation sample in which the touch panel electrode 3 and the electrode protective layer 7 are formed on the transparent substrate 1 in the form shown in FIG. 2 and evaluation results. The invention is not limited by these examples. “%” Means “% by mass”.

[Deposition and patterning of adhesive layer 4 and metal layer 5]
An adhesive layer 4 containing indium and a metal layer 5 were successively formed on a glass substrate as a transparent substrate 1 (“EAGLE XG” manufactured by Corning) with a sputtering apparatus. The adhesive layer 4 containing indium was formed with a thickness of 20 nm using a transparent conductive film made of ITO. The metal layer 5 was formed of copper with a film thickness of 300 nm. Thereafter, a resist pattern was formed by a known photolithography method, and the adhesion layer 4 and the metal layer 5 made of ITO were patterned by wet etching using a mixed acid of phosphoric acid and ferric chloride. After etching, the resist pattern was stripped with an alkaline aqueous solution.

[Preparation of Black Resin Composition to be the Black Antireflection Layer 6]
The following composition mixture was stirred well to obtain a black resin composition No. 1-No. 10 was obtained.

(Preparation of black resin composition No. 1)
12.2 g of bisphenolfluorene type epoxy resin (solid content 50.0%), 1.5 g of dipentaerythritol penta / hexaacrylate mixture (“KAYARDADDHA” manufactured by Nippon Kayaku Co., Ltd.), carbon black dispersion (solid content 22. 7%) 14.8 g, photo radical polymerization initiator (“NCI-831” manufactured by ADEKA) 0.4 g, thermal radical polymerization initiator (“VA-061” manufactured by Wako Pure Chemical Industries, Ltd.) 0.4 g, C.I. I. 2.7 g of Pigment Yellow 139 dispersion (solid content 22.7%), 2.7 g of silica fine particle dispersion (solid content 22.7%), 1% propylene glycol monomethyl of a surface conditioner ("BYK-323" manufactured by BYK Chemie) Add 0.7 g of acetate solution, 0.7 g of 10% propylene glycol monomethyl ether acetate solution of silane coupling agent (Shin-Etsu Chemical "KBE-9007") and 65.3 g of propylene glycol monomethyl ether acetate, and stir well. Black resin composition Item No. 1 was obtained.

(Preparation of black resin composition No. 2)
12.2 g of bisphenolfluorene type epoxy resin (solid content 50.0%), 1.5 g of dipentaerythritol penta / hexaacrylate mixture (“KAYARDADDHA” manufactured by Nippon Kayaku Co., Ltd.), carbon black dispersion (solid content 22. 7%) 14.8 g, photo radical polymerization initiator (“NCI-831” manufactured by ADEKA) 0.4 g, thermal radical polymerization initiator (“VA-061” manufactured by Wako Pure Chemical Industries, Ltd.) 0.4 g, C.I. I. 2.7 g of Solvent Yellow 83 solution (solid content 22.7%), 2.7 g of silica fine particle dispersion (solid content 22.7%), 1% propylene glycol monomethyl acetate of surface conditioner ("BYK-323" manufactured by BYK Chemie) Add 0.7 g of solution, 0.7 g of 10% propylene glycol monomethyl ether acetate solution of silane coupling agent (Shin-Etsu Chemical "KBE-9007") and 65.3 g of propylene glycol monomethyl ether acetate, and stir well. Black resin composition No. 2 was obtained.

(Preparation of black resin composition No. 3)
13.4 g of bisphenolfluorene type epoxy resin (solid content 50.0%), 1.7 g of dipentaerythritol penta / hexaacrylate mixture (“KAYARDADDHA” manufactured by Nippon Kayaku Co., Ltd.), titanium nitride dispersion (solid content 22. 7%) 12.2 g, 0.4 g of photo radical polymerization initiator (“NCI-831” manufactured by ADEKA), 0.4 g of thermal radical polymerization initiator (“VA-061” manufactured by Wako Pure Chemical Industries, Ltd.), C.I. I. 2.8 g of Pigment Red 177 dispersion (solid content 22.7%), 2.7 g of silica fine particle dispersion (solid content 22.7%), 1% propylene glycol monomethyl of surface conditioner ("BYK-323" manufactured by BYK Chemie) Add 0.7 g of acetate solution, 0.7 g of 10% propylene glycol monomethyl ether acetate solution of silane coupling agent (Shin-Etsu Chemical "KBE-9007") and 66.4 g of propylene glycol monomethyl ether acetate, and stir well. Black resin composition Item No. 3 was obtained.

(Preparation of black resin composition No. 4)
13.4 g of bisphenolfluorene type epoxy resin (solid content 50.0%), 1.7 g of dipentaerythritol penta / hexaacrylate mixture (“KAYARDADDHA” manufactured by Nippon Kayaku Co., Ltd.), titanium nitride dispersion (solid content 22. 7%) 12.2 g, 0.4 g of photo radical polymerization initiator (“NCI-831” manufactured by ADEKA), 0.4 g of thermal radical polymerization initiator (“VA-061” manufactured by Wako Pure Chemical Industries, Ltd.), C.I. I. 2.8 g of Solvent Red 124 solution (solid content 22.7%), 2.7 g of silica fine particle dispersion (solid content 22.7%), 1% propylene glycol monomethyl acetate of surface conditioner ("BYK-323" manufactured by BYK Chemie) Add 0.7 g of solution, 0.7 g of 10% propylene glycol monomethyl ether acetate solution of silane coupling agent (Shin-Etsu Chemical "KBE-9007") and 66.4 g of propylene glycol monomethyl ether acetate, and stir well. Black resin composition No. 4 was obtained.

(Preparation of black resin composition No. 5)
12.7 g of bisphenolfluorene type epoxy resin (solid content 50.0%), 1.6 g of dipentaerythritol penta / hexaacrylate mixture (“KAYARDADDHA” manufactured by Nippon Kayaku Co., Ltd.), C.I. I. Solvent Black 7 solution (solid content 22.7%) 11.0 g, radical photopolymerization initiator (ADEKA, “NCI-831”) 0.4 g, thermal radical polymerization initiator (Wako Pure Chemical Industries, Ltd. “VA-061”) ) 0.4 g, C.I. I. Pigment Yellow 139 dispersion (solid content 22.7%) 2.8 g, C.I. I. 2.7 g of Pigment Red 177 dispersion (solid content 22.7%), 2.7 g of silica fine particle dispersion (solid content 22.7%), 1% propylene glycol monomethyl of surface conditioner ("BYK-323" manufactured by BYK Chemie) Add 0.7 g of acetate solution, 0.7 g of 10% propylene glycol monomethyl ether acetate solution of silane coupling agent (Shin-Etsu Chemical "KBE-9007") and 65.7 g of propylene glycol monomethyl ether acetate, and stir well. Black resin composition Item No. 5 was obtained.

(Preparation of black resin composition No. 6)
12.2 g of bisphenolfluorene type epoxy resin (solid content 50.0%), 1.5 g of dipentaerythritol penta / hexaacrylate mixture (“KAYARDADDHA” manufactured by Nippon Kayaku Co., Ltd.), carbon black dispersion (solid content 22. 7%) 14.8 g, photo radical polymerization initiator (“NCI-831” manufactured by ADEKA) 0.4 g, thermal radical polymerization initiator (“VA-061” manufactured by Wako Pure Chemical Industries, Ltd.) 0.4 g, C.I. I. 2.7 g of Pigment Yellow 139 dispersion (solid content 22.7%), 2.7 g of magnesium fluoride fine particle dispersion (solid content 22.7%), 1% propylene of a surface conditioner ("BYK-323" manufactured by BYK Chemie) Add 0.7 g of glycol monomethyl acetate solution, 0.7 g of 10% propylene glycol monomethyl ether acetate solution of silane coupling agent (Shin-Etsu Chemical "KBE-9007") and 65.3 g of propylene glycol monomethyl ether acetate and stir well. Resin composition No. 6 was obtained.

(Preparation of black resin composition No. 7)
12.2 g of bisphenolfluorene type epoxy resin (solid content 50.0%), 1.5 g of dipentaerythritol penta / hexaacrylate mixture (“KAYARDADDHA” manufactured by Nippon Kayaku Co., Ltd.), carbon black dispersion (solid content 22. 7%) 14.8 g, photo radical polymerization initiator (“NCI-831” manufactured by ADEKA) 0.4 g, thermal radical polymerization initiator (“VA-061” manufactured by Wako Pure Chemical Industries, Ltd.) 0.4 g, C.I. I. 2.7 g of Pigment Yellow 139 dispersion (solid content 22.7%), 2.7 g of cryolite (sodium hexafluoroaluminate) fine particle dispersion (solid content 22.7%), surface conditioner ("BYK-" manufactured by Big Chemie) 323 ”) 1% propylene glycol monomethyl acetate solution 0.7 g, silane coupling agent (Shin-Etsu Chemical“ KBE-9007 ”) 10% propylene glycol monomethyl ether acetate solution 0.7 g and propylene glycol monomethyl ether acetate 65.3 g In addition, the mixture was well stirred and the black resin composition No. 7 was obtained.

(Preparation of black resin composition No. 8)
15.6 g of bisphenolfluorene type epoxy resin (solid content 50.0%), 2.0 g of dipentaerythritol penta / hexaacrylate mixture (“KAYARDADDHA” manufactured by Nippon Kayaku Co., Ltd.), carbon black dispersion (solid content 22. 7%) 13.1 g, photo radical polymerization initiator (“NCI-831” manufactured by ADEKA) 0.4 g, thermal radical polymerization initiator (“VA-061” manufactured by Wako Pure Chemical Industries, Ltd.) 0.4 g, surface conditioning 0.7 g of 1% propylene glycol monomethyl acetate solution of the agent (BYK-323 manufactured by Big Chemie), 0.7 g of 10% propylene glycol monomethyl ether acetate solution of the silane coupling agent (Shin-Etsu Chemical "KBE-9007") and propylene Add 68.5 g of glycol monomethyl ether acetate Ku stirred, black resin composition No. 8 was obtained.

(Preparation of black resin composition No. 9)
14.6 g of bisphenolfluorene type epoxy resin (solid content 50.0%), 1.8 g of dipentaerythritol penta / hexaacrylate mixture (“KAYARDADDHA” manufactured by Nippon Kayaku Co., Ltd.), carbon black dispersion (solid content 22. 7%) 15.2 g, radical photopolymerization initiator (ADEKA “NCI-831”) 0.4 g, thermal radical polymerization initiator (Wako Pure Chemical Industries “VA-061”) 0.4 g, surface conditioning 0.7 g of 1% propylene glycol monomethyl acetate solution of the agent (BYK-323 manufactured by Big Chemie), 0.7 g of 10% propylene glycol monomethyl ether acetate solution of the silane coupling agent (Shin-Etsu Chemical "KBE-9007") and propylene Add 67.6 g of glycol monomethyl ether acetate Ku stirred, black resin composition No. 9 was obtained.

(Preparation of black resin composition No. 10)
15.9 g of bisphenolfluorene type epoxy resin (solid content 50.0%), 2.0 g of dipentaerythritol penta / hexaacrylate mixture (“KAYARDADDHA” manufactured by Nippon Kayaku Co., Ltd.), titanium nitride dispersion (solid content 22. 7%) 12.6 g, radical photopolymerization initiator (“NCI-831” manufactured by ADEKA) 0.4 g, thermal radical polymerization initiator (“VA-061” manufactured by Wako Pure Chemical Industries, Ltd.) 0.4 g, surface conditioning 0.7 g of 1% propylene glycol monomethyl acetate solution of the agent (BYK-323 manufactured by Big Chemie), 0.7 g of 10% propylene glycol monomethyl ether acetate solution of the silane coupling agent (Shin-Etsu Chemical "KBE-9007") and propylene Add 68.7 g of glycol monomethyl ether acetate and stir well. And, black resin composition No. 10 was obtained.

(Separation for Examples and Comparative Examples)
As described above, the black resin composition No. 1 to 7 contain a reflectance adjusting agent and a reflection color adjusting agent, so that they are for samples of Examples 1 to 7, respectively. Since 8-10 did not contain a reflectance adjusting agent and a reflective color adjusting agent, they were used for samples of Comparative Examples 1-4, respectively.

[Formation of black reflection suppression layer 6]
On the pattern of the adhesive layer 4 and the metal layer 5 on the glass substrate, the black resin composition no. Each of 1 to 10 coating films was formed. After drying, it was pre-baked for 1 minute on a 115 ° C. hot plate. Next, the coating film of the black resin composition was irradiated with ultraviolet light using a super high pressure mercury lamp (illuminance 26 mW / cm ² ) through a photomask having an opening width of 6 μm. After the exposure, development was performed with a 2.5% by mass aqueous sodium carbonate solution, a black antireflection layer 6 having a thickness of 1.5 μm was formed so as to cover the pattern of the adhesive layer 4 and the metal layer 5, and the touch panel electrode 3 was formed.

[Preparation of transparent resin composition to be electrode protective layer 7]
A transparent resin composition was obtained by stirring a mixture having the following composition with a dissolver at 40 ° C. for 3 hours and then filtering with a filter.
Irgacure 184 (BASF photopolymerization initiator) 10%
U-6HA (Shin-Nakamura Chemical Co., Ltd. polymerizable polyfunctional monomer) 50%
Aronix M-305 (Toagosei Co., Ltd. polymerizable polyfunctional monomer) 15%
Aronix M-402 (Polymerizable polyfunctional monomer manufactured by Toagosei Co., Ltd.) 5%
US-TD-12P (polymerizable polyfunctional monomer manufactured by Osaka Organic Chemical Co., Ltd.) 5%
KBM-503 (Shin-Etsu Chemical Silane Coupling Agent) 10%
BYK-350 (Surface conditioner manufactured by Big Chemie Japan) 3%
BYK-410 (Modified urea thickener manufactured by Big Chemie Japan) 2%

[Formation of Electrode Protection Layer 7]
The transparent resin composition was applied on the touch panel electrode 3 on which the black antireflection layer was formed, using a screen printing plate (mesh 500, emulsion thickness 10 μm, ridge thickness 20 μm). Next, pre-baking was performed in an oven at 90 ° C. for 2 minutes to remove the solvent, and exposure was performed at 0.5 J / cm ² with a high-pressure mercury lamp (Conveyor UV irradiation device manufactured by Eye Graphics Co., Ltd.). Baking was performed at 120 ° C. for 30 minutes in an oven, and an electrode protective layer 7 having a thickness of 4 μm was formed on the touch panel electrode 3 and the glass substrate in the samples of Examples 1 to 7 and Comparative Examples 1 to 3. In Comparative Example 4, the electrode protective layer 7 was not formed.

<Evaluation method>
[OD value of black reflection suppression layer]
A black reflection suppression layer is formed on a glass substrate so as to have a film thickness of 1 μm, and using a microspectrophotometer (“LCF-1100” manufactured by Otsuka Electronics Co., Ltd.), transmittance is measured over a wavelength range of 400 to 700 nm The luminous transmittance (T) was obtained from the obtained spectral transmittance curve according to JIS R3106, and the OD value was obtained by the following formula.
OD = -Log ₁₀ T

[Reflectance]
The reflectance of Examples 1 to 7 and Comparative Examples 1 to 4 in the form shown in Fig. 2 was measured over a wavelength range of 400 to 700 nm using a microspectrophotometer ("LCF-1100" manufactured by Otsuka Electronics Co., Ltd.). This was carried out with a D65 light source using aluminum as a reference, and the luminous reflectance was determined from the obtained spectral reflectance curve according to JIS R3106.

[A ^* , b ^* ]
The CIELab color space display system is based on the XYZ color system and recommended by the CIE (International Commission on Illumination) in 1976. L ^* indicates brightness, and the higher the value from 0 to 100, the brighter the value. Become. Chromaticity ^a *, expressed in ^{b *,} a *, the achromatic color in the case of ^{b *} are both 0. Therefore, in order that the touch panel electrode is not visually recognized, it is better that L ^* , a ^* , and b ^* are closer to 0. For Examples 1 to 7 and Comparative Examples 1 to 4, a ^* and b ^* were measured from the spectral reflectance curves obtained by the reflectance measurement according to JIS 8781-4.

[Pencil hardness]
Scratch hardness (pencil method) was carried out according to “JIS K 5600 Paint General Test Method”, and the pencil hardness on the glass substrate on which the wiring pattern and each film were formed was measured.

<Evaluation results>
Table 1 summarizes sample conditions and evaluation results of Examples 1 to 7 and Comparative Examples 1 to 4. In addition, when the measured / calculated value is not within the following range, x is entered in Table 1.
OD ≧ 3.0 (/ μm)
Luminous reflectance ≦ 5.0%
-0.5 <a ^* <+ 0.5
−0.5 <b ^* <+ 0.5

From the results shown in Table 1, a black antireflection layer having an OD of 3.0 (/ μm) or more containing a black pigment or black dye suitable for a touch panel electrode, a reflectance adjusting agent, and a reflecting color adjusting agent is formed, and 4H or more. By laminating an electrode protective layer having a pencil hardness of 5.0, the luminous reflectance becomes 5.0% or less, and the a ^* and b ^* values in the CIELab color space display system are −0.5 <a ^* <+ 0.5. In addition, since −0.5 <b ^* <+ 0.5, the touch panel electrode is hardly visible, and the display device is not colored reddish / yellowish. It can be formed with a high yield.

  The color filter substrate according to the present invention can be used for a display device with a touch panel function for various electronic devices such as a mobile phone and a portable information terminal.

1, 14, 24... Transparent substrate 2... Color filter 3... (First) touch panel electrode 4... Adhesive layer 5. .... Black reflection suppression layer 7 ... Electrode protective layer 8 ... Transparent resin layer 9 ... Transparent electrodes 10, 20 ... ... Array substrates 11, 12, 13, 21 , 22, 23... Insulating layers 15 and 25... Pixel electrode 16... Common electrode 17 ... Second touch panel electrodes 18, 19, 28 and 29. , Retardation plate)
30, 40... Liquid crystal layer 50... Viewing side 100, 200... Color filter substrate 500, 600.

Claims (6)

A color filter substrate having a color filter on a first surface of a transparent substrate and a touch panel electrode on a second surface,
The touch panel electrode includes an adhesive layer, a metal layer, a black reflection suppression layer, and an electrode protective layer in this order on the transparent substrate.
The adhesive layer, the metal layer, and the black antireflection layer are patterned,
The optical density (OD) of the black antireflection layer is 3.0 (/ μm) or more per unit film thickness, and the black antireflection layer comprises a black pigment or black dye, a reflectance adjusting agent, and a reflecting color adjusting agent. Contains at least,
The reflectance adjusting agent is at least one selected from silica fine particles, magnesium fluoride fine particles, cryolite (sodium hexafluoroaluminate) fine particles,
The reflection color adjusting agent is at least one selected from a yellow pigment, a red pigment, a yellow dye, and a red dye,
The electrode protective layer contains a polymerizable polyfunctional monomer, a binder resin, a thermal polymerization initiator and / or a photopolymerization initiator, and comprises a transparent resin composition having a pencil hardness of 4H or more,
The luminous reflectance in the XYZ color system viewed from the electrode protective layer side of the touch panel electrode is 5.0% or less, and the a ^* and b ^* values in the CIELab color space display system are −0.5 <a ^*. <+0.5 and −0.5 <b ^* <+ 0.5.   The color filter substrate according to claim 1, wherein the adhesive layer contains indium, and the metal layer is a copper layer, a copper alloy layer, or both.   The color filter substrate according to claim 1, wherein the black pigment is at least one selected from carbon black and titanium nitride.   The color filter substrate according to claim 1, wherein the black dye is aniline black.   The reflection color adjusting agent is a yellow pigment C.I. I. Pigment Yellow 139, yellow dye C.I. I. Solvent Yellow 83, red pigment C.I. I. Pigment Red 177, red dye C.I. I. The color filter substrate according to any one of claims 1 to 4, wherein the color filter substrate is at least one selected from SolventRed124.   A display device comprising the color filter substrate according to claim 1.