JP2013061527A - Color filter substrate, and liquid crystal display device provided with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter substrate with which prime cost of liquid crystal display device can be decreased by reducing a used amount of liquid crystal to be used in the liquid crystal display device, and a liquid crystal display device provided with the same.SOLUTION: The color filter substrate for the liquid crystal display device includes at least a black matrix layer and coloring pixels of respective colors comprising a plurality of coloring compositions of respective colors. In a non-display area of the liquid crystal display screen, there are provided projections having the height of 1 μm or more and lower than the liquid crystal layer thickness by 0.2 μm or less, and in which total area of top faces in a plan view is 50% or more and 90% or less of the non-display area.

Description

  The present invention relates to a color filter substrate for a liquid crystal display device and a liquid crystal display device including the same, and in particular, a color filter substrate capable of reducing the amount of liquid crystal used and contributing to resource saving and cost reduction. About.

  Liquid crystal display devices are rapidly spreading mainly in computer terminal display devices, television image display devices, mobile phones, portable information devices and the like. Among them, in particular, the spread to television image display devices is rapid, and the enlargement of the screen is remarkable. As the screen becomes larger, the amount of liquid crystal used in the liquid crystal display device has also increased.

  In an active matrix liquid crystal display device, in general, a TFT substrate in which a thin film transistor (TFT) element is formed for each pixel on a glass substrate, a color filter substrate in which a color filter and a uniform transparent electrode are formed on the glass substrate, However, they are arranged opposite to each other with a liquid crystal in between. The shutter action of the liquid crystal of each pixel is controlled by the switching action of each TFT element on the TFT substrate.

  Recently, in line with higher image quality such as larger size, higher definition, wide viewing angle and higher contrast of liquid crystal display devices, VA (vertical alignment) type liquid crystal display devices called liquid crystal alignment and liquid crystal alignment There are MVA (Multi-domain Vertical Alignment) type liquid crystal display devices having alignment control protrusions for controlling the IPS, and IPS (In Plane Switching) type liquid crystal display devices in which an electric field for driving liquid crystals is applied in the horizontal direction of the pixels. It has been adopted.

  In a liquid crystal display device using TFT, a TFT substrate and a color filter substrate are arranged to face each other with a predetermined interval, and these substrates are bonded together by a sealing agent in which reinforcing fibers are mixed with epoxy resin or the like. Composed. Liquid crystal is sealed between the color filter substrate and the TFT substrate, but if the distance between the color filter substrate and the TFT substrate is not accurately maintained, the thickness of the liquid crystal layer will differ, resulting in a difference in the optical rotation characteristics of the liquid crystal. This causes a phenomenon in which coloring is caused by or a partial color unevenness occurs and the image is not displayed correctly. For this reason, conventionally, a large number of particles or rods made of resin, glass, alumina or the like having a diameter of 2 μm to 10 μm, called spacers, are mixed in the liquid crystal to maintain the cell gap (holding interval) of the liquid crystal.

Since the spacer is a transparent particle, if the spacer is included in the pixel together with the liquid crystal, light leaks through the spacer during black display. Further, in a normal liquid crystal display device, a large amount of particles of about 100 particles / mm ² are mixed in the liquid crystal as a spacer, so that the liquid crystal is mixed with a highly viscous liquid crystal and within the interval between the color filter substrate and the TFT substrate. In the case of injection into the spacer, the spacer may not be uniformly dispersed, and the spacer may be partially biased. When such a phenomenon occurs, the alignment of the liquid crystal molecules in the vicinity of the part where the spacers gather is disturbed, and light leakage occurs in this part, resulting in a problem that the contrast is lowered and the display quality is adversely affected. There was also a problem in terms of accurately maintaining the cell gap.

Therefore, as a technique for solving such a problem, for example, a photosensitive resin is used, and a protrusion having a spacer function is formed at a position of a light shielding layer between pixels by a photofabrication method of partial pattern exposure to development. A method has been proposed. Patent Document 1 discloses a technique in which spacer columns are formed on at least one of the opposing substrates at a position corresponding to the intersection of the gate wiring and drain wiring in a region not facing the switching element. Document 2 discloses a technique for defining the cell gap by the sum of the stacked structure on the array substrate and the height of the pillars on the counter substrate, both of which are liquid crystal displays that keep the cell gap constant without using spacers. The device is tightened.

  By the way, when the columnar spacers are formed at a certain density in the plane, if the cross-sectional area of the columnar spacers is small, the gap between the substrates is difficult to be uniform in the panel assembly process, and color unevenness occurs in the liquid crystal display device. It becomes easy to do. That is, the cross-sectional area of the columnar spacer is greater than a certain size. Further, when an excessive load is locally applied, color unevenness or the like is likely to occur in the liquid crystal display device. On the other hand, when the cross-sectional area of the columnar spacer is large, the gap between the substrates becomes uniform in the panel assembling process, but vacuum bubbles are easily generated in the liquid crystal cell.

  As a method for solving this problem, for example, Patent Document 3 discloses a first columnar spacer that holds a gap between substrates, a height that is lower by about 0.2 to 0.3 μm than the first columnar spacer, and a cross-sectional area. A method for forming a color filter having a large second columnar spacer (sub-spacer) is disclosed. Similarly, Patent Document 4 discloses a display panel for a display device having a substrate spacing member having two or more different heights or contact areas.

JP-A-8-262484 Japanese Patent Laid-Open No. 10-48636 Japanese Patent No. 3925142 JP 2004-118200 A

  On the other hand, the price of a television image display device using a liquid crystal display device is rapidly decreasing, and there is a strong demand for cost reduction. In particular, liquid crystal is indispensable for a liquid crystal display device, but its price is very high, so there has been a strong demand for reducing the amount of use.

  However, as described above, a number of technical proposals have been made regarding the conventional technology for defining the cell gap that directly affects the amount of liquid crystal used. However, the aperture of the liquid crystal display device is ensured and the display quality is improved. No technology has been proposed that can reduce the amount of liquid crystal used while maintaining a prescribed cell gap determined by the operating characteristics.

  The present invention has been made in view of the circumstances as described above, and includes a color filter substrate capable of reducing the cost of the liquid crystal display device by reducing the amount of liquid crystal used in the liquid crystal display device, and the color filter substrate. An object is to provide a liquid crystal display device.

The invention according to claim 1 of the present invention is a color filter substrate for a liquid crystal display device having, on a transparent substrate, at least a black matrix layer and colored pixels of respective colors composed of a plurality of colored compositions,
In the non-display area in the liquid crystal display screen, the height is 1 μm or more and 0.2 μm or less lower than the thickness of the liquid crystal layer, and the total area of the upper surface portion in plan view is 50% or more of the area of the non-display area 90 It is a color filter substrate characterized by having protrusions that are not more than%.

  The invention according to claim 2 of the present invention has a photo spacer for maintaining the thickness of the liquid crystal layer, and the protrusion is made of the same material as the photo spacer. The color filter substrate described in 1.

  The invention according to claim 3 of the present invention is characterized in that the projection is formed by stacking at least one colored composition on the black matrix layer. A color filter substrate to be described.

  Next, an invention according to claim 4 of the present invention is a liquid crystal display device comprising the color filter substrate according to any one of claims 1 to 3.

  The present invention relates to a non-display area in a liquid crystal display screen in a color filter for a liquid crystal display device having at least a black matrix layer and colored pixels of respective colors made of a plurality of colored compositions on a transparent substrate. In addition, the color filter substrate is characterized in that it has projections whose height is smaller than the thickness of the liquid crystal layer of the liquid crystal display device and whose total area is 50% or more of the area of the non-display area. When incorporated in the device, the amount of liquid crystal used can be reduced, and the cost of the liquid crystal display device can be reduced. Further, since the protrusion can be formed simultaneously with the formation of the photo spacer or the formation of the colored pixel, it can be performed without increasing the number of steps.

It is a schematic diagram which shows one embodiment of the color filter substrate of this invention in a cross section. It is a schematic diagram which shows the cross section of another embodiment of the color filter substrate of the present invention.

  Hereinafter, the color filter substrate of the present invention will be described in detail based on one embodiment.

  As shown in FIGS. 1 and 2, the color filter substrate 10 of the present invention includes at least a black matrix layer 2 and colored pixels 3R and 3G of respective colors composed of a plurality of colored compositions on a transparent substrate 1. 3B and, if necessary, a photo spacer 5 for maintaining the thickness of the liquid crystal layer, and further, protrusions 6 and 6 ′ are provided separately from the photo spacer. FIG. 1 is an example of a color filter substrate having a protrusion 6 formed of the same material as that of the photo spacer 5 through the transparent electrode 4. FIG. 2 shows an example of a color filter substrate having protrusions 6 'formed by stacking colored compositions. In this case, the transparent electrode 4 is formed so as to cover the protrusions 6'.

  In the color filter substrate of the present invention, the protrusions 6 and 6 ′ have a height of 1 μm or more on the non-display area of the liquid crystal display screen, that is, on the black matrix layer 2 which is a light shielding layer, and 0 from the photo spacer. It is formed so that the total area of the upper surface portion in plan view is 50% or more and 90% or less of the area of the non-display area. The color filter substrate 10 of the present invention having the projections is illustrated through the photo spacer 5 with the resin black matrix layer 2, the colored pixels 3, and the projections 6 and 6 ′ facing the liquid crystal 7 sandwiching surface side. The TFT is bonded to the array substrate 20 on which the TFTs that are not formed are formed, and is incorporated into a liquid crystal display device. The photo spacer 5 can be provided not on the color filter substrate 10 side but on the array substrate 20 side.

  This protrusion is usually formed in a non-display area in the liquid crystal display screen, that is, an area where the resin black matrix is formed, and occupies a part of the volume of the layer in which the liquid crystal is sandwiched, so that the liquid crystal display device The amount of liquid crystal used can be reduced.

  The height of the protrusion is preferably 1 μm or more, and if it is less than 1 μm, the effect of reducing the amount of liquid crystal used cannot be sufficiently obtained. Further, it is preferably 0.2 μm or more lower than the thickness of the liquid crystal layer of the liquid crystal display device, that is, the height of the photo spacer. If the difference between the thickness of the liquid crystal layer and the height of the photo spacer is less than 0.2 μm, it will be in contact with the counter substrate holding the liquid crystal when a pressure is applied to the liquid crystal display device, causing display defects. End up.

  Further, the protrusion is formed such that the total area of the upper surface portion in plan view is 50% or more and 90% or less of the area of the non-display area. The total area is preferably 50% or more of the area of the non-display area of the liquid crystal display device. If it is less than 50%, the effect of reducing the amount of liquid crystal used cannot be sufficiently obtained. As long as the liquid crystal display device is manufactured by the dropping method (ODF), there is no essential upper limit, but 90% is the upper limit in consideration of the area for arranging the photo spacer and the like.

  When the color filter substrate has a photo spacer, the protrusion is preferably performed simultaneously with the formation of the photo spacer. However, it is also possible to form the protrusion by stacking the coloring composition on the black matrix layer when forming the colored pixel. is there.

  Hereinafter, a method for obtaining the color filter substrate of the present invention will be described. The color filter substrate of the present invention comprises at least a resin black matrix layer and a colored layer on a transparent substrate, and the colored layer usually forms a pixel composed of a colored composition of a plurality of colors. Examples of the plurality of colors include a combination of red, green, and blue (RGB) and a combination of yellow, magenta, and cyan (YMC).

  The transparent substrate preferably has a certain degree of transmittance with respect to visible light, and more preferably has a transmittance of 80% or more. Generally used for liquid crystal display devices, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali aluminoborosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate and polyethylene terephthalate are used. It is done. In addition, a transparent electrode made of a combination of metal oxides such as indium oxide, tin oxide, zinc oxide and antimony oxide is formed on the surface of the glass plate or resin plate for driving the liquid crystal after the liquid crystal panel is formed. Also good.

  The resin black matrix layer is not particularly limited in composition and formation method as long as it can achieve the required light shielding properties, that is, optical density. However, at least a photopolymerization initiator and a polymerizable monomer are added to a dispersion in which a black pigment such as a carbon black pigment is dispersed in a resin from the viewpoint of easy formation and relatively preferable uniformity. The photosensitive black resin composition obtained by addition is generally formed by a so-called photoresist method in which an appropriate method is applied to a transparent substrate, pattern exposure, development, and baking. In addition, a printing method, an etching method, or the like can be used.

  Examples of the pigment that can be used in the black composition include a carbon black pigment, a titanium carbon black pigment, and the like, and if necessary, a red pigment, a green pigment, and a blue pigment may be mixed and used. As carbon black used as a light-shielding agent, carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850 manufactured by Mitsubishi Chemical Corporation, MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44 , # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234 , Diamond black I, diamond black LI, diamond black II, diamond Rack 339, diamond black SH, diamond black SHA, diamond black LH, diamond black H, diamond black HA, diamond black SF, diamond black N550M, diamond black E, diamond black G, diamond black R, diamond black N760M, diamond black LR . Carbon black thermax N990, N991, N907, N908, N990, N991, N908 made by Cancarb. Carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa's carbon black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw1, ColorBlack Fw1, ColorBlack F170, BlackBlack 170, BlackBlack 170 , SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, PrintexU, PrintexV, Printex140U, Printex140V And the like.

  The resin used for the black composition includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin.

  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. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group 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 Neopentyl 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 amount added is preferably as long as it does not impair applicability and development suitability, and is about 20% by mass to 80% by mass, more preferably about 50% by mass to 70% by mass, based on the total solid content of the black composition. is there. If the addition amount is less than this range, the crosslinkability is insufficient and the liquid crystal resistance deteriorates. If the addition amount is larger than this range, unevenness and pinholes are likely to occur when the black composition is applied, and the applicability is remarkably deteriorated, or the solubility in the developer is remarkably lowered, resulting in poor development suitability.

  When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the black composition. Examples of the photopolymerization initiator include 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 ' Benzophenone-based compounds such as methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4- Thioxanthone compounds such as diisopropylthioxanthone and 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 (trichloro) Methyl) -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 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4 ′ -Methoxy-naphthyl) ethylidene) oxime ester compounds such as hydroxylamine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-tri Phosphine compounds such as tilbenzoyldiphenylphosphine oxide, quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds, and the like are used. . 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 black 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 black 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, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 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 black 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) diglycidyl ether. Also about these, it can use individually or in mixture of 2 or more types.

Examples of organic solvents that can be used for the black composition 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, and methyl-n. Examples include amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, and petroleum solvents, and these are used alone or in combination.

  The above-mentioned photosensitive black composition is applied on a transparent substrate and prebaked. Spin coating, dip coating, die coating, etc. are usually used as the means for coating, but it is not limited to these as long as it is a method capable of coating with a uniform film thickness on a 40 to 60 cm square substrate. Prebaking is preferably performed at 50 to 120 ° C. for about 1 to 20 minutes. The coating film thickness is arbitrary and is usually about 1 to 2 μm after pre-baking. A photosensitive black composition is applied and exposed through a pattern mask. A normal high-pressure mercury lamp or the like may be used as the light source.

  Subsequently, development is performed. An alkaline aqueous solution is used as the developer. Examples of the alkaline aqueous solution include a sodium carbonate aqueous solution, a sodium hydrogen carbonate aqueous solution, a mixed aqueous solution of the two, or a mixture obtained by adding an appropriate surfactant to them. After the development, washing and baking are performed to obtain a patterned resin black matrix layer.

  As a method for forming a colored layer to be a pixel, any known method such as an inkjet method, a printing method, a photoresist method, or an etching method 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 photoresist method is preferred in which a step of forming a single color pixel by coating and forming, pattern exposure and development is repeated for each color to produce a color filter.

  The colored pixels of the color filter of the present invention are prepared according to, for example, the following method when a photosensitive coloring composition is prepared and formed by a photolithography method. 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.

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

  Examples of red coloring compositions 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, Red pigments such as H.264, 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, 1 73, 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 coloring composition for forming a green pixel include C.I. I. Pigment Green 7, 10, 36, 37, 58, or other green pigments can be used. The green coloring composition can be used in combination with the same yellow pigment as the red coloring composition.

  Examples of the blue coloring composition for forming a blue pixel include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 80, etc., preferably C.I. I. Pigment Blue 15: 6 can be used. In addition, C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like, preferably C.I. I. Pigment Violet 23 can be used in combination.

  In combination with the organic pigment, an inorganic pigment may be used in combination in order to ensure good coatability, sensitivity, developability and the like while balancing saturation and lightness. 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 lower the heat resistance.

  The transparent resin that can be 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. If necessary, the transparent resin can be used alone or in admixture of two or more monomers or oligomers that are precursors thereof that are cured by irradiation with radiation to produce a transparent resin.

  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. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group 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 Neopentyl 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 crosslinkability is insufficient and the liquid crystal resistance deteriorates. If the added amount is larger than this range, unevenness and pinholes are likely to occur when the colored composition is applied, and the applicability is remarkably deteriorated, or the solubility in the developer is remarkably lowered, resulting in poor development suitability.

  When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the coloring composition. Examples of the photopolymerization initiator include 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 ' Benzophenone-based compounds such as methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4- Thioxanthone compounds such as diisopropylthioxanthone and 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 (trichloro) Methyl) -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 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4 ′ -Methoxy-naphthyl) ethylidene) oxime ester compounds such as hydroxylamine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-tri Phosphine compounds such as tilbenzoyldiphenylphosphine oxide, quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds, and the like are used. . 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 color 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, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 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) 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.

  On the transparent substrate, the above-mentioned photosensitive coloring composition is applied and prebaked. Spin coating, dip coating, die coating, etc. are usually used as the means for coating, but it is not limited to these as long as it is a method capable of coating with a uniform film thickness on a 40 to 60 cm square substrate. Prebaking is preferably performed at 50 to 120 ° C. for about 10 to 20 minutes. The coating film thickness is arbitrary, but considering the spectral transmittance and the like, the film thickness after pre-baking is usually about 2 to 2.5 μm. A photosensitive coloring composition is applied and exposed through a pattern mask. A normal high-pressure mercury lamp or the like may be used as the light source.

  Subsequently, development is performed. An alkaline aqueous solution is used as the developer. Examples of the alkaline aqueous solution include a sodium carbonate aqueous solution, a sodium hydrogen carbonate aqueous solution, a mixed aqueous solution of the two, or a mixture obtained by adding an appropriate surfactant to them. After development, it is washed with water and fired to obtain a pixel of any one color coloring composition.

  By repeating the above-described series of steps by changing the photosensitive coloring composition and pattern as many times as necessary, it is possible to obtain a pixel having a coloring pattern in which the required number of colors are combined, that is, a coloring composition of a plurality of colors.

  Photo spacers (PS) can be formed in the color filter of the present invention as needed.

  The PS of the color filter of the present invention is, for example, according to the following method when a photosensitive composition is prepared and formed by photolithography. The photosensitive composition is prepared by dissolving a resin, a photocrosslinking agent, and a photoinitiator in a suitable solvent.

  The resin used for the photosensitive composition includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin.

  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. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group 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 Neopentyl 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 based on the total solid content of the photosensitive composition, about 20% to 80% by weight, more preferably about 50% to 70% by weight. It is. If the addition amount is less than this range, the crosslinkability is insufficient and the liquid crystal resistance deteriorates. When the addition amount is larger than this range, unevenness and pinholes are likely to occur when the photosensitive composition is applied, and the applicability is remarkably deteriorated, or the solubility in the developer is remarkably lowered, resulting in poor development suitability.

  When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the photosensitive composition. Examples of the photopolymerization initiator include 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 ' Benzophenone-based compounds such as methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4- Thioxanthone compounds such as diisopropylthioxanthone and 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 (trichloro) Methyl) -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 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4 ′ -Methoxy-naphthyl) ethylidene) oxime ester compounds such as hydroxylamine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-tri Phosphine compounds such as tilbenzoyldiphenylphosphine oxide, quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds, and the like are used. . These photopolymerization initiators can be used alone or in combination.

  The amount of the photopolymerization initiator used is preferably 0.05 to 50% by mass, more preferably 0.5 to 30% by mass based on the total solid content of the photosensitive composition.

  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.

  Examples of the organic solvent that can be used in the photosensitive composition 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- nAmyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, etc. are used, and these are used alone or in combination.

  The above-described photosensitive composition is applied on a substrate on which a black matrix layer, colored pixels, and the like are formed, and prebaked. Spin coating, dip coating, die coating, etc. are usually used as the means for coating, but it is not limited to these as long as it is a method capable of coating with a uniform film thickness on a 40 to 60 cm square substrate. Prebaking is preferably performed at 50 to 120 ° C. for about 10 to 20 minutes. The coating thickness needs to be adjusted appropriately so that a predetermined spacer height can be obtained. Since the spacer height depends on the thickness of the liquid crystal layer, it is usually about 2 to 5 μm. A photosensitive composition is applied and exposed through a pattern mask. A normal high-pressure mercury lamp or the like may be used as the light source.

Subsequently, development is performed. An alkaline aqueous solution is used as the developer. Examples of the alkaline aqueous solution include a sodium carbonate aqueous solution, a sodium hydrogen carbonate aqueous solution, a mixed aqueous solution of the two, or a mixture obtained by adding an appropriate surfactant to them. After development, the photo spacer is obtained by washing with water and baking.

  The protrusions of the color filter substrate of the present invention can be formed in the same pattern forming step using the photosensitive composition for forming the PS. It can be performed in a separate process from the PS formation process or in the same process.

  The protrusions of the color filter of the present invention can also be formed by stacking at least one color composition on the resin black matrix layer. By appropriately designing a pattern mask used for exposure of each layer and appropriately adjusting the number of layers to be stacked, it is possible to form protrusions having a predetermined height and area.

  Hereinafter, the present invention will be described with reference to specific examples. However, the present invention is not limited to these examples without departing from the spirit of the present invention. In the following description, all parts and% are parts by mass and% by mass.

<Example 1>
[Preparation of photosensitive black composition]
The photosensitive black composition was prepared by mixing and stirring a mixture having the following composition (pigment concentration in solid content: 30.7%).
Carbon black dispersion: 28.5 parts made by Mikuni Dye (TPBK-2016) Resin: V259-ME (manufactured by Nippon Steel Chemical Co., Ltd.) (solid content 56.1%) 10.3 parts Monomer: DPHA ( Nippon Kayaku Co., Ltd.) 2.58 parts ・ Initiator: OXE-02 (Ciba Specialty Chemicals Co., Ltd.) 0.86 parts ・ Solvent: Propylene glycol monomethyl ether acetate
Ethyl-3-ethoxypropionate 92.0 parts ・ Leveling agent 1.3 parts [Formation of resin black matrix layer]
The black composition was applied on a glass substrate by spin coating so as to have a film thickness of 1.5 μm. After drying at 100 ° C. for 3 minutes, the pattern exposure is 200 mJ with an exposure machine, developed with an alkali developer for 60 seconds, heat-treated at 230 ° C. for 60 minutes, fixed, and the grid-like black matrix layer is formed. It formed on the glass substrate. The alkaline developer has the following composition. In the following examples and comparative examples, development is performed using this alkaline developer.
・ Sodium carbonate 1.5%
・ Sodium bicarbonate 0.5%
・ Anionic surfactant 8.0%
("Peralex NBL" manufactured by Kao Corporation)
・ Water 90%
[Preparation of red coloring composition]
A mixture having the following composition was uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a red pigment dispersion.
-Red pigment: C.I. I. Pigment Red 254
("Ilgar Forred B-CF" manufactured by Ciba Specialty Chemicals)
18 parts red pigment: C.I. I. Pigment Red 177
("Chromophthal Red A2B" manufactured by Ciba Specialty Chemicals)
2 parts / dispersant (“Ajisper PB821” manufactured by Ajinomoto Fine-Techno Co., Ltd.) 2 parts / acrylic varnish (solid content: 20%) 50 parts. Filtration gave a red colored composition.
72 parts of the above red pigment dispersion 8 parts of caprolactone-modified dipentaerythritol hexaacrylate (“Kayarad DPCA-30” manufactured by Nippon Kayaku Co., Ltd.)
・ 10 parts of dipentaerythritol hexaacrylate (“Kayarad DPHA” manufactured by Nippon Kayaku Co., Ltd.)
・ Methylated melamine resin 10 parts (“MW30” manufactured by Sanwa Chemical Co., Ltd.)
・ Photoinitiator
("Irgacure 907" manufactured by Ciba Specialty Chemicals) 3 parts-Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 1 part-253 parts of cyclohexanone [Preparation of green colored composition]
A mixture having the following composition was uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using a glass bead having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a green pigment dispersion.
Green pigment: C.I. I. Pigment Green 36
(Toyo Ink Mfg. Co., Ltd. “Lionol Green 6YK”) 16 parts Yellow pigment: C.I. I. Pigment Yellow 150
(Bayer's "Funcheon First Yellow Y-5688") 8 parts Dispersant (Big Chemie's "Disperbyk-163") 2 parts Acrylic varnish (solid content 20%) 102 parts Thereafter, a mixture having the following composition was homogeneous Then, the mixture was stirred and mixed to obtain a green colored composition by filtration through a 5 μm filter.
-128 parts of the above-mentioned dispersion of green pigment-14 parts of trimethylolpropane triacrylate (Shin Nakamura Chemical Co., Ltd. "NK ester ATMPT")
・ Photoinitiator
("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.) 4 parts-Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 2 parts-257 parts cyclohexanone [Preparation of blue colored composition]
A mixture having the following composition was uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a blue pigment dispersion.
Blue pigment: C.I. I. Pigment Blue 15
("Rionol Blue ES" manufactured by Toyo Ink Co., Ltd.) 30 parts-Purple pigment: C.I. I. Pigment Violet 23
(BASF "Paliogen Violet 5890") 2 parts Dispersant (Zeneca "Sols Birds 20000") 6 parts Acrylic varnish (solid content 20%) 200 parts Thereafter, a mixture of the following composition is made uniform After stirring and mixing, the mixture was filtered through a 5 μm filter to obtain a blue colored composition.
-238 parts of the above-mentioned blue pigment dispersion-19 parts of trimethylolpropane triacrylate ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
・ Photoinitiator
("Irgacure 907" manufactured by Ciba Specialty Chemicals) 4 parts · Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 2 parts · 214 parts cyclohexanone [Formation of colored layer]
Using the obtained red colored composition, green colored composition, and blue colored composition, a colored layer serving as a pixel was formed in the following manner.
On the glass substrate on which the resin black matrix layer described above was formed, the red coloring composition was applied by spin coating so as to have a film thickness of 2 μm. After drying, a striped pattern was exposed with an exposure machine, developed with an alkali developer for 90 seconds, and fixed by heating at 230 ° C. for 20 minutes to form a striped red colored layer on the transparent substrate. .

  Next, the green coloring composition was similarly applied by spin coating so that the film thickness was 2 μm. After drying, the green colored layer adjacent to the red colored layer was formed by exposing and developing the striped colored layer in a position different from the red colored layer with an exposure machine.

  Further, in the same manner as red and green, the blue colored composition was formed with a blue colored layer adjacent to the red colored layer and the green colored layer with a film thickness of 2 μm.

  Next, a transparent conductive layer was formed by forming a film of indium tin oxide by sputtering on the transparent substrate on which the resin black matrix layer and the colored layers of each color were formed. The thickness of the transparent conductive layer was 140 nm.

[Preparation of photosensitive resin composition for forming photo spacer]
A photosensitive resin composition for forming a photospacer was prepared as follows. In a 5-liter reaction vessel with an internal volume of 2 liters, 686 g of propylene glycol monomethyl ether acetate (PGMAc), 332 g of glycidyl methacrylate (GMA), azobis 6.6 g of isobutyronitrile (AIBN) was added and heated at 80 ° C. for 6 hours while blowing nitrogen to obtain a polymer solution of GMA.
Next, 168 g of acrylic acid (AA), 0.05 g of methoquinone (MQ), 0.5 g of triphenylphosphine (TPP) are added to the obtained polymer solution of GMA, and heated at 100 ° C. for 24 hours while blowing air. An acrylic acid adduct solution of GMA resin was obtained.
Next, 186 g of tetrahydrophthalic anhydride was added to the resulting acrylic acid adduct solution of GMA resin and heated at 70 ° C. for 10 hours to obtain a resin a solution.
Thereafter, a mixture having the following composition was diluted with cyclohexanone so that the solid content in the resist was 30% to prepare a photosensitive resin composition.
-80 parts of pentaerythritol triacrylate ("PET-30" manufactured by Nippon Kayaku Co., Ltd.)-20 parts of resin a solution-14 parts of photopolymerization initiator ("Irgacure 907" manufactured by BASF) [Formation of photo spacer]
Photo spacers were formed using the photosensitive resin composition for forming photo spacers described above.
The photosensitive resin composition was spin-coated on the glass substrate on which the resin black matrix layer, the colored layer, and the transparent conductive layer were formed, so that the finished film thickness was 4 μm, and dried at 90 ° C. for 2 minutes. Next, light from a high-pressure mercury lamp was irradiated at a dose of 100 mJ / cm ² through a photomask for forming a circular photospacer having a mask opening diameter of 8 μmφ. Note that the exposure (exposure gap) between the photomask and the substrate was 100 μm. Thereafter, development was performed using an alkali developer similar to the formation of the resin black matrix layer and the colored layer, and after washing with water, post-baking was performed at 230 ° C. for 30 minutes to form a photo spacer on the color filter.

[Formation of protrusions]
Projections were formed using the photosensitive resin composition for forming a photospacer.
The photosensitive resin composition is spin-coated on the glass substrate on which the resin black matrix layer, the colored layer, the transparent conductive layer, and the photo spacer are formed, so that the final film thickness is 3 μm, and dried at 90 ° C. for 2 minutes. did. Next, light from a high-pressure mercury lamp was irradiated at a dose of 100 mJ / cm ² through a photomask for forming protrusions so that the opening area was set to 60% of the non-display area. Note that the exposure (exposure gap) between the photomask and the substrate was 100 μm. Thereafter, development is performed using an alkaline developer similar to the formation of the resin black matrix layer and the colored layer, and after washing with water, post-baking is performed at 230 ° C. for 30 minutes to form protrusions on the color filter. A color filter substrate of Example 1 having the black matrix layer, the colored layer, the transparent conductive layer, the photospacer, and the protrusion and having the cross-sectional configuration shown in FIG. 1 was obtained.

<Example 2>
In the same manner as in Example 1, a resin black matrix layer, a red colored layer, a green colored layer, and a blue colored layer were formed on a glass substrate. When forming the colored layer of each color, by adjusting the exposure pattern so that the end portions of the colored layer overlap each other, protrusions were formed so as to be 60% of the non-display area due to the overlapping of the colored layers. Further, a photo spacer is formed on the above color filter in the same manner as in Example 1, and has a cross-sectional configuration shown in FIG. 2 having a resin black matrix layer, a colored layer, a transparent conductive layer, a photo spacer, and a protrusion. A color filter substrate of Example 2 was obtained.

<Comparative Example 1>
Comparative example having the resin black matrix layer, the colored layer, the transparent conductive layer, and the photospacer, adjusted so that the colored layers do not overlap each other in the same process as in Example 2 to form the colored layer. 1 color filter substrate was obtained.

  Table 1 shows the results of producing liquid crystal display devices using the color filter substrates of Example 1, Example 2 and Comparative Example 1 and comparing the amounts of liquid crystal used. In the liquid crystal display device using the color filter substrate of Example 1 and Example 2, the amount of liquid crystal used could be reduced as compared with the liquid crystal display device using the color filter substrate of Comparative Example 1.

1. ・ Transparent substrate (glass substrate) 2. ・ Black matrix layer
3. ・ Colored layer (3R, 3G, 3B) 4. ・ Transparent conductive layer 5. ・ Photo spacer 6. ・ Protrusions (projections formed of photo spacer material)
6 ′ ・ ・ Protrusions (projections formed by stacking colored layers)
7. Liquid crystal 10. Color filter substrate 20. Array substrate

Claims (4)

In a color filter substrate for a liquid crystal display device having at least a black matrix layer and colored pixels of respective colors composed of a plurality of colored compositions on a transparent substrate,
In the non-display area in the liquid crystal display screen, the height is 1 μm or more and 0.2 μm or less lower than the thickness of the liquid crystal layer, and the total area of the upper surface portion in plan view is 50% or more of the area of the non-display area 90 %, A color filter substrate having protrusions that are less than or equal to%.   The color filter substrate according to claim 1, further comprising a photo spacer for maintaining a thickness of the liquid crystal layer, wherein the protrusion is made of the same material as the photo spacer.   2. The color filter substrate according to claim 1, wherein the protrusion is formed by stacking at least one color composition on the black matrix layer.   A liquid crystal display device comprising the color filter substrate according to claim 1.

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