JP2013171281A - Method for manufacturing color filter, color filter, and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a color filter preventing generation of failures such as pattern peeling, non-uniformity in line width, defective shapes and residues, and to provide a color filter manufactured by the method and a liquid crystal display device using the color filter.SOLUTION: The method for manufacturing a color filter comprises: applying a photosensitive resin composition comprising at least one pigment (A) selected from the group consisting of black, red, green and blue pigments, an alkali-soluble resin (B) having an acid value of 200 mg to 300 mg/KOH, a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), on a transparent substrate and drying the coating film; exposing the film through a photomask; and developing the film by use of an alkali developing solution containing at least a basic compound (F) and an anionic polymeric surfactant (G).

Description

  The present invention relates to a method for manufacturing a color filter for a liquid crystal display device using a photolithography technique, a color filter manufactured using the method, and a liquid crystal display device including the color filter.

  In recent years, color liquid crystal display devices are installed in car navigation systems, laptop computers, desktop computer monitors, color television receivers, mobile phones, mobile game machines, etc. due to their energy saving and space saving features. As a result, it has formed a large market and continues to increase as an alternative to conventional CRT display devices.

  A color filter, which is a main component of a color liquid crystal display device, generally has a light-shielding portion called a black matrix (BM) that defines a pixel region, and a colored layer disposed in the pixel region through a light transmission material such as glass or plastic. Formed on a conductive substrate.

  BM is a resin layer containing a light shielding material such as carbon black, in which colored layer defining regions are arranged in a plurality of matrices. The colored layers are red (R), green (G), and blue (B). It is a resin layer containing the pigment or dye which comprises the pixel of either color.

  As a method of forming a BM or a colored layer, a photosensitive black composition or a photosensitive colored composition is applied on a substrate to form a photosensitive layer, pattern exposure is performed using a photomask, and then unexposed portions are removed by development. Then, a photolithography method in which a cured film corresponding to the pattern is formed by performing a treatment such as heating as necessary has become the mainstream.

  In order to obtain the desired pattern with this method, the solubility of the photosensitive composition in the developer is important. If the balance is lost, pattern peeling, line width non-uniformity, shape defect, residue, etc. A malfunction occurs. In order to solve these problems, two types of resist compositions having different acid values and molecular weights (Patent Document 1) and compositions in which pigments are coated with an acid group-containing reactant (Patent Document 2) are disclosed. Yes. Moreover, the developing solution which added the specific nonionic surfactant is disclosed (patent documents 3-5).

  In recent years, particularly in color filters for liquid crystal display devices for mobile devices, there has been a strong demand for high definition for high resolution, and accordingly, fine BM patterns with high precision and coloring arranged accurately in fine BM patterns. Although a layer pattern is required, the above-mentioned patent document does not mention a method for thinning a BM pattern or a method for reducing variations in the line width of a colored layer pattern.

  Regarding the fine line BM pattern, a method of adding a thiol compound that is a chain transfer agent for a photopolymerization reaction to a photosensitive black composition (Patent Document 6), a reaction product of epoxidized bisphenols and (meth) acrylic acid, A method of using an alkali-soluble resin obtained by reacting dicarboxylic acids and tetracarboxylic acids (Patent Document 7), carbon black particle diameter, specific surface area, dibutyl phthalate oil absorption, carbon black derivative, Although a method for specifying a dispersant (Patent Document 8) has been disclosed, the line width for high definition is insufficient.

When further reducing the BM line width, there is a method of increasing the development time, but the pattern is peeled off,
Problems such as line width non-uniformity and shape defects are likely to occur. There is also a method of developing using a photomask with a narrow opening line width in the exposure process and developing in a development time that does not cause pattern peeling, line width non-uniformity, and shape defect, but removal of unexposed areas is insufficient It becomes easy to generate residue. Furthermore, when the line width of the colored layer is managed with high accuracy, a uniform colored layer pattern cannot be formed on a fine BM by a conventionally known method, as in the case of BM.

JP 2006-145753 A JP 2006-022164 A JP 2005-326813 A Japanese Patent Laid-Open No. 2001-312073 JP 2000-329927 A JP 2004-325735 A JP 2006-276421 A JP 2008-310000 A

  The present invention has been made in view of the above circumstances, and a color filter manufacturing method free from defects such as pattern peeling, line width non-uniformity, shape defect, residue, etc., a color filter manufactured by the manufacturing method, and An object is to provide a liquid crystal display device using the same.

  As means for solving the above-mentioned problems, the invention according to claim 1 is characterized in that at least one pigment (A) selected from the group of black, red, green, and blue, the resin acid value is 200 mg to 300 mg / The film | membrane which apply | coated the photosensitive composition containing the alkali-soluble resin (B) which is KOH, a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E) on the transparent substrate, and was dried. Is an alkaline developer containing at least a basic compound (F) and an anionic polymer surfactant (G) having an average molecular weight of 5,000 to 10,000 after exposure through a photomask, The proportion of the basic compound (F) in the alkaline developer is 0.1 to 10.0% by weight relative to the total amount of the developer, and the proportion of the anionic polymer surfactant (G) is relative to the total amount of the developer. 0.05-5.00% by weight A method of manufacturing a color filter, which comprises forming a black matrix pattern or a coloring layer is developed with a certain alkaline developer. The invention according to claim 2 is the method for producing a color filter according to claim 1, wherein the basic compound (F) is an inorganic alkali compound.

  Since the photosensitive composition in the present invention contains an alkali-soluble resin (B) having an acid value of 200 to 300 KOHmg / g which is highly soluble in an alkali developer, pattern peeling due to development and line width non-uniformity are present. It is easy to happen. On the other hand, since the alkaline developer contains an anionic polymer surfactant (G) that lowers the solubility of the photosensitive black composition, shape defects and residues are likely to occur. In the present invention, it is possible to suppress problems that may occur during the development process by combining the two. That is, the photosensitive black composition has a development accelerating effect and the alkaline developer has a development inhibitory effect, so that the solubility of the photosensitive composition in the alkaline developer is balanced.

  When the acid value of the alkali-soluble resin (B) is less than 200 mg / KOH, the solubility in an alkaline developer is lowered, which causes a decrease in productivity due to a delay in development time, shape defects, and generation of residues. On the other hand, when the acid value exceeds 300 mg / KOH, the solubility in an alkaline developer becomes too high, which causes pattern peeling and non-uniformity in line width.

  When the average molecular weight of the anionic polymer surfactant (G) is less than 5,000, a sufficient development suppressing effect cannot be obtained, resulting in pattern peeling and line width non-uniformity. When the average molecular weight exceeds 10,000, the development suppressing effect becomes strong, which causes a decrease in productivity due to a delay in development time, shape defects, and generation of residues.

When the proportion of the basic compound (F) in the developer is less than 0.1% by weight based on the total amount of the developer, sufficient developability (solubility of the photosensitive black composition in the developer) cannot be obtained. , Causing a decrease in productivity due to a delay in development time, shape defects, and generation of residues. When the proportion of the basic compound (F) in the developer exceeds 10% by weight with respect to the total amount of the developer, the development inhibiting effect due to the addition of the anionic polymer surfactant (G) is not exhibited, and the pattern is peeled off. It causes line width non-uniformity. When the ratio of the anionic polymer surfactant (G) is less than 0.05% by weight with respect to the total amount of the developer, sufficient development suppressing effect cannot be obtained, resulting in pattern peeling and line width non-uniformity. . When the proportion of the anionic polymer surfactant (G) exceeds 5% by weight with respect to the total amount of the developer, the development time is lowered due to the generation of bubbles, and the development suppressing effect is strengthened. This may cause a decrease in productivity, shape defects, and residue generation.
According to a third aspect of the present invention, there is provided a color filter manufactured by the color filter manufacturing method according to the first or second aspect.
According to a fourth aspect of the present invention, there is provided a liquid crystal display device comprising the color filter according to the third aspect.

  By using the limited photosensitive composition and developer according to the method for producing a color filter of the present invention, there is no occurrence of defects such as pattern peeling, line width non-uniformity, shape defects, and residues that may occur in the development process. A color filter and a liquid crystal display device can be provided.

(A)-(f) is an example of the schematic structure sectional drawing which showed the manufacturing process of the color filter for liquid crystal display devices of this invention.

  Hereinafter, modes for carrying out the present invention will be described from a photosensitive composition. The photosensitive composition of the present invention comprises at least one pigment (A) selected from the group of black, red, green, and blue, an alkali-soluble resin (B) having an acid value of 200 mg to 300 mg / KOH, and photopolymerization. Containing a functional compound (C), a photopolymerization initiator (D), and a solvent (E). In addition, you may contain an additive as needed.

<Black pigment>
Examples of the black pigment used in the photosensitive black composition of the present invention include carbon black, titanium black, acetylene black, and aniline black. Among these, carbon black is particularly preferable from the viewpoint of light shielding properties and cost. Specific examples of the carbon black pigment include carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88 manufactured by Mitsubishi Chemical Corporation. # 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 Black 3 9, Diablack SH, Diablack SHA, Diablack LH, Diablack H, Diablack HA, Diablack SF, Diablack N550M, Diablack E, Diablack G, Diablack R, Diablack N760M, Diablack 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 Color Black Fw200, Color Black Fw2, Color Black Fw2V, Color Black Fw1, Color Black Fw , Color Black S170, Color Black S160, Special Black 6, Special Black 5, Special Black 4, Special Black 4A, PrintEXU, PrintEXV, PrintEXV, PrintX 40V etc. are mentioned.

An organic pigment may be added as an auxiliary pigment to the above inorganic pigment. The following effects can be obtained by appropriately selecting and adding organic pigments that exhibit complementary colors of inorganic pigments. For example, carbon black exhibits a reddish black color. Therefore, by adding an organic pigment having a blue color which is a complementary color of red as an auxiliary pigment to the carbon black, the redness of the carbon black disappears, and a more preferable black color as a whole is exhibited. Specific examples of organic pigments include color index <C. I. > Indicated by number.
C. I. Pigment Blue 1, 1: 2, 1: X, 9: X, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 24, 24: X, 56, 60, 61, 62, Pigment Green 1, 1: X, 2, 2: X, 4, 7, 10, 36, Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 59, 60, 61, 62, 64, Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 3, 81: X, 83, 88, 90 112, 119, 122, 123, 144, 146, 149, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 224, 226, 254, Pigment Violet 1, 1: X, 3, 3: 3, 3: X, 5: 1, 19, 23, 27, 32, 42, Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 24, 55, 60, 65, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150 151,152,153,154,156,175
<Red pigment>
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, 264, Red pigments such as 272 and 279 can be used. A yellow pigment and an orange pigment can be used in combination with the red coloring composition.

<Yellow pigment>
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 1
0, 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, 173, 174, 175, 176, 177, 179, 180, 81,182,185,187,188,193,194,199,213,214, and the like.

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

<Green pigment>
Examples of the green coloring composition for forming a green pixel include C.I. I. Green pigments such as Pigment Green 7, 10, 36, 37, and 58 can be used. The green coloring composition can be used in combination with the same yellow pigment as the red coloring composition.

<Blue pigment>
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.

<Purple pigment>
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 pepper (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.

  Since these pigments are aggregated as they are, they need to be dispersed. A mill base is prepared by adding a dispersant and a solvent to the pigment, and the mill base can be dispersed by a method such as a ball mill, a sand mill, a bead mill, a three roll, a paint shaker, an ultrasonic wave, or a bubble homogenizer. Two or more of these processing methods can be combined. Resin or a well-known dispersing agent can be used for a dispersing agent.

<Alkali-soluble resin (B) whose acid value is 200 mg to 300 mg / KOH>
The acid value of the alkali-soluble resin used in the photosensitive black composition of the present invention is preferably 200 mg to 300 mg / KOH, and more preferably 230 to 280 mg / KOH. When the acid value is less than 200 mg / KOH, the solubility in an alkaline developer is lowered, which causes a reduction in productivity due to a delay in development time, shape defects, and generation of residues. On the other hand, when the acid value exceeds 300 mg / KOH, the solubility in an alkaline developer becomes too high, which causes pattern peeling and non-uniformity in line width.

  Representative examples of the alkali developable resin will be described. 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, etc. A resin synthesized with a molecular weight of about 5000 to 100,000 using about 5 types of monomers is used.

  Further, a resin obtained by adding an unsaturated double bond to a part of an acrylic resin includes the above acrylic resin, an isocyanate ethyl acrylate having an isocyanate group and at least one vinyl group, a methacryloyl isocyanate and an epoxy group. A photosensitive copolymer obtained by reacting a compound such as glycidyl acrylate having one or more vinyl groups can also be used as appropriate.

  Furthermore, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, polycarboxylic acid glycidyl ester, polyol polyglycidyl ester, aliphatic or cycloaliphatic epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, Ordinary photopolymerizable resins such as epoxy (meth) acrylate obtained by reacting an epoxy resin such as a cardo resin or a dihydroxybenzene type epoxy resin with (meth) acrylic acid can also be used.

<Photopolymerizable compound (C)>
The photopolymerizable compound (C) is a photopolymerizable monomer or oligomer. Examples of the photopolymerizable compound (C) include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β- Carboxyethyl (meth) acrylate, polyethylene 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, methylolated melamine (meth) acrylate, epoxy (meth) acrylate and Various acrylic esters or methacrylic esters such as urethane acrylate; (meth) acrylic acid; styrene; vinyl acetate; hydroxyethyl vinyl ether; ethylene glycol divinyl ether; pentaerythritol trivinyl ether; (meth) acrylamide; N-hydroxymethyl (meth) Mention may be made of acrylamide; N-vinylformamide; and acrylonitrile. These can be used alone or in admixture of two or more.

<Photopolymerization initiator (D)>
As the photopolymerization initiator (D) applied in the present invention, it is desirable to use at least one selected from oxime photopolymerization initiators and aminoketone photopolymerization initiators.

Examples of the oxime compound include 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -bicycloheptyl-1-one oxime-o-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -adamantylmethane-1-one oxime-o-benzoate, 1- [9
-Ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -adamantylmethane-1-one oxime-o-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -tetrahydrofuranylmethane-1-one oxime-o-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -tetrahydrofuranylmethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -thiophenylmethane-1-one oxime-o-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -thiophenylmethane-1-one oxime-o-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -morophonylmethane-1-one oxime-o-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -morophonylmethane-1-one oxime-o-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-o-bicycloheptanecarboxylate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-o-tricyclodecanecarboxylate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-o-adamantane carbosichelate, 1,2-octanediene, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)] (Ciba Irgacure OXE01), Ethanone, 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) (Ciba Specialty Irgacure OXE02) manufactured by Chemicals Corporation.

  Examples of amino ketone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxy Ethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- And oligomers of (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and the like. In particular, it is desirable to use 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, Irgacure 369 manufactured by Ciba Specialty Chemicals.

  As the photopolymerization initiator (D), at least one photopolymerization initiator among the above oxime-based and aminoketone-based compounds is used. Examples of compounds that can be used include triazine compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, and imidazole compounds.

Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-Phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5- Triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloro Methyl) -1, 5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (pipronyl) -4,6-bis (trichloromethyl) -1, 3, 5-triazine and the like. Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3, 3 ′, 4, 4′-tetra (tert-butylperoxy). Carbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

  When the photosensitive composition contains at least one kind or two kinds of compounds described above as the photopolymerization initiator (D), it can be efficiently activated by a very small amount of light. This is because the compounds having different electronic band spectra coexist so that the photopolymerization initiator broadens the net wavelength range of light having high sensitivity, or at least two kinds of compounds interact. Thus, by further increasing the sensitivity and development margin of the photosensitive composition, it becomes easier to make the black matrix pattern and the colored layer have a high linearity and a good form without peeling or residue.

  Furthermore, in order to adjust the sensitivity, a polyfunctional thiol compound having two or more thiol (SH) groups may be used. When used with the above-mentioned photopolymerization initiator (D), the polyfunctional thiol acts as a chain transfer agent in the radical polymerization process after light irradiation, and generates a thiyl radical that is not easily inhibited by oxygen. Therefore, when a polyfunctional thiol is further contained, the photosensitive black 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.

<Solvent (E)>
Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2- Methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butane Diol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-di Chlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyla Coal, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sEc-butylbenzene, tErt -Butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene Glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl Ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene Glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether , Propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobuty Ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate and dibasic acid esters. These are used alone or in combination.

<Other ingredients>
The photosensitive composition of the present invention further comprises a leveling agent, an antifoaming agent, a surfactant, a plasticizer, a flame retardant, an antioxidant, an ultraviolet absorber, an antifungal agent, an antistatic agent, a magnetic substance, depending on the purpose. Further, a conductive material or the like may be contained.

  Next, the alkaline developer of the present invention will be described. The alkaline developer of the present invention contains a basic compound (F) and an anionic polymer surfactant (G). In addition, a nonionic surfactant or an anionic low molecular surfactant may be used as necessary.

<Basic compound (F)>
As a basic compound (F) applied in this invention, the inorganic alkali compound or organic alkali compound which can be melt | dissolved in water can be used.

  Examples of inorganic alkali compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, Examples thereof include sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide.

  Examples of the organic alkali compound include triethanolamine, diethanolamine, butylamine, phenylhydrazine, tetramethylammonium hydroxide, and choline.

The above basic compounds can be used alone or in admixture of two or more, but it is preferable to select two or more inorganic alkali compounds selected so as to have a buffering action. Specific examples include a combination of sodium carbonate and sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate, and the like.

  The ratio of the basic compound (F) used in the alkaline developer of the present invention to the total amount of the developer is preferably 0.1 to 10% by weight, more preferably 0.5 to 8% by weight, and 1 to 5%. It is particularly preferred that it is wt%. When the proportion of the basic compound (F) in the developer is less than 0.1% by weight based on the total amount of the developer, sufficient developability (solubility of the photosensitive black composition in the developer) cannot be obtained. , Causing a decrease in productivity due to a delay in development time, shape defects, and generation of residues. When the proportion of the basic compound (F) in the developer exceeds 10% by weight with respect to the total amount of the developer, the development inhibiting effect due to the addition of the anionic polymer surfactant (G) is not exhibited, and the pattern is peeled off. It causes line width non-uniformity.

<Anionic polymer surfactant (G)>
Examples of the anionic polymer surfactant (G) applied in the present invention include a light metal salt of a styrene / maleic anhydride copolymer, a light metal salt of an ethylene / maleic anhydride copolymer, and propylene / maleic anhydride. Low foaming properties such as light metal salt of copolymer, light metal salt of isobutylene / maleic anhydride copolymer, light metal salt of polyacrylic acid, light metal salt of polycarboxylic acid, light metal salt of polysulfonic acid, light metal salt of acrylic acid polymer A water-soluble polymer compound is mentioned. Here, examples of the light metal include sodium, potassium, and lithium.

  The ratio of the anionic polymer surfactant (G) used in the alkaline developer of the present invention to the total amount of the developer is preferably 0.05 to 5% by weight, and more preferably 1 to 3% by weight. When the ratio of the anionic polymer surfactant (G) in the developer is less than 0.05% by weight with respect to the total amount of the developer, sufficient development inhibition effect cannot be obtained, pattern peeling, and line width non-uniformity. Cause. When the proportion of the anionic polymer surfactant (G) exceeds 5% by weight with respect to the total amount of the developer, the development time is lowered due to the generation of bubbles, and the development suppressing effect is strengthened. This may cause a decrease in productivity, shape defects, and residue generation.

<Other ingredients>
The alkaline developer of the present invention may further contain a nonionic surfactant and an anionic low molecular surfactant as required. Examples of nonionic surfactants include polyoxyethylene alkyl ether and polyoxyethylene alkyl allyl ether. Examples of the anionic low molecular surfactant include sodium alkylbenzene sulfonate and sodium alkyl naphthalene sulfonate.

  Next, the color filter of the present invention will be described. The color filter includes a light shielding portion called a black matrix (BM) for defining a pixel region formed from a photosensitive black composition on a transparent substrate, and a filter segment formed from the photosensitive coloring composition. A typical color filter includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment, or at least one magenta color filter segment, at least one cyan color filter segment , And at least one yellow filter segment.

A photolithography method is generally used as a method for manufacturing a color filter. FIGS. 1A to 1F are partial schematic cross-sectional views showing an example of a method for manufacturing a color filter for a liquid crystal display device of the present invention. Is shown. The substrate 11 is made of a transparent material that transmits light. For example, the substrate 11 is made of a polyester resin such as polyethylene terephthalate, a polyolefin resin such as polypropylene or polyethylene, a thermoplastic resin sheet of polycarbonate, or a thermosetting resin sheet such as an epoxy resin. . In addition, as other materials, the substrate is quartz glass, etc.
Various glasses can be used.

  For the preparation of the BM pattern, a photosensitive black composition is applied on the substrate 11 and preliminarily dried using a roll coater, curtain coater, various kinds of printing, dipping, or other coating film forming means. The black photosensitive layer 21 shown in FIG. Moreover, as a formation method of the black photosensitive layer 21, after forming the coating film of the photosensitive black composition once on support bodies, such as a film, it can also transfer on the board | substrate 11. FIG.

  Next, the black photosensitive layer 21 on the substrate 11 is subjected to pattern exposure through a photomask using an active light source such as ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, etc., development, film curing The process is performed to form the BM 21b shown in FIG.

  The film thickness of BM21b is preferably in the range of 0.2 μm to 3.0 μm, more preferably in the range of 0.5 μm to 2.0 μm. If the film thickness of the BM 21b is less than 0.2 μm, sufficient light shielding properties cannot be obtained at the time of panel display, and backlight light leaks, resulting in display defects. On the other hand, when the thickness of the BM 21b exceeds 3.0 μm, the step between the central portion of the colored layer 30 and the end portion of the colored layer 30 riding on the BM becomes large. Causes alignment defects (disclination, etc.) of the liquid crystal.

  Next, a photosensitive red composition is applied on the substrate 11 on which the BM 21b is formed and dried to form a red photosensitive layer shown in FIG. 1C, and pattern exposure, development, and film curing are performed through a photomask. The process is performed to produce a red layer 31R shown in FIG.

  By performing this operation on the photosensitive green composition and the photosensitive blue composition in the same manner, the green layer 32G shown in FIG. 1E and the blue layer 33B shown in FIG. A color filter for a liquid crystal display device can be obtained in which the colored layer 30 including the BM 21b, the red layer 31R, the green layer 32G, and the blue layer 33B is formed.

  The thickness of the colored layer 30 is preferably in the range of 0.5 μm to 4.0 μm, more preferably in the range of 1.0 μm to 2.5 μm. When the thickness of the colored layer 30 is less than 0.5 μm, it is necessary to increase the pigment concentration in the photosensitive coloring composition, thereby increasing the viscosity of the photosensitive coloring composition and forming a uniform pattern. It becomes difficult. When the thickness of the colored layer 30 exceeds 4.0 μm, it may be difficult to adjust the cell gap when manufacturing a liquid crystal display panel.

  A liquid crystal display device using the color filter for a liquid crystal display device of the present invention will be described. The liquid crystal display device includes the color filter configured as described above. The color filter is formed with structures such as transparent electrodes and spacers (not shown). Such a color filter is arranged so as to face, for example, a TFT array substrate (not shown) on which TFT elements for driving liquid crystal are arranged, and liquid crystal is filled between the color filter and the TFT array substrate. Has been. The color filter, the liquid crystal, and the TFT array substrate are sandwiched between, for example, a pair of polarizing plates arranged in crossed Nicols, and a liquid crystal display device is configured.

  Examples and comparative examples according to the present invention will be specifically described, but the present invention is not limited to these examples without departing from the spirit of the present invention.

  The alkali-soluble resin (B) of the photosensitive black composition used in Examples and Comparative Examples was synthesized as follows.

<Synthesis of alkali-soluble resin (B) -1>
370 parts by weight of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 38 parts by weight of methacrylic acid, 6 parts by weight of 2-hydroxyethyl methacrylate, 21 parts by weight of benzyl methacrylate, n -A mixture of 16 parts of butyl methacrylate and 21 parts by weight of paracumylphenol ethylene oxide-modified acrylate (“Axix M110” manufactured by Toa Gosei Co., Ltd.) and 0.4 parts by weight of 2,2′-azobisisobutyronitrile for 2 hours The polymerization reaction was carried out dropwise. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts by weight of azobisisobutyronitrile dissolved in 10 parts by weight of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. An alkali-soluble resin solution was obtained. The resin acid value determined by an acid value reduction titration method using an aqueous potassium hydroxide (KOH) solution was 230 mg / KOH.

<Synthesis of alkali-soluble resin (B) -2>
370 parts by weight of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 45 parts by weight of methacrylic acid, 5 parts by weight of 2-hydroxyethyl methacrylate, 18 parts by weight of benzyl methacrylate, n -2 parts of a mixture of 14 parts by weight of butyl methacrylate and 18 parts by weight of paracumylphenol ethylene oxide modified acrylate (“Acnics M110” manufactured by Toagosei Co., Ltd.) and 0.4 part by weight of 2,2′-azobisisobutyronitrile The polymerization reaction was carried out dropwise over time. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts by weight of azobisisobutyronitrile dissolved in 10 parts by weight of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. An alkali-soluble resin solution was obtained. The resin acid value determined by an acid value reduction titration method using an aqueous potassium hydroxide (KOH) solution was 280 mg / KOH.

<Synthesis of alkali-soluble resin (B) -3>
Put 370 parts by weight of cyclohexanone in a reaction vessel, heat to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 28 parts by weight of methacrylic acid, 8.5 parts by weight of 2-hydroxyethyl methacrylate, 23 parts by weight of benzyl methacrylate. , N-butyl methacrylate 18 parts by weight, paracumylphenol ethylene oxide-modified acrylate (Toa Gosei Co., Ltd. “Acnics M110”) 23 parts by weight, 2,2′-azobisisobutyronitrile 0.4 part by weight Was added dropwise over 2 hours to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 0.2 part by weight of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. An alkali-soluble resin solution was obtained. The resin acid value determined by acid value reduction titration using an aqueous potassium hydroxide (KOH) solution was 160 mg / KOH.

<Synthesis of alkali-soluble resin (B) -4>
370 parts by weight of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 54 parts by weight of methacrylic acid, 4 parts by weight of 2-hydroxyethyl methacrylate, 16 parts by weight of benzyl methacrylate, n -2 parts of a mixture of 10 parts by weight of butyl methacrylate and 16 parts by weight of paracumylphenol ethylene oxide modified acrylate (“Acnics M110” manufactured by Toagosei Co., Ltd.) and 0.4 part by weight of 2,2′-azobisisobutyronitrile The polymerization reaction was carried out dropwise over time. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts by weight of azobisisobutyronitrile dissolved in 10 parts by weight of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. An alkali-soluble resin solution was obtained. The resin acid value determined by an acid value reduction titration method using an aqueous potassium hydroxide (KOH) solution was 350 mg / KOH.

  The alkaline developers used in the examples and comparative examples were prepared as follows.

<Adjustment of alkaline developer 1>
Sodium carbonate was added to pure water so that the sodium salt of propylene / maleic anhydride copolymer having an average molecular weight of 7000 and sodium bicarbonate of 0.5% by weight and sodium bicarbonate of 0.5% by weight was 0.5% by weight, It was adjusted by stirring and dissolving.

<Adjustment of alkali developer 2>
Sodium carbonate was added to pure water and stirred so that the sodium salt of propylene / maleic anhydride copolymer having an average molecular weight of 7000 and sodium bicarbonate of 1.5% by weight and sodium bicarbonate of 1.5% by weight was 2% by weight. It was adjusted by dissolving.

<Adjustment of alkali developer 3>
Sodium carbonate was added to pure water so that the sodium salt of propylene / maleic anhydride copolymer having an average molecular weight of 9000 was 0.5% by weight, and sodium bicarbonate was 0.5% by weight, and sodium bicarbonate was 0.5% by weight. It was adjusted by stirring and dissolving.

<Adjustment of alkali developer 4>
Sodium carbonate was added to pure water so that the sodium salt of propylene / maleic anhydride copolymer with 0.05 wt% sodium bicarbonate and 0.01 wt% sodium bicarbonate and an average molecular weight of 7000 was 0.5 wt%, It was adjusted by stirring and dissolving.

<Adjustment of alkali developer 5>
Sodium carbonate was added to pure water so that the sodium salt of 7.5% by weight and sodium bicarbonate was 4.5% by weight, and the sodium salt of propylene / maleic anhydride copolymer having an average molecular weight of 7000 was 0.5% by weight, It was adjusted by stirring and dissolving.

<Adjustment of alkali developer 6>
Sodium carbonate was added to pure water so that the sodium salt of propylene / maleic anhydride copolymer having an average molecular weight of 7000 and sodium bicarbonate of 0.5% by weight and sodium bicarbonate of 0.5% by weight was 0.01% by weight, It was adjusted by stirring and dissolving.

<Adjustment of alkali developer 7>
Sodium carbonate was added to pure water and stirred so that the sodium salt of propylene / maleic anhydride copolymer having an average molecular weight of 7000 and sodium bicarbonate of 0.5% by weight and sodium bicarbonate of 0.5% by weight was 8% by weight. It was adjusted by dissolving.
<Adjustment of alkaline developer 8>
Sodium carbonate was added to pure water so that the sodium salt of propylene / maleic anhydride copolymer with 1.5 wt% sodium bicarbonate and 0.5 wt% sodium bicarbonate and an average molecular weight of 3000 was 0.5 wt%, It was adjusted by stirring and dissolving.
<Adjustment of alkaline developer 9>
Sodium carbonate is added to pure water so that the sodium salt of propylene / maleic anhydride copolymer having an average molecular weight of 15000 and sodium bicarbonate of 0.5% by weight and 0.5% by weight of sodium bicarbonate is 0.5% by weight, It was adjusted by stirring and dissolving.
<Example 1>
<Adjustment of photosensitive black composition>
16.5 parts by weight of a solution in which a black pigment is dispersed in a solvent together with a dispersant (TPBK-234C manufactured by Mikuni Dye Co., Ltd.), 12.1 parts by weight of the alkali-soluble resin 1 and dipentaerythritol hexaacrylate as a photopolymerizable compound ( 3.9 parts by weight of DPHA manufactured by Nippon Kayaku Co., Ltd., ethanone as a photopolymerization initiator, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1, 1- ( O-acetyloxime) (Irgacure OXE02 manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.8 parts by weight, cyclohexanone 32 as a solvent
. 9 parts by weight, 32.9 parts by weight of propylene glycol-1-monomethyl ether-2-acetate, and 0.003 parts by weight of BYK-330 (by Big Chemie) as a leveling agent are mixed and stirred to give a resin acid value of 230 mg / KOH A photosensitive black composition was obtained.

<Sample preparation>
The obtained photosensitive black composition was applied onto a glass substrate using a spin coater to form a coating film having a thickness of 2.0 μm. After prebaking at 100 ° C. for 3 minutes, exposure was performed using a super high pressure mercury lamp lamp as a light source through a mask having a stripe pattern with an opening line width of 6 μm. Next, the unexposed area was removed by performing shower development for 50 seconds and 80 seconds using the alkali developer 1, and washed with water and post-baked at 230 ° C. for 60 minutes to form a black matrix pattern.

<Evaluation>
Pattern removal of the substrate after 80 seconds of shower development, linearity, cross-sectional shape, and residue of the substrate after 50 seconds of shower development using a scanning electron microscope (Hitachi Electronics: S-4500) for 50 seconds, And the line | wire width of the board | substrate which performed the shower image development for 80 second was evaluated with the optical microscope. Each criterion is shown below.

  Pattern peeling: A case where no peeling occurred, a case where peeling was less than half of the whole, and a case where peeling was more than half of the whole.

  Linearity: A case where there is no chipping or rattling of the pattern end, and a case where the pattern occurs are x.

  Cross-sectional shape: A forward tapered shape is indicated by ◯, a vertical shape is indicated by Δ, and a reverse tapered shape is indicated by ×.

  Residue: An unexposed portion of the substrate was observed, and a case where it did not occur was indicated as ◯, and a case where it occurred was indicated as x.

  Line width: It is preferable that the line width difference of each substrate is less than 1.5 μm. When the line width difference exceeds 1.5 μm, the accuracy is insufficient as a high-definition BM pattern, which causes a display defect of the liquid crystal display device.

The above evaluation items are affected by the development time. Pattern peeling, linearity, and cross-sectional shape deteriorate as the development time increases, and residues tend to occur when the development time is short. Regarding the line width, it is thick when the development time is short, and thin when the development time is long. Therefore, each sample substrate was prepared and evaluated so that the quality of the formed BM pattern did not change even when the development time changed, that is, from the viewpoint of securing a development margin.
<Example 2>
A photosensitive black composition was prepared in the same manner as in Example 1 except that the alkaline developer 2 was used, and samples were prepared and evaluated.
<Example 3>
A photosensitive black composition was prepared in the same manner as in Example 1 except that the alkaline developer 3 was used, and samples were prepared and evaluated.
<Example 4>
A photosensitive black composition was prepared in the same manner as in Example 1 except that the alkali-soluble resin (B) -2 was used, and samples were prepared and evaluated.
<Example 5>
A photosensitive black composition was prepared in the same manner as in Example 4 except that the alkaline developer 2 was used, and samples were prepared and evaluated.
<Example 6>
A photosensitive black composition was prepared in the same manner as in Example 4 except that the alkaline developer 3 was used, and samples were prepared and evaluated.
<Example 7>
<Adjustment of photosensitive red 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. 18 parts of PigMentREd254 (“Ilgar For Red B-CF” manufactured by Ciba Specialty Chemicals)
Red pigment: C.I. I. 2 parts of PigMentREd177 (“Chromophthal Red A2B” manufactured by Ciba Specialty Chemicals)
Dispersant (“Ajisper PB821” manufactured by Ajinomoto Fine Techno Co., Ltd.) 2 parts Alkali-soluble resin (B) -1 108 parts After that, the mixture having the following composition was stirred and mixed to be uniform and then filtered through a 5 μm filter. A photosensitive red composition having an acid value of 230 mg / KOH was obtained.
130 parts Alkali-soluble resin (B) -1 100 parts Polyfunctional polymerizable monomer ("Aronix M-400" manufactured by Toa Gosei) 25 parts Photoinitiator ("Irgacure 369" manufactured by Ciba Specialty Chemicals) 15 parts Sensitizer 4, 4'-bis (diethylamino) benzophenone 5 parts ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
325 parts of cyclohexanone <Sample preparation>
The obtained photosensitive red composition was applied onto a glass substrate using a spin coater to form a coating film having a thickness of 2.5 μm. After prebaking at 70 ° C. for 20 minutes, exposure was performed using an ultrahigh pressure mercury lamp lamp as a light source through a mask having a stripe pattern with an opening line width of 30 μm. Next, an unexposed portion was removed by performing shower development with an alkali developer 1 for 40 seconds, 50 seconds, and 60 seconds, washed with water, and post-baked at 230 ° C. for 30 minutes to form striped red pixels.

<Evaluation>
Pattern removal of the substrate after 50 seconds and 60 seconds of shower development, linearity, cross-sectional shape, and residue of the substrate after 40 seconds of development with a scanning electron microscope (Hitachi Electronics: S-4500) evaluated. Each criterion is shown below.

  Pattern peeling: A case where no peeling occurred, a case where peeling was less than half of the whole, and a case where peeling was more than half of the whole.

  Linearity: A case where there is no chipping or rattling of the pattern end, and a case where the pattern occurs are x.

  Cross-sectional shape: A forward tapered shape is indicated by ◯, a vertical shape is indicated by Δ, and a reverse tapered shape is indicated by ×.

  Residue: An unexposed portion of the substrate was observed, and a case where it did not occur was indicated as ◯, and a case where it occurred was indicated as x.

The above evaluation items are affected by the development time. Pattern peeling, linearity, and cross-sectional shape deteriorate as the development time increases, and residues tend to occur when the development time is short. Therefore, each sample substrate was prepared and evaluated so that the quality of the formed stripe pattern did not change even when the development time changed, that is, from the viewpoint of securing a development margin.
<Example 8>
A photosensitive red composition was prepared in the same manner as in Example 7 except that the alkaline developer 2 was used, and samples were prepared and evaluated.
<Example 9>
A photosensitive red composition was prepared in the same manner as in Example 7 except that the alkaline developer 3 was used, and samples were prepared and evaluated.
<Example 10>
A photosensitive red composition was prepared in the same manner as in Example 7 except that the alkali-soluble resin (B) -2 was used, and samples were prepared and evaluated.
<Example 11>
A photosensitive red composition was prepared in the same manner as in Example 10 except that the alkaline developer 2 was used, and a sample was prepared and evaluated.
<Example 12>
A photosensitive red composition was prepared in the same manner as in Example 10 except that the alkaline developer 3 was used, and samples were prepared and evaluated.
<Example 13>
Green pigment: C.I. I. PigMentGrEEn36
("Rionol Green 6YK" manufactured by Toyo Ink Manufacturing Co., Ltd.)
Yellow pigment: C.I. I. PigMentYEllOw150
(Bayer's "Funcheon First Yellow Y-5688")
A photosensitive green composition was prepared in the same manner as in Example 7 except that was used, and samples were prepared and evaluated.
<Example 14>
Blue pigment: C.I. I. Pigment Blue 15
("Rionol Blue ES" manufactured by Toyo Ink Co., Ltd.)
Purple pigment: C.I. I. Pigment Violet 23
(BASF “Paliogen Violet 5890”)
A photosensitive blue composition was prepared in the same manner as in Example 7 except that was used, and samples were prepared and evaluated.

<Comparative Example 1>
A photosensitive black composition was prepared in the same manner as in Example 1 except that the alkali-soluble resin 3 was used, and samples were prepared and evaluated.

<Comparative example 2>
A photosensitive black composition was prepared in the same manner as in Example 1 except that the alkali-soluble resin 4 was used, and samples were prepared and evaluated.

<Comparative Example 3>
A photosensitive black composition was prepared in the same manner as in Example 1 except that the alkaline developer 4 was used, and samples were prepared and evaluated.

<Comparative example 4>
A photosensitive black composition was prepared in the same manner as in Example 1 except that the alkaline developer 5 was used, and samples were prepared and evaluated.

<Comparative Example 5>
A photosensitive black composition was prepared in the same manner as in Example 1 except that the alkaline developer 6 was used, and samples were prepared and evaluated.

<Comparative Example 6>
A photosensitive black composition was prepared in the same manner as in Example 1 except that the alkaline developer 7 was used, and samples were prepared and evaluated.

<Comparative Example 7>
A photosensitive black composition was prepared in the same manner as in Example 1 except that the alkaline developer 8 was used, and samples were prepared and evaluated.

<Comparative Example 8>
A photosensitive black composition was prepared in the same manner as in Example 1 except that the alkaline developer 9 was used, and samples were prepared and evaluated.

<Comparative Example 9>
A photosensitive red composition was prepared in the same manner as in Example 7 except that the alkali-soluble resin 3 was used, and samples were prepared and evaluated.

<Comparative Example 10>
A photosensitive red composition was prepared in the same manner as in Example 7 except that the alkali-soluble resin 4 was used, and samples were prepared and evaluated.

<Comparative Example 11>
A photosensitive red composition was prepared in the same manner as in Example 7 except that the alkali developer 4 was used, and samples were prepared and evaluated.

<Comparative Example 12>
A photosensitive red composition was prepared in the same manner as in Example 7 except that the alkaline developer 5 was used, and samples were prepared and evaluated.

<Comparative Example 13>
A photosensitive red composition was prepared in the same manner as in Example 7 except that the alkaline developer 6 was used, and samples were prepared and evaluated.

<Comparative example 14>
A photosensitive red composition was prepared in the same manner as in Example 7 except that the alkali developer 7 was used, and samples were prepared and evaluated.

<Comparative Example 15>
A photosensitive red composition was prepared in the same manner as in Example 7 except that the alkaline developer 8 was used, and samples were prepared and evaluated.

<Comparative Example 16>
A photosensitive red composition was prepared in the same manner as in Example 7 except that the alkaline developer 9 was used, and a sample was prepared and evaluated.

  Table 1 shows the evaluation results of Examples 1 to 6, Table 2 shows the evaluation results of Comparative Examples 1 to 8, Table 3 shows the evaluation results of Examples 7 to 12, and Table 4 shows the evaluation results of Comparative Examples 9 to 16. Shown in

As shown in Table 1, after exposing the coating film of the photosensitive black composition whose acid value of the alkali-soluble resin is 200 mg to 300 mg / KOH, the content ratio of the basic compound is 0.1 to 10% by weight, and the molecular weight is 5000. In an example developed using an alkaline developer containing 0.05 to 5% by weight of an anionic polymer surfactant of 10000 to 10000, a fine line BM pattern is formed without causing problems in the development process. It is possible to manufacture a color filter for a high-definition liquid crystal display device and a liquid crystal display device including the color filter.

On the other hand, as shown in Table 2, the acid value of the alkali-soluble resin of the photosensitive black composition, the ratio of the basic compound in the alkali developer, the molecular weight of the anionic polymer surfactant, and the ratio are outside the scope of the present invention. In a comparative example, this is a result of occurrence of a defect in the development process.

As shown in Table 3, after exposing the coating film of the photosensitive red composition whose acid value of the alkali-soluble resin is 200 mg to 300 mg / KOH, the content ratio of the basic compound is 0.1 to 10% by weight, and the molecular weight is 5000. In an example developed using an alkaline developer having an anionic polymer surfactant content of 10000 to 10000% by weight, red, green, and blue without causing problems in the development process The colored layer pattern can be formed, and a color filter for a high-definition liquid crystal display device and a liquid crystal display device including the same can be manufactured.

On the other hand, as shown in Table 4, the acid value of the alkali-soluble resin of the photosensitive red composition, the basic compound ratio in the alkali developer, the molecular weight of the anionic polymer surfactant, and the ratio are outside the scope of the present invention. In a comparative example, this is a result of occurrence of a defect in the development process.

11 ... Substrate 21 ... Black photosensitive layer 21b ... BM
30 ... colored layer 31 ... colored photosensitive layer 31R ... red layer 32G ... green layer 33B ... blue layer 100 ... color filter for liquid crystal display device

Claims (4)

  At least one or more pigments (A) selected from the group of black, red, green and blue, alkali-soluble resin (B) having a resin acid value of 200 mg to 300 mg / KOH, photopolymerizable compound (C), photopolymerization A film obtained by applying a photosensitive composition containing an initiator (D) and a solvent (E) onto a transparent substrate and drying the film is exposed through a photomask, and then averaged with at least the basic compound (F). An alkaline developer containing an anionic polymer surfactant (G) having a molecular weight of 5000 to 10,000, wherein the proportion of the basic compound (F) in the alkaline developer is relative to the total amount of the developer Development is performed using an alkaline developer that is 0.1 to 10.0% by weight and the proportion of the anionic polymer surfactant (G) is 0.05 to 5.00% by weight with respect to the total amount of the developer. Black matrix putter Or method of manufacturing a color filter, which comprises forming a colored layer.   The method for producing a color filter according to claim 1, wherein the basic compound (F) is an inorganic alkali compound.   A color filter manufactured by the color filter manufacturing method according to claim 1.   A liquid crystal display device comprising the color filter according to claim 3.