JP2015041104A - Colored photosensitive resin composition, and color filter and display device including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition containing an oxime ester compound as a photopolymerization initiator, and 4-hydroxy-4-methyl-2-pentanone as a solvent, and a color filter and a display device excellent in storage stability, sensitivity and adhesiveness.SOLUTION: A colored photosensitive resin composition contains a coloring agent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The photopolymerization initiator contains an oxime ester compound. The solvent contains 4-hydroxy-4-methyl-2-pentanone.

Description

  The present invention relates to a colored photosensitive resin composition, a color filter including the same, and a display device.

  Color filters are widely used in image sensors, liquid crystal display devices (LCDs), and the like, and their application range is rapidly expanding. Color filters used in color liquid crystal display devices and image sensors are usually spin-coated with a colored photosensitive resin composition containing pigments corresponding to red, green, and blue colors on a substrate on which a black matrix is patterned. The coating film formed by heating and drying (hereinafter also referred to as “pre-baking”) is exposed and developed, and if necessary, further heat-cured (hereinafter also referred to as “post-baking”). It is manufactured by repeating the operation for each color and forming pixels of each color. Here, the black matrix on which the pattern is formed is usually formed of a black photosensitive resin composition.

  As such a colored photosensitive resin composition, many compositions containing a photopolymerizable compound and a photopolymerization initiator are used together with a pigment and a binder resin.

  Recently, in order to improve the yield in the process, the colored photosensitive resin composition is required to have the same sensitivity and adhesion even with a small exposure amount.

  Recently, the coloring material of the colored photosensitive resin composition has been made finer in order to satisfy required performance such as high color purity and high luminance. Therefore, when forming a pixel using this, the colored layer formed on the cloth has a problem of development residue that is not removed during development. A conventional technique for solving this is generally a method of adjusting the acid value and molecular weight of the binder resin or the acid value of the binder resin and the composition. When the value is excessively high, there is a problem that adhesion is insufficient, a surface defect is caused, and residues remaining on the metal oxide film and the silicon nitride film are difficult to solve.

Korean Registered Patent No. 10-1222390

  In the present invention, a photopolymerization initiator containing an oxime ester compound and a solvent containing 4-hydroxy-4-methyl-2-pentanone are used to produce a colored photosensitive resin composition. And it aims at manufacturing the color filter and display apparatus excellent in adhesiveness.

  In order to achieve the above object, the present invention provides a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the photopolymerization initiator comprises: The coloring photosensitive resin composition characterized by including the oxime ester type compound of following General formula (1), and the said solvent containing 4-hydroxy-4-methyl- 2-pentanone is provided.

R ₁ is an alkyl group having 1 to 8 carbon atoms, an OR ₃ group, an aryl group having 6 to 10 carbon atoms substituted with a halogen group, or an arylalkyl group having 7 to 24 carbon atoms substituted with a halogen group. And R ₂ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 24 carbon atoms, and R ₃ is an alkyl group having 1 to 20 carbon atoms. Group or an alkoxy group having 1 to 20 carbon atoms.

  The present invention also provides a color filter comprising the colored photosensitive resin composition.

  Furthermore, the present invention provides a display device including the color filter.

  The colored photosensitive resin composition of the present invention contains the oxime ester compound of the general formula (1) as a photopolymerization initiator and 4-hydroxy-4-methyl-2-pentanone as a solvent, so that the storage stability is improved. A color filter having excellent sensitivity and adhesion can be produced.

  In addition, the color filter has an advantage that pattern short-circuiting hardly occurs during the development process, and the productivity of the color filter can be improved.

  Hereinafter, the present invention will be described in more detail.

  The present invention is a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the photopolymerization initiator is an oxime represented by the following general formula (2): The present invention relates to a colored photosensitive resin composition comprising an ester compound, wherein the solvent comprises 4-hydroxy-4-methyl-2-pentanone.

R ₁ is an alkyl group having 1 to 8 carbon atoms, an OR ₃ group, an aryl group having 6 to 10 carbon atoms substituted with a halogen group, or an arylalkyl group having 7 to 24 carbon atoms substituted with a halogen group. And R ₂ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 24 carbon atoms, and R ₃ is an alkyl group having 1 to 20 carbon atoms. Group or an alkoxy group having 1 to 20 carbon atoms.

  When the photopolymerization initiator containing the general formula (2) is used, the absorbance of the propylene glycol methyl ether acetate solution containing the photopolymerization initiator at a concentration of 0.01% by weight or more is 0.5 at 405 nm. As described above, when a color filter pattern is formed by exposure with a 405 nm laser exposure device, the initiation efficiency is high, and the high sensitivity and excellent sensitivity of the colored photosensitive resin composition can be obtained without using an excessive photopolymerization initiator. Reliable.

  Moreover, the solubility of the said photoinitiator can be increased by using the solvent in which 4-hydroxy-4-methyl-2-pentanone is contained.

  The colored photosensitive resin composition produced with the composition can express a high concentration and high transmittance, has good dispersion stability, excellent characteristics due to time change, and forms a colored pattern constituting a color filter. The colored photosensitive resin composition can contain an additive as necessary.

  Hereinafter, the colored photosensitive resin composition of the present invention will be described in detail for each component.

(A) Colorant The colorant contains one or more pigments, one or more dyes, or a mixture thereof.

(A1) Pigment As the pigment, an organic pigment or an inorganic pigment generally used in the art can be used. If necessary, the pigment may be atomized by a resin treatment, a surface treatment using a pigment derivative having an acidic group or a basic group introduced, a pigment surface graft treatment with a polymer compound or the like, or a sulfuric acid atomization method. It is also possible to perform a treatment, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment of ionic impurities by an ion exchange method, or the like.

  As the organic pigment, various pigments used for printing ink, inkjet ink, and the like can be used. Specifically, a water-soluble azo pigment, an insoluble azo pigment, a phthalocyanine pigment, a quinacridone pigment, an isoindolinone pigment, Examples thereof include isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, ansanthrone pigments, indanthrone pigments, flavantron pigments, pyranthrone pigments, and diketopyrrolopyrrole pigments.

  Further, as the inorganic pigment, metal compounds such as metal oxides and metal complex salts can be used. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, Examples thereof include antimony, carbon black, organic black pigments, titanium black, and metal oxides or composite metal oxides such as pigments that are mixed with red, green, and blue to exhibit black.

  In particular, examples of the organic pigment and the inorganic pigment include compounds classified as pigments by a color index (published by The Society of Dyers and Colorists), and more specifically, the following colors: Examples include, but are not necessarily limited to, pigments having index (CI) numbers.

  C. I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185; I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71; C.I. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264; I. Pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38; I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76; C.I. I. Pigment Green 7, 10, 15, 25, 36, 47 and 58; C.I. I. Pigment brown 28; C.I. I. And pigments such as CI Pigment Black 1 and 7.

  Preferably, C.I. I. Pigment yellow 138, 139, 150, 185; I. Pigment orange 38; C.I. I. Pigment red 255; C.I. I. Pigment violet 23; C.I. I. Pigment blue 15: 3, 15: 6; and C.I. I. One or more selected from the group consisting of CI Pigment Green 7, 36, 58 is used.

  The pigment is preferably a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of the method for uniformly dispersing the pigment particle diameter include a method of dispersing by adding a pigment dispersant (a2). The pigment is uniformly dispersed in the solution by the above method. A pigment dispersion can be obtained.

(A2) Pigment dispersant The pigment dispersant is added to disaggregate and maintain stability of the pigment. Specific examples of the pigment dispersant include cationic, anionic, nonionic, and amphoteric. These include surfactants such as polyesters, polyesters, and polyamines, and these can be used alone or in combination of two or more.

  Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, or quaternary ammonium salts.

  Specific examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, and the like. And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.

  Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan Examples include fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

  Other examples include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines.

  The pigment dispersant preferably contains an acrylate dispersant (hereinafter referred to as an acrylate dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Examples of commercially available acrylate dispersants include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150. The acrylate dispersants may be used alone or in combination of two or more. Can be used as a mixture.

  As the pigment dispersant, other resin type pigment dispersants can be used in addition to the acrylate-based dispersant. Examples of the other resin-type pigment dispersants include known resin-type pigment dispersants, in particular, polycarboxylic acid esters represented by polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, and polycarboxylic acid (partial). A) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl groups-containing polycarboxylic acids, and their modified products, or free (Free) Oily dispersants such as amides formed by the reaction of polyesters having carboxyl groups with poly (lower alkyleneimines), or salts thereof; (meth) acrylic acid-styrene copolymers, (meth) acrylic Acid- (meth) acrylate ester copolymer, styrene - maleic acid copolymer, polyvinyl alcohol or water-soluble resin or a water-soluble polymeric compounds such as polyvinyl pyrrolidone; polyesters; modified polyacrylate; ethylene oxide / propylene oxide addition product of; and and phosphate esters.

  Examples of commercially available products of the other pigment-type pigment dispersants include, for example, BYK (BIC) Chemie's trade names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162. , DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF Corporation trade names: EFKA-44, EFKA-46, EFKA-47, EFKA -48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, E KA-4510, EFKA-4800; trade names of Lubilzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; trade names of Kawaken Fine Chemicals: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; Ajinomoto brand names: AJISPER PB-821, Ajisper PB-822, Azisper PB-823; Kyoeisha Chemical brand names: FLORENE DOPA-17HF, FLOREN DOPA-15BHF, FLOREN DOPA -33, florene DOPA-44 and the like.

  In addition to the acrylate-based dispersant, other resin-type pigment dispersants can be used alone or in admixture of two or more, and can also be used in combination with an acrylate-based dispersant.

  The pigment dispersant is contained in an amount of 5 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content in the pigment. When the content of the pigment dispersant exceeds 60 parts by weight, the viscosity increases, and when it is less than 5 parts by weight, it may be difficult to atomize the pigment or cause problems such as gelation after dispersion. .

(A3) Dye The dye can be used without limitation as long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye that has solubility in an organic solvent and can secure reliability such as solubility in an alkali developer, heat resistance, and solvent resistance.

  As the dye, an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, or a derivative thereof can be used. Besides these, azo, xanthene, and phthalocyanine acid dyes, and derivatives thereof may also be selected. Preferably, the dye may be a compound classified as a dye in the color index (published by The Society of Dyers and Colorists), or a known dye described in a dye note (Color Dye).

  Specific examples of the dye include C.I. I. As a solvent dye, C.I. I. Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146 and 179; C.I. I. Solvent Blue 5, 35, 36, 37, 44, 59, 67 and 70; C.I. I. Solvent violet 8, 9, 13, 14, 36, 37, 47 and 49; C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 and 162; C.I. I. Solvent Orange 2, 7, 11, 15, 26 and 56; C.I. I. And dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35.

  C. above. I. Among solvent dyes, C.I. I. Solvent Red 8, 49, 89, 111, 122, 132, 146 and 179; I. Solvent Blue 35, 36, 44, 45 and 70; C.I. I. Solvent Violet 13 is excellent in solubility in an organic solvent, preferably C.I. I. Solvent Red 8, 122 and 132.

  In addition, C.I. I. As an acid dye, C.I. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422 and 426; I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243 and 251; I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169 and 173; I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335 and 340; C.I. I. Acid Violet 6B, 7, 9, 17, 19 and 66; C.I. I. And dyes such as Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109.

  C. above. I. Among acid dyes, C.I. I. Acid Red 92; I. Acid Blue 80, 90; and C.I. I. Acid Violet 60 has excellent solubility in organic solvents.

  In addition, C.I. I. As a direct dye, C.I. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246 and 250; I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138 and 141; C.I. I. Direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106 and 107; C.I. I. Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190,192,193,194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293; . I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104; I. Examples thereof include dyes such as direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, and 82.

  In addition, C.I. I. As a modern dye, C.I. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62 and 65; C.I. I. Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94 and 95; I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47 and 48; C.I. I. Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 44, 48, 49, 53, 61, 74, 77, 83 and 84; I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58; I. Dyes such as modern green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53 may be mentioned.

  The dyes can be used alone or in combination of two or more.

  The content of the dye in the colorant is 0.5 to 80% by weight, preferably 0.5 to 60% by weight, more preferably 1 to 50% by weight based on the total weight of the solid content in the colorant. preferable. When the content of the dye in the colorant is 0.5 to 80% by weight, it is possible to prevent the problem of lowering the reliability of the dye eluting with an organic solvent after pattern formation, and the sensitivity is increased. .

  The content of the colorant is 5 to 60% by weight, preferably 10 to 45% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When the colorant is contained in the amount of 5 to 60% by weight, the color density of the pixel is sufficient when a thin film is formed, the drop-off property of the non-pixel portion does not deteriorate during development, and a residue is hardly generated. .

  In the present invention, the weight of the solid content in the colored photosensitive resin composition means the total weight of the remaining components excluding the solvent of the colored photosensitive resin composition.

(B) Manufactured by copolymerizing an ethylenically unsaturated monomer having a carboxyl group as an essential component in order to be soluble in an alkaline developer used in the development processing step when forming an alkali-soluble resin pattern. To do.

  Specific examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; Anhydrides; mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate, and acrylic acid and methacrylic acid are preferred.

  In order to secure additional developability to the alkali-soluble resin, a hydroxyl group can be added. Examples of the method for imparting a hydroxyl group include a method in which an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group are copolymerized and an ethylenically unsaturated monomer having a carboxyl group. A method of producing a copolymer of saturated monomers by additionally reacting a compound having a glycidyl group, and an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group For example, there is a method in which a copolymer is additionally reacted with a compound having a glycidyl group.

  Specific examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3- There are phenoxypropyl (meth) acrylate, N-hydroxyethyl acrylamide, etc. Among them, 2-hydroxyethyl (meth) acrylate is preferable, and the ethylenically unsaturated monomer having the hydroxyl group is used in combination of two or more. can do.

  Specific examples of the compound having a glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl. Examples include ether, benzyl glycidyl ether, glycidyl 4-t-butylbenzoate, glycidyl stearate, aryl glycidyl ether, and glycidyl methacrylate, preferably butyl glycidyl ether, aryl glycidyl ether, and glycidyl methacrylate. The compounds having a glycidyl group can be used in combination of two or more.

  Although the unsaturated monomer copolymerizable at the time of manufacture of the said alkali-soluble resin is illustrated below, it is not necessarily limited to these.

  Specific examples of the polymerizable monomer having an unsaturated bond capable of copolymerization include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, Aromatic vinyl compounds such as o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether; N- Cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, Nm- N-substituted maleimide compounds such as tilphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide; methyl (meth) acrylate, Ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl ( Alkyl (meth) acrylates such as meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decan-8-yl (Meta) Alicyclic (meth) acrylates such as acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4 -Hydroxyethyl (meth) acrylates such as hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N-hydroxyethylacrylamide; aryl such as phenyl (meth) acrylate and benzyl (meth) acrylate (Meth) acrylates; 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethylo Cetane, 3- (methacryloyloxy) -2-phenyl oxetane, and the like 2- (methacryloyloxy) oxetane, 2- (methacryloyloxy) -4-unsaturated oxetane compounds such as trifluoromethyl oxetane.

  The monomers exemplified above can be used alone or in combination of two or more.

  In order to ensure the compatibility of the alkali-soluble resin with the dye and the storage stability of the colored photosensitive resin composition, the acid value is preferably 30 to 150 mgKOH / g. When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, the development speed of the colored photosensitive resin composition is slow, and when it exceeds 150 mgKOH / g, the adhesion with the substrate is reduced, and a pattern short circuit is likely to occur. There is a problem of compatibility with the dye, and the dye in the colored photosensitive resin composition is precipitated or the storage stability is lowered and the viscosity is likely to increase.

  Moreover, content of the said alkali-soluble resin is 10 to 80 weight% with respect to the total weight of solid content in a coloring photosensitive resin composition, Preferably it is 10 to 70 weight%. If the content of the alkali-soluble resin is 10 to 80% by weight, the developer is excellent in solubility and pattern formation is easy, and the reduction of the film of the pixel portion of the exposed portion during development is prevented. The drop-off property is improved.

(C) Photopolymerizable compound The photopolymerizable compound (C) must be a compound that can be polymerized by the action of the following photopolymerization initiator (D).

  The number of functional groups is not particularly limited, but a polyfunctional photopolymerizable compound having two or more functional groups is preferable, and a polyfunctional photopolymerizable compound having three or more functional groups that is excellent in polymerizability and can be cured sufficiently is more preferable.

  Specific examples of the bifunctional photopolymerizable compound include 2-hydroxy-1,3-dimethacryloxypropane and 2-hydroxy-1-acryloxy-3-methacryloxypropane.

  Specific examples of the trifunctional or higher functional polyfunctional photopolymerizable compound include pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and two or more kinds can be used in combination. Commercially available products include trade names 701 (NK ESTER), 701A (NK ESTER), A-TMM-3L (NK ESTER), KAYARAD DPHA (Nippon Kayaku) and the like.

  The photopolymerizable compound (C) is contained in an amount of 5 to 45% by weight, preferably 7 to 45% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When the photopolymerizable compound (C) is contained in the range of 5 to 45% by weight, the strength and smoothness of the pixel portion are improved.

(D) Photopolymerization initiator The photopolymerization initiator (D) includes an oxime ester compound (d1) in which an ethyl carbazole structure represented by the following general formula (3) is substituted with NO _2. To do. In addition, the absorbance at 405 nm of a propylene glycol methyl ether acetate solution containing the photopolymerization initiator at a concentration of 0.01% by weight or more must be 0.5 or more.

R ₁ is an alkyl group having 1 to 8 carbon atoms, an OR ₃ group, an aryl group having 6 to 10 carbon atoms substituted with a halogen group, or an arylalkyl group having 7 to 24 carbon atoms substituted with a halogen group. And R ₂ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 24 carbon atoms, and R ₃ is an alkyl group having 1 to 20 carbon atoms. Group or an alkoxy group having 1 to 20 carbon atoms.

  When the photopolymerization initiator containing the oxime ester compound of the general formula (3) is contained in a concentration of 0.01% by weight or more and the absorbance at 405 nm is 0.5 or more, 405 nm When the pattern is formed by exposure with a laser exposure device, the starting efficiency is high, and the excellent sensitivity and reliability of the colored photosensitive resin composition can be obtained without using an excessive photopolymerization initiator. .

  In addition, a photopolymerization initiator (d2) other than those described above can be additionally used within the range not impairing the effects of the present invention. As an example of the photopolymerization initiator (d2), one or more compounds selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, and thioxanthone compounds are used. Is preferred.

  Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylcatetal, 2-hydroxy-1- [4- (2-hydroxyethoxy). ) Phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and 2- (4-methylbenzyl) ) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the like.

  Specific examples of the benzophenone compounds include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) benzophenone, and 2,4,6-trimethylbenzophenone.

  Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4 -Methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2 , 4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4- Diethylamino-2-methylphenol Nyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine It is done.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl). -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2 ' -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4', 5,5'- Examples thereof include tetraphenyl-1,2′-biimidazole, and an imidazole compound in which the phenyl group at the 4,4 ′, 5,5 ′ position is substituted with a carboalkoxy group. Of these, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-Tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole are preferred.

  Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

  The photopolymerization initiator may further contain a photopolymerization initiation auxiliary agent (d3) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. When the colored photosensitive resin composition according to the present invention contains the photopolymerization initiation auxiliary agent (d3), the sensitivity becomes higher and the productivity can be improved.

  As the photopolymerization initiation auxiliary agent (d3), for example, one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group can be preferably used.

  As the amine compound, an aromatic amine compound is preferably used. Specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, 4-dimethyl Ethyl aminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (Common name: Michler's ketone), 4,4′-bis (diethylamino) benzophenone, and the like can be used.

  The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid. , Dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

  Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate).

  The photopolymerization initiator is contained in an amount of 0.1 to 30% by weight, preferably 1 to 20% by weight, based on the total weight of the solid content in the colored photosensitive resin composition of the present invention. When the photopolymerization initiator is in the range of 0.1 to 30% by weight, the sensitivity of the colored photosensitive resin composition is increased, the exposure time is shortened, the productivity is improved, and high resolution is maintained. be able to. Further, the strength of the pixel portion formed using the composition and the smoothness on the surface of the pixel portion can be improved.

  The oxime ester compound (d1) of the general formula (3) contains 10 to 100% by weight, preferably 20 to 100% by weight, based on the total weight of the total photopolymerization initiator. When the proportion of the oxime ester compound (d1) of the general formula (3) is less than 10% by weight in the entire photopolymerization initiator, the decrease in sensitivity due to the dye cannot be overcome, and a pattern short circuit occurs during the development process. Is likely to occur.

  When the photopolymerization initiation auxiliary agent (d3) is additionally used, the photopolymerization initiation auxiliary agent (d3) is 0 with respect to the total weight of the solid content in the colored photosensitive resin composition of the present invention. 0.1 to 30% by weight, preferably 1 to 20% by weight. When the content of the photopolymerization initiation auxiliary (d3) is in the range of 0.1 to 30% by weight, the sensitivity of the colored photosensitive resin composition is further increased and formed using the composition. The effect of improving the productivity of the color filter occurs.

(E) Solvent In the present invention, the solvent necessarily contains 4-hydroxy-4-methyl-2-pentanone.

  Further, the solvent is not particularly limited as long as it is effective for dissolving other components contained in the colored photosensitive resin composition, and the solvent used in the ordinary colored photosensitive resin composition is not particularly limited. In particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides and the like are preferable.

  Examples of the ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether. .

  Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

  Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

  Examples of the alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

  Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3- Methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 2-amino-2 -Methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, ethyl lactate, propylene glycol, n-propyl ester Ter, ethyl-3-ethoxypropionate, propylene glycol monobutyl ether, 3-methoxy-1-butyl acetate, ethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, 1,2-propylene glycol diacetate, dipropylene glycol monomethyl ether, Ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, gamma butyrolactone, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether acetate ethylene glycol monomethyl ether acetate Ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, and Examples thereof include γ-butyrolactone.

  Among the above-exemplified solvents, organic solvents having a boiling point of 100 ° C. to 200 ° C. are preferable in terms of coating properties and drying properties. For example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl Lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like can be used.

  The above exemplified solvents may be used alone or in admixture of two or more, and are 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition of the present invention. It should be included. When the solvent is in the range of 60 to 90% by weight, the coating property is improved when applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), or an ink jet. provide.

  The 4-hydroxy-4-methyl-2-pentanone is preferably contained in an amount of 5 to 20% by weight based on the total weight of the solvent in the colored photosensitive resin composition of the present invention. When the content of the 4-hydroxy-4-methyl-2-pentanone is less than 5% by weight, the dye in the colored photosensitive resin composition may precipitate and foreign matter may be generated, and the contrast may be reduced. is there. Moreover, when it exceeds 20 weight%, the dispersibility of a coloring photosensitive resin composition falls and the problem which a viscosity raises generate | occur | produces.

(F) Additive The additive can be selectively added as necessary. Examples thereof include other polymer compounds, curing agents, surfactants, adhesion promoters, ultraviolet absorbers, and anti-aggregation agents. 1 or more types selected from the group consisting of can be included.

  Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Is mentioned.

  The curing agent is used to enhance deep curing and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds and the like.

  Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, and other aromatics. Epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of the above epoxy resins, epoxy resins, and aliphatic, alicyclic or aromatic epoxies other than brominated derivatives thereof Examples thereof include compounds, butadiene (co) polymer epoxidized products, isoprene (co) polymer epoxidized products, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

  Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylate bisoxetane.

  The curing agent can be used in combination with a curing auxiliary compound that enables ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators. What is marketed as an epoxy resin hardening | curing agent can be used for the said polyhydric carboxylic acid anhydrides. Specific examples of the epoxy resin curing agent include ADEKA HARDNER EH-700 (manufactured by ADEKA INDUSTRY CO., LTD.), RIKACID HH (manufactured by Shin Nippon Rika Co., Ltd.), MH-700 (manufactured by Shin Nippon Rika Co., Ltd.) Is mentioned. The exemplified curing agents can be used alone or in admixture of two or more.

  The surfactant can be used to further improve the formation of a colored photosensitive resin composition film, and is based on silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric. Surfactants and the like can be preferably used. Specifically, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified Examples thereof include polyurethanes and polyethyleneimines. Examples of the silicone surfactant include commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, SH8400 manufactured by Dow Corning Toray Silicone Co., Ltd., TSF-4440, TSF-4300, TSF- 4445, TSF-4446, TSF-4460, TSF-4442, and the like. Examples of the fluorosurfactant include Megapiece F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink and Chemicals, Inc. as commercially available products. Other commercially available products include KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (POLYFLOW) (Kyoeisha Chemical Co., Ltd.), FTOP (EFTOP) (Tochem Products), MegaFac (MEGAFAC) (Dainippon Ink Chemical Co., Ltd.), Florad (Sumitomo 3M), Asahi guard, Surflon (above, Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) , EFKA (EFKA Chemicals), PB821 (Ajinomoto Co., Inc.), Disperbyk-series (BYK-chemi), and the like. The exemplified surfactants can be used alone or in combination of two or more.

  The kind of the adhesion promoter is not particularly limited, and specific examples of the adhesion promoter that can be used include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and N- (2-aminoethyl). ) -3-Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Propylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane 3 isocyanate propyl trimethoxysilane, and 3-isocyanate propyl triethoxy silane. The exemplified adhesion promoters can be used alone or in combination of two or more. The adhesion promoter is usually contained in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of the solid content in the colored photosensitive resin composition.

  Although the kind of the ultraviolet absorber is not particularly limited, specific examples that can be used include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone, and the like. Can be mentioned.

  The type of the anti-aggregation agent is not particularly limited, and specific examples that can be used include sodium polyacrylate.

  The method for producing the colored photosensitive resin composition of the present invention will be described with reference to examples.

  First, the pigment (a1) in the colorant (A) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle size of the pigment is about 0.2 μm or less. At this time, if necessary, the pigment dispersant (a2), a part or all of the alkali-soluble resin (B), or the dye (a3) can be mixed with the solvent (E) to be dissolved or dispersed.

  In the mixed dispersion, the dye (a3), the remainder of the alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D), and, if necessary, an additive (F) and a solvent ( The colored photosensitive resin composition according to the present invention can be produced by further adding E) to a predetermined concentration.

  Moreover, this invention provides the color filter manufactured with the coloring photosensitive resin composition, and a display apparatus provided with the same.

  It can manufacture by apply | coating the said colored photosensitive resin composition on a base material as follows, and photocuring and developing and forming a pattern.

  First, a colored photosensitive resin composition is applied on a substrate (usually glass) or a layer made of a solid content of a colored photosensitive resin composition previously formed, and then dried by heating to remove volatile components such as a solvent. Remove to obtain a smooth coating.

  As the coating method, for example, spin coating, soft coating method, roll coating method, slit and spin coating, or slit coating method may be used. After application, heat drying (pre-baking) or drying after reduced pressure heats to volatilize volatile components such as a solvent. Here, heating temperature is 70-200 degreeC normally, Preferably it is 80-130 degreeC. The thickness of the coating after heat drying is usually about 1 to 8 μm. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so that parallel light rays are uniformly irradiated on the entire exposure unit and accurate alignment between the mask and the substrate is performed. When the ultraviolet ray is irradiated, the portion irradiated with the ultraviolet ray is cured.

  As the ultraviolet rays, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like can be used. The irradiation amount of ultraviolet rays can be appropriately selected as necessary, and is not limited in the present invention. When the cured coating film is brought into contact with a developing solution to dissolve the non-exposed portion and developed, a spacer having a target pattern shape can be obtained.

  The developing method may be any of a liquid addition method, a dipping method, a spray method, and the like. Further, the substrate may be tilted at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate. , Potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Etc.

  These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.

  As the surfactant in the alkaline developer, at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, or a cationic surfactant can be used.

  Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan Examples include fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

  Specific examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.

  Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, or quaternary ammonium salts. These surfactants can be used alone or in combination of two or more.

  The concentration of the surfactant in the developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight. After development, it is washed with water, and if necessary, post-baking can be performed at 150 to 230 ° C. for 10 to 60 minutes.

  Using the colored photosensitive resin composition of the present invention, a specific pattern can be formed on the substrate through the above-described steps.

Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various different forms, and the scope of the present invention should not be construed to be limited to the embodiments detailed below. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.
<Production of pigment dispersion composition>
Production Example 1 As a production pigment of the pigment dispersion composition (M1), C.I. I. Pigment Red 254 13.5 parts by weight, DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant 5.0 parts by weight, propylene glycol monomethyl ether acetate 61.5 parts by weight as a solvent, and 4-hydroxy-4-methyl-2 -20 parts by weight of pentanone was mixed and dispersed by a bead mill for 12 hours to produce a pigment dispersion composition M1.

Production Example 2 As a production pigment of the pigment dispersion composition (M2), C.I. I. Pigment Green 58 13.5 parts by weight, DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant 5.0 parts by weight, propylene glycol monomethyl ether acetate 61.5 parts by weight as a solvent, and 4-hydroxy-4-methyl-2 -A pigment dispersion composition M2 was prepared by mixing and dispersing 20 parts by weight of pentanone by a bead mill for 12 hours.

Production Example 3 As a production pigment of the pigment dispersion composition (M3), C.I. I. 13.5 parts by weight of Pigment Red 254, 5.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, and 81.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed by a bead mill for 12 hours. A pigment dispersion composition M3 was produced.

Synthesis Example 1 In a flask equipped with a synthetic stirrer of alkali-soluble resin, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, 120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, acrylic acid 13 parts by weight, 10 parts by weight of benzyl methacrylate, 57 parts by weight of 4-methylstyrene, 20 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecyl mercapto were added and switched to a nitrogen atmosphere. Then, it stirred and raised the temperature of the reaction liquid to 110 degreeC, and reacted for 6 hours. The acid value of the solid content of the alkali-soluble resin produced by the above method was 100.2 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 15110.

Synthesis Example 2 Synthesis of photopolymerization initiator (d1) Step 1.
In a nitrogen atmosphere reactor, 37.3 g of AlCl ₃ and 112.0 g of dichloroethane were charged, and the temperature was maintained at 5 ° C. and stirred. In 17.27 g of the acetyl chloride solution, 240.3 g of dichloroethane and 48.1 g of nitrocarbazole were dissolved, and the dissolved solution was added dropwise to the reactor for 1 hour. Thereafter, the temperature was raised to 15 ° C. and further stirred for 2 hours. Distilled water was added to the reaction solution, and after washing and separation, the solvent was dried to obtain a reaction product 1 having a purity of 94%.

Step2.
A reactor in a nitrogen atmosphere was charged with 35.0 g of the above reactant 1, 11.1 g of hydroxylamine hydrochloride, 15.1 g of sodium acetate, 90 g of ethanol, and 30 g of distilled water, and the mixture was stirred for 5 hours while maintaining the temperature at 80 ° C. did. Thereafter, distilled water was added, and the precipitate was separated and dried to obtain a reaction product 2 having a purity of 92%.

Step3.
In a nitrogen atmosphere reactor, 26.0 g of the reaction product 2 and 78 g of dichloromethane were added and stirred at room temperature. Thereafter, a mixed solution obtained by diluting 15.0 g of acetic anhydride with 15.0 g of dichloroethane was dropped into the reactor for 1 hour, followed by stirring for 1 hour. After stirring, distilled water was added, washed several times, and then dichloromethane was evaporated to obtain a chemical formula (4) having a purity of 90%. The chemical formula (4) is a structure in which R ₁ and R _{2 in} the general formula (3) are methyl groups, and can be represented as follows. In addition, the compound of the following chemical formula (4) was measured to have an absorbance at 405 nm of 0.523 in a propylene glycol methyl ether acetate solution having a concentration of 0.01% by weight.

<Production of colored photosensitive resin composition>
Example 1.
38.89 parts by weight of the pigment dispersion composition M1 produced in Production Example 1, 10.65 parts by weight of the resin produced in Synthesis Example 1, 3.55 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, synthesis 0.71 parts by weight of the photopolymerization initiator produced in Example 2 (the absorbance at 405 nm of a propylene glycol methyl ether acetate solution containing the photopolymerization initiator at a concentration of 0.01% by weight or more) is 4- (as a solvent). A colored photosensitive resin composition of Example 1 was produced by mixing 0.72 parts by weight of hydroxy-4-methyl-2-pentanone and 45.48 parts by weight of propylene glycol monomethyl ether acetate.

Example 2
38.89 parts by weight of the pigment dispersion composition M2 produced in Production Example 2, 10.65 parts by weight of the resin produced in Synthesis Example 1, 3.55 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, synthesis 0.71 parts by weight of the photopolymerization initiator produced in Example 2 (the absorbance at 405 nm of a propylene glycol methyl ether acetate solution containing the photopolymerization initiator at a concentration of 0.01% by weight or more) is 4- (as a solvent). A colored photosensitive resin composition of Example 2 was produced by mixing 0.72 parts by weight of hydroxy-4-methyl-2-pentanone and 45.48 parts by weight of propylene glycol monomethyl ether acetate.

Example 3 FIG.
36.94 parts by weight of pigment dispersion composition M1 produced in Production Example 1 and C.I. I. 0.26 parts by weight of Solvent Yellow 21; 10.79 parts by weight of the resin produced in Synthesis Example 1, 3.59 parts by weight of KAYARAD DPHA (Nippon Kayaku) as the photopolymerizable compound, and the photopolymerization initiator produced in Synthesis Example 2. (A propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more has an absorbance at 405 nm of 0.52) 0.72 parts by weight, 4-hydroxy-4-methyl-2-pentanone as a solvent 1.11 parts by weight and 46.59 parts by weight of propylene glycol monomethyl ether acetate were mixed to produce a colored photosensitive resin composition of Example 3.

Example 4
36.94 parts by weight of pigment dispersion composition M2 produced in Production Example 2 and C.I. I. 0.26 parts by weight of Solvent Yellow 21; 10.79 parts by weight of the resin produced in Synthesis Example 1, 3.59 parts by weight of KAYARAD DPHA (Nippon Kayaku) as the photopolymerizable compound, and the photopolymerization initiator produced in Synthesis Example 2. (A propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more has an absorbance at 405 nm of 0.52) 0.72 parts by weight, 4-hydroxy-4-methyl-2-pentanone as a solvent A colored photosensitive resin composition of Example 4 was produced by mixing 1.11 parts by weight and 46.59 parts by weight of propylene glycol monomethyl ether acetate.

Comparative Example 1
38.89 parts by weight of the pigment dispersion composition M1 produced in Production Example 1, 10.65 parts by weight of the resin produced in Synthesis Example 1, 3.55 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, light Irgacure OXE-01 as a polymerization initiator (absorbance at 405 nm of propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more at 0.013, BASF) 0.71 part by weight, as a solvent A colored photosensitive resin composition of Comparative Example 1 was produced by mixing 0.72 parts by weight of 4-hydroxy-4-methyl-2-pentanone and 45.48 parts by weight of propylene glycol monomethyl ether acetate.

Comparative Example 2
38.89 parts by weight of the pigment dispersion composition M1 produced in Production Example 1, 10.65 parts by weight of the resin produced in Synthesis Example 1, 3.55 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, light Irgacure OXE-02 as a polymerization initiator (absorbance at 405 nm of a propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more at 0.004, BASF) 0.71 part by weight, as a solvent A colored photosensitive resin composition of Comparative Example 2 was produced by mixing 0.72 parts by weight of 4-hydroxy-4-methyl-2-pentanone and 45.48 parts by weight of propylene glycol monomethyl ether acetate.

Comparative Example 3
38.89 parts by weight of the pigment dispersion composition M1 produced in Production Example 1, 10.65 parts by weight of the resin produced in Synthesis Example 1, 3.55 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, light N-1919 as a polymerization initiator (absorbance at 405 nm of a propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more at 0.015, Adeka) 0.71 part by weight, 4 as a solvent A colored photosensitive resin composition of Comparative Example 3 was produced by mixing 0.72 parts by weight of -hydroxy-4-methyl-2-pentanone and 45.48 parts by weight of propylene glycol monomethyl ether acetate.

Comparative Example 4
38.89 parts by weight of the pigment dispersion composition M2 produced in Production Example 2; 10.65 parts by weight of the resin produced in Synthesis Example 1; 3.55 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound; Irgacure OXE-01 as a polymerization initiator (absorbance at 405 nm of propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more at 0.013, BASF) 0.71 part by weight, as a solvent A colored photosensitive resin composition of Comparative Example 4 was produced by mixing 0.72 parts by weight of 4-hydroxy-4-methyl-2-pentanone and 45.48 parts by weight of propylene glycol monomethyl ether acetate.

Comparative Example 5
38.89 parts by weight of the pigment dispersion composition M2 produced in Production Example 2; 10.65 parts by weight of the resin produced in Synthesis Example 1; 3.55 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound; Irgacure OXE-02 as a polymerization initiator (absorbance at 405 nm of a propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more at 0.004, BASF) 0.71 part by weight, as a solvent A colored photosensitive resin composition of Comparative Example 5 was produced by mixing 0.72 parts by weight of 4-hydroxy-4-methyl-2-pentanone and 45.48 parts by weight of propylene glycol monomethyl ether acetate.

Comparative Example 6
36.94 parts by weight of pigment dispersion composition M1 produced in Production Example 1 and C.I. I. 0.26 parts by weight of Solvent Yellow 21; 10.79 parts by weight of the resin produced in Synthesis Example 1, 3.59 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, and Irgacure OXE-02 ( The propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more has an absorbance at 405 nm of 0.004, BASF) 0.72 parts by weight, and 4-hydroxy-4-methyl-2 as a solvent. -A colored photosensitive resin composition of Comparative Example 6 was produced by mixing 1.11 parts by weight of pentanone and 46.59 parts by weight of propylene glycol monomethyl ether acetate.

Comparative Example 7
36.94 parts by weight of pigment dispersion composition M1 produced in Production Example 1 and C.I. I. 0.26 parts by weight of Solvent Yellow 21; 10.79 parts by weight of the resin prepared in Synthesis Example 1, 3.59 parts by weight of KAYARAD DPHA (Nippon Kayaku) as the photopolymerizable compound, and N-1919 (light) as the photopolymerization initiator. The propylene glycol methyl ether acetate solution containing a polymerization initiator at a concentration of 0.01% by weight or more has an absorbance at 405 nm of 0.015, Adeka Company) 0.72 parts by weight, and 4-hydroxy-4-methyl-2-2 as a solvent. A colored photosensitive resin composition of Comparative Example 7 was produced by mixing 1.11 parts by weight of pentanone and 46.59 parts by weight of propylene glycol monomethyl ether acetate.

Comparative Example 8.
38.89 parts by weight of the pigment dispersion composition M3 produced in Production Example 3, 10.65 parts by weight of the resin produced in Synthesis Example 1, 3.55 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, light N-1919 as a polymerization initiator (absorbance of 0.015% propylene glycol methyl ether acetate solution at 405 nm is 0.015, Adeka) 0.71 part by weight, propylene glycol monomethyl ether acetate 46.2 as a solvent The colored photosensitive resin composition of Comparative Example 8 was produced by mixing parts by weight.

Comparative Example 9
36.94 parts by weight of the pigment dispersion composition M3 produced in Production Example 3 and C.I. I. 0.26 parts by weight of Solvent Yellow 21; 10.79 parts by weight of the resin produced in Synthesis Example 1, 3.59 parts by weight of KAYARAD DPHA (Nippon Kayaku) as the photopolymerizable compound, and the photopolymerization initiator produced in Synthesis Example 2. (The absorbance at 405 nm of a propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more is 0.52) 0.72 parts by weight, 47.7 parts by weight of propylene glycol monomethyl ether acetate as a solvent By mixing, a colored photosensitive resin composition of Comparative Example 9 was produced.

Experimental Example 1 Color Filter Production After the colored photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 9 were applied on a 2-inch square glass substrate (manufactured by Corning, “EAGLE XG”) by spin coating, The film was placed on a heating plate and maintained at 100 ° C. for 3 minutes to form a thin film. Next, a test photomask having a pattern in which the transmittance is changed stepwise in the range of 1 to 100% and a line / space pattern of 1 μm to 50 μm is placed on the thin film, and the distance from the test photomask is 300 μm. Then, ultraviolet rays were irradiated. At this time, the ultraviolet light source is irradiated with an illuminance of 40 mJ / cm ² using a 1 KW high-pressure mercury lamp including all g, h, and i rays, and no special optical filter is used. The thin film irradiated with ultraviolet rays was developed by immersing in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes. The glass plate coated with the thin film was washed with distilled water, dried by spraying nitrogen gas, and heated in a heating oven at 230 ° C. for 25 minutes to produce a color filter. The film thickness of the manufactured color filter was 2.3 μm.

Experimental Example 2. Color filter production test Each color filter was produced in the same manner as in Experimental Example 1 except that no photomask was used.

Experimental Example 3. Measurement of physical properties of color filters of Experimental Example 1 and Experimental Example 2 Adhesion and pattern line width were measured with each color filter manufactured in Experimental Example 1, and solvent resistance was measured with each color filter manufactured in Experimental Example 2. did. The physical property measurement results are shown in Table 1 below.

(1) Adhesion When the generated pattern was observed with an optical microscope, the degree of peeling phenomenon on the pattern was evaluated.
○: No peeling on the pattern,
Δ: 1 to 3 peelings on the pattern,
X: 4 or more peelings on the pattern
(2) Pattern line width The line width of the generated pattern was measured using a scanning electron microscope. When the line width of the pattern is measured to be equal to or larger than the line width of the photomask, it can be said that the sensitivity of the colored photosensitive resin composition is sufficient and the line width is increased.

(3) Solvent resistance After immersing the color filter in NMP solution at room temperature for 30 minutes, washing with ultrapure water and drying on a hot plate heated to 120 ° C. for 2 minutes, the chromaticity before and after immersion is then measured. It was measured. At this time, the formula to be used is calculated by the following formula (1) indicating the color change in the three-dimensional colorimeter defined by L *, a *, and b *. The smaller the color change value, the higher the reliability. Color filters can be manufactured.

  Through the above results, the colored photosensitive resin composition of the present invention containing the compound of the chemical formula (4) produced in Synthesis Example 2 as a photopolymerization initiator and 4-hydroxy-4-methyl-2-pentanone as a solvent is used. The color filters of Examples 1 to 4 showed superior results in adhesion, pattern line width, and solvent resistance than the color filters of Comparative Examples 1 to 9.

  Therefore, it turned out that the colored photosensitive resin composition of this invention has the more excellent effect in storage stability, a sensitivity, and adhesiveness.

Claims (10)

A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the photopolymerization initiator is an oxime ester compound of the following general formula (1) The colored photosensitive resin composition, wherein the solvent contains 4-hydroxy-4-methyl-2-pentanone.

(Wherein R ₁ is an alkyl group having 1 to 8 carbon atoms, OR ₃ group, an aryl group having 6 to 10 carbon atoms substituted with a halogen group, or an arylalkyl group having 7 to 24 carbon atoms substituted with a halogen group. R ₂ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 24 carbon atoms, and R ₃ is an alkyl group having 1 to 20 carbon atoms. An alkyl group or an alkoxy group having 1 to 20 carbon atoms.)   The absorbance of a propylene glycol methyl ether acetate solution containing a photopolymerization initiator containing the oxime ester compound of the general formula (1) at a concentration of 0.01% by weight or more is 0.5 or more at 405 nm. The colored photosensitive resin composition according to claim 1.   5 to 60% by weight of the colorant, 10 to 80% by weight of the alkali-soluble resin, 5 to 45% by weight of the photopolymerizable compound, and the total weight of the solid content in the colored photosensitive resin composition 2. The colored photosensitive composition according to claim 1, comprising 0.1 to 30% by weight of a photopolymerization initiator and 60 to 90% by weight of the solvent based on the total weight of the colored photosensitive resin composition. Resin composition.   The said photoinitiator contains 10-100 weight% of compounds of General formula (1) of Claim 1 with respect to the total weight of a photoinitiator, The coloring of Claim 3 characterized by the above-mentioned. Photosensitive resin composition.   The colored photosensitive resin composition according to claim 3, wherein the solvent contains 5 to 20% by weight of 4-hydroxy-4-methyl-2-pentanone based on the total weight of the solvent.   The colored photosensitive resin composition according to claim 1, wherein the colorant contains one or more pigments or one or more dyes.   The colored photosensitive resin composition according to claim 1, wherein the alkali-soluble resin has an acid value of 30 to 150 mg KOH / g.   The photopolymerization initiator may additionally contain one or more compounds selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, and thioxanthone compounds. The colored photosensitive resin composition according to claim 1, wherein   A color filter comprising the colored photosensitive resin composition according to claim 1.   A display device comprising the color filter according to claim 9.