TW201507999A - A color photosensitive resin composition, color filter and display device comprising the same - Google Patents

Abstract

The present invention relates to a color photosensitive resin composition, color filter and display device comprising the same. The color photosensitive resin composition comprises the colorant, the alkaline-soluble resin, the photo-polymerizable compound, the photo-polymerizable initiator, and the solvent, and which is characterized in that the photo-polymerizable initiator comprises the Proxetil compound and the solvent comprises the 4-hydroxyl-4-methyl-2-pentanone.

Description

Coloring photosensitive resin composition, color filter and display device therewith

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

Color filters are widely used in imaging devices, liquid crystal display devices (LCDs), etc., and their applications are rapidly expanding. A color filter used for a color liquid crystal display device, an image pickup element, or the like is generally uniformly coated with a coloring photosensitive resin composition containing pigments of various colors such as red, green, and blue by spin coating to form a black matrix. After the substrate, the coating film formed by heat drying (hereinafter, also referred to as "prebaking") is exposed and developed, and further heat curing is repeated for each color as needed (hereinafter, also referred to as "post-baking"). The operation is performed by forming primitives of various colors. Here, the patterned color matrix is usually formed of a black photosensitive resin composition.

A coloring resin composition containing a pigment and a binder resin, a photopolymerizable compound, and a photopolymerization initiator are often used.

Recently, in order to improve the yield on the engineering, the colored photosensitive resin composition requires the same sensitivity and adhesion even with a small amount of exposure. The colored photosensitive resin composition.

Further, recently, the coloring material of the colored photosensitive resin composition is micronized in order to satisfy performance requirements such as high color purity and high brightness. Therefore, when the element is formed using the same, the coloring layer formed on the substrate has a problem of development residue which is not removed at the time of development. The prior art for solving the problem is generally a method for adjusting the acid value and molecular weight of the binder resin or the acid value of the binder resin and the composition, but the application range is limited, and when the acid value is too high, the adhesion is insufficient and the surface is poor. For this reason, in addition, even the residues remaining on the metal oxide film or the tantalum nitride film have limitations that are difficult to solve.

[Patent Literature]

Patent Document 1: Korean Patent No. 10-1222390

An object of the present invention is to produce a storage stability by using a photopolymerization initiator containing an oxime ester compound and a solvent containing 4-hydroxy-4-methyl-2-pentanone to produce a colored photosensitive resin composition. Color filter and display device with excellent sensitivity and adhesion.

In order to achieve the above object, a coloring photosensitive resin composition comprising a coloring agent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the photopolymerization initiator comprises the oxime ester of the following Chemical Formula 1 is provided a compound of the type comprising 4-hydroxy-4-methyl-2-pentanone.

In the formula, 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 by a halogen group, or an aralkyl group having 7 to 24 carbon atoms substituted by 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 aralkyl group having 7 to 24 carbon atoms, and R ₃ is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. Oxygen.

Further, the present invention provides a color filter comprising the colored photosensitive resin composition.

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

The colored photosensitive resin composition of the present invention contains the oxime ester compound of the above Chemical Formula 1 as a photopolymerization initiator and contains 4-hydroxy-4-methyl-2-pentanone as a solvent, thereby enabling storage stability and sensitivity. And a color filter with excellent adhesion.

Further, this color filter has an advantage that pattern short-circuiting is less likely to occur in the development process, and the productivity of the color filter can be improved.

The invention is described in more detail below.

The present invention relates to a coloring photosensitive resin composition comprising a coloring agent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the photopolymerization initiator contains an oxime ester compound of the following Chemical Formula 1, The aforementioned solvent contains 4-hydroxy-4-methyl-2-pentanone.

In the formula, 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 by a halogen group, or an aralkyl group having 7 to 24 carbon atoms substituted by 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 aralkyl group having 7 to 24 carbon atoms, and R ₃ is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. Oxygen.

When the photopolymerization initiator containing the above Chemical Formula 1 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 or more is 0.5 or more at 405 nm, and exposure is performed with a 405 nm laser exposure device. When the pattern of the color filter is formed, the initial efficiency is increased, and high sensitivity and excellent reliability of the colored photosensitive resin composition can be obtained without using too much photopolymerization initiator.

Further, by using a solvent containing 4-hydroxy-4-methyl-2-pentanone, the solubility of the aforementioned photopolymerization initiator can be increased.

The colored photosensitive resin composition produced by the above composition can be found to have high concentration and high transmittance, has good dispersion stability, and is excellent in characteristics over time, and can be effectively used as a raw material for forming a colored pattern constituting a color filter, and is colored. The photosensitive resin composition may contain an additional additive as needed.

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

(A) colorant

The aforementioned colorants are characterized by comprising more than one pigment, more than one dye, or a mixture thereof.

(a1) pigment

As the aforementioned pigment, an organic pigment or an inorganic pigment which is generally used in the field can be used. Further, if necessary, the pigment may be subjected to a resin treatment, a surface treatment such as a pigment derivative in which an acidic or basic group is introduced, a graft treatment in which a polymer compound or the like is grafted onto a pigment surface, a sulfuric acid micronization method, or the like. The micronization treatment, the cleaning treatment for removing impurities by an organic solvent or water, or the removal treatment of removing ionic impurities by an ion exchange method or the like.

As the organic pigment, various pigments used in printing inks, inkjet inks, and the like can be used, and specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, and isoindoles. Ketone pigment, isoindoline pigment, anthraquinone pigment, anthrone Materials, dioxazine pigments, anthraquinone pigments, diterpene pigments, pyrimidine pigments, anthrone (thantithrone) pigments, indanthrone pigments, flavanone pigments, dermatanone pigments and diketopyrrolopyrrole Pigments, etc.

In addition, examples of the inorganic pigment include metal compounds such as metal oxides and metal complex compounds, and specific examples thereof include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, and zinc. An oxide of a metal such as ruthenium, carbon black, an organic black pigment, titanium black, or a mixture of red, green, and blue pigments, or a composite metal oxide.

In particular, specific examples of the organic pigment and the inorganic pigment include compounds classified as pigments under the color rendering index (published by The Society of Dyers and Colourists), and more specifically, the following are exemplified. The color index (CI) number of pigments, but is not necessarily limited to this.

CI 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; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71; CI Pigment Red 9, 97, 105, 122, 123, 144, 149 , 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264; CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38; CI Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64 and 76; CI Pigment Green 7, 10, 15, 25, 36, 47 and 58; C.I. Pigment Brown 28; C.I. Pigment Black 1 and 7 and other pigments.

Preferably, from CI Pigment Yellow 138, 139, 150 and 185, CI Pigment Orange 38, CI Pigment Red 255, CI Pigment Violet 23, CI Pigment Blue 15:3, 15:6, CI Pigment Green 7, 36 and One or more selected from the group consisting of 58.

The pigment is preferably a pigment dispersion liquid whose particle diameter is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment is a method in which a pigment dispersant (a2) is dispersed and treated, and according to the method, pigment dispersion in a state in which the pigment is uniformly dispersed in a solution can be obtained. liquid.

(a2) pigment dispersant

The pigment dispersant is added to maintain deflocculation and stability of the pigment. Specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, and polyamine. These pigment dispersants may be used singly or in combination of two or more kinds, such as a surfactant.

Specific examples of the cationic surfactant include an amine salt such as octadecylamine hydrochloride and lauryl trimethylammonium chloride, or a quaternary ammonium salt.

Specific examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleate sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and twelve. An alkylarylsulfonate such as sodium alkylbenzenesulfonate or sodium dodecylnaphthalenesulfonate.

Specific examples of the aforementioned nonionic surfactants include polyoxyethylene alkyl groups. Ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitol Anhydride fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

Other examples include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, for example, tertiary amines. Polyurethanes, polyethyleneimine, etc.

Further, the pigment dispersant preferably contains an acrylate dispersant (hereinafter, an acrylate dispersant) containing butyl methacrylate (BMA) or methacrylic acid-N, N-dimethyl methacrylate Aminoethyl ester (DMAEMA). The commercially available product of the acrylate-based dispersant may, for example, be DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 or DISPER BYK-2150, and the acrylate-based dispersant may be used alone or in combination of two or more.

In addition to the aforementioned acrylic dispersant, the above-mentioned pigment dispersant can also use other resin-based pigment dispersants. Examples of the other resin-based pigment dispersant include a known resin-based pigment dispersant, particularly a polycarboxylate represented by polyurethane or polyacrylate, an unsaturated polyamine, a polycarboxylic acid, and a polycarboxylic acid. (partial) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polyoxyalkylene oxides, long chain polyaminoguanamine phosphates, hydroxyl-containing polycarboxylic acid esters, and their modifications a product, or a decylamine formed by the reaction of a polyester having a free carboxyl group with a poly(lower alkyleneimine) or an oily dispersant such as these salts; (meth)acrylic acid-styrene Copolymer, (meth)acrylic acid-(meth)acrylic acid Water-soluble resin or water-soluble polymer compound such as olefin copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; polyester; modified polyacrylate; ethylene oxide/epoxy An addition product of propane, a phosphate ester, or the like.

In the commercially available product of the above-mentioned other resin-type pigment dispersant, examples of the cationic resin-dispersing agent include: BYK (Chemical Co., Ltd.): 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; trade names of BASF: 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, EFKA-4510, EFKA-4800 Lubirzol's trade name: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Chuanyan Fine Chemicals Co., Ltd. (HINOACT) T-6000, HINOACTT-7000, HINOACTT-8000; Ajinomoto company's trade name: (AJISPUR) PB-821, AJISPURPB-822, AJISPURPB-823; Gongrongshe Chemical Company's trade name: (FLORENE) DOPA-17HF, FLORENEDOPA-15BHF, FLORENEDOPA-33, FLORENEDOPA-44, etc.

In addition to the acrylate-based dispersant, other resin-based pigment dispersants may be used singly or in combination of two or more kinds, or may be used together with an acrylate-based dispersant.

The pigment dispersant is in the range of 5 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment. When the content of the pigment dispersant exceeds 60 parts by weight, the viscosity is increased, and when the content is less than 5 parts by weight, problems such as microparticulation of the pigment or gelation after dispersion are difficult to occur.

(a3) dye

The dye can be used without limitation as long as it has solubility in an organic solvent. Preferably, a dye having solubility in an organic solvent and ensuring reliability against solubility, heat resistance, solvent resistance, and the like of an alkali developer is preferably used.

As the dye, a dye selected from an acid dye having an acidic group such as a sulfonic acid or a carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, or the like, and a derivative thereof can be used. It is also possible to select azo, xanthene, phthalocyanine acid dyes and their derivatives. Preferably, the dye is a compound classified as a dye in a color rendering index (published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (dyeing company).

In the specific examples of the aforementioned dye, as the CI solvent dye, CI solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146 and 179; CI solvent blue 5, 35, 36, 37, 44, 59, 67 and 70; CI solvent violet 8, 9, 13, 14, 36, 37, 47 and 49; CI solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 and 162; C.I. Solvent Oranges 2, 7, 11, 15, 26 and 56; C.I. Solvent Greens 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35.

CI solvent dyes, CI solvent red 8, 49, 89, 111, 122, 132, 146, 179; CI solvent blue 35, 36, 44, 45, 70; CI solvent violet 13 is excellent in solubility in organic solvents, Good CI solvent red 8, 122, 132.

Further, examples of the CI acid dye include: CI 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; CI 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; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52 , 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169 and 173; CI 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; CI Acid Violet 6B, 7, 9, 17, 19 and 66; CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105 , 106 and 109.

Among the acid dyes, C.I. Acid Red 92; C.I. Acid Blue 80, 90; C.I. Acid Violet 60 is excellent in solubility in an organic solvent.

Further, as the CI direct dye, CI 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; CI 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; CI Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106 and 107; CI 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; CI Direct Violet 47 , 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104; CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82.

Further, as the CI mordant dye, CI mordant yellows 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65; 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; CI mordant oranges 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47 and 48; CI mordant 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; CI mord Agent violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58; CI mordant green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53.

These dyes can be used individually or in combination of 2 or more types, respectively.

The content of the dye in the colorant is from 0.5 to 80% by weight, preferably from 0.5 to 60% by weight, more preferably from 1 to 50% by weight, based on the total weight of the solid content of the colorant. When the content of the dye in the coloring agent is from 0.5 to 80% by weight, the pattern can be prevented from deteriorating the reliability of elution of the dye by the organic solvent, 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 coloring agent is 5 to 60% by weight, even if a film is formed, the color density of the element is sufficient, and the defect of the non-pixel portion at the time of development does not decrease, and it is difficult to generate a residue.

In the present invention, the weight of the solid component in the colored photosensitive resin composition means the total content of the remaining components after the solvent is removed from the colored photosensitive resin composition.

(B) alkali soluble resin

It is produced by copolymerizing an ethylenically unsaturated monomer having a carboxyl group as an essential component in order to be soluble in the alkaline developing solution used in the developing treatment step at the time of pattern formation.

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; and dicarboxylic acid; An acid anhydride or a mono(meth)acrylate such as a ω-carboxypolycaprolactone mono(meth)acrylate having a carboxyl group and a hydroxyl group at both terminals, preferably acrylic acid or methacrylic acid.

In order to ensure additional developability to the alkali-soluble resin, a hydroxyl group can be provided. For the supply of hydroxyl The method of the base has a method of producing a copolymer of an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group; and a copolymer of an ethylenically unsaturated monomer having a carboxyl group and having a shrinkage a method of producing a glycerol-based compound by additional reaction; and further reacting a copolymer of an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group with a compound having a glycidyl group The method of manufacture.

Specific examples of the above ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. The ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, N-hydroxyl and acrylamide, etc., among them, 2-hydroxyethyl (meth)acrylate is preferred. The above ethylenically unsaturated monomer having a hydroxyl group may be used in combination of two or more kinds.

Specific examples of the compound having a glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, and glycidyl butyrate. , glycidyl methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, benzyl glycidyl ether, glycidyl-4-tert-butylbenzoic acid Ester, glycidyl stearate, aryl glycidyl ether, glycidyl methacrylate, etc., preferably, butyl glycidyl ether, aryl glycidyl ether, methacrylic acid shrinkage The glyceride and the above compound having a glycidyl group can be used in combination of two or more.

The unsaturated monomer copolymerizable in the production of the alkali-soluble resin can be exemplified as follows, but is not necessarily limited thereto.

As a specific example of a polymerizable monomer having a copolymerizable unsaturated bond, there is phenylethyl Alkene, vinyl toluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, methylene Aromatic vinyl compounds such as benzylbenzyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether; N- Cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenyl malayan Amine, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmale N-substituted Malay such as imine, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide a quinone imine compound; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( Isobutyl methacrylate, sec-butyl (meth) acrylate, (meth)acrylic acid alkyl esters such as t-butyl (meth)acrylate; cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate , (meth)acrylic acid tricyclo [5.2.1.02,6]decane-8-yl ester, (meth)acrylic acid-2-dicyclopentyloxyethyl ester, (meth)acrylic acid isobornyl ester and other alicyclic Group (meth) acrylates; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylate - Hydroxyethyl (meth)acrylate such as 2-hydroxy-3-phenoxypropyl ester or N-hydroxyethyl acrylamide; (A) aryl (meth) acrylate such as phenyl (meth) acrylate or benzyl (meth) acrylate; 3-(methacryloxymethyl) oxetane, 3-(methacryl)醯Oxymethyl)-3-ethyloxetane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxyloxy) Methyl)-2-phenyloxetane, 2-(methacryloxymethyl)oxetane, 2-(methacryloxymethyl)-4-trifluoromethyl An unsaturated oxetane compound such as a oxetane or the like.

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

The acid value is preferably from 30 to 150 mgKOH/g in order to ensure compatibility with the dye of the alkali-soluble resin and storage stability of the colored photosensitive resin composition. 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 to the substrate is lowered, and pattern short-circuiting is likely to occur, and a phase with the dye is generated. The solubility problem causes the dye in the colored photosensitive resin composition to precipitate, the storage stability is lowered, and the viscosity is increased.

Further, the content of the alkali-soluble resin is from 10 to 80% by weight, preferably from 10 to 70% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When the content of the alkali-soluble resin is from 10 to 80% by weight, the solubility in the developer is excellent, the pattern is easily formed, and the film in the element portion of the exposed portion is prevented from being reduced during development, and the defect in the non-image portion is improved. .

(C) Photopolymerizable compound

The photopolymerizable compound (C) is used as long as it is in the following photopolymerization initiator (D) The compound which can be polymerized can be used.

The number of the functional groups is not particularly limited, and a difunctional or higher polyfunctional photopolymerizable compound is preferably used, and a trifunctional or higher polyfunctional photopolymerizable compound which is excellent in polymerizability and sufficiently cured is preferably used.

Specific examples of the aforementioned difunctional photopolymerizable compound include 2-hydroxy-1,3-dimethylpropenyloxypropane, 2-hydroxy-1-propenyloxy-3-methylpropenyloxypropane Wait.

Specific examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and two or more kinds thereof may be used in combination. Commercially available products include trade name 701 (NK ESTER), 701A (NK ESTER), A-TMM-3L (NK ESTER), KAYARAD DPHA (Japan Chemical).

The total amount of the photopolymerizable compound (C) relative to the solid content in the colored photosensitive resin composition is 5 to 45% by weight, preferably 7 to 45% by weight. When the photopolymerizable compound (C) is 5 to 45% by weight, the strength and smoothness of the element portion are good.

(D) Photopolymerization initiator

The photopolymerization initiator (D) is characterized by comprising an oxime ester compound (d1) in which an ethyl carbazole structure represented by the following Chemical Formula 1 is substituted with NO ₂ . The propylene glycol methyl ether acetate solution containing the photopolymerization initiator at a concentration of 0.01% by weight or more must have an absorbance at 405 nm of 0.5 or more.

[Chemical Formula 1]

In the formula, 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 by a halogen group, or an aralkyl group having 7 to 24 carbon atoms substituted by 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 aralkyl group having 7 to 24 carbon atoms, and R ₃ is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. Oxygen.

When the propylene glycol methyl ether acetate solution containing the photopolymerization initiator of the oxime ester compound of the above Chemical Formula 1 at a concentration of 0.01% by weight or more or more has an absorbance at 405 nm of 0.5 or more, exposure is performed with a 405 nm laser exposure device. On the other hand, when the pattern is formed, the initial efficiency is high, and high sensitivity and excellent reliability of the colored photosensitive resin composition can be obtained without using too much photopolymerization initiator.

Further, the photopolymerization initiator (d2) other than the above may be additionally used insofar as the effects of the present invention are not impaired. The above photopolymerization initiator (d2) is preferably one selected from the group consisting of an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, and a thioxanthone compound. The above compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzoin dimethyl ketal. 2-hydroxy-1-[4- (2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2- Morpholinylpropan-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) Butane-1-one and the like.

As the benzophenone compound, for example, benzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenylsulfide Ether, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)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-piperidin-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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan) -2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl) Vinyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3, 5-triazine and the like.

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis ( 2,3-Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'- Tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole, 2,2 -bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and An imidazole compound or the like in which a phenyl group at the 4, 4', 5, 5' position is substituted with an alkoxycarbonyl group. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro) is preferred. Phenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl- 1,2'-biimidazole.

As the aforementioned thioxanthone compound, for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxy group Thioxanthone and the like.

In addition, the photopolymerization initiator may further contain a photopolymerization initiation aid (d3) in order to increase the sensitivity of the coloring photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention contains a photopolymerization initiation aid (d3), so that sensitivity is higher, and productivity can be improved.

The photopolymerization initiation aid (d3) can preferably be, 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.

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

The carboxylic acid compound is preferably an aromatic heteroacetic acid, and specific examples thereof include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, and methylethylphenylthioethyl. Acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthalene Thioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

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

The total amount of the photopolymerization initiator relative to the solid content in the colored photosensitive resin composition of the present invention is 0.1 to 30% by weight, preferably 1 to 20% by weight. 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, productivity is improved, and high resolution can be maintained. Further, the strength of the element portion formed using the composition described above and the smoothness of the surface of the above-described element portion become good.

The total weight of the oxime ester compound (d1) of the above Chemical Formula 1 is from 10 to 100% by weight, preferably from 20 to 100% by weight, based on the total weight of all the photopolymerization initiators. When the proportion of the oxime ester compound (d1) of Chemical Formula 1 in all the photopolymerization initiators is less than 10% by weight, the decrease in sensitivity due to the dye cannot be overcome, and pattern short-circuiting easily occurs in the development step.

In the case where the photopolymerization initiating auxiliary (d3) is additionally used, the total weight of the photopolymerization initiating auxiliary (d3) relative to the solid content in the colored photosensitive resin composition of the present invention The amount is 0.1 to 30% by weight, preferably 1 to 20% by weight. When the content of the photopolymerization initiation aid (d3) is in the range of 0.1 to 30% by weight, the sensitivity of the colored photosensitive resin composition is further improved, and the productivity of the color filter formed using the composition is improved. effect.

(E) solvent

In the present invention, the solvent is characterized in that it is necessary to contain 4-hydroxy-4-methyl-2-pentanone.

In addition, the solvent to be used in the coloring photosensitive resin composition can be used without particular limitation, and it is particularly preferable that it is an ether, an aromatic hydrocarbon, or a ketone, as long as it is effective to dissolve other components contained in the coloring photosensitive resin composition. Classes, alcohols, esters or guanamines.

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, and diethylene glycol diethyl ether. Dipropylene glycol dipropyl ether and diethylene glycol dibutyl ether.

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

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, and ethyl acetate. Butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, acetic acid Oxyvalyl ester, ethylene glycol monoacetate, ethylene glycol Diacetate, 3-methoxymethyl propionate, propylene glycol methyl ether acetate, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3 -propylene glycol, ethyl lactate, propylene glycol, n-propyl ether, 3-ethoxyethyl propionate, propylene glycol monobutyl ether, acetic acid-3-methoxy-1-butyl ester, ethylene glycol monobutyl ether, two Ethylene glycol methyl ethyl ether, 1,2-propylene glycol diacetate, dipropylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, dipropylene glycol monoethyl ether, γ-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, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol ethylene glycol monoacetate, propylene glycol diacetate, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, γ-butyrolactone, and the like.

In the solvent of the above-mentioned example, from the viewpoint of coatability and drying property, an organic solvent having a boiling point of 100 ° C to 200 ° C is preferable, and for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, or a ring can be used. Hexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The solvent of the above-mentioned example can be used singly or in combination of two or more kinds, and may be contained in an amount of 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. When a solvent is in the range of 60 to 90% by weight, a roll coater, a spin coater, a slit spin coater, a slit coater (also referred to as a slot coater), an ink jet type, or the like is used. When the coating device is applied, the coating property is excellent.

Further, the aforementioned 4-hydroxy-4-methyl-2-pentanone is colored relative to the colorimetric tree of the present invention. The total weight of the solvent in the fat composition is preferably from 5 to 20% by weight. 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 is precipitated to generate foreign matter, and the contrast is lowered. In addition, when it exceeds 20% by weight, the dispersibility of the colored photosensitive resin composition is lowered and the viscosity is increased.

(F) additive

The above-mentioned additives may be optionally added as needed, and for example, may be one or more selected from the group consisting of other polymer compounds, curing agents, surfactants, adhesion promoters, ultraviolet absorbers, and deflocculants.

Specific examples of the other polymer compound include curable resins such as epoxy resins and maleic imine resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylic acid. Thermoplastic resins such as esters, polyesters, and polyurethanes.

The curing agent is used to improve deep curing and mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, and the like.

In the above curing agent, examples of the epoxy compound include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, and novolak type. Epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, glycidyl ester resin, glycidylamine resin or the above-mentioned epoxy resin brominated derivative, epoxy resin and brominated derivative thereof Aliphatic alicyclic or aromatic epoxy compounds, epoxides of butadiene (co)polymers, epoxides of isoprene (co)polymers, glycidyl (meth)acrylates ( Common) polymer, isocyanuric acid triglycoside Oil esters, etc.

Among the above curing agents, the oxetane compound may, for example, be a carbonate dioxetane, xylene dioxetane, adipic acid dioxetane or dioxyethylene terephthalate. Heterocyclobutane, cyclohexanedicarboxylic acid di-oxetane, and the like.

The curing agent may be used in combination with a curing agent to form a curing auxiliary compound for ring-opening polymerization of an epoxy group of an epoxy compound or an oxetane skeleton of an oxetane compound. Examples of the curing auxiliary compound include polycarboxylic acids, polycarboxylic anhydrides, acid generators and the like. As the carboxylic acid anhydride, a commercially available product as an epoxy resin curing agent can be used. Specific examples of the aforementioned epoxy resin curing agent can be exemplified EH-700 (made by Asahi Electric Co., Ltd.), HH (manufactured by Nippon Chemical Co., Ltd.), MH-700 (manufactured by Nippon Chemical Co., Ltd.), etc. The curing agents of the foregoing examples may be used singly or in combination of two or more.

The surfactant can be used to further improve the film formability of the photosensitive resin composition, and organic hydrazines, fluorines, esters, cations, anions, nonionics, amphoteric surfactants, and the like are preferably used. Specific examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, and tertiary amines. Polyurethanes, polyethyleneimine, etc. Further, the above-mentioned organic terpene surfactants are, for example, DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc. of Toray Dow Corning Organic Co., Ltd., and TSF-4440, TSF-4300, TSF of GE Toshiba Organic Co., Ltd. -4445, TSF-4446, TSF-4460, TSF-4452, etc. The fluorosurfactant is, for example, a commercially available product of Dainippon Ink Chemical Industry Co., Ltd. F-470, F-471, F-475, F-482, F-489, etc. In addition, other commercially available products which can be used include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products Co., Ltd.), MEGAFAC (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Flourad (manufactured by Sumitomo 3M), Asahi guard, Surflon (above, manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Jielikon), EFKA (manufactured by EFKA Chemical Co., Ltd.), PB821 (manufactured by Ajinomoto Co., Ltd.), Disperbyk-series (BYK) -chemi) and so on. The surfactants of the foregoing examples can be used singly or in combination of two or more.

The type of the adhesion promoter is not particularly limited, and specific examples of the adhesion promoter which can be used include vinyl trimethoxy decane, vinyl triethoxy decane, and vinyl tris(2-methoxyethoxy). ) decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropane Triethoxy decane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)B Trimethoxy decane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethyl Oxydecane, 3-isocyanate propyl trimethoxy decane, 3-isocyanate propyl triethoxy decane, and the like. The adhesion promoters of the foregoing examples can be used singly or in combination of two or more. The total weight of the adhesion promoter to the solid content in the colored photosensitive resin composition is usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight.

The type of the ultraviolet absorber is not particularly limited, and specific examples thereof which can be used include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and an alkane. Oxyl Benzophenone and the like.

The type of the deflocculant is not particularly limited, and specific examples of usable may be sodium polyacrylate or the like.

The method for producing the colored photosensitive resin composition of the present invention will be described below by way of example.

First, the pigment (a1) in the coloring agent (A) is mixed with the solvent (E), and dispersed by using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, a part or all of the pigment dispersant (a2) or the alkali-soluble resin (B) or the dye (a3) may be mixed, dissolved or dispersed together with the solvent (E) as needed.

Further, the dye (a3), the balance of the alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D), and the additive (F) and the solvent as needed are further added to the above-mentioned mixed dispersion liquid. (E) The colored photosensitive resin composition of the present invention can be produced by forming a predetermined concentration.

Further, the present invention provides a color filter manufactured from the above-described colored photosensitive resin composition and a display device including the color filter.

The display device can be produced by applying the coloring photosensitive resin composition onto a substrate as described below, and performing photocuring and development to form a pattern.

First, after the colored photosensitive resin composition is applied onto a substrate (usually glass) or a layer formed of a solid component of a colored photosensitive resin composition which is formed in advance, a volatile component such as a solvent is removed by heating and drying. Smooth coating.

The coating method can be, for example, a spin coating method, a flexible coating method, a roll coating method, or a slit spin coating method. Or a slit coating method or the like. After heating and drying (prebaking) after application, or drying under reduced pressure, heating is performed to volatilize volatile components such as a solvent. Here, the heating temperature is usually from 70 to 200 ° C, preferably from 80 to 130 ° C. The thickness of the coating film after heat drying is usually about 1 to 8 μm. The coating film thus obtained was irradiated with ultraviolet rays by a mask for forming a target pattern. At this time, the entire exposed portion is uniformly irradiated with parallel rays, and a device such as a mask aligner or a stepper is preferably used to align the mask and the substrate to the correct position. When ultraviolet rays are irradiated, the portion irradiated with ultraviolet rays is solidified.

As the ultraviolet light, a g-line (wavelength: 436 nm), an h-line, an i-line (wavelength: 365 nm), or the like can be used. The amount of ultraviolet rays to be irradiated can be appropriately selected as needed, and the present invention is not limited thereto. When the cured coating film is brought into contact with the developing solution and the non-exposed portion is dissolved and developed, a target pattern shape can be formed.

The development method may be any one of a liquid addition method, a dipping method, and a spray coating. In addition, the substrate can be tilted at any angle during development. The developer is usually an aqueous solution containing a basic compound and a surfactant. The basic compound may be any of an inorganic as well as an organic basic compound. Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, potassium citrate, Sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonium borate, and the like. Further, specific examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, and trisole. Ethylamine, monoisopropylamine, diisopropylamine, ethanolamine, and the like.

These inorganic and organic basic compounds may be used alone or in combination of two. Used on. The concentration of the basic compound in the alkali developing solution is preferably 0.01 to 10% by weight, and more preferably 0.03 to 5% by weight.

The surfactant in the alkali developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, and oxyethylene/oxypropylene blocks. Copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene oxide Alkylamine and the like.

Specific examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleate sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and dodecane. An alkylarylsulfonate such as sodium benzenesulfonate or sodium dodecylnaphthalenesulfonate.

Specific examples of the cationic surfactant include an amine salt such as octadecylamine hydrochloride and lauryltrimethylammonium chloride, or a quaternary ammonium salt. These surfactants may 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, and more preferably 0.1 to 5% by weight. After the development, the water is washed, and if necessary, it may be post-baked 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 by the above respective procedures.

Hereinafter, in order to specifically describe the present invention, an exemplary embodiment will be described in detail. However, the embodiments of the present invention are susceptible to various modifications and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more fully illustrate the present invention by those skilled in the art.

<Manufacture of Pigment Dispersion Composition>

Production Example 1, Production of Pigment Dispersion Composition (M1)

15.5 parts by weight of pigment CI Pigment Red 254, pigment dispersant DISPERBYK-2001 (manufactured by BYK) 5.0 parts by weight, propylene glycol monomethyl ether acetate as solvent 61.5 parts by weight, and 4-hydroxy-4-methyl- 20 parts by weight of 2-pentanone was mixed by a bead mill for 12 hours, and it was dispersed to produce a pigment dispersion composition M1.

Production Example 2, Production of Pigment Dispersion Composition (M2)

15.5 parts by weight of pigment CI Pigment Green 58, 5.0 parts by weight of pigment dispersant DISPERBYK-2001 (manufactured by BYK Corporation), 61.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 4-hydroxy-4-methyl- 20 parts by weight of 2-pentanone was mixed by a bead mill for 12 hours, and dispersed to prepare a pigment dispersion composition M2.

Production Example 3, Production of Pigment Dispersion Composition (M3)

5.0 parts by weight of pigment CI Pigment Red 254, a pigment dispersant DISPERBYK-2001 (manufactured by BYK), 5.0 parts by weight, and 81.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed by a bead mill for 12 hours. Dispersion to produce a pigment dispersion composition M3.

Synthesis Example 1, Synthesis of alkali soluble resin

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, 13 parts by weight of acrylic acid, 10 parts by weight of benzyl methacrylate, 57 parts by weight of 4-methylstyrene, methyl group 20 parts by weight of methyl acrylate and 3 parts by weight of n-dodecyl mercaptan were placed in a flask including a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, and replaced with a nitrogen atmosphere. Thereafter, stirring was carried out to raise the temperature of the reaction liquid to 110 ° C and react for 6 hours. The alkali-soluble resin produced by the above method had a solid content acid value of 100.2 mgKOH/g, and the weight average molecular weight Mw measured by GPC was 15,110.

Synthesis Example 2 Synthesis of Photopolymerization Initiator (d1)

step 1

37.3 g of AlCl ₃ and 112.0 g of dichloroethane were placed in a reactor under a nitrogen atmosphere, stirred at a temperature of 5 ° C, and 240.3 g of dichloroethane and 48.1 were dissolved in 17.27 g of an acetonitrile chloride solution. The nitrocarbazole of g was dropped into the reactor in 1 hour. Thereafter, the temperature was raised to 15 ° C and further stirred for 2 hours. Distilled water was placed in the reactor, washed and separated, and the solvent was dried to obtain a reactant 1 having a purity of 94%.

Step 2

35.0 g of the aforementioned reactant 1, 11.1 g of hydroxylamine hydrochloride, 15.1 g of sodium acetate, 90 g of ethanol and 30 g of distilled water were placed in a reactor under a nitrogen atmosphere, and the temperature was maintained at 80 ° C and stirred for 5 hours. Thereafter, distilled water was placed, and the precipitate was separated and dried to obtain a reactant 2 having a purity of 92%.

Step 3

26.0 g of the reactant 2 and 78 g of dichloromethane were added to a reactor under a nitrogen atmosphere, and stirred at normal temperature. Thereafter, a mixed solution of 15.0 g of acetic anhydride diluted with 15.0 g of dichloroethane was added dropwise to the reactor over 1 hour, followed by stirring for 1 hour. After stirring, the mixture was washed with distilled water for several times, and then dichloromethane was evaporated to obtain a chemical formula 2 having a purity of 90%. Further, Chemical Formula 2 is a structure in which R ₁ and R ₂ of Chemical Formula 1 are a methyl group, and can be represented as follows. Further, the compound of the following Chemical Formula 2 was determined to have an absorbance at 405 nm of 0.523 with a 0.01% by weight concentration of a propylene glycol methyl ether acetate solution.

<Manufacture of Colored Photosensitive Resin Composition>

Example 1

38.89 parts by weight of the pigment dispersion composition M1 produced in the above-mentioned Production Example 1, 10.65 parts by weight of the resin produced in Synthesis Example 1, and 3.55 parts by weight of KAYARAD DPHA (Nippon Chemical Co., Ltd.) as a photopolymerizable compound, and light produced in Synthesis Example 2 a polymerization initiator (absorbance of a propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more at a 405 nm of 0.52) of 0.71 part by weight, 4-hydroxy-4-methyl-2- as a solvent 0.72 parts by weight of pentanone and 45.48 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition of Example 1.

Example 2

38.89 parts by weight of the pigment dispersion composition M2 produced in the above Production Example 2, 10.65 parts by weight of the resin produced in Synthesis Example 1, and 3.55 parts by weight of KAYARAD DPHA (Nippon Chemical Co., Ltd.) as a photopolymerizable compound, and light produced in Synthesis Example 2 a polymerization initiator (absorbance of a propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more at a 405 nm of 0.52) of 0.71 part by weight, 4-hydroxy-4-methyl-2- as a solvent 0.72 parts by weight of pentanone and 45.48 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition of Example 2.

Example 3

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

Example 4

36.94 parts by weight of the pigment dispersion composition M2, 0.26 produced in the above Production Example 2 a part by weight of CI solvent yellow 21 as a dye, 10.79 parts by weight of a resin produced in Synthesis Example 1, 3.59 parts by weight of KAYARAD DPHA (Nippon Chemical Co., Ltd.) as a photopolymerizable compound, and a photopolymerization initiator produced in Synthesis Example 2 (at 0.01) The absorbance at 405 nm of the propylene glycol methyl ether acetate solution containing the photopolymerization initiator at a concentration of more than % by weight or more is 0.52), 0.72 parts by weight, and 1.11 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent. 46.59 parts by weight of propylene glycol monomethyl ether acetate was mixed to prepare a colored photosensitive resin composition of Example 4.

Comparative example 1

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

Comparative example 2

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

Comparative example 3

38.89 parts by weight of the pigment dispersion composition M1 produced in the above-mentioned Production Example 1, 10.65 parts by weight of the resin produced in Synthesis Example 1, and 3.55 parts by weight of KAYARAD DPHA (Nippon Chemical Co., Ltd.) as a photopolymerizable compound, as a photopolymerization initiator N-1919 (absorbance of propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more at a 405 nm of 0.015, Asahi Electric Co., Ltd.) 0.71 part by weight, 4-hydroxy-4-methyl as a solvent 0.72 parts by weight of 2-pentanone and 45.48 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition of Comparative Example 3.

Comparative example 4

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

Comparative Example 5

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

Comparative Example 6

36.94 parts by weight of the pigment dispersion composition M1 produced in the above-mentioned Production Example 1, 0.26 parts by weight of CI Solvent Yellow 21 as a dye, 10.79 parts by weight of a resin produced in Synthesis Example 1, and KAYARAD DPHA as a photopolymerizable compound (Japanese) Medicine: 3.59 parts by weight of Irgacure OXE-02 as a photopolymerization initiator (absorbance of a propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more at a 405 nm of 0.004, BASF) 0.72 by weight The mixture was mixed with 1.11 parts by weight of 4-hydroxy-4-methyl-2-pentanone as a solvent and 46.59 parts by weight of propylene glycol monomethyl ether acetate to prepare a colored photosensitive resin composition of Comparative Example 6.

Comparative Example 7

36.94 parts by weight of the pigment dispersion composition M1 produced in the above-mentioned Production Example 1, 0.26 parts by weight of CI Solvent Yellow 21 as a dye, 10.79 parts by weight of a resin produced in Synthesis Example 1, and KAYARAD DPHA as a photopolymerizable compound (Japanese) Medicine: 3.59 parts by weight of N-1919 as a photopolymerization initiator (absorbance of propylene glycol methyl ether acetate solution containing photopolymerization initiator at a concentration of 0.01% by weight or more at 405 nm of 0.015, Asahi Electric Co., Ltd.) 0.72 parts by weight , as a solvent, 4-hydroxy-4-methyl-2-pentanone 1.11 The amount of the mixture and 46.59 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition of Comparative Example 7.

Comparative Example 8

38.89 parts by weight of the pigment dispersion composition M3 produced in the above Production Example 3, 10.65 parts by weight of the resin produced in Synthesis Example 1, and 3.55 parts by weight of KAYARAD DPHA (Nippon Chemical Co., Ltd.) as a photopolymerizable compound, as a photopolymerization initiator N-1919 (absorbance of propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% by weight or more at a 405 nm of 0.015, Asahi Electric Co., Ltd.) 0.71 part by weight, propylene glycol monomethyl ether acetate as a solvent 46.2 The colored photosensitive resin composition of Comparative Example 8 was produced by mixing in parts by weight.

Comparative Example 9

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

Experimental Example 1, Manufacturing of Color Filters

The colored photosensitive resin compositions of the above Examples 1 to 4 and Comparative Examples 1 to 9 were applied onto a 2 square inch glass substrate ("EAGLE XG" manufactured by Corning Incorporated) by spin coating, and then placed in a heating. The sheet was held at a temperature of 100 ° C for 3 minutes to form a film. Next, a test photomask having a pattern in which the light transmittance is changed in a range of 1 to 100% and a line width/space pattern of 1 μm to 50 μm is placed on the film, and the interval from the test photomask is placed. It was set to 300 μm and irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated with a illuminance of 40 mJ/cm ² using a 1 KW high-pressure mercury lamp including all of g, h, and i rays, and no special filter was used. The film irradiated with the above ultraviolet rays was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes to be developed. The glass plate coated with the above-mentioned film was washed with distilled water, dried with nitrogen gas, and heated in a heating furnace at 230 ° C for 25 minutes to produce a color filter. The film thickness of the above-described color filter was 2.3 μm.

Experimental Example 2, Manufacturing of Color Filters

A color filter was separately manufactured in the same manner as in Experimental Example 1, except that the test photomask was not used.

Physical properties of color filters of Experimental Example 3, Experimental Example 1 and Experimental Example 2

The adhesion and the line width of the pattern were measured for each of the color filters manufactured in Experimental Example 1, and the solvent resistance of each of the color filters manufactured in Experimental Example 2 was measured. The physical property measurement results are shown in Table 1 below.

(1) Adhesion

When the generated pattern was observed by an optical microscope, the degree of peeling phenomenon on the pattern was evaluated.

○: no peeling on the pattern

△: 1~3 peelings on the pattern

×: There are more than 4 strips on the pattern.

(2) pattern line width

The line width of the resulting pattern was measured by a scanning electron microscope. When the line width of the pattern is measured to be equal to or greater than the line width of the photomask, the sensitivity of the colored photosensitive resin composition is sufficient, and the line width is enlarged.

(3) Solvent resistance

The color filter was immersed in a normal temperature NMP solution for 30 minutes, washed with ultrapure water, and dried on a hot plate heated to 120 ° C for 2 minutes, and then the chromaticity before and after the immersion was measured. The formula used at this time is calculated by the following mathematical expression 1 indicating the color change under the three-dimensional colorimeter defined by L*, a*, b*, and the smaller the color change value, the more reliable the filter can be manufactured. Color.

[Math 1] △Eab*=[(△L*)2+(△a*)2+(△b*)2]^0.5

By the above results, the coloring photosensitive resin composition of the present invention containing the compound of Chemical Formula 2 produced as the photopolymerization initiator and the 4-hydroxy-4-methyl-2-pentanone as a solvent is used. The color filters of Examples 1 to 4 exhibited excellent results in any of the properties of adhesion, pattern line width, and solvent resistance as compared with the color filters of Comparative Examples 1 to 9.

Therefore, it is understood that the colored photosensitive resin composition of the present invention has more excellent effects in storage stability, sensitivity, and adhesion.

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 comprises an oxime ester compound of the following Chemical Formula 1, the solvent comprising 4 Hydroxy-4-methyl-2-pentanone, In the formula, 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 by a halogen group, or an aralkyl group having 7 to 24 carbon atoms substituted by 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 aralkyl group having 7 to 24 carbon atoms, and R ₃ is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. Oxygen. The colored photosensitive resin composition of Claim 1, wherein the propylene glycol methyl ether acetate solution containing the photopolymerization initiator at a concentration of 0.01% by weight or more has an absorbance of 0.5 or more at 405 nm, and the photopolymerization initiator contains The oxime ester compound of Chemical Formula 1. The colored photosensitive resin composition of claim 1, wherein the colored photosensitive resin composition contains 5 to 60% by weight of a coloring agent, 10 to 80% based on the total weight of the solid content of the colored photosensitive resin composition. % by weight of alkali-soluble resin, 5 to 45 weight The amount of the photopolymerizable compound and 0.1 to 30% by weight of the photopolymerization initiator contains 60 to 90% by weight of the solvent based on the total content of the colored photosensitive resin composition. The colored photosensitive resin composition of claim 3, wherein the photopolymerization initiator contains 10 to 100% by weight of the compound of Chemical Formula 1 of Claim 1 with respect to the total weight of the photopolymerization initiator. The colored photosensitive resin composition of claim 3, wherein the solvent contains 5 to 20% by weight of 4-hydroxy-4-methyl-2-pentanone with respect to the total weight of the solvent. The colored photosensitive resin composition of claim 1, wherein the colorant comprises one or more pigments or more than one dye. The colored photosensitive resin composition of claim 1, wherein the alkali-soluble resin has an acid value of 30 to 150 mgKOH/g. The colored photosensitive resin composition of claim 1, wherein the photopolymerization initiator further comprises an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, and a thioxanthone More than one compound in the group consisting of compounds. A color filter comprising the colored photosensitive resin composition of claim 1. A display device comprising a color filter as in claim 9.