Colored photosensitive resin composition, color filter, and image display device

Abstract

To provide a colored photosensitive resin composition which can achieve a fine colored pattern excellent in pattern adhesion and residue characteristics in light exposure using an ultrashort-wavelength exposing device of 300 nm or less and has high resolution.SOLUTION: A colored photosensitive resin composition is provided, including a coloring agent, alkali-soluble resin, a photopolymerization initiator, a photopolymerizable compound, and a solvent, wherein the photopolymerization initiator includes a compound represented by a specific chemical formula.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a colored photosensitive resin composition, a color filter, and an image display device. More specifically, the present invention relates to a colored photosensitive resin composition capable of realizing a high-resolution fine colored pattern excellent in pattern adhesion and residue characteristics during exposure using an ultra-short wavelength exposure device of 300 nm or less, a color filter formed using the same, and an image display device including the color filter.

Background Art

[0002] A solid-state imaging device is an element that converts an image captured by light energy into electrical information, and a color filter may be included below a lens. For example, a complementary metal-oxide-semiconductor (CMOS) image sensor (CIS) employs a color filter with a fine pitch patterned at a higher resolution than a color filter corresponding to pixels of a general display device. The color filter of the CIS usually has colored patterns of three primary colors, red (R), green (G), and blue (B), and plays a role of decomposing transmitted light into the three primary colors.

[0003] The colored pattern is formed using a colored photosensitive resin composition containing a pigment or a dye. Processing of the colored pattern using the colored photosensitive resin composition is usually performed in a lithography process, and a light source using g-line (wavelength 436 nm) or i-line (wavelength 365 nm) is generally used.

[0004] In recent years, solid-state imaging devices included in digital cameras and the like have been required to further reduce the pixel size for higher pixel counts and improved image quality. Along with this, the colored pattern has also been required to be ultra-fine and thin-film. However, it can be said that the size of the pattern that can be realized has reached its limit with a light source using a wavelength in the range of 463 to 365 nm used for forming the existing colored pattern.

[0005] In order to overcome such limitations, research has been conducted to form patterns using light sources with ultra-short wavelengths of 300 nm or less. However, the content of the colorant in the colored photosensitive resin composition increases, resulting in a decrease in the adhesion between the colored film and the support. As a result, it is difficult to ensure pattern characteristics and residues are generated.

[0006] Therefore, there has been a demand for the development of a colored photosensitive resin composition that is excellent in sensitivity to an ultra-short wavelength light source and has excellent pattern characteristics such as developability, adhesion, and residue or remaining film characteristics so that fine patterning is possible.

[0007] Korean Patent Publication No. 10-2009-0072754 discloses a composition for a color filter containing a pigment and a binder resin, but it is not suitable for application to the color filter for a high-resolution solid-state imaging device described above.

Summary of the Invention

Problems to be Solved by the Invention

[0008] One object of the present invention is to provide a colored photosensitive resin composition that can exhibit a high-resolution fine colored pattern with excellent adhesion and residue characteristics of the pattern during exposure using an ultra-short wavelength exposure device of 300 nm or less.

[0009] Another object of the present invention is to provide a colored pattern formed using the colored photosensitive resin composition.

[0010] Still another object of the present invention is to provide a color filter including the colored pattern.

[0011] A further object of the present invention is to provide an image display device including the color filter.

[0012] Still a further object of the present invention is to provide a solid-state imaging device including the color filter.

Means for Solving the Problems

[0013] On the one hand, the present invention provides a colored photosensitive resin composition containing a colorant, an alkali-soluble resin, a photopolymerization initiator, a photopolymerizable compound, and a solvent, wherein the photopolymerization initiator contains a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2.

[0014]

Chemical formula

[0015] In the above formula, R 1 is -(CH2) n R 4 and R 2 is an alkyl group of C1-C 20 and R 3 is

[0016]

Chemical formula

[0017] and R 4 is hydrogen or a cycloalkyl group of C3-C6, and n is an integer of 1 to 5.

[0018] In one embodiment of the present invention, the weight ratio of the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 may be 25:75 to 85:15.

[0019] The colored photosensitive resin composition according to one embodiment of the present invention may be used for manufacturing a color filter of a solid-state imaging device using an ultraviolet light exposure apparatus of 300 nm or less.

[0020] In one embodiment of the present invention, the ultraviolet light exposure apparatus of 300 nm or less may be a KrF scanner exposure apparatus.

[0021] On the other hand, the present invention provides a colored pattern formed using the colored photosensitive resin composition.

[0022] On the other hand, the present invention provides a color filter including the colored pattern.

[0023] On the other hand, the present invention provides an image display device characterized in that the color filter is provided.

[0024] On the other hand, the present invention provides a solid-state imaging device characterized in that the color filter is provided.

[0025] In one embodiment of the present invention, the solid-state imaging device may include a CMOS image sensor.

Effects of the Invention

[0026] The colored photosensitive resin composition according to the present invention contains a photopolymerization initiator containing a carbazole-based compound and an acetophenone-based compound having a specific structure, and thus has excellent pattern adhesion and residue characteristics during exposure when using an ultra-short wavelength exposure device of 300 nm or less, and can realize a high-resolution fine colored pattern.

Modes for Carrying Out the Invention

[0027] Hereinafter, the present invention will be described in more detail.

[0028] One embodiment of the present invention is a colored photosensitive resin composition containing a colorant (A), an alkali-soluble resin (B), a photopolymerization initiator (C), a photopolymerizable compound (D), and a solvent (E), wherein the photopolymerization initiator (C) contains a carbazole-based compound and an acetophenone-based compound having a specific structure.

[0029] Hereinafter, the colored photosensitive resin composition according to one embodiment of the present invention will be described in detail for each component.

[0030] [Colorant (A)] In one embodiment of the present invention, the colorant (A) may be an organic pigment, an inorganic pigment, or a dye generally used in the art.

[0031] The organic pigment may be various pigments used in printing inks, inkjet inks, etc. Specifically, phthalocyanine water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, pyranthrone pigments, or diketopyrrolopyrrole pigments, etc. may be mentioned.

[0032] The pigments may be surface-treated with a resin treatment, a pigment derivative having an acidic group or a basic group introduced as necessary, graft treatment on the pigment surface with a polymer compound, etc., micronized treatment by a sulfuric acid micronization method, etc., or washed with an organic solvent, water, etc. for removing impurities, and ionic impurities may be removed by an ion exchange method, etc.

[0033] Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Specifically, metal oxides or composite metal oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, or carbon black may be mentioned.

[0034] As the pigment used in the present invention, an organic pigment or an inorganic pigment generally used in the art may be used, and these may be used alone or in combination of two or more.

[0035] In particular, as the pigment, specifically, compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists) may be used. More specifically, pigments with the following Color Index (C.I.) numbers may be used, but are not necessarily limited thereto.

[0036] C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185, and 242 C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71 C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255, 264, and 277 C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37, and 38 C.I. Pigment Blue 15 (such as 15:3, 15:4, 15:6, etc.), 21, 28, 60, 64, and 76 C.I. Pigment Green 7, 10, 15, 25, 36, 47, 58, 59, 62, and 63 C.I. Pigment Brown 28 C.I. Pigment Black 1 and 7, etc. Among the exemplified C.I. pigment dyes, preferably, a pigment selected from C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15:6, C.I. Pigment Green 7, C.I. Pigment Green 36 or C.I. Pigment Green 58 may be used.

[0037] It is preferable to use a pigment dispersion liquid in which the particle size of the pigment is uniformly dispersed. As an example of a method for uniformly dispersing the particle size of the pigment, a method of performing a dispersion treatment by containing a pigment dispersant can be mentioned. According to this method, a pigment dispersion liquid in a state where the pigment is uniformly dispersed in the solution can be obtained.

[0038] Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, positive, polyester-based, and polyamine-based surfactants, and these may be used alone or in combination of two or more.

[0039] Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, etc. Other examples include products sold under trade names such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tokem Products Co., Ltd.), MEGAFAC (manufactured by Dainippon Ink and Chemicals, Inc.), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Zeneca Limited), EFKA (manufactured by EFKA Chemicals), PB 821 (manufactured by Ajinomoto Co., Inc.), and the like.

[0040] The pigment dispersant is usually used in an amount of 1 part by weight or less, preferably in the range of 0.05 to 0.5 part by weight, per 1 part by weight of the pigment. When the pigment dispersant is used in such a content, it is preferable because a pigment with a uniform particle size can be obtained.

[0041] The dye may be used without particular limitation as long as it has solubility in an organic solvent. Preferably, a dye having solubility in an organic solvent and capable of ensuring reliability such as solubility in an alkaline developer, heat resistance, and solvent resistance may be used.

[0042] As the dye, those selected from acidic dyes having acidic groups such as sulfonic acid and carboxylic acid, salts of acidic dyes and nitrogen-containing compounds, sulfonamide derivatives of acidic dyes, and their derivatives may be used. In addition, azo-based, xanthene-based, and phthalocyanine-based acidic dyes and their derivatives can also be selected.

[0043] Preferably, the dye includes compounds classified as dyes in the Color Index (published by The Society of Dyers and Colourists) and known dyes described in the Dyeing Notes (Color Dyeing Co., Ltd.).

[0044] Specific examples of the dye include, as C.I. solvent dyes, yellow dyes such as C.I. Solvent Yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; red dyes such as C.I. Solvent Red 8, 45, 49, 122, 125, 130; orange dyes such as C.I. Solvent Orange 2, 7, 11, 15, 26, 56; blue dyes such as C.I. Solvent Blue 35, 37, 59, 67; green dyes such as C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc.

[0045] Also, as C.I. acid dyes, yellow dyes such as C.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, 251; Red dyes such as C.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, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; Orange dyes such as C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; Blue dyes such as C.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, 340; Violet dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19; Examples include green dyes such as C.I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109.

[0046] Also, as C.I. Direct dyes, Yellow dyes such as C.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, 141; Red dyes such as C.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, 250; Orange dyes such as C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; Blue dyes such as C.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, 293; Violet dyes such as C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; Examples include green dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82.

[0047] Also, as C.I. mordant dyes, Yellow dyes such as C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; Red dyes such as C.I. Mordant 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, 95; Orange dyes such as C.I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; Blue dyes such as C.I. 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, 84; Violet dyes such as C.I. Mordant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; Examples include green dyes such as C.I. Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53.

[0048] One or more of the above pigments or dyes may be used in combination.

[0049] The colorant (A) may be contained in an amount of 5 to 80% by weight, preferably 30 to 70% by weight, based on 100% by weight of the total solid content in the colored photosensitive resin composition. When the content of the colorant (A) is within the above range, there are advantages that the color density of the pixels becomes sufficient during film formation, and the loss of the non-pixel portion during development is reduced and no residue is generated.

[0050] In the present invention, the solid content in the colored photosensitive resin composition means the sum of the components obtained by removing the solvent.

[0051] [Alkali-soluble resin (B)] In one embodiment of the present invention, the alkali-soluble resin (B) may be selected and used without particular limitation from resins known in the art as long as it has reactivity and alkali solubility by the action of light or heat, acts as a dispersion medium for the solid content containing a colorant, and functions as a binder resin.

[0052] Specifically, the alkali-soluble resin (B) is preferably a copolymer of a monomer containing an unsaturated carboxyl group and another monomer copolymerizable therewith.

[0053] Examples of the monomer containing an unsaturated carboxyl group include unsaturated carboxylic acids having one or more carboxyl groups in the molecule, such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids.

[0054] Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, etc. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, etc. The unsaturated polyvalent carboxylic acid may be an acid anhydride, and specifically, maleic anhydride, itaconic anhydride, citraconic anhydride, etc. may be mentioned. Further, the unsaturated polyvalent carboxylic acid may be a mono(2-methacryloyloxyalkyl) ester thereof, for example, succinic acid mono(2-acryloyloxyethyl), succinic acid mono(2-methacryloyloxyethyl), phthalic acid mono(2-acryloyloxyethyl), phthalic acid mono(2-methacryloyloxyethyl), etc. The unsaturated polyvalent carboxylic acid may be a mono(meth)acrylate of a dicarboxylic polymer having both ends thereof, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, etc.

[0055] The carboxyl group-containing monomers may be used alone or in admixture of two or more thereof.

[0056] Examples of other monomers copolymerizable with the carboxyl group-containing monomer include, for example, 3,4-epoxytricyclo[5.2.1.0 2,6 dec-9-yl acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6Epoxy (meth)acrylate compounds such as decan-8-yl acrylate, glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether; aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and indene;Unsaturated carboxylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate;Unsaturated carboxylic acid aminoalkyl esters such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate, glycidyl methacrylate; Vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl methacrylamide; Unsaturated imides such as maleimide, N-phenyl maleimide, N-cyclohexyl maleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; And macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane, etc. These monomers may be used alone or in admixture of two or more.;

[0057] The method for producing the copolymer is not particularly limited, and a conventionally known polymerization method may be used. Among the known polymerization methods, a solution polymerization method is preferred. Also, the polymerization temperature and polymerization time vary depending on the type and ratio of the monomers to be introduced, the molecular weight and acid value of the desired alkali-soluble resin. For example, polymerization may be carried out at 60 to 130 ° C for 1 to 10 hours.

[0058] When a solvent is used in the polymerization, a solvent used in a normal radical polymerization reaction may be used. Specifically, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide, etc. may be used. These solvents may be used alone or in combination of two or more.

[0059] As the polymerization initiator used in the polymerization, a commonly used polymerization initiator may be added, and there is no particular limitation. Specifically, organic peroxides such as diisopropylbenzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate; nitrogen compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate) and the like can be mentioned. These may be used alone or in combination of two or more.

[0060] During the polymerization, a chain transfer agent may be used to control the molecular weight and molecular weight distribution of the copolymer. As the chain transfer agent, mercapto compounds such as n-dodecanethiol, mercaptoacetic acid, methyl mercaptoacetate; α-methylstyrene dimer, etc. may be used.

[0061] The acid value of the alkali-soluble resin (B) is preferably 30 to 200 mgKOH / g. When the acid value of the alkali-soluble resin (B) is less than 30 mgKOH / g, it is difficult for the colored photosensitive resin composition to ensure a sufficient development rate. When it exceeds 200 mgKOH / g, the adhesion to the substrate is reduced and short circuits in the pattern are likely to occur.

[0062] Also, an alkali-soluble resin having a polystyrene-reduced weight average molecular weight (hereinafter simply referred to as "weight average molecular weight") measured by gel permeation chromatography (GPC; using tetrahydrofuran as an eluent solvent) of 3,000 to 100,000, preferably 5,000 to 50,000, is preferred. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film rate is increased, and the solubility of the unexposed portion in the developer is excellent, and the resolution tends to be improved, which is preferable.

[0063] The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the alkali-soluble resin (B) is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. When the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is 1.5 to 6.0, it is preferable because the developability is excellent.

[0064] The alkali-soluble resin (B) may be contained in an amount of 1 to 30% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition. When the content is within the above range, the solubility in the developer is sufficient, pattern formation is easy, and the film reduction of the pixel portion in the exposed portion is suppressed during development, and the drop-out property of the non-pixel portion is improved, which is preferable.

[0065] [Photopolymerization initiator (C)] In one embodiment of the present invention, the photopolymerization initiator (C) includes a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2.

[0066] [Chemical formula]

[0067] In the above formula, R 1 is -(CH2) n R 4 and R 2 is an alkyl group of C1-C 20 and R 3 is

[0068]

Chemical formula

[0069] and R 4 is hydrogen or a C3-C6 cycloalkyl group, n is an integer from 1 to 5.

[0070] The C1-C 20 alkyl group used in this specification means a linear or branched hydrocarbon consisting of 1 to 20 carbon atoms. For example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, nonyl, decyl, etc. are included, but not limited thereto.

[0071] The C3-C6 cycloalkyl group used in this specification means a monocyclic or condensed cyclic hydrocarbon consisting of 3 to 6 carbon atoms. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. are included, but not limited thereto.

[0072] The colored photosensitive resin composition according to an embodiment of the present invention uses a compound represented by the above chemical formula 1 and a compound represented by the above chemical formula 2 as a photopolymerization initiator, which is easy to adjust the sensitivity, and can improve the adhesion and residue characteristics of the pattern under a short wavelength of 300 nm or less, particularly 248 nm.

[0073] Since the compound represented by the above Chemical Formula 1 has a high absorbance at short wavelengths of 300 nm or less and excellent sensitivity, the adhesion of the pattern can be improved.

[0074] Specific examples of the compound represented by the above Chemical Formula 1 include ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetoxime) (trade name: Irgacure OXE-02, manufactured by BASF), 1-propanone, 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetoxime) (trade name: TR-PBG-304, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), and the like.

[0075] In addition, the compound represented by the above Chemical Formula 2 can improve the residue characteristics of the pattern by appropriately adjusting the sensitivity of the compound represented by Chemical Formula 1, and can form an ultra-fine pattern of 0.5 μm or less with a thin film having a thickness of about 0.5 μm.

[0076] The weight ratio of the compound represented by the above Chemical Formula 1 and the compound represented by Chemical Formula 2 is preferably 25:75 to 85:15 from the viewpoint of sensitivity adjustment during exposure using a light source with an ultra-short wavelength of 300 nm or less, and more preferably 25:75 to 50:50. The photopolymerization initiator (C) may further contain a photopolymerization initiator commonly used in the art as long as the object of the present invention is not impaired.

[0077] Examples of the photopolymerization initiator include one or more compounds selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, biimidazole-based compounds, oxime-based compounds, and thioxanthone-based compounds from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, and the like.

[0078] Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 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, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, and the like.

[0079] Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

[0080] Specific examples of the triazine-based 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-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like.

[0081] 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'-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'-tetraphenyl-1,2'-biimidazole, or a biimidazole compound in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboxyalkoxy groups. Among 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 preferably used.

[0082] Specific examples of the oxime-based compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, 1,2-octanedione, -1-(4-phenylthio)phenyl, -2-(o-benzoyloxime) (trade name: Irgacure OXE-01, manufactured by BASF), methanone, [8-[(acetyloxy)imino][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]-11-(2-ethylhexyl)-11H-benzo[a]carbazol-5-yl]-, (2,4,6-trimethylphenyl) (trade name: Irgacure OXE-03, manufactured by BASF), ethanone, 1-[9-ethyl-6-(1,3-dioxolane, 4-(2-methoxyphenoxy)-9H-carbazol-3-yl]-, 1-(o-acetyloxime) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA), methanone, (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy-2-methylphenyl]-, o-acetyloxime (trade name: ADEKA ARKULES NCI-831, manufactured by ADEKA), 1-propanone, 3-cyclopentyl-1-[2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-, 1-(o-acetyloxime) (trade name: TR-PBG-314, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), ethanone, 2-cyclohexyl-1-[2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-, 1-(o-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), ethanone, 2-cyclohexyl-1-[2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-, 1-(o-acetyloxime) (trade name: TR-PBG-331, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 1-octanone, 1-[4-[3-[1-[(acetyloxy)imino]ethyl]-6-[4-[(4,6-dimethyl-2-pyrimidinyl)thio]-2-methylbenzoyl]-9H-carbazol-9-yl]phenyl]-, 1-(o-acetyloxime) (trade name: EXTA-9, manufactured by Union Chemical Co., Ltd.), and the like.

[0083] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

[0084] In addition, the photopolymerization initiator (C) may be used in combination with a photopolymerization initiator aid (c1) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to an embodiment of the present invention can improve productivity by further increasing the sensitivity by containing the photopolymerization initiator aid (c1).

[0085] As the photopolymerization initiator aid (c1), for example, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and organic sulfur compounds having a thiol group may be preferably used.

[0086] Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, and aromatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-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. In particular, it is preferable to use an aromatic amine compound.

[0087] The carboxylic acid compound is preferably an aromatic heteroacetic acid, and specific examples include 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.

[0088] 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), tetraethylene glycol bis(3-mercaptopropionate), and the like.

[0089] The photoinitiator (C) may be contained in the range of 0.1 to 5% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition of the present invention. The crosslinking characteristics by exposure can be improved and high resolution can be effectively realized within the above range.

[0090] When the photoinitiator assistant (c1) is further used, the photoinitiator assistant (c1) may be contained in the range of 0.1 to 3% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition of the present invention. The sensitivity of the colored photosensitive resin composition can be further increased and the productivity of the color filter formed using the composition can be improved within the above range.

[0091] [Photopolymerizable Compound (D)] In one embodiment of the present invention, the photopolymerizable compound (D) is a compound that can be polymerized by the action of the above-described photoinitiator (C), and examples thereof include monofunctional photopolymerizable compounds, bifunctional photopolymerizable compounds, or polyfunctional photopolymerizable compounds having three or more functional groups.

[0092] Specific examples of the monofunctional photopolymerizable compound include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc. Commercially available products include Aronix M-101 (manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S (manufactured by Nippon Kayaku Co., Ltd.), or Biscoat 158 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), etc.

[0093] Specific examples of the bifunctional photopolymerizable compound include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. Commercially available products include Aronix M-210, M-1100, M-1200 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA (manufactured by Nippon Kayaku Co., Ltd.), Biscoat 260 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), AH-600, AT-600, or UA-306H (manufactured by Kyoeisha Chemical Co., Ltd.), etc.

[0094] Specific examples of the polyfunctional photopolymerizable compound having three or more functional groups include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, etc. Commercially available products include NK ESTER ATM-4E (manufactured by Shin-Nakamura Chemical Co., Ltd.), NK ESTER A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix M-309, M-520 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), etc.

[0095] The photopolymerizable compounds exemplified above may be used alone or in admixture of two or more.

[0096] The photopolymerizable compound may be contained in the range of 0.5 to 45% by weight, preferably 1 to 30% by weight, based on 100% by weight of the total solid content in the colored photosensitive resin composition of the present invention. When the photopolymerizable compound is contained within the above range, there is no reduction in photosensitivity, the strength of the film is sufficient, there is no disappearance of the pattern during development, the pattern construction is good even in the fine pattern portion, and the smoothness of the resist tends to be good, which is preferable.

[0097] [Solvent (E)] In one embodiment of the present invention, the solvent may be used without particular limitation as long as it is effective in dissolving other components contained in the colored photosensitive resin composition of the present invention, and solvents used in ordinary colored photosensitive resin compositions may be used. In particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, etc. are preferred.

[0098] Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone.

[0099] Among the solvents, it is more preferable to use an organic solvent having a boiling point of 100°C to 200°C from the viewpoints of coatability and drying properties. Examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

[0100] The solvents may be used alone or in combination of two or more thereof.

[0101] The solvent may be contained in the range of 30 to 95% by weight, preferably 40 to 85% by weight, based on 100% by weight of the entire colored photosensitive resin composition of the present invention. When the solvent is in the range of 30 to 95% by weight, it has an effect of improving coatability when coated with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes also referred to as a die coater), or an inkjet.

[0102] [Additive (F)] The colored photosensitive resin composition of the present invention may be used in combination with additives such as other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-aggregation agents, as necessary.

[0103] Specific examples of the other polymer compounds include thermosetting resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

[0104] The curing agent is used to enhance deep curing and mechanical strength. Specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

[0105] Specific examples of the epoxy compound in the hardener include bisphenol A-based epoxy resins, hydrogenated bisphenol A-based epoxy resins, bisphenol F-based epoxy resins, hydrogenated bisphenol F-based epoxy resins, novolak-type epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of such epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co)polymer epoxidized products, isoprene (co)polymer epoxidized products, glycidyl (meth)acrylate (co)polymers, triglycidyl isocyanurate, and the like.

[0106] Specific examples of the oxetane compound in the hardener include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like.

[0107] The hardeners exemplified above may be used alone or in admixture of two or more.

[0108] The hardener may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the hardener. Examples of the curing auxiliary compound include polycarboxylic acids, polycarboxylic acid anhydrides, acid generators, and the like. As the polycarboxylic acid anhydrides, those commercially available as epoxy resin hardeners may be used. Specific examples of the epoxy resin hardeners include, for example, Adeka Hardener EH-700 (manufactured by Adeka Corporation), Rica Sid HH (manufactured by Shin Nippon Rika Co., Ltd.), MH-700 (manufactured by Shin Nippon Rika Co., Ltd.), and the like.

[0109] The surfactant may be used to further improve the film-forming property of the colored photosensitive resin composition, and fluorine-based surfactants, silicone-based surfactants, and the like may be preferably used.

[0110] Examples of the silicone surfactant include commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 manufactured by Dow Corning Toray Silicone Co., Ltd., and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, and TSF-4452 manufactured by GE Toshiba Silicone Co., Ltd. Examples of the fluorine surfactant include commercially available products such as Megafac F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink and Chemicals, Inc. The surfactants exemplified above may be used alone or in combination of two or more.

[0111] Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like. The adhesion promoters exemplified above may be used alone or in combination of two or more.

[0112] Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like.

[0113] Specific examples of the ultraviolet absorber include 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, and the like.

[0114] Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

[0115] The colored photosensitive resin composition according to an embodiment of the present invention can be manufactured, for example, by the following method.

[0116] First, the pigment among the colorants (A) is mixed with the solvent (E), and dispersed using a bead mill or the like until the average particle size of the pigment becomes about 0.2 μm or less. At this time, if necessary, a pigment dispersant, a part or all of the alkali-soluble resin (B), or a dye may be mixed with the solvent (E) and dissolved or dispersed. To the mixed dispersion liquid, the remaining alkali-soluble resin (B), the photopolymerizable compound (D), the photopolymerization initiator (C), and the additive (F), and if necessary, the solvent (E) are further added so as to have a predetermined concentration, whereby the colored photosensitive resin composition according to the present invention can be manufactured.

[0117] The colored photosensitive resin composition according to the present invention may be used in forming a colored pattern. Further, as will be described later, the colored pattern may be used, for example, for a color filter, specifically, a color filter included in an image display device or a solid-state imaging device.

[0118] Therefore, an embodiment of the present invention relates to a colored pattern and a color filter formed using the above-described colored photosensitive resin composition. The color filter according to an embodiment of the present invention may be manufactured by applying the above-described colored photosensitive resin composition on a substrate and performing exposure and development in a predetermined pattern to form a colored pattern.

[0119] For example, the above-described colored photosensitive resin composition may be applied on a substrate and dried to form a pre-colored film.

[0120] When the color filter is applied to an image display device, the substrate may be a glass substrate without any coating, or a glass substrate coated with SiN x (protective film) having a thickness of 500 to 1,500 Å.

[0121] When the color filter is applied to a solid-state imaging device, the substrate may include a photoelectric conversion element substrate (e.g., a silicon substrate for CCD or CMOS) utilized in the solid-state imaging device. The substrate may also include a black matrix or black stripe for isolating each pixel.

[0122] The coating step may include a coating or printing process such as roll coating, spin coating, slit coating, inkjet printing, etc.

[0123] Next, the preliminary colored film may be exposed and developed to form a colored pattern corresponding to each pixel.

[0124] The exposure step may include laser exposure using a mask for selectively exposing the pixel region. As the light source, g-line (wavelength: 436 nm), h-line, KrF (248 nm), i-line (wavelength: 365 nm), etc. may be used. In particular, a KrF scanner may be utilized for the implementation of an ultra-fine pattern. The KrF scanner is an exposure device with a wavelength band of 248 nm for a laser oscillated using a krypton fluoride source.

[0125] Next, the colored pattern may be formed by selectively removing the non-exposed region with a developer.

[0126] The developing solution may contain, for example, an inorganic or organic alkaline compound. 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. Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, and the like. These may be used alone or in combination of two or more thereof.

[0127] After the developing step, for example, a post-baking step may be performed at 150 to 230 °C.

[0128] One embodiment of the present invention relates to an image display device including the above-described color filter.

[0129] The color filter of the present invention is applicable to various image display devices such as a normal liquid crystal display (LCD), an electroluminescent display device (EL), a plasma display device (PDP), a field emission display device (FED), and an organic light emitting element (OLED).

[0130] The image display device of the present invention includes a configuration known in the art except that it includes the above-described color filter.

[0131] In addition to the color filter described above, the image display device according to an embodiment of the present invention may further include a color filter including a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles. In such a case, the emitted light of the light source applied to the image display device is not particularly limited, but from the aspect of better color reproducibility, preferably, a light source that emits blue light may be used.

[0132] In addition to the color filter described above, the image display device according to an embodiment of the present invention may further include a color filter including only two types of hue pattern layers among the red pattern layer, the green pattern layer, and the blue pattern layer. In such a case, the color filter further includes a transparent pattern layer that does not contain quantum dot particles. When only two types of hue pattern layers are provided, a light source that emits light having a wavelength indicating the remaining hue that is not included may be used. For example, when only the red pattern layer and the green pattern layer are included, a light source that emits blue light may be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the blue light passes through the transparent pattern layer to show blue.

[0133] An embodiment of the present invention relates to a solid-state imaging device provided with the color filter described above.

[0134] The solid-state imaging device may include, for example, a CMOS image sensor (CIS).

[0135] The solid-state imaging device includes a support including a semiconductor element or a photoelectric conversion element and a microlens, and the color filter may be disposed between the support and the microlens.

Examples

[0136] Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples, and Experimental Examples. It should be noted that these Examples, Comparative Examples, and Experimental Examples are merely for explaining the present invention, and it is obvious to those skilled in the art that the scope of the present invention is not limited thereto.

[0137] [Examples 1 - 5 and Comparative Examples 1 - 7: Production of Colored Photosensitive Resin Compositions] Each component was mixed according to the composition shown in Table 1 below to produce a colored photosensitive resin composition (unit: wt%).

[0138] Experimental Example 1: Using the colored photosensitive resin compositions produced in Examples 1 - 5 and Comparative Examples 1 - 5, colored patterns were formed, and the adhesion and residues of the colored patterns were measured by the following methods. The measurement results are shown in Tables 1 and 2 below.

[0139] The colored photosensitive resin compositions of the above Examples and Comparative Examples were each applied onto the surface of an 8 - inch silicon wafer by the spin - coating method, and then placed on a hot plate and maintained at a temperature of 100°C for 90 seconds to form a preliminary colored layer. After the wafer with the preliminary colored layer formed was cooled to 23°C, it was exposed using a KrF scanner. The exposed coating film was developed with a 0.2 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) and post - heated at 200°C for 180 seconds to form a colored pattern. The thickness of each colored pattern was 0.5 μm, and the minimum line width (resolution) was 0.5 μm.

[0140] The adhesion and residues of the formed colored patterns were evaluated according to the following criteria, and the results are shown in Tables 1 and 2 below.

[0141] (1) Evaluation of Adhesion Whether 100% of the formed pattern remained without missing was observed by CD - SEM and evaluated according to the following evaluation criteria.

[0142] <Evaluation Criteria for Adhesion> 5: 100% of the formed pattern remained without missing 4: The formed pattern remains at 90% or more and less than 100% 3: The formed pattern remains at 70% or more and less than 90% 2: The formed pattern remains at 50% or more and less than 70% 1: The formed pattern remains less than 50% (2) Evaluation of Residue The residue of the obtained colored pattern was observed by CD-SEM and evaluated according to the following evaluation criteria.

[0143] <Evaluation Criteria for Residue> 5: No residue was observed between the colored patterns 4: There is a residue distribution with the ratio of the total area between the colored patterns being more than 0% and less than 10% 3: There is a residue distribution with the ratio of the total area between the colored patterns being 10% or more and less than 20% 2: There is a residue distribution with the ratio of the total area between the colored patterns being 20% or more and less than 30% 1: There is a residue distribution with the ratio of the total area between the colored patterns being 30% or more Experimental Example 2: Except that exposure was performed using an i-line scanner instead of a KrF scanner, colored patterns were formed using the colored photosensitive resin compositions produced in Comparative Examples 6 and 7 in the same manner as in Experimental Example 1, and the adhesion and residue of the colored patterns were measured.

[0144] The measurement results are shown in Table 2 below.

[0145]

Table 1

[0146]

Table 2

[0147] As shown in Table 1 above, it was confirmed that the colored photosensitive resin compositions of Examples 1 to 5 containing a carbazole-based compound and an acetophenone-based compound with specific structures as photoinitiators are excellent in pattern adhesion and residue characteristics when exposed using a light source with an ultra-short wavelength of 300 nm or less.

[0148] In contrast, it was confirmed that the colored photosensitive resin compositions of Comparative Examples 1 to 5 using a photoinitiator that does not contain any of the above-mentioned compounds with specific structures had poor adhesion or residue characteristics when exposed using a light source with an ultra-short wavelength of 300 nm or less.

[0149] Also, it was confirmed that the colored photosensitive resin compositions of Comparative Examples 6 and 7 containing a carbazole-based compound and an acetophenone-based compound with specific structures as photoinitiators had poor adhesion when exposed using a light source with a wavelength exceeding 300 nm.

[0150] As described in detail above for specific parts of the present invention, it is obvious to those with ordinary knowledge in the technical field to which the present invention pertains that such specific descriptions are merely preferred embodiments and do not limit the scope of the present invention. Those with ordinary knowledge in the technical field to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above content.

[0151] Therefore, it can be said that the substantial scope of the present invention is defined by the claims and their equivalents.

Claims

1. A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerization initiator, a photopolymerizable compound, and a solvent, The photopolymerization initiator includes a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2. 【Chemistry 1】 In the above formula, R １ is -(CH ２ ) ｎ R ４ and R ２ is C １ -C ２０ is an alkyl group of the formula R ３ teeth, 【Chemistry 2】 and R ４ is hydrogen or C ３ -C ６ is a cycloalkyl group of the formula: n is an integer from 1 to 5.

2. 2. The colored photosensitive resin composition according to claim 1, wherein a weight ratio of the compound represented by Chemical Formula 1 to the compound represented by Chemical Formula 2 is from 25:75 to 85:

15.

3. 2. The colored photosensitive resin composition according to claim 1, which is for producing a color filter of a solid-state imaging device using an exposure device for an ultrashort wavelength of 300 nm or less.

4. 4. The colored photosensitive resin composition according to claim 3, wherein the ultrashort wavelength exposure device of 300 nm or less is a KrF scanner exposure device.

5. A colored pattern formed by using the colored photosensitive resin composition according to any one of claims 1 to 4.

6. A color filter comprising the colored pattern according to claim 5 .

7. An image display device comprising the color filter according to claim 6.

8. A solid-state imaging device comprising the color filter according to claim 6.

9. 9. The solid-state imaging device of claim 8, comprising a CMOS Image Sensor (CIS).

Images